Note: Descriptions are shown in the official language in which they were submitted.
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FUEL COMPOSITIONS EXHIBITING IMPROVED FUEL STABILITY
Field of the Invention
The present invention relates to enhanced structured fuel
compositions for use in jet, turbine, diesel, gasoline, and other
combustion systems. More particularly, the present invention relates to
fuel compositions using viscous hydrocarbons, which are substantially
neutral pH, and which employ a silicon based combustion catalyst.
Background of the Invention
International patent application Nos. PCT/US95/02691,
PCT/US95/06758, and PCT/US96/09653, are incorporated in their
entirety herein by reference, and disclose fuel compositions and
combustion techniques for achieving vapor phase combustion based on
an enhanced combustion structure ("ECS"). This enhanced
combustion structure includes a combustible metallic and free radical
generating oxygenated compound. It has been found that such free
radical generating oxygenates include C2 - C12 aldehydes, aldehydic
acids, C2 -C 12 ethers, C 1 - C 15 alcohols, C2 - C 12 oxides, C3 - C 15
ketones, ketonic acids, C3 - C15 esters, othroesters, C3 - C12 diesters,
C5 -C12 phenols, C5 - C20 glycol ethers, C2 - C12 glycols) C3 - C20
alkyl carbonates, C3 - C20 dialkyl carbonates, C3 - C20 di-carbonates,
C 1 to C20 organic and inorganic peroxides, hydroperoxides, carboxylic
acids, amines, nitrates, di-nitrates, oxalates) phenols, acetic acids)
boric acids, orthoborates, hydroxyacids, orthoacids, anhydrides,
acetates, acetyls, formic acids, nitrates, di-nitrates) nitro- ethers, which
can meet minimum burning velocity (BV) and latent heats of
vaporization (LHV) requirements of aforementioned PCT Applications.
Specific compounds can be found in detail in Organic Chemistry 6th
Ed, T.W.G. Solomons, John Wiley & Sons) N.Y., (1995), Physical
Chemistry, 5th Ed, P.W. Atkins, Oxford University Press, U.K. (1994),
Physical Organic Chemistry, 2 Ed, N.S. Issacs, John Wiley & Sons,
N.Y. (1995) and Lange's Handbook of Chemistry, 14th Ed, J.A. Dean,
McGraw-Hill, N.Y. (1992), and their minimum BV/LHV requirements in
aforementioned PCT Applications, which are herein by incorporated by
reference.
Said enhanced combustion structure oxygenates, when in
combination with a combustible non-lead metal or non-metal (as set
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forth below), exhibit high heats of enthalpy capable, improved
combustion, thermal efficiency, fuel economy, and power. Of
particularly interest to this invention are the enhanced combustion
struture oxygenates of symmetrical dialkyl carbonates, especially
dimethyl and diethyl carbonates.
However) it has been reported symmetrical dialkyl carbonates,
such as dimethyl carbonate can be problematical fuel additives due to
their potential instability in fuel compositions, which can result in
undesired hydrolysis in acidic and aqueous environments. See EPO
Application # 91306278.2 Karas. Thus, it would be reasonable to
expect fuels containing lower dialkyl carbonates to store and perform
optimally only when in moderately strong or strongly alkaline
environments) i.e., pH's exceeding 11 or more. Fuels having pH's lower
than 11, e.g. moderately alkaline, nuetral and acidic would be expected
to be problematic.
In addition, conventional thinking and regulatory standards
encourage the utilization of more refined less viscous base fuel
hydrocarbons. The longer chain or more complex hydrocarbons, e.g.,
heavy oils, heavy fuel oils, diesels, etc., are typically not preferred as
fuels due to handling, emission and combustion concerns.
Summary of the Invention A primary object of the present
invention is the development and utilization of fuels having enhanced
combustion structure which have increased stability. A further object of
the present invention is the development of enhanced combustion
structured in which the base fuel may be more viscous, or not as highly
refined, as now required to meet minimum fuel standards. A further
object is the employment of a co-metallic catalyst, which further
enhances the combustion structure of the DMC and metal/non-metals
component, further improving thermal efficiency, fuel economy) power
and emissions.
In accordance therewith, the substantially non-alkaline fuel
compositions of the present invention exhibits improved stability, with
no apparent hydrolysis after storage for six months or more. In
addition, the presence of lower dialkyl carbonates and metals in the
fuel compositions of the present invention allows for the use of highly
viscous base fuels.
The improved fuels described herein contain a base hydrocarbon
fuel or propellant (including hydrogen) co-fuel, as provided in the PCT
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applications referenced above. Such co-fuels may be viscous,
moderately viscous, or highly viscous (e.g. having viscosities outside
industry standards). Said viscous fuels are combined with high energy
non-lead metallic or non-metallics (presented below), together with
symmetrical dialkyl carbonates, e.g., dimethyl or diethyl carbonate, and
preferably a silicon co-metallic combustion catalyst. When the fuel
compositions of the present invention are then constructed to a weakly
alkaline (7.5 to 11.0 pH), substantially neutral (6.5 to 7.5 pH), or acidic
(4.5 to 6.5 pH), whether or not water is present, they exhibit improved
stability with no substantial hydrolytic propensity.
Detailed Descri~ation of the Present Invention
The improved fuel composition of the present invention includes
an alkyl carbonate (dimethyl andlor diethyl carbonate) a metal or non-
metallic compound, more fully described below, and optionally a silicon
catalyst, co-fuel(propellant), andlor oxidizer. So long as the
composition is not strongly alkaline, i.e., has a pH of from 3.0 to about
70.5, hydrolysis of the fuel composition is avoided. A desirable pH
range of the fuel composition of the present invention is from
approximately 4.5 to approximately 10.5, with a more desirable pH
range of from approximately 4.5 to approximately 9.5. An even more
desireable pH range is from approximately 4.5 to 9Ø Another highly
preferred pH range is from approximately 5.5. to 8Ø A preferred pH
range is from approximately 4.5 to approximately 6.5. The most
preferred pH range for the fuel composition of the present invention is
from approximately 6.3 to approximately 6.8.
When the pH of the fuel composition of the present invention is
less than 11.0, preferably 10.5 or below, 9.5 or below) and more
preferably 8.5 or below, the fuel, whether anhydrous or hydrous, may
be stored at ambient temperature for up to 6 six months without
substantial apparent hydrolysis.
For example, Fuel A containing 5% by volume dimethyl
carbonate, 95% by volume unleaded regular grade commercially
available 87 octane (R+M)/2, 1/8 gram Mn/gal of
methylcyclopentadienyl manganese tricarbonyl, a pH of 7.0, and 5% by
volume of water, was stored for six months, the fuel exhibited no
apparent hydrolysis.
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When such fuel composition was titrated with acetic acid to a pH
of 6.4, still containing 5% by volume of water (Fuel B) and was then
stored for six months, the fuel exhibited no apparent hydrolysis.
However, when a fuel composition containing dimethyl carbonate
and cyclopentadienyl manganese tricarbonyl was prepared with a pH of
approximately 11, contained 5% by volume of water and was stored for
six months, the fuel showed slight evidence of hydrolysis. The same
fuel at a pH of 12.5, however, showed stronger evidence of hydrolysis.
It should be appreciated that although acetic acid was used to
acidify the pH of the fuel in the present case, many other fuel soluble
acids, including but not limited to benzoic acid derivatives e.g. 2,4-
dimethyl benzoic acid, methyl red, p-tert- butyibenzoic acid, 2-(1-
methylethyl) benzoic acid, benzoic acid anhydride, 4-benzoyl benzoic
acid, 2,4-dihdroxy benzoic acid, 2,4- dimethyl-benzoic acid, 3-ethoxy
benzoic acid, 2-hydroxy-4-methyl benzoic acid, 2-hydroxy benzontrile,
4-methoxy benzotrile, acetic acid derivatives) e.g. anhydride acetic
acid, chloroacetic acid, decyl ester acetic acid, dibromoacetic acid) and
the like, may be employed. See for example CRC Handbook of
Chemistry and Physics, 75th Ed, Lide, CRC Press (1994-1995)
"Dissociation Constants for inorganic Acids and Bases," and
"Dissociation Constants for Organic Acids and Bases," incorporated
herein by reference.
Naturally, acidic fuel components, which are indigenous to the
either the base fuel composition, e.g. individual fuel components,
metallic, DMC, or an additional ECS component (e.g. aldehydic acids,
ketonic acids, carboxylic acids, hydroxyacids, orthoacids, formic acids,
and the like) are desireable, and should be employed/modified first to
achieve minimum pH's, prior to addition of an additive acid. Thus, the
pH of the composition may be tailored using normal hydrocarbon fuel
components, dialkyl carbonates, and metallic(s) to achieve requisite
pH. However, individual circumstances will dictate proper approach and
additive acids are contemplated.
Naturally) acidic metals of this invention may be used individually
and/or in conjunction with one or more other metallics to reduce pH.
Non-limiting examples of such acidic metallics include binary, ternary
and higher metallic acid salts, hydroxy acids, etc. Other non-limiting
compounds are set forth below and include for example, oxamic acid,
lithium acetate acid, lithium salt acetic acid, propanoic acid lithium salt,
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cyclohexanebutyric acid lithium salt, aminobenzoie acid lithium salt,
borate ester, dimethyl borate) di- n-butyl borate, dicyclohexyl borate,
didodecylborate) di-p-cresyl borates, boric acids, orthoborates,
henylboronic acid) diphenylboronic acid, o-tolylboronic acid, p-
tolylboronic acid, m- tolylboronic acid, cylohexylboronic acid,
cylohexenylboronic acid, cyclopentylboronic acid, methylphenylboronic
acid, methylcylohexyl- boronic acid, methylcyclopentylboronic acid,
methylbenzylboronic acid, dimethylphenylboronic acid,
dimethylcylohexylboronic acid, dimethylcyclopentylboronic acid,
dimethylbenzylboronic acid, diphenylboronic acid, dibenzylboronic acid,
dicylohexylboronic acid, dicylohexenylboronic acid,
dicyclopentylboronic acid, methyldiphenylboronic acid,
bis[(methyl)cylohexyl]boronic acid) bis[(rnethyl)cyclopentyl]boronic acid,
bis[(methyl)benzyl]boronic acid, bis[(dimethyl)phenyl]boronic acid,
bis[(dimethyl)- cylohexyl]boronic acid, bis[(dimethyl)cyclopentyl]boronic
acid, or bis[(dimethyl)benzyl]boronic acid. Many other acidic metallics
are set forth below and contemplated.
If an additive acid is employed, it is preferred it be compatible
with the base fuel and have low toxicity, low corrosivity, and be as
envirnomentally friendly as possible.
PCT/US95/02691 and PCT/US95/06758 disclose compositions
and methods achieving vapor phase combustion employing
symmetrical dialkyl carbonates and certain non-leaded high energy
metals and non-metals (herein "metals"). It has been discovered in the
construction of a fuel composition, which employs one metal or a
mixture of metals, together with at least one C3 to C13 dialkyi
symmetrical carbonate, as taught therein, improved fuel stability can be
obtained when the pH is kept as close to neutral as possible, such that
if alkaline, it is only weakly alkaline (i.e., preferably equal or less than
11.0, 10.5, 10.0, 9.5, 9.0, 8.5, 8.0 pH), but that it preferably be either
substantially neutral (i.e., 6.5 to 7.5) or slightly acidic (6.3 to 6.9 pH).
Anhydrous fuels or substantially anhydrous fuels are
contemplated and particularly preferred when employing water reactive
group la, Ila, Ilb, IIIA metals and derivative compounds. Other
circumstances will require anhydrous fuels as well, e.g. jet aviation
applications, etc. Although anhydrous fuels are preferable, when the
fuel compositions of the present invention have a pH in the preferred
range of from approximately 10.5 to 4.5, there is no apparent
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hydrolysis, even when such fuels include an aqueous layer. When the
pH of the fuel composition is in the preferred range, the composition
may contain water up to 10.0% by volume of the fuel with no apparent
hydrolysis of the organic phase after six months of storage.
It should be appreciated in the practice of this invention and the
examples set forth herein, it is only required that a hydrocarbon fuel
containing a lower dialkyl carbonate have a pH of less than 10.5. The
addition of metals or non-metals herein, co-metallics, viscous
hydrocarbons are further embodiments, and not necessary elements to
this aspect of the invention. Thus, the claims below may reflect only a
hydrocarbon fuel containing a lower dialkyl carbonate having a pH of
less than 10.5, absent any additional limitation. As example, a
composition of this invention includes a hydrocarbon base together with
dimethyl carbonate or diethyl carbonate, said composition adjusted
such that its maximum pH is 10.5 of less, a more preferred pH is 6.8 or
less.
Acidity level of fuels is sometimes measured in terms of
equivalents, e.g., equivalents of KOH required to neutralize the fuel
composition. The fuels of the present invention show improved
operation at acidity levels which are 100%, 150%, 200%, 300%, or
more, above such standards. Acidity levels below such standards,
including those at least 50% less, are expressly contemplated. Also by
way of example, when the fuel compositions of the present invention
are used in jet turbine engines, such fuels typically must meet ASTM D
1655 specifications {incorporated herein by reference) or other
international specifications, including maximum acidity levels ASTM D
3242 and IP 354 standards. However, it is believed that the increased
efficiency of the fuels of the present invention are less destructive to
engines during combustion, and operation with lower pH's than
presently acceptable. International, industry and government fuel
standards, including ASTM, IP, GOST, DERD, MIL, AN, U.S. Clean Air
Act, California Air Resources Board, and Swedish/European EPEFET
standards, etc., governing hydrocarbon fuels containing applicant's
alkyl dicarbonateslmetal are incorporated herein by reference.
When the fuel compositions of the present invention have a pH in
the desired range of from approximately 4.5 to 11.0, stability is
maintained and hydrolysis is substantially avoided so long as fuel
storage temperature is at or below 90°F. Preferably, the fuel
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compositions of the present invention have pH's less than 10.5 and are
stored at or below 65°F. When Fuels A and B, described above, were
stored at 65°F during the period from 6 months after mixing to 9
months after mixing, fuel stability was maintained without apparent
hydrolysis.
In addition to the preferred pH ranges described above, it is
further contemplated that Applicant's pH adjusted hydrocarbon based
fuels will additionally contain known additive, including but not limited
to antioxidants, co-solvents, metal deactivators, detergents,
dispersants, corrosion inhibitors, mutual solvents, oxygenated anti-
knock compound (e.g. hydrocarbyl ethers, alcohois, etc.), other
additive, and additive set forth in incorporated PCT Applications. Said
known additive is incorporated herein by reference.
A preferred fuel of the present invention comprises 1) dimethyl
carbonate or dimethyl carbonate, representing 0.1 % to 99.5% wt of
composition; 2) at least one metal as set forth below, representing
0.01 % to 99.5% wt of composition; optionally a metal deactivator
representing 0.00001 % to 10.0% wt of composition, or an antioxidant
representing 0.00001 % to 10.0% wt, or a detergent/dispersant
representing 0.00001% to 10.0% wt, or an ignition promoter
representing 0.000001 % to 20.0% wt, or a demulsifier representing
0.00001 % to 10.0% wt, or a co-solvent or salt representing 0.000001
to 40.0% wt, or a hydrocarbon representing 0.1 % to 99.0% volume of
the composition, or a silicon based combustion catalyst {described
below) representing 0.000001 % to 80.0% wt, or mixture. Said fuel is
constructed with a pH no greater than 11.0 or 10.5, and preferrably
less than 9.5. More preferably, the pH is from 6.3 to 6.8. When such
fuel is a jet aviation turbine hydrocarbon based-fuel, preferred acidity
does not exceed equivalent of 0.1 mg KOH/g.
As described in the aforementioned PCT applications, the
presence of a co-solvent is also preferred, so long as pH is maintained.
Co-solvents that enhance mutual solubility of fuel components, fuel
stability, water tolerance are preferred {e.g. C1 to C12 alcohols,
alkanolamines, etc.). These are known in the art and incorporated
herein by reference. Additionally, co-solvents that increase flash point
or reduce vapor pressure are contemplated. Non-limiting examples
include, ethanetriols, propanetriols, butanetriols, 1,2,3 butanetriol,
pentanetriols, 1,2,3 pentanetriol, 2,3,4 pentanetriol, hexanetriols,
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septanetriols, octanetriols, or tertraethylene glycol, triethylene glycol,
1-octene, high flash point ketone, naphthalenes, triethylene glycol,
trimethylene glycol, isopropyl acetone) diisopropyl acetone, diisopropyl
diacetone, diethylene acetate, diethylene diacetate, ethylene acetate
compound, phenol, or other flash point temperature reducing co-solvent
set forth in aforementioned PCT Applications. Co-solvents should not
be corrosive or hazardous to fuel systems.
It is desirable the resultant fuel be constructed to have an
average latent heat of vaporization (LHV) no less than typical industry
standards. Prefered LHV's are generally greater. For example, the
latent heat of vaporization or enthalpy of vaporization ( vapH(Tb)/kJ
mol-7 ) for commercial grade diesel, gas turbine, or fuel oils range from
about 90 to 105 btu/lb (at 60°F) or 18 to 21 jK/mole or (at boiling
temperatures). Likewise, commercial motor gasolines have a LHV
ranging from 135 to 145 btu/Ib or 27 to 29 jK/mole, aviation gasolines
about 130 to 150 btu/Ib or 26 to 30 jk/mole, and aviation jet fuels about
105 to 115 btu/Ib or 21 to 23 jKlmole.
Thus, it is preferred that the LHV for commercial grade diesel,
gas turbine, or fuel oils at 60°F exceed 105 btu/Ib or 21 jK/mole (at
boiling temperatures), for commercial motor gasolines LHV's should
exceed 145 btu/Ib or 29 jK/mole, for aviation gasolines LHV's should
exceed 150 btu/lb or 30 jk/mole, and for aviation jet fuels LHV's should
exceed 115 btu/lb or 23 jK/mole. LHV's at least 2%, 5%, 10%, 20%,
30% or greater than these amounts are however preferred.
The burning velocities (as measured by laminar Bunsen burner
flame) for commercial grade diesel, gas turbine, and fuel oils range
from about 35-37 crn/sec, kerosine about 36 cmlsec, automotive
gasoline about 47-50 cm/sec, aviation gasoline about 45-47 cm/sec,
aviation jet fuels about 36-38 cm/sec. Methanol is reported at 57.2
cm/sec. Thus, in Applicant's fuels it is desireable that burning
velocities for commercial grade diesel) gas turbine, and fuel oils exceed
37 cm/sec, kerosine exceed 36 cm/sec, automotive gasoline exceed 50
cm/sec, aviation gasoline exceed 47 cm/sec, and aviation jet fuels
exceed 38 cm/sec. However, BV's at least 2%, 5%) 10%, 20%, 30%, or
greater than above speeds are preferred.
It is also desirable that the hydrocarbon based fuels have high
possible allowable densities. High densities of base fuels permit higher
concentrations of metallics and dialkyl carbonates. For example,
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aviation turbine densities equal or exceeding 841 kg/m3 @ 15°C are
contemplated. More generally, the fuel compositions of the present
invention allow for base fuel densities of from 840 to 1200 kg/m3 @
15°C, and even 900 to over 1200 kg/ m3 @ 15°C. Moderate, low) to
very low densities are also contemplated so long as the increased
burning velocity object of above PCT Applications is accomplished and
a pH is not greater than 10.5, preferably below 9.0, and most
preferably from 6.3 to 6.8 is maintained.
Moreover, highly viscous hydrocarbon fuel bases with viscosities
above fuel specification, are unexpectedly brought to within fuel
viscosity limits by the addition of dialkyl carbonates and metal. For
example, is has been found that a diesel fuel oil having a viscosity of
2.6 mm2/S at 40o C was acceptably combined with dimethyl carbonate
representing 5% volume of the composition, and 2.0 grs Mn/gai of
methylcyclopentadienyl manganese tricarbonyl (MMT). The resultant
fuel composition had a lower viscosity of 2.4 mm2/S at 40o C. In this
way, highly viscous fuels can be adapted by the addition of applicant's
ingredients, whereby non-conforming highly viscous fuels can be made
less viscous and brought into compliance with ASTM or other
specification (herein incorporated by refererence).
Also by way of example, Jet A hydrocarbon bases having a
viscosity of 8.1 to 15.0 or more, (ASTM 445) can be adapted to meet
the current 8.0 mm2/sL at -20°C standard by addition of the
components described above. Alternatively, base fuel viscosity of from
13.5 to 23.0 Cs at -30°F, or more, may be met by the addition of the
components described above.
Similarly, a gas oil turbine hydrocarbon base may have maximum
kinetic viscosities at 40°C equal or exceeding 2.45 to 7.0, or greater,
mm2/s for ASTM D 445 No. 1-GT fuels, and be adapted to meet the 2.4
standard, by addition of the components described herein.
Alternatively, base fuel kinetic viscosities of 4.15 to 6.0, or more,
mm2/s for ASTM D 445 No. 2-GT fuels, may be adapted to meet the
4.1 standard by addition of applicantps additives, as described herein.
In an analogous manner, a diesel fuel oil base may have
maximum kinetic viscosities at 40°C equal or exceeding 2.45 to 7.0) or
greater, mm2ls for ASTM D 445 low sulfur or regular No. 1-D fuels, and
be adapted to meet the 2.4 standard by addition of appiicantbs
additives. Alternatively, a diesel fuel oil base having maximum kinetic
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viscosities of 4.15 to 9.0 or more, mm2/s for ASTM D 445 low sulfur or
regular No. 2-D fuels, and be adapted to meet the 4.1 standard, by
addition of applicantbs additives. Similarly, fuels having a maximum
kinetic viscosity of 24.5 to 60.0 ore more mm2/s for ASTM D 445 No. 4-
D fuels, and be adapted to meet 24.0 by addition of applicantps
additives. Additionally, a low emission diesel base may have
viscosities exceeding 2.45 to 5.5, or more, cSt at 40°C (where 1 mm2/s
= 1 cSt), and be adapted to meet the 2.4 standard.
Furthermore, a fuel oil base may have kinetic viscosities equal or
exceeding 2.15 10.0, or more, rnm2/s at 40°C ASTM D 445 for No. 1
fuels, and can be adapted to the 2.1 standard by addition of
applicantps additives. A fuel base having kinetic viscosities of from
3.45 to 10,0, or more, mm2/s at 40°C ASTM D 445 for No. 2 fuels can
be similarly adapted to meet 3.4. A fuel base having kinetic viscosities
of 5.55 to 25.0 or more, mm2/s at 40°C ASTM for D 445 No. 4 fuels
(Light), may be similarly adapted to meet 5.5. A fuel base having
kinetic viscosities of from 24.5 to 40.0, or more, mm2/s at 40°C ASTM
D 445 for No. 4 fuels (regular), may be adapted to meet 24. A fuel
base having kinetic viscosities of from 8.95 to 25.0, or more, mm3/s at
100°C ASTM D 445 for No. 5 fuels (Light), may be adapted to meet 8.9.
A fuel base having kinetic viscosities of from 15.0 to 30.0, or more)
mm3/s at 100°C ASTM D 445 for No. 5 fuels (Heavy), may be adapted
to meet 14.9. A fuel base having kinetic viscosities of from 50.5 to
80.0, or more, mm3/s at 100°C ASTM D 445 for No. 6 fuel oils, and
adapted to meet 50Ø
Similarly, a heavy diesel, locomotive or marine engine base fuel,
exceeding ISO DIS 8217, BS MA 100, government andlor other
industry viscosity specifications, but adapted to meet such standards
(incorporated by reference), typically uncorrected viscosity exceeds
such standards by 1.0, 2.0,10.0, 50.0) or more centistokes at 50°C.
Applicant has discovered by incorporating his lower dialkyl carbonates
and metals, fuels having excessive viscosities can meet government, or
other viscosity standards.
By way of further example, an enhanced combustion aviation
turbine fuel composition of the present invention includes a symmetrical
alkyl dicarbonate, preferably dimethyl carbonate, a metal, an aviation
turbine hydrocarbon base having a viscosity of from 8.1 to 9.0 MM2/S
(ASTM 445); optionally one or more of the following: a salt, a co-
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solvent, antioxidant, freeze point additive, anti- icing additive, metal
deactivator, corrosion inhibitor, hydroscopic control additive, lubricity
agent, lubricant or friction modifier, anti-wear additive, combustion
chamber or deposit control additive, any other recognized additive,
additive disclosed in aforementioned PCT Applications, or mixture
thereof. The resultant fuel is characterized as being slightly alkaline,
substantially neutral or acidic, and having a maximum viscosity equal
or less than 8.2 MM2/S1 (ASTM 445). The fuel preferably has a density
of from 840.5 to 850, or greater, kg/m3 @ 15°C, a flash point of at
least
38°C, a maximum vapor pressure of 21 kPa @ 38°C, minimum thermal
stability meeting ASTM D 1655 standards, a heat of combustion or
equivalent equal to or exceeding 42.8 MJ/kg (lower heats of
combustion are contemplated, including those less than or equal to
42.5, 42, 41, 40, 39, 38, 37, 36 MJ/kg, based upon additive heats of
individual components), and a maximum freezing temperature of from -
40 to - 50°C) optionally a LHV not less than 115 btullb or 23 jK/mole,
optionally a burning velocity exceeding 37 cm/sec.
A diesel fuel composition of the present invention includes
dimethyl carbonate representing 0.01 % to 40.0% oxygen by weight of
the fuel; a compound or element containing a combustion improving
amount of transition metal, alkaline metal, alkaline earth, group II fa,
IVa, Va, Vla, Vlla element or derivative compound, or mixture,
optionally in an concentration of 0.001 to about 100.0 gr element/gal,
preferably 2.0 to 20.0 gr element/gal; and a No. 1 (ASTM) diesel fuel
base having a viscosity of from 2.45 to 3.0, MM2/S at 40°C,; said fuel
base optionally characterized as having one or more of the following: a
density ranging from 880 to 800 kg/rn3 , a cetane index of 40 to 70, an
aromatic content by vol. ranging from approximately 0 to
35%,prefereably 0% to 10%, provided that 3-ring + aromatics not to
exceed 0.16 volume %; a T10 fraction temperature of about 190 to
230°C, a T 50 fraction temperature of about 220 to 280°C, a T90
fraction of about 260 to 340°C, a cloud point temperature of °C -
10) -
28, -32 or 6°C above tenth percentile minimum ambient temperature, a
sulfur content preferably not greater than 250 ppm, more preferably not
greater than 50 ppm, most preferably not exceeding 5 ppm, a Bunsen
laminar burning velocity of at preferably greater than 37, more
preferably greater than 44, most preferably 50 ore more, cm/sec, a
latent heat of vaporization of preferably at least 105, more preferably at
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least 120, most preferably 130 or more, BTUlIb. The resultant fuel is
characterized as having a pH less than 10.5 and a viscosity equal to or
less than 2.4 MM2/S at 40°C, optionally a LHV at 60°F equal or
in
excess of 105 btu/Ib or 21, 22, 23, 25, 27 jK/mole (at boiling
temperatures), optionally a minimum laminar bunsen burner flame of
37, 39, 40, 41 cm/sec.
An aviation gasoline fuel composition of the present invention
includes a dialkyl carbonate, a metal and an aviation gasoline base.
The resultant fuel is characterized as having a pH less than 7.0 and a
minimum octane or performance number of from 87 to 130 (ASTM 909).
It is further characterized as having a distillation fraction wherein the
sum of the T-10 plus T-50 fractions are 307°F, the T-40 temperature is
167°F and the T-90 temperature is less than 250°F, a maximum
sulfur
content of 0.05 wt%, or sulfur free, a latent heat of vaporization
preferably exceeding 120, more preferably exceeding 150, most
preferably exceeding 160 BTU/lb, a laminar Bunsen burning velocity
preferably equal to or in excess of 40, more preferably greater than 48,
most preferably greater than 52 cm/sec, a heat of combustion (as
measured by the sum of fuel ingredients) equal or less than 43.0 kJ/kg,
or equal or less than from 18,720 to 15,000, or less, BTU/!b.
A gasoline composition of the present invention includes an
dialkyl carbonate, a metal and an unleaded base fuel composition. The
resultant composition is characterized as having a pH less than 10.5,
and optionally being phosphorus free hydrocarbons, a maximum Reid
Vapor Pressure of from 6.0 to 12.0 psi, 6.0 to 10 psi, 6.0 to 9.0 psi; a
maximum of 12% to 5.0% by volume, or less of olefins, a maximum of
30% to 20% or less by volume of aromatics (more preferably 15% to
10%, or less), a maximum of 2.0% to 0.8% or less benzene, a
maximum of 40 ppm sulfur, most preferably sulfur free, a total 02
concentration ranging of 0.5% to 10.0% wt of dimethyl carbonate, a
manganese tricarbonyl compound at 1/64 to 3/16 gr. Mn/gal (preferably
1132 gr. Mn) or other metallic in a combustion improving amount, a
maximum T-90 temperature of 330°F to 280°F, a T-50 temperature
of
approx. 170°F to 230°F., 175°F preferred, a minimum
(R+M)/2 octane
of 85, to 92, a bromine number of 20 or less, an average latent heat of
vaporization of 880 to 920, or more, BTU/gal at 60°F; a heating value
greater than 106,000 btu/gal at 60°F (more preferably greater than
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108,000, 114,000 btu/gal), as measured by the sum of individual fuel
substituents.
Another gasoline composition of the present invention includes
an dialkyl carbonate, a metal and an unleaded base fuel composition,
characterized as having a pH less than 10.5, and optionally
characterized as having one or more of the following: being phosphorus
free hydrocarbons, with a maximum Reid Vapor Pressure of 12.0 psi, a
maximum of 12% olefins, a maximum of 30% aromatics, a maximum of
2.0% benzene, a maximum of 50 ppm sulfur or sulfur free, a total 02
concentration ranging from 0.5% to 10.0% wt of dialkyl carbonate, a
combustible metal or non-metal selected from groups set forth below
including (but not limited to ) those consisting of the preferred
manganese, silicon, potassium, and iron compounds, or mixture, a
maximum T-90 temperature of 330°F to 280°F, a T-50 temperature
of
approx. 170°F to 230°F., a rninimum (R+M)/2 octane of 85, to 92,
a
bromine number of 20 or less, an average latent heat of vaporization of
880 to 920 BTU/gal at 60°F, a heating value greater than 106,000
btu/gal at 60°F (as measured by the sum of individual fuel
substituents), a burning velocity exceeding 50 cm/sec, a latent heat of
vaporization exceeding 29 jK/mole (or equivalent).
In the practice of this invention it is contemplated at least one
combustible reactive non-lead transition metal, alkaline metal, alkaline
earth, group Ills, IVa (except carbon), Va, Vla (except oxygen), Vlla
element, or derivative thereof, as set forth herein, or mixture (herein
referred to as "metal" or "metallic") be together with at least one C3 to
C13 symmetrical dialkyl ester of carbonic acid, and mixture, in a fuel
stable composition; said composition optionally containing a
combustion catalyst as set forth below, a hydrocarbon, and/or an
oxidizer; resultant composition as having a pH slightly alkaline, neutral
or acidic.
Non-limiting examples of suitable dialkyl carbonates include,
dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl
carbonate, dibutyl carbonate, diisobutyl carbonate, ditertiary butyl
carbonate, diisoamyl carbonate, methyl ethyl carbonate, Biphenyl
carbonate, or mixture. C3 to C8 symmetrical dialkyl carbonates are
more desirable, with C3 to C5 being preferred. It is contemplated that
such carbonates will be introduced into the composition in
concentrations of 0.01 to 100.0 volume percent in an amount sufficient
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to improve combustion. The carbonates may be additionally combined
with one or more oxygenated compounds, including but not limited to
alkyl butyl ethers (e.g. MTBE) ETBE, TAME, ETAME, etc.), alkyl
alcohols, and/or known co- solvents. In the practice of this invention
methylal, ethylal, C1 to C6 aliphatic alcohols, may be substituted for
dialkyl carbonates, absent compromise of vapor phase combustion.
Non-limiting examples of optional fuel, which may be additionally
contained with the dialkyl carbonate and metal, include hydrogen or
any hydrocarbon, including but not limited to carbonaceous liquid or
solid fuels, alternative fuels, gaseous fuels (including natural gas,
methane, ethane, propane, butane) etc.}, automotive gasolines, diesel
fuel oils, heavy diesel fuel oils, aviation gasoline, gas oils, fuel oils,
aviation jet turbine oils, coal, coal oils, coal liquids, and the like.
Industry specifications, including ASTM and all others known in the art,
and above PCT Applications) and Criteria for Quality of Petroleum
Products, J.P. Allison, 1973 (and subsequent editions), are
incorporated herein by reference.
METALS PRACTICE
in the practice of this invention contemplated metallics include all
non-lead metals, metalloids, and non-metals (herein "metals" or
"metallics")) and their derivative compounds, whose combustion
product accomplishes primary object of vapor phase combustion, which
is evidenced by a brilliant luminous reaction zone extending some
distance from the metal's surface. Such combustion does not take
place on the surface of the metal) or on and/or within the molten layer
of oxide covering the metal, typical of heretofore metallic combustion.
Distinguishing vapor phase combustion is that its combustion is
expansive with elevated exhaust velocities, and resultant metallic oxide
particles are formed in the submicron range. Typically fuel economy,
power output, exhaust emissions, combustion temperatures are
materally improved.
Thus, a very wide range of acceptable metals and derivative
compounds are contemplated. Group IA (alkali metals), IIA (alkaline
earths) elements, the transition elements/metals of group Illb, IVb, Vb,
Vlb, Vllb, Vlllb [8, 9, 10], the elements of group Ib, Ilb, Illa, IVa (absent
carbon), and group Va) Vla) Vlla elements are contemplated. Non-
limiting examples include aluminum, boron, bromine, bismuth,
beryllium, calcium, cesium, chromium, cobalt, copper, francium,
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gallium, germanium, iodine, iron, indium, lithium, magnesium,
manganese, molybdenum, nickel, niobium, phosphorus, potassium,
palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon,
vanadium, strontium, barium, radium, scandium, yttrium, lanthanum,
actinium, cerium, thorium, titanium, zirconium, hafium, praseodymium,
protactinium, tantalum, neodyium, uranium, tungsten, promethium,
neptunium, samarium, plutonium, ruthenium, osmium) europium,
americium, rhodium) iridium, gadolinium, curium, platinum, terbium,
berkelium, silver, gold, dysprosium, californium, cadmium, mercury,
holmium, titanium, erbium, thulium, arsenic, antimony, ytterbium,
selenium, tellurium, polonium, lutetium, and astatine, including their
organic and inorganic derivative compounds, which are capable of
vapor phase combustion, are contemplated in the claims hereto and
incorporated herein by reference. Applicant's metals, including
derivative compound, may be organo-metallic or inorganic. Accordingly,
the inorganic and organic compounds of CRC Handbook of Chemistry
and Physics, Lide, 75th (1994-7995) and earlier editions, Ann Arbor,
CRC Press; Sigma-Aldrich Chemical Directory) Aldrich Chemical
Company (1997), Chemical Abstract Service (CAS)) on line Registry
File [1], American Chemical Society, Chemical Abstract Service, Ohio
State University) A Manual of Inorganic Chemistry, Thorpe, N.Y.,
Putnam & Son's (1896), Inorganic Materials, 2 ed., Ducan, N.Y. J.Wiley
& Son (1996), Handbook of Inorganic Compounds, Perry) Phillips, CRC
Press, Boco Raton, {1995), Inorganic Chemistry, Phillips, Williams,
N.Y. Oxford University Press (1965-1966), Inorganic Materials
Chemistry, D. Seneeta, G.E. R & D Center, N.Y., CRC Press (1997),
Inorganometallic Chemistry, Fehlner, N.Y., Plenum (1992),
Nontransition-Metal Compounds, Eisch, N.Y., Academic Press (1981),
Metal & Metalloid Amides, Horwood, N.Y., Halsted Press (1980), Kirk-
Othmer Encyclopedia of Chemical Technology, 2nd and subsequent
editions, John Wiley & Sons (1963), Dictionary of Chemical Names &
Synonyms, Howard) Neal, Lewis Publishers, Ann Arbor, (1992),
Dictionary of Chemical Solubilities) Inorganic, Comey, MacMillian Press
(1921 ), Solubilities of Inorganic and Metal Organic Substances, Seidell,
N.Y., Van Nostrand {1940-1941 ), Solubility of Inorganic and Metal-
Organic Compounds, Like, Princeton N.J., Van Nostrand (1958-1965),
Organometallics (cite omitted), Organo Metallic Chemistry, F.G.A.
Stone, Academic Press ( 1972 and subsequent years), Organo Metallic
CA 02274607 1999-06-09
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Compounds, 2 Ed, Michael Dub, Springer-Verlag, New York Inc. (1966
Vol. 1 to 3, and subsequent volumes/supplments), Organo-metallic
Compounds, Coates, Edward, New York, Wiley (1960), Comprehensive
Organometallic Chemistry II (A Review of the Literature 1982-1994),
Abel, Stone, Wilkinson, EI Sevier Science Ltd (1995), Handbook of
Organometallic Compounds, Kaufman) D. Van Nostranl Company Inc.
(1961), Handbook of Organometallic Compounds, Hagihara, Kumanda,
Okawars, W.A. Benjamin Inc (1968), Organometallic Chemistry,
Mehrotra, Singh) John Wiley and Sons, {1991 ), Organometallic
Chemistry, Chemical Society (1971 and all subsequent publications),
London, Metal- Organic Compounds, American Chemical Society (1959
to present), Chemical Abstracts, American Chemical Society, Chemical
Abstract Service, Ohio State University, (From 1907 to present),
Structure Reports 1913 to 1973 (Metals and Inorganic Compounds),
International Union of Crystallography, Bohn, Scheltena & Hellema
(volumes 1-40), The Merck Index, 12th Ed., Budavari, O'Neil, Merck
Research Laboratories, N.J. (1996), which are capable of vapor phase
combustion, together with said publications (including afl
related/subsequent editions, volumes, supplements, updates, or related
publications) are incorporated herein by reference.
Cyclomatic compounds are particularly desireable. Non-limiting
examples of cyclomatic compounds include compounds with one or
more rings systems, including alicylic or aromatic ring systems. Ring
systems which may be wholely organic, wholely inorganic, or
heterocyclic. Such ring systems may include cyclic borons (borazoles),
cyclic silanes (silacyclobutane, 2,4,6,8,10-
pentamethylcyclopentasilazane, cyclohexasilanes, cyclopropenyl
silanes, etc.), cyclic nitrogens (pyrazoles, pyridines, pyrroles,
piperazines, imidazals, etc.), cyclic oxygens (benzoyls, furans, pyrans,
e.g. tetrahydropyran) pyrones, dioxins, etc,), cyclic sulfurs (thiophens,
dithiles, etc.) or other cyclic inorganics. Cyclomatic organic ring
systems include saturated rings (cyclopropyl, cyciobutyl, cyclopentyl,
cyclohexyl, cyclooctyl, etc.), unsaturated rings, rings with one or more
multiple or double bonds (cyclohexadiene, cyclopentadiene,
cyclotetraene, etc.)) aromatic rings/cycloalkyl radicals (phenyl, benzyl,
styryl, etc.), fused rings, fused aromatic rings (naphthls, naphthenates,
etc.), fused ring with cyclopentadienyl moiety, rings containing oxygen
or a hydroxyl (phenol, etc.). The disclosed metallic cyclomatics
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contained in Heterocyclic Chemistry, Katritzy, Boulton) Academic Press
(1966 to 1997 all volumes), Benzenoid-Metal Complexes, Zeiss)
Wheatley, Winkler, The Ronald Press Co (1966), The Ring Index 2 Ed,
Patterson, Capell, American Chemical Society, Reinhold Publishing
Corp (19fi0 and subsequent editions), Ring Enlargement of Organic
Chemistry, Hesse, VCH Publishers (1991), Rings, Cluster, and Plymers
of Main Group Elements, Cowley, American Chemical Society {1983),
which are capable of vapor phase combustion, together with said
publications (including subsequent editions, volumes, or supplements),
are incorporated herein by reference.
Desireable metal containing cyclomatic compounds are those
with cyclic rings having high burning velocities. The higher the burning
the velocity, generally the higher the preference. Generally larger rings
have higher burning velocities compared to smaller rings. Thus, a
cyclooctane ring is preferred over cyclohexane, which is perferred over
a cyclobutane ring. Saturated rings are normally more perferred over
unsaturated rings. The more saturated the ring the more preferred.
Thus, cyclohexane is preferred over benzene. Ring systems where the
metal is in turn attached to one or more a hydroxyl, carbonyl, an
alkyloxy radicals is preferred.
Non-limiting examples of desireable ring systems/complexes
include: cyclohexane, cyclohexene, cyclopentane, cyclobutane,
cyclopentadiene, phenyl, benzene, and naphthalene. More desireable
are cyclohexane, cyclohexene, and cyclopentadienyl. It is contemplated
each elemental metal of this invention can be employed in a cyclomatic
compound.
Transition metal ring systems are well known in the art and
highly desireabie. See U.S. Patents Nos. 2,818,416, 3,127,351,
2,818,417, 2,839,552, 2,680, ; 2,804,468; 3,341,311, 3,272,606,
3,718,444)) Canadian Patent #1073207, European Patent Application #
93303488.6, pages 6-8 {1993), incorporated herein by reference.
As contemplated herein, attachment may be direct or indirect.
Attachment may be via molecular bond, ionic bond, coordination bond
or other bond known in the art. Indirect attachment may be via one or
more radical or element, or be via other bond as described below or
known in the art. See The Chemistry of Organometallic Compounds,
Rochow, Hurd, Lewis, New York, John Wiley & Sons, Inc. (latest
edition), incorporated by reference.
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One or more radicals (including cyclic radicals), side chains,
saturated or unsaturated, may be attached to one or more locations on
the ring, and/or to one or more locations of each metal. Thus, the metal
may contain between one to as many radicals as available valence
electrons (oxidation states) permit. See Handbook of Data on Organic
Compounds Zed, Weast, Grasselli, CRC (185).
Non-limiting examples of radicals, include organic or inorganic,
saturated or unsaturated, or combinations thereof, including: hydrogen
(hydride), hydroxyl, hydrocarbyl group radicals, including alkyl radicals
(e.g. methyl, ethyl, propyl, issopropyl) butyl, isobutyl, sec-butyl, tert-
butyl, amyl, pentyl, hexyl, etc.), alkyloxy radicals, various positional
isomers thereof (e.g. 1- methyl-butyl, 2-methyl-butyl, 3-methyl-butyl,
1,1-dimethyl-propyl, 1,2-dimethyl-propyl, etc.), corresponding straight
and branched chain isomers (e.g. hexyl, hepyl, octyl, nonyl, decyl,
etc.), alkenyl radicals (ethyl, /\1-propenyl, /\2-propenyl, isopropenyi,
etc.), corresponding branch chain isomers thereof, other isomers
thereof (e.g. heptenyl) octenyl, nonyl, decenyl, etc.), alkenyloxy
radicals, aryl radicals (e.g. phenyl, a-napthyl, b-naphthyl, a- anthryl, b-
anthryl, etc.)) aryloxy radicals, including monovalent radicals of such
aromatics (e.g. indene, isoindene, acenaphthene, flourene,
phenanthrene, naphthacene, chrysene) pyrene, triphenylene, etc.),
aralkyl radicals (e.g. benzyl, a-phenyl-ethyl, b-phenyl-ethyl, a-phenyl-
propyl, etc.), aralkyloxy radicals, various positional isomers thereof
(e.g. derivatives of 1-methyl- butyl, 2-methyl-butyl, 3-methyl-butyl, 1,1
dimethyl-propyl, etc.), corresponding alkyl derivatives of phenanthrene,
flourene) acenapthene, etc., afkaryl radicals, (e.g. o-tolyl, m-tolyl, p-
tolyl, o-ethylphenyl, etc.), arylalkenyl, cycloalkyl radicals (benzyl, etc.),
cycloalkyloxy radicals, aliphatic radicals, mesityl. See generally
Canadian Patent 1073207, pages 4-7, European Patent Application #
93303488.6, pages 6-8, 10/11/93), Handbook of Data on Organic
Compounds 2 Ed, Weast, Grasselli, CRC 1985, CRC Handbook of
Chemistry and Physics, 75th and earlier editions, sections re:
"Nomenclature For inorganic Ions and Radicals," "Organic Radicals
and Ring Systems," Nomenclature of Inorganic Chemistry
(Recommendations), Blackwell Scientific Publications, Offord 1990;
Richer, J.C., Panico, R., and Powell, W.H. A Guide to IUPAC
Nomenclature of Organic Compounds, Blackwell Scientific Publications,
Offord 1993, Weast, R.C., and Grasselli, J.C., Handbook of Data on
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Organic Compounds, 2nd Ed. CRC Press, Boca Raton, FL, 1989;
incorporated by reference.
Hydroxyl) alkanol, alkanolamine) oxy and/or oxygen containing
radicals, including derivatives of thereof and derivative of above radical
are also contemplated. Non-limiting examples include hydroxy,
methoxide, ethoxide, propoxide, isopropoxide, butoxide, isobutoxide,
sec-butoxide, tert-butoxide, pentoxide, amyloxide,
phenyloxidesperhydroxy, methoxy, methylol, methylenedioxy, ethoxy,
ethylol, ethylenedioxy, enanthyl, propoxy, proprylol, propylene- dioxy,
isopropoxy) isopropylol, isopropylenedioxy, butoxy, butylenedioxy,
butylol, iso-butoxy, iso-butylol, isobutyfenedioxy, isobutyryl, sec-butoxy,
sec-butylol, sec-butylenedioxy, tert- butoxy, tert-butylol, tert-
butylenedioxy, butyryl, caproyl, capryl, caprylrl, pentoxy, pentylol)
pentalenedioxy, amylol, amylenedioxy) phenoxy, phenylol,
phenylenedioxy, phenylmethoxy, diphenylmethoxy, benzoyl, benzyloxy,
benzoxy, iso-benzoyl, napthoxy) napthylol, hexylol, hexamethylol,
amylenedioxy, hexadecanoyl, heptanedioyl, hexylenedioxy)
carbomethoxy) carbethoxy, carbobenzoxy, carbpropoxy,
carbisopropoxy, carbutoxy, phenacyl, phenacylidene, propionyl
radicals, methylenedioxyl, carbonyldioxy, etc., including derivatives,
homologes, analoges, and isomers thereof.
Additional non-limiting oxygen containing radicals include acetyl,
acetamido, acetoacetyl, acetonyl, acetonylidene, acrylyl, alanyl, B-
alanyl, allophanoyl, anisyl, benzamido, butryl, carbonyl, carboxy,
carbazoyl, caproyl, capryl, caprylrl, carbamido, car- bamoyl, carbamyl,
carbazoyl, chromyl, cinnamoyl, crotoxyl, cyanato, decanoly)
disiloxanoxy, epoxy, formamido, formyl, furyl, furfuryl, furfurylidene,
glutaryl, glycinamido, glycolyl, glycyl, glyocylyl, heptadecanoyl,
heptanolyl, hydroperoxy, hydroxamino, hydroxylamido,
hydrazido/hydrazide, hydroxy, iodoso, isoccyanato, isonitroso, keto,
lactyl, methacrylyl, malonyl, nitroamino, vitro, nitrosamino, nitrosimino,
nitrosyl/nitroso, nitrilo, oxamido, peroxy, phosphinyl,
phosphide/phosphido, phosphite/phosphito, phospho, phosphono)
phosphoryl, seleninyl) selenonyl, siloxy, succinamyl, sulfamino,
sulfamyl, sulfeno) thiocarboxy, toluyl, ureido, valeryl radicals, etc.,
including derivatives, hornologes, analoges, and isomers thereof.
Additional non-limiting examples of other radicals, include:
acetimido, amidino, amido, amino, aniline, anilino, arsino, azido, azino,
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azo, azoxy, benzylidine, benzldyne, biphenylyl, butylene, iso-butylene,
sec-butylene, tert-butylene, cyano, cyanamido, diazo, diazoamino,
ethylene, disilanyl, glycidyl, guanidino, guanyl, heptanamido,
hydrazino, hydrazo, hypophosphite (hypophosphito), imido,
isobutylidene, isopropylidene, silyl, silylene, methylene, mercapto,
methylene, ethylene, naphthal, napthobenzyl, naphthyl, naphthylidene,
propylene, propylidene, pryidyl, pyrryl, phenethyl, phenylene, pyridino,
sulfinyl, sulfo, sulfonyl, tetramethylene, thenyl, thienyl, thiobenzyi,
thiocarbamyl, thiocarbonyl, thiocyanato, thionyl, thiuram, toiuidino)
tolyi, a-tolyl, tolylene, a-tolylene, tosyl) triazano, ethenyl (vinyl),
selenyl,
trihydrocarbylamino, trihaloamino, trihydrocarbyl phosphite,
trihalophosphine, trimethylene, trityl, vinylidene, xenyl, xylidino, xyfyl,
xylylene, 1,3-diene, hydrocarbyl radicals, etc., including derivatives,
homologes, analoges, and isomers thereof. Thus, ring compounds or
metals themselves may directly or indirectly contain one or more
chelating radicals (e.g. carbonyl, cyano, etc.).
One or more of the above radicals may be attached directly or
indirectly to another. Indirect attachment may be via one or more
intermediate atom, including but not limited to carbon, nitrogen,
oxygen, phosophorus, silicon, boron, sulfur, or another metal.
Metallic compounds may have one or more non-ring radicals
attached. Desireable metals may for example have one or more alkyl,
alkylene or similar radical attached to the metal, or one or more
hydroxyl, carbonyl, alkyloxy, alkanol radicals, or combination thereof.
Other metallic compounds may have one or more ring systems
attached directly or indirectly to a metal, with or without an attached
non- ring radical to the metal.
One or more cyclic rings maybe attached, fused or indirectly
attached together or finked together via one or more radicals, one or
more atoms, including but not limited to carbon, nitrogen, oxygen,
phosophorus, silicon, boron, sulfur, or a metal.
One or more metals may be attached to each other, for example
hexamethyldisilane, which is a preferred metallic. Indirect attachment
herein includes attachment via one or more radicals, and/or one or
more atoms, including but not limited to carbon, nitrogen, oxygen,
phosophorus, silicon, boron, sulfur, or another metal.
As contemplated herein said carbon, nitrogen, oxygen,
phosophorus, silicon, boron, sulfur, or other metal atom, may be
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attached to itself or to another herein, one or more times, with each
atom optionally having one or more hydrogen andlor radical(s). Said
attachment may be independent of attachment to any other radical or
metal, or may include an attachment to another radical or metal.
Likewise one or more cyclic rings may be attached directly to the
metal, or indirectly via one or more non-ring radicals, and/or via one or
more intermediate atoms, including but not limited to carbon, nitrogen,
oxygen, phasophorus, silicon, boron) sulfur, or another metal.
Thus, one or more metals may be attached at one, or up to every
location possible on the ring system, directly and/or indirectly.
Likewise, one or more ring systems may be attached at one, or up to
every metal location possible, directly and/or indirectly.
A non-ring radical may be independently attached directly or
indirectly to the metal, absent its attachment of a ring system. In the
practice of this invention the attachment of one or more non-ring
radicals) to a metal, absent a ring system is expressly contemplated.
Contemplated oxygenated metallic compounds include metallic
alkanols, ethers, ketones) hydroxides, alkyloxy, including methoxy,
dimethoxy, trimethoxy, ethoxy, diethoxy, triethoxy, oxalate, carbonate,
dicarbonate, tricarbonate, and similar structured compounds, including
mixture thereof. For example trimethoxymethylsilane (as set forth
below) is desireable. Metallic carbonates, including dimetallic
carbonates, dimetallic dicarbonates, and the like, are also
contemplated. It is contemplated these oxygenated metallic or organo-
metallic compounds may be employed absent a dialkyl carbonate or
other oxygenated ECS structure.
Likewise one or more non-ring radicals may be independently
attached directly or indirectly to the ring system, absent attachment of
a metal. An independent attachment of a metal may be via intermediate
radical, one or more intermediate atoms, including but not limited to
carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or
another metal.
A cyclic ring/radical/side chain may be indirectly attached to the
metal through one of more atom, including but not limited to carbon,
nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or a metal.
Indirect attachment via oxygen is contemplated but less desireable.
Cyclic rings may be attached to one or more non-ring radicals,
atoms and/or ring systems prior to a direct or indirect attachment of the
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metal. For example, [2-(cyclohexenyl)ethyl]triethoxysilane contains a
ethyl radical attached to the cyclohexenyl ring, which is then attached
to silicon. This is a preferred metallic structure.
Thus, cyclomatic compounds may contain one or more ring
systems, optionally with one or more non-ring radicals attached thereto.
Said rings) then may be attached directly or indirectly to a metal, with
said metal in turn optionally attached directly or indirectly to a radical,
with said radical being optionally a non- ring radical selected from one
or more hydrogen, hydroxyl, alkyl, aryl, carbonyl, alkanol,
alkanolamine, alkyloxy, oxy or oxygen containing radical. Non-limiting
examples include methylcyclopentadienyl manganese tricarbonyl, [2-
(cyclohexenyl)ethyl]triethoxysilane, and cyclohexenyl
dimethoxymethylsilane.
A class of metallics, which are capable of vapor phase
combustion include spiral compounds based for example upon
ferricyanhydric acid derivatives, namely ferricyanides. See Dictionary of
Chemical Solubilties, supra, pages 334-342, which lists various
ferrocyanides, incorporated herein by reference. Alkali metals and
alkali earth metals are desireable ferricyanides. Potassium
hexacyanoferrate (II) and potassium hexacyanoferrate (III) are
desireable. Non-limiting examples of substitutes include potassium
hexacyanocobalt II- ferrate, potassium Hexacyanocobalt III, potassium
hexachloroosmate (IV), potassium hexachloroplatinate (IV), potassium
hexafluorosilicate, potassium hexafluoromanganate (IV), potassium
Hexaflourozirconate. potassium hexathiocyanatoplatinate (IV),
potassium sodium ferricyanide, potassium hexacyanoplatinate,
potassium hexacyanoruthinate (//)hydrate, potassium
hexacyanoplatinate (IV), potassium hexafluoroaluminate, potassium
hexafluoroarsenate, potassium hexafluorophosphite, potassium
hexafluorophosphite) potassium hexafluorosilicate, potassium
hexahydroxyantimonate, potassium hexafluoro titante, Potassium
copper ferracyanide, potassium cyanide, iron {III) ferrocyanide, sodium
ferrocyanide decahydrate. Naturally other cyano-spiral, including
hexacyano compounds are contemplated. Substitutions for potassium
and/or iron are also contemplated. Examples of such substitution
include potassium hexacyanocobaltate (III), sodium
hexacyanocobaltate (lll), etc. Structurally similar compounds,
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analogues, and homologues, ect., are incorporated herein by
reference.
It is contemplated these compounds will require a solvent inorder
to be adapted to Applicant's invention. Non-limiting examples of
solvents, include alkyl ketones (acetone, etc.), alkyl alcohols, alkyl
ethers, glycerofs, alkanol amines (ethanolamine, etc.), and the like.
Other contemplated solvents are known in the art and those which are
both soluable with said hexacyanides and DMC are incorporated herein
by reference.
An example of this fuel composition would include those already
provided herein, except the metal component would be a hexacyanide,
preferrably potassium hexacyanoferrate (il) or (III).
Other example, would be a fuel composition including DMC and
potassium hexacyanoferrate (II) with a mutual solvent, optionally
containing trimethoxymethylsilane) a hydrocarbon/hydrogen, and/or an
oxidizer, formulated to acheive vapor phase combustion. Said
composition may also be constructed to have maximum pH of 10.5.
Another class of desireable metallics include metal hydrides or
metallic hydryls. Examples of metallic hydryls include sodium hydride,
lithium hydride, aluminum hydride, aluminum borohydride, boron
hydride, boron anhydride, beryllium borohydride, lithium
borohydride,lithium aluminum hydride, lithium borohydride, sodium
borohydride, transition-metal hydrides, transition-metal carbonyl
hydrides, transition-metal cyclopentadienyl hydrides, and mixture.
Those hydrides known in the art and those disclosed in Metal Hydrides,
Bambakidis, New York, Plenum Press (1981), Boron Hydride
Chemistry, Muetterties, New York, Academic Press (1975), which
accomplish primary vapor phase combustion object of this invention,
are contemplated in the claims below and incorporated herein by
reference.
Organometallic nitrosyls are also desireable. See for example
Metal Nitrosyls, Richter-Addo, Oxford University Press, U. K. { 1992).
Alkyl metal carbonates, multi-metal alkyl carbonates, or
carbonates including those with a hydrogen (e.g. LiHC03, Na2C03,
NaHC03, MnC03, MgC03, CaC03, CaMg(C03)2, etc.), alkali metal
carbonates, and other metal carbonates (e.g. AgC03, T12C03, etc.)
are contemplated. Contemplated salts also include acid salts
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containing replaceable hydrogen. Double oxides and hydroxides are
also contemplated.
Transition metals and their known cyclomatic compounds,
including carbonyl compounds are expressly contemplated. See
Fundamental Transition Metal Organometallic Chemistry, Lukehart,
Monteray, Calif, Brooks/Cole (1985), Transition Metal Compounds,
King, New York, Academic Press (1965), Transition-Metal
Organometallic Chemistry, King) New York, Academic Press (1969),
Fundamental Transition Metal Organometallic Chemistry, lukehart,
Monterey, Ca., Brooks/Cole (1985), incorporated herein by reference. A
preferred cyclomatic transition metallic is MMT.
As contemplated herein non-transition-metal compounds known
in the art. See Nontransition-Metal Compounds, Eisch, New York,
Academic Press (1981). Non-transition metal compounds that
accomplish primary object of vapor phase combustion are
contemplated in the claims below and incorporated herein by reference.
Likewise known metallocenes are contemplated. Non-limiting
examples include alkylmetallocenes, arylmetallocenes, including
dicyclopentadienyl-metal with the general formula (C5H5)2M,
dicyclopentadienyl-metal halides with the general formula
{C5H5)2MX1-3, monocyclopentadienyl-metal compounds with the
general formula C5H5MR1-3) where R is CO, NO, halide group, alkyl
group, etc. Non-limiting examples include napthacenes, ferrocene,
methylferrocene, cobaltocene, nickelocene, titanocene dichloride,
zirconocene dichloride, uranocene, decamethylferrocene,
decamethylsilicocene, decamethylgermaniumocene,
decamethylstannocene, decamethylphosocene, decamethylosmocene,
decamethylruthenocene, decamethylzirconocene, silicocene,
decamethylsilicocene, etc.). are also contemplated. Metallocenes that
accomplish primary object of vapor phase combustion are
contemplated in the claims below and incorporated herein by reference.
See also Hawley's Condensed Chemical Dictionary 12th ed, Lewis, Van
Nostrand Reinhold Company, New York (1993), also incorporated by
reference.
Carbonyl compounds are expressly contemplated. A limited
number of examples include decacarbonyl dimanganese,
{acetylacetonato)di- carbonylrhodium. See for example Carbonylation:
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Direct Synthesis of Carbonyl Compounds, H.M. Colquhoun, Plenum
Press (199'!), incorporated herein by reference.
Alkyl metal and alkyl earth metal salts and derivative compound
are expressly contemplated. For example, potassium salts are
contemplated including those commercially marketed by Shell
Chemical, known as "SparkAid or SparkAde." Other acceptable
potassium salts include potassium alkanols, e.g. potassium methoxide,
potassium ethoxide, potassium propoxide, potassium isopropoxide,
potassium butoxide, potassium sec-butoxide, potassium tent-butoxide,
potassium pentoxide, potassium tert-pentoxide, etc. Other non-limiting
examples of potassium salts include potassium hydrogenphthalate,
potassium hydrogensulfate, monopotassium acetylenedicarboxylic acid,
potassium phenoxide, potassium pyrophosphate, potassium
dihydrogenphosphate, potassium benzoate, potassium chloride,
potassium hexoate (potassium salt hexoic acid), potassium acetate,
potassium diphenylphosphide, potassium trimethylsilonalate, potassium
phthalic acid, P-aminobenzoic acid potassium salt, monopotassium L-
aspartic acid. Corresponding sodium, Lithium, rubidium, sesium
compounds are contemplated.
As noted above, non-limiting non-leaded simple binary/ternary
metallic compounds, including binary/ternary and higher metallic salts,
acid salts, including those with replaceable hydrogen, etc., are
contemplated. Hydroxy acids, perchlorates, sulfates, nitrates,
carbonates, hydroxides, methylates, ethylates, propylates, and others,
are also contemplated. Non-limiting examples include potassium nitrite,
sodium nitrite, lithium nitrite, and hexamethylphosphoric triamide.
Silicon containing metallics are particularly preferred. Non-
limiting examples preferred silicons include [2-
(cyclohexenyl)ethyl]triethoxysilane, cyclohexenyl
dimethoxymethylsilane, benzyltrimethylsilane, N-(3-
(trimethoxysilyl)propyl)ethylenediamine, N-1-(3-
(trimethoxysilyl)propyl)diethylenetriamine, N-(3-
(trimethoxysilyl)propyl)ethylenediamine, 1- (trimethyl(silyl)pyrrolidine,
triphenylsilanol, octamethyltrisiloxane, 2,2,4,4,6,6-
hexamethylcyclotrisilazane, hexamethylcyctrisiloxane,
hexamethyldisilane, 1,1,1,3,3,3- hexamethyl disilazane,
hexamethyldisiloxane, hexamethyldisilthiane, allyltributylsilane,
tetraalkyfsilanes (e.g. tetraethylsilane) tetrabutylsilane, etc.), 3-
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aminopropyltriethoxysiiane, benzytrimethylsilane, benzytriethylsilane,
N- benzyltrimethylsilylamine, diphenylsilanediol, dihexylsilanediol,
(trimethylsilyl)cyclopentadiene, including homologues, analogues and
derivative thereof.
An an example of a desirable fuel composition of this invention
would then include a lower molecular weight dialkyl carbonate
(preferrably DMC or EMC), a silane selected from preferred silicons
immediately above (or as set forth elsewhere in this specification), and
optionally trimethoxymethyisilane as a co- metallic, a hydrogen or a
hydrocarbon co-fuel, and/or an oxidizer.
Preferrable tin compounds include benzltriphenyltin and
allyltributyltin. A preferrable phosphorus compound includes
benzyld iethylphosphite.
It is also within the scope and practice of this invention to employ
oxygenated containing metallic compounds, including oxygenated
organo metallic compounds, which are metallic alcohols,
alkanolamines, ketones, esters) ethers, carbonates, and the like, which
are themselves ECS compounds, in hydrocarbon fuels with or absent
additional dialkyl carbonate or other ECS structure. Those metallics are
incorporated herein by reference. Additionally, this invention
contemplates one or more similar organo oxygen containing metallics,
including mixture, with or without an ECS compound, to act as neat
"stand alone" fuel. Thus, it is an express embodiment to use metallic
compounds alone, as singular means of enhancing fuel combustion.
However, it is perferred the metallic be added to DMC, optionally a co-
fuel, an oxidizer, catalyst, and/or a hydrocarbon.
The compositions of this invention contemplate usage of an
oxidizer and other ingredients. See incorporated references, including
aforementioned PCT applications, for the definitions incorporated in the
claims below.
It is also within the practice of this invention to employ a metallic
compound, including homologue, analogue) isomer, or derivative
thereof, having a structure or structure similar to M-Rn, Rn-M-M-Rn,
Rn-M-Q-M-Rn, Rn-M-Q'-M-Rn, Rn-M-R'-M-Rn, wherein M is one or
more non-leaded metal{s), metalloid(s), or non-metal element(s), and R
is one or more hydrogen, cyclic ring system/radical/side chain(s),
andlor non-ring radical/side chains) as provided herein above,
including but not limited to alkyl, aryl, alkyloxy, alkylanol {alkanol),
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hydroxyl, aryloxy, polyalkyl, polyaryl, polyalkyloxy, polyalkylanol,
polyaryloxy, polyhydroxyl radicals. R' is one or more cyclic ring
systemlradical/side chain(s), and/or non-ring radical/side chains) as
provided herein. If R is greater than 1, then subsequent R's may be
same or different radical, etc. R also be a single radical or one radical
attached to one or more radicals. "n" is an interger ranging from 1 to
the number of valence electrons (or common oxidation states) available
of M. Q is an atom having a minimum oxidation available of 2, including
but not limited to carbon, nitrogen, oxygen, phosophorus, silicon,
boron, sulfur, or a differing metal than M. Q' is an atom with a minimum
available oxidation state of 2, including but not limited to carbon,
nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or a differing
metal than M, also containing one or more radicals.
Additional oxygenated-organo or oxygenated metallic structure
includes M1-O(CO)O-M2, wherein M1 or M2 are the same or different
metal or element. M1 may be a double valence cation, wherein M2 is
absent from above structure, unless additional carbonate is included.
Preferred M valences are 1 or 2. M valences or multiple M1M2
combinations having combined valence greater than two are
acceptable. In which case, additional carbonate structure would be
added) e.g. CaMg(C03)2.
In the immediate structure above, M1/M2 valence's may be
greater than one, wherein excess valence is occupied by same or
additional metal (element), and/or wherein M1 or M2 are substituted for
a single or double bond oxygen, and/or by one or more radicals. M1 or
M2 also may be substituted for single bond oxygen, or nitrogen) and/or
by one or more radicals, including methyl, hydrogen, hydroxy, ethoxy,
carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy,
methyoxy, isonitro, isonitroso, or methylenedioxyl radical. Non-limiting
examples include carbonates of lithium [Li2O2(CO)], ammonium
manganese, potassium [K2O2(CO)], sodium, calcium, cesium, copper,
rubidium, lithium hydrogen, sodium hydrogen, potassium hydrogen)
potassium sodium, magnesium, and the like.
It is contemplated that C2 to C8 metallic ethers, C2 to C4/C5
metallic ethers being more desireable, will be used as metallic structure
in this invention. For example, M'1-CH2-CH2-O-CH2-CH2- M'2
structure is contemplated wherein M'1 and M'2 may be same or
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different metallic or wherein one M'1 or M'2 may be hydrogen) or other
atom, or radical with one available valence.
Other contemplated structure include metallic ketone, ester,
alcohol, acid, and the like. Non-limiting examples include M'1-C- OH3-
R, wherein M'1 is one or more metallic comprising valence of 3 or
greater, and R is radical, whereby resulting structure is ketone, ester)
acid, alcohol, or ether. Other structure include M'1-C2O4, wherein M'1
has a valence of 2. M1-C-C-O-C-C-M2 structure is also contemplated
wherein M1 and M2 may be same or different metallic or wherein M2
may be hydrogen or atom of one valence. Other structure includes RO-
M, where RO is an alkanol and M is a metal. Similar structure is
contemplated for M have available valence greater than 1.
It is preferred when an oxygenated organo-metallic compound is
employed, it have ECS properties when ever possible) e.g. higher
heats of vaporization, high burning velocities, favorable decomposition
characteristic (e.g. decomposition at post ignition pre-combustion
temperatures into enhanced combustion or free radicals structure), be
thermally stable at normal handling temperatures, etc.; and have high
heat and energy releasing characteristics of metals, etc.. Non
limiting examples of lithium derivative compounds of this invention,
include: lithium bis(dimethyisilyl)amide, lithium bis(trimethylsifyl)amide)
oxamic acid, P-aminosalicylic acid lithium salt, lithium salt 5-nitroorotic
acid, lithium D-gluconate, lithium hexacyanoferrate(III) (Li3Fe(CN)6),
lithium diphenylphosphide, lithium acetate, lithium acetate acid, lithium
salt acetic acid, lithium acetamide, lithium anilide, lithium azide, lithium
benzamide, lithium antimonide, lithium orthoarsenate, lithium
orthoarsenite, lithium meta-arsenite, lithium diborane, lithium
pentaborate, lithium dihydroxy diborane, lithium borohydride, lithium
cadium iodide, lithium chloride, lithium calcium chloride, lithium
carbide, lithium carbonate) lithium hydrogen carbonate, lithium
carbonate, lithium carbonyl, lithium cobalt (II) cyanide, lithium cobalt
(III) cyanide, lithium cobaltinitrite, lithium cynomanganate (II), lithium
cynomanganate (III), lithium citrate, lithium ferricyanide, lithium
ferrocyanide) lithium hydride, lithium hydroxide, lithium manganate,
lithium permanganate, lithium methionate, lithium napthenate, lithium
nitride, lithium nitrate, lithium nitrite, lithium nitrobenzene (e.g. lithium-
p-nitrobenzene), lithium nitrophenoxide, lithium etherate, lithium
chromate, lithium oleate, lithium oxalate, lithium oxalatoferrate (II),
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lithium oxalatoferrate (I11), lithium monoxide, lithium oxide, lithium
peroxide, lithium , lithium mono- orthophosphate, lithium
hypophosphite, lithium orthophosphite, lithium hydroxoplumbate,
lithium rhodium cyanide, lithium selenide, lithium selenite, lithium
selenocynate, lithium selenocyanoplatinate, lithium disilicate, lithium
metasilicate, lithium sodium carbonate, lithium sodium ferricyanide,
lithium hydroxostannate, lithium disufide, lithium hydrosulfide, lithium
pentasulfide, lithium tetrasulfide, lithium trisulfide, lithium telluride,
lithium thioarsenate, lithium thioarsenite, lithium trithiocarbonate,
lithium thiocyanate) lithium amide, lithium salt (E,E)-2,4-hexadienoic
acid, dilithium fluorophosphate) dilithium fluorophosphite, trilithium
phosphate, trilithium phosphite, lithium perchlorate, propanoic acid
lithium salt, lithium formate, lithium cyanate, lithium
hexacyanocobaltate (ill), lithium hypophosphite, lithium
hexaflurorsilicate, lithium nitroprusside, lithium phenoxide, lithium
phosphate (dibasic, monobasic) tribasic), lithium salicylate, lithium
seienide, lithium tetracyanonickelate (II), lithium tetrafluoroborate,
lithium xanthogenate, lithium -p-aminobenzoate, lithium copper
ferrocynanide, lithium cupric ferrocyanide, lithium hexafluorophosphate,
lithium hexanitricobaltate Ill, lithium naphthenate, lithium -B-
naphthoxide, lithium polysulfide, lithium - sodium phosphate, lithium
stearate, lithium sulfide, lithium sulfite, lithium sulfate, lithium
thiocyanate, lithium xanthate, lithium fluorosilicate, N-
lithiumethylenediamine, oxalic acid dilithium salt, lithium beta-
hydropyruvic acid, lithium 1,1- dimethylurea, lithium 1,1-diethylurea,
lithium 1,1-diepropylurea, lithium xanthate, lithium ethylxanthate,
lithium methyixanthate, lithium salt thiophenol, lithium
triphenylmethyllithium, methyl- lithium, ethyllithium,
lithiumethynyl(acetylide), propyllithium, isopropyllithium, butyllithium,
isobutyllithium, secbutyllithium, tertbutyllithium, pentalithium,
hexyllithium, heptafithium, amyllithium, isoamyllithium, benzyllithium,
dimethylbenzyllithium, tolyllithium, dodecyllithium,
cyclopentadienyllithium, methyl- cyclopentadienyllithium,
cyciohexyllithium, lithiumheptyl, lithiumdodecyl, lithium tetradecyl,
lithium hexadecyl, lithium octadecyl, phenyllithium, lithium o-tolyl,
lithium m-tolyl, lithium p-tolyl, lithium-p-chlvrophenyl, lithium p-
bromophenyl, lithium lithium o- anisyl, lithium m-anisyl, lithium p-anisyl,
lithium diethoxyphenyl, lithium dimethoxyphenol, lithium m-cumyl,
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lithium p-ethoxyphenyl, lithium m-dimethylaminophenyl, lithium 9-
flourene, lithium a-napthyl, lithium b-napthyl, lithium p-phenylphenyl,
lithium 9-phenylanthryl, lithium 9-anthryl, lithium 9-methyl- phenanthryl,
lithium pyridyl, lithium 2-pyridyl, lithium 3-pyridyl, lithium 6-bromo-2-
pyridyl, lithium 5-bromo-2-pyridyl, lithium dibenzofuryl, lithium 3-
quinoyl) lithium 2-lepidyl, lithium triphenylmethyl, lithium 2,4,6-
trimethylphenyl, lithium 2,4,6- triisopropylphenyl, lithium 2,3,5,6-
tetraisopropylphenyl, lithium tetrabutylphenyl, thiophenedilithium,
toluenedilithium, dipheny- lethylenedilithium, lithiumamylethynyl,
lithiumphenylethynyl, lithiummethoxybromophenyl, lithium
phenylisopropyl, lithium tetraphenylboron, lithium tetramethylboron,
lithium a-thienyi, lithium m-trifluoromethylphenyl, phenylethynyllithium,
3-furyl- lithium, phenylisopropyllithium, dibenzofuranyllithium, lithium
dimethylbenzyl, lithium selenocyanate, lithium trimethylsilanolate,
diphenylphosphide, lithium benzoate, lithium tert-butyl carbonate,
lithium azide, di-lithiumcyanamide, lithium cyanide, lithium
dicyanamide, cyclohexanebutyric acid lithium salt, cyclohexane acid
lithium salt, cyclopentadientyllithium, lithium tri-tert-butoxy- aluminum
hydride, lithium triethylborohydride, lithium trimethyl- borohydride,
lithium tripropylborohydride) lithium triisopropyl- borohydride, lithium
tributylborohydride, lithium triisobutyl- borohydride, lithium tri-sec-
butylborohydride, lithium tri-tert- butylborohydride, lithium
trisiamylborohydride, lithium chlorate, lithium tert-butoxide, lithium sec-
butoxide, iso-butoxide, lithium antimonate, lithium diphenylphosphide,
lithium bis(trismethylsilyl) amide, trilithium phosphite, lithium
selenocyanate, lithium tri- sec-butylborohydride, lithium
triethylsilanolate, lithiumthiocyan- ate, lithium acetylide, lithium
chlorate, lithium salicylate, lithium di-lithium tetracarbonylferrate,
lithium tetraphenylborate, lithium triethylborohydride, lithium
triacetoxyborohydride, lithium triphenylborane, lithium hydroxide,
lithium diphenylphosphide, lithium methoxide, lithium ethoxide, lithium
tri-sec-butyl- borohydride, tri-tert-butylborohydride, lithium triethylboro-
hydride, lithium triphenylborohydride, lithium trisiamylboro- hydride,
lithium metavanadate, lithium cyclohexanebutyrate, lithium
hexachloroplatinate, lithium thiocyanate, lithium selenocyanate, lithium
cyanate, lithium floride) lithium hexafluoroantimonate, lithium
hexafluoroaluminate, lithiumaluminate, lithiumaluminum-tri- tert-
butoxide, lithium hexafluoroarsenate, lithium hexafluorosili- cate,
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lithium hexacyanocobait(II)ferrate(II), lithium ferrosilicon,
difithiumhexacyanocobalt(II)ferrate(II), lithium hexafluorotitan- ate,
lithium hexafluorozirconate, lithium hexahydroxyantimonate, lithium
hexachlororuthenate, lithium hexachloropalladate, lithium formate,
lithium tetracyanonickeiate, lithium tetrafluoroaluminate, lithium
tetrafluoroborate, lithium thioacetate, L-glutamic acid monolithium salt,
fumaric acid lithium salt, oxamic acid lithium salt, lithium salt diphenyl-
phospane, P-aminobenzoic lithium salt, aminobenzole acid lithium salt,
alpha-napthaleneacetic acid lithium salt, dilithium salt 2,6-
naphthalenedicarboxlic acid) lithium cyclcohexanetherate; lithium
phthalimide, P-aminosalicylic acid lithium salt, lithium salt 3,5-
dimethylcyclohexyl sulfate, indolebutyric acid lithium sait,indofe-3-
butyric acid lithium salt, diphenylphosphide, lithium dimethylsilanolate,
lithium triethyl- borohydride, lithium propoxide, lithium isopropoxide,
lithium butoxide, lithium sec-butoxide, lithium pentoxide, lithium tert-
pentoxide, lithium hydrogenphthalate, lithium oxalate, lithium
hydrogensulfate, monolithium acetylenedicarboxylic acid, lithium
pyrophosphate, lithium dihydrogenphosphate, lithium hexoate (lithium
salt hexoic acid), lithium diphenylphosphide, lithium trimethylsilonalate,
lithium phthalic acid, P-aminobenzoic acid lithium salt, monolithium L-
aspartic acid, tetraphenyldilithium (C6H5)2CLi2C(C6H5)2,
lithiumethylphenyl (LiCH2C6H5), lithium bromate, lithium
hydrogenphospate, monlithium salt D-shaccharic acid, DI-asparatic
lithium salt, (R)-alpha-hyroxymethylaspartic acid lithium salt, lithium
fluoride, lithium iodate, lithium salt ethyl malonate, lithium thioacetate,
lithium phenol, lithium salt aminobenzoic acid, lithium aminophenol salt,
lithium cyclohexenol, lithium methylcyclohexenol, lithium cyclopropanol,
lithium methylcyclopropanol, lithium cyclobutanol, lithium methyl-
cyclobutanol, lithium methylcyclopentanol, lithium cyclopentanol,
lithium cyclohexenol, lithium methylcyclohexenol, lithium dimethyl-
cyclohexenols (e.g. lithium 3,5-dimethylcyclohexanol, lithium 2,3-
dimethylcyclohexanol) lithium 2,6-dimethylcyclohexanol, lithium 2,5-
dimethylcyclohexanol, 3,5-dimethylcyclohexanol), lithium o-
ethylxanthic acid) monolithium salt 2-ketoglutaric acid, dilithium salt,
ketomalonic acid, lithium salt lactic acid, dilithium thiosulfate, lithium
antimony tartrate, lithium dichloroacetate, lithium dimethylacetate,
lithium diethylacetate, lithium dipropyl- acetate, lithium metaborate,
lithium tetraborate, lithium tetra- chlorocuprate, lithium acetoacetate)
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lithium diisopropylamide, lithium diethylamide, lithium dimethylamide,
lithium bis(dimethyl- silyl)amide, dilithium phthalocyanine,
dilithiumtetrabromocuprate, dilithium tetrabromonickelate,
dilithiumtetrachloromanganate, dilithiumbutadiyne, lithium
cyclopentadienide) lithium dicyclo- hexylamide, lithium diethylamide,
lithium dimethylamide, lithium dipropylamide, lithium diisopropylamide,
lithium thexylborohydride, lithium tri-tert-butoxyaluminohydride, lithium
trimethyl- silyl)acetylide, lithium triethylsilyl)acetylide, lithium tris[(3-
ethyl-3-pentyl)oxy]aluminohydride, (phenylethynyl)lithium, 2-
thienyllithium) lithium diethyldihydroaluminate, lithium dimethyl-
dihydroaluminate, lithium aluminum hydride, lithium bifluoride, lithium
biphenyl, lithium biselenite, lithium bis(2-methoxyethoxy)-aluminum
hydride, lithium bismuthate, lithium borate, lithium chlorite, lithium
cobaltnitrite, lithium cyanoborohydride, lithium cyclopentadienide,
lithium dicyanamide, lithium hexametaphosphate, lithium
hexanitrocolbaltate, lithium hydrogenphosphite, lithium
hydrogenselenite, lithium hydrogensulfite, lithium hydrosulfite, lithium
hypochloride, lithium metaarsenite, lithium metabisulfide, lithium
metaperiodate) lithium methacrylate, lithium nitrofer- ricyanide,
oxybate, lithium pentamethylcyclopentadienide, lithium phenolate,
polyphosphate, lithium polyphosphite, lithium propion- ate, lithium
pyrophosphate, lithium selenate, lithium selenite, lithium
tetrachloroaluminate, lithium thiomethoxide, lithium thiosulfate, lithium
thiosulfide, lithium thiosulfite, lithium tri- actoxyborohydride, lithium
lithium trimethylsilonate, lithium triethylsilonate, lithium tris(1-
pyrazoly)borohydride, including analogues, homologue, isomers and
derivatives thereof. See Lithium Chemistry: A Theorical and
Experimental Overview, Sapse, Schleyer, John Wiley & Sons, N.Y.
(1995), incorporated herein by reference.
Non limiting examples of the boron derivative compounds of this
invention include: alkyl boron compounds, aryl boron compounds,
1,3,2-benzodioxaborole, diisopropoxymethylborane, ethylborane)
diethylborane, diemthylborane, dicyclohexylborane, boric acid esters
(e.g. borate ester, dimethyl borate, di-n-butyl borate, dicyclohexyl
borate, didodecylborate, di-p-cresyl borates), phenyiboronic acid, 2-
phenyl-1,3,2-dioxborinane, pyrrolyboranes (e.g. 1-pyrrolyborane, 2-
pyrrolyborane), tetrabutylammonium borohydride,
tetramethylammonium borohydride, tetraisoproplyam- monium
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borohydride, tetrapropylammonium borohydride, tetraethylam- monium
borohydride) tetraisobutylammonium borohydride, tetra-tert-
butylammonium borohydride, tetra-sec-butylammonium borohydride,
tetrabutylammonium cyanoborohydride, tetramethylammonium cyano-
borohydride, tetraisoproplyammonium cyanoborohydride, tetra-
propylammonium cyanoborohydride, tetraethylammonium cyanoboro-
hydride) tetraisobutylammonium cyanoborohydride, tetra-tert-
butylammonium cyanoborohydride, tetra-sec-butylammonium
cyanoboro- hydride, tetramethylammonium triacetoxyborohydride,
thiopheneboric acid, 2-thiopheneboric acid, 3-thiopheneboric acid,
tolylboronic acid (e.g. o-tolylboronic acid, p-tolylboronic acid, m-
tolylboronic acid), tributoxyborane, tributylborane, tri-sec-butylborane,
tri- tert-butylborane, tributylborate, tri-tert-butylborate, tri-
methoxyboroxine, trimethylamineboran, trimethylborate, trimethyl-
boroxine) trimethylborazine, trimethylene borate, triphenylborate,
triphenylborane, tribenzyl borate, borate, trisiamylborane, tris(2-
methoxyethyl)borate, boron hydride, lithium borohydride, sodium
borohydride, boron hydrate, boron hydride, boron anhydride,
triethylboron {C2H5)3, decaborane, borazoles) aluminimum boro-
hydride, beryllium borohydride, lithium borohydride, hexamethyl-
diamineborane (CH3)3NBH(CH3)3), (CH3)2B1, berylliumborohydride
(Be(BH4)2), trimethoxytriborate (BO)3(OCH3)3, C4H9B(OH)2,
AI(BH4)2, Be(BH4)2, LiBH4, B(OC2H5)3, B(OCH3)3,
trimethoxytriborane, 3- bromophenylboronic acid, trimethoxy borate,
triethoxy borate, triproxyborate, tributoxyborate, triisobutoxyborate, tri-
tert- butoxyborate, tri-sec-butoxyborate, tri-phenoxyborate, tri-
phenoxyboroamine) tri-phenoxyborane, phenylboronic acid, benzyl-
boronic acid, cylohexylboronic acid, cyiohexenylboronic acid,
cyclopentylboronic acid, methylphenylboronic acid, methylcylohexyl-
boronic acid, methylcyclopentylboronic acid, methylbenzylboronic acid,
dimethylphenylboronic acid, dimethylcylohexylboronic acid,
dimethylcyclopentylboronic acid, dimethylbenzylboronic acid,
diphenylboronic acid, dibenzylboronic acid, dicylohexylboronic acid,
dicylohexenylboronic acid, dicyclopentylboronic acid,
methyldiphenylboronic acid, bis[(methyl)cylohexyl]boronic acid,
bis[(methyl)cyclopentyl]boronic acid, bis[(methyl)benzyl]boronic acid,
bis[(dimethyl)phenyl]boronic acid, bis[(dimethyl)- cylohexyf]boronic
acid, bis[(dimethyl)cyclopentyl]boronic acid,
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bis[(dimethyl)benzyl]boronic acid, phenylboroncarbonyl, benzyl-
boroncarbonyl, cylohexylboroncarbonyl, cylohexenylboroncarbonyl,
cyclopentylboroncarbonyl, methylphenylboroncarbonyl, methyl-
cylohexylboroncarbonyl, methylcyclopentylboroncarbonyl, methylben-
zylboroncarbonyl, phenylboronic acid carbonyl, benzylboronic acid
carbonyl, cylohexylboronic acid carbonyl, cylohexenylboronic acid
carbonyl, cyclopentylboronic acid carbonyl, methylphenylboronic acid
carbonyl) methylcylohexylboronic acid carbonyl, methyl-
cyclopentylboronic acid carbonyl, methylbenzylboroncarbonyl,
dimethylphenylboroncarbonyl, dimethylcyfohexyiboroncarbonyl,
dimethylcyclopentylboroncarbonyl, dimethylbenzylboroncarbonyl,
diphenylboroncarbonyl, dibenzyiboroncarbonyl, dicylohexylboroncar-
bonyl, dicylohexenylboroncarbonyl, dicyclopentylboroncarbonyl,
methyldiphenylboroncarbonyl, di[(methyl)cylohexyl]boroncarbonyl,
di[(methyl)cyclopentyl]boroncarbonyl, di[(methyl)benzyl)boron-
carbonyl, di[(dimethyl)phenyl]boroncarbonyl, di[(dimethyl)cylo-
hexyl]boroncarbonyl, di[(dimethyl)cyclopentyl]boroncarbonyl,
di[(dimethyl)benzyl]boroncarbonyl, phenylboromethoxide (pheny-
Iborodimethoxide C6H5B(OCH3)2), benzylboromethoxide, cylohexyl-
boromethoxide, cyfohexenylboromethoxide, cyclopentylboromethoxide,
methylphenylboromethoxide, methylcylohexylboromethoxide, methyl-
cyclopentylboromethoxide, methylbenzylboromethoxide, methyiphenyl-
boromethoxide, dimethylphenylboromethoxide, methylcylohexyl-
boromethoxide, dimethylcylohexylboromethoxide, methylcycfopentyl-
boromethoxide, dimethylcyclopentylboromethoxide, methylbenzyl-
boromethoxide, dimethylbenzylboromethoxide, diphenylboromethoxide,
dibenzylboromethoxide, dicylohexylboromethoxide, dicylohexenyl-
boromethoxide, dicyclopentylboromethoxide, di(methylphenyl)boro-
methoxide, di(methylcylohexyl)boromethoxide, di( methylcyclo-
pentyl)boromethoxide, di(methylbenzyl)boromethoxide, di(dimethyl-
phenyl)boromethoxide, di(dimethylcylohexyl)boromethoxide, di(di-
methylcyclopentyl)boromethoxide, di(dimethylbenzyl)boromethoxide,
phenylboroethoxide (phenylborodiethoxide C6H5B(OCH3)2), benzyl-
boroethoxide, cylohexylboroethoxide, cylohexenylboroethoxide)
cyclopentylboroethoxide, methylphenylboroethoxide) methyfcylohexyl-
boroethoxide, methylcyclopentylboroethoxide, methylbenzyl-
boroethoxide, methylphenylboroethoxide, dimethylphenylboroethoxide,
methylcylohexylboroethoxide) dimethyicyiohexylboroethoxide,
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methylcyclopentylboroethoxide, dimethylcyclopentylboroethoxide,
methylbenzylboroethoxide, dimethylbenzyiboroethoxide, diphenyl-
boroethoxide, dibenzyfboroethoxide, dicylohexylboroethoxide,
dicylohexenylboroethoxide, dicyclopentylboroethoxide, di(methyl-
phenyl)boroethoxide, di(methylcylohexyl)boroethoxide, di(methyl-
cyclopentyl)boroethoxide, di(methylbenzyl)boroethoxide, di(di-
methylphenyl)boroethoxide, di(dimethylcylohexyl)boroethoxide,
di(dimethylcyclopentyl)boroethoxide, di(dimethylbenzyl)boro- ethoxide,
phenyfboric acid, benzylboric acid, cylohexylboric acid,
cylohexenylboric acid, cyclopentylboric acid, methylphenylboric acid,
methyicylohexylboric acid, methylcyclopentylboric acid)
methylbenzylboric acid, dimethylphenylboric acid, dimethyl-
cylohexylboric acid) dimethylcyciopentylboric acid, dimethylbenzyl-
boric acid, dibenzylboric acid, dicylohexylboric acid, dicylo-
hexenylboric acid, dicyclopentylboric acid, methyldiphenylboric acid)
bis(methylcylohexyl)boric acid, bis[methylcyclopentyl]boric acid,
bis[methylbenzyl]boric acid, bis[dimethylphenyl]boric acid,
bis[dimethylcylohexyl]boric acid, bis[dimethylcyclopentyl]boric acid,
bis[dimethylbenzyl]boric acid, aminophenylboronic acid,3-
aminophenylboronic acid, diborane, tetramethoxydiborane,
tetraethoxydiborane, boric acid, borazine, borocarbonate, borane- tert-
butylamine, tetraethylammonium borohydride, tetraethyl- ammonium
tetrafiuoroborate, tetrapropylammonium tetrafluoroborate,
naphthylboronic acids (e.g. 1-naphthylboronic acid, 2-naphthyl- boronic
acid, 3-naphthylboronic acid) 4-naphthylboronic acid),
methylnaphthlboronic acid, biphenylboronic acid, carborane,
cyclohexylamine diborane, methylbenzeneboric acid, dimethylben-
zeneboric acids (e.g. 3,5-dirnethylbenzeneboric acid), hexadecane-
boronic acid, tetreadecaneboronic acide, phenylethylboroamine)
methylborazine, dimethylborazine, trimethylborazine, ethylborazine,
diethylborazine, triethylborazine, carboborazine, dicarboborazine,
tricarboborazine, triisopropoxyboroxine, tripropoxyboroxine, trimenthyl
borate, trimenthyl borine, trimenthyl borane, trimethal- lyl borate,
trimethallyl bovine, tripentyl borate, tripentyl bovine, tripentyl borane,
trimethyl borate, trimethylborine, triethylborine, triethylborane)
triethylborate, tripropylborane, tripropylborine, tripropylborate
{tripropoxyborane)) triisopropyl- borane, triisopropylborate,
triisopropylborine, tri-iso-butyl- borane, tri-iso-butylborate, tri-sec-
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borane, tri-sec-borate, tri- sec-bovine, tributyl borate, tributyl bovine,
tributyl borane, tri- tert-butyl borate, tri-tert-butyl bovine, tri-tert-butyl
borane, triphenyl borate, triphenyl borane, tricyclohexylborate, tri-
cyclohexylborane, dimethyl boric acid, diethylboric acid, dipropyl- boric
acid, diisopropylboric acid, di-iso-butylboric acid, di-sec- boric acid,
dibutylboratic acid, di-tert-butylboric acid, diphenyl- boric acid,
dicyclohexylboric acid, boron tribromide, sodium tetrafluoroborane,
sodium trimethylborohydride, triethyl- borohydride, sodium
tripropylborohydride, sodium triisopropyl- borohydride, sodium
tributylborohydride, sodium triisobutyl- borohydride, sodium-tert-
butylborohydride, sodium-sec-butyl- borohydride,
sodiumphenylborohydride, potassium tetrafluoroborane, potassium
trimethylborohydride, triethylborohydride, potassium
tripropylborohydride, potassium triisopropylborohydride, potassium
tributylborohydride, potassium triisobutylborohydride, potassium- tert-
butylborohydride, potassium-sec-butylborohydride, potassium
phenylborohydride, butylboronic acid, sodiumborohydride,
methyldichloroborane, ethyldichloroborane) propyldichloroborane,
isopropyldichloroborane, butyldichloroborane, isobutyldi- chloroborane,
tertbutyldichloroborane, secbutyldichloroborane, phenyfdichloroborane,
methylboric acid, ethylboric acid, trichloro- borazine, borane-
tetrahydrofuran, tetrafluoroboric acid, boron trichloride, tre-sec-
butylborane, boran-trimethylamine, borane- triethylamine, borane-N,N-
diethylaniline, boran-pyridine, borane- tert-butylamine, borane-
morpholine, borane-dimethylamine, borane- diethylamine,
trisiamylborane, trisiamylborate, disiamylborane, disiamylborate,
trimesitylborane, sodium metaborate, lithium metaborate, potassium
metaborate, sodium metaborane, borane- tributylphosphine, lanthanum
hexaboride, boran-triphenylphosphine, boran-tributylphosphine,
cyclopentadienylboran, methyfcyclopen- tadienylboran, boran-N,N-
diisopropylborohydride, N,N'-bis(mono- isoipinocampheylborane)-
N,N,N'N'-tetramethylethylenediamine, boron nitride, 4-(borane-
dimethylamine)benzene, 4-(borane-dimethylamine)- pyridyl) 3-
(methylthio)proplyborane, tris(dimethylamino)borane,
butyldiisopropoxyborane, triphenyl borane sodium, sodium-
tetraphenylborane, sodiumtetraphenylborane, sodium tetrakis(1-
imidazolyl)borane, sodium tetrakis(1-imidazolyl)borate, diisopro-
poxyphenylborate, diisopropoxymethylborate, diisopropoxyethyl-
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borate, boron-ammonia) borontrifluoride, diethyl(3-pyridyl)borane,
dimethyl(3-pyridyl)borane) lithium thexylborohydride, dichloro-
methyldiisopropylborate, diethylmethoxyborane, dipro-
pylmethoxyborane, diisopropylmethoxyborane, diethylethoxyborane,
dipropylethoxyborane) diisopropylethoxyborane, boran-piperidine,
diphenylborinic anhydride, tris(trimethylsilyl)borate, tris(tri-
methylsilyl)borane, trimethylacetic acid with diethylboinic acid, (2-
methylpropyl)borinic acid, boroglycine, boron alchois, boron etherates,
boron acetates (e.g, propylborodiacetate, phenyl- borodiacetate, boron
tris(trifluoro)acetate), sodium tris(1- pyrazolyl)borohydride, sodium
perborate, tolylboronic acid, aluminum diboride,
chlorodicyclohexylborane, methyldicyclohexyl- borane,
ethyldicyclohexylborane, propyldicyclohexylborane,
isopropyldicyclohexylborane, dimethyicyclohexylborane, diethyl-
cyclohexylborane, dipropylcyclohexylborane, diisopropylcyclohexyl-
borane, lithium tetramethylboron, lithium tetraethylboron, lithium
tetrapropyllboron, lithium tetraisopropylboron, tetrabutyiboron, lithium
tetraisobutylboron, lithium tetra-sec-butylboron, tetra- tert-butylboron,
lithium tetraphenylboron, potassium hydroxide with trimethylboron,
potassium hydroxide with triethylboron, potassium hydroxide with
tripropyllboron, potassium hydroxide with tri- isopropylboron,
tributylboron, potassium hydroxide with tri- isobutylboron, potassium
hydroxide with tri-sec-butylboron) tri- tert-butylboron, potassium
hydroxide with triphenylboron, vinyl- phenylboronic acid, 4-
vinylphenylboronic acid, boron phosphide, boron carbide)
borinoaminoborine, boroethane, pentaborane) hexaborane,
decaborane, triselenideborane, hexasilicide borane, trisilicide borane,
trichloroborine dimethyletherate, trichloro- borine trimethlyammine,
trimethylborine trimethlyammine, trimethyl- borine triethlyammine,
triethylborine trimethlyammine, tricyclo- hexylborine, tri-n-hexyltriborine
trioxane, triisoamylborate, triisoamylborine, tri-p-anisylborine,
trimethoxyboroxine, tri- methylamrninoborine, triethylamminoborine,
tripropyiamminoborine, triisopropylamminoborine,
triisobutylamminoborine, tributylam- minoborine, tri-sec-
butylamminoborine, tri-tert-butylamrninoborine, triphenylamminoborine,
tribenzylamminoborine, trimethylamminoboric acid, triethyfamminoboric
acid, tripropylamminoboric acid, triisopropylamminoboric acid,
triisobutylamminoboric acid, tributylamminoboric acid, tri-sec-
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butyiamminoboric acid, tri-tert- butylamminoboric acid,
triphenylamminoboric acid, tribenzylam- minoboric acid,
trimethyldiborane, triethyldiborane, tripropyl- diborane,
trimethyltriborinetriamine (B), triethyltriborinetriamine (B),
trimethyltriborinetriamine (N), triethyltriborinetriamine (N),
trimethyltriborinetriamine (N-B-B'), triethyltriborinetriamine (N-B-B'), tri-
B-naphthylborate, tri-a-naphthaborate, tripehnyl- borineammine, tri-p-
tolyborine, tri-p-xylxborine, including analogues, homologues, isomers
and derivatives thereof. Corresponding compounds of aluminum,
gallium, indium, and thallium are contemplated. See Organo Boron
Chemistry, Volumes I & II (and subsequent volumes, editions, or
supplements), Howard Steinberg, InterScience Publishers (1966),
Boron-Nitrogen Compounds) Niedenzu, Dawson, New york, Academic
Press (1965), The Organic Compounds of Boron, Aluminum, Gallium,
Indium, and Thallium, Nesrneianov, Nikolaevich, Amterdam, North-
Holland Pub. Co. (1967), Peroxides, Superperoxides, and azomides of
Alkali and Alkali Earth Metals, Perekisi, N.Y., Plenum Press (19966),
incorporated herein by reference.
Non-limiting examples of sodium derivative compounds of this
invention include: sodium bis(dimethylsilyl)arnide, sodium
bis(trimethylsilyl)amide, oxamic acid, P-aminosalicylic acid sodium salt,
sodium salt 5-nitroorotic acid, sodium D-gluconate, sodium
hexacyanoferrate(III) (Li3Fe(CN)6), sodium diphenylphosphide, sodium
acetate, sodium acetate acid) sodium salt acetic acid, sodium
acetamide, sodium anilide, sodium azide, ammonium diisodium
amminepentacyanoferrate, sodium benzamide, sodium antimonide,
sodium orthoarsenate, sodium orthoarsenite, sodium meta-arsenite,
sodium diborane, sodium pentaborate, sodium dihydroxy diborane,
sodium borohydride, sodium cadium iodide, sodium chloride, sodium
calcium chloride, sodium carbide, sodium carbonate, sodium hydrogen
carbonate, sodium carbonate, sodium carbonyl, sodium cobalt (II)
cyanide, sodium cobalt (III) cyanide, sodium cobaltinitrite, sodium
cynomanganate (li), sodium cynomanganate (I11), sodium citrate,
sodium ferrosilicon, sodium ferricyanide, sodium ferrocyanide, sodium
nitroferricyanide, sodium amminepentacyanide, sodium hydride, sodium
hydroxide, sodium manganate, sodium permanganate, sodium
methionate, sodium napthenate, sodium nitride, sodium nitrate, sodium
nitrite, sodium nitrobenzene (e.g. sodium-p- nitrobenzene), sodium
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nitrophenoxide, sodium etherate, sodium chromate, sodium oleate,
sodium oxalate, sodium oxalatoferrate (II), sodium oxalatoferrate (III))
sodium monoxide, sodium oxide, sodium peroxide, sodium, sodium
mono-orthophosphate, sodium hypophosphite, sodium orthophosphite,
sodium hydroxoplumbate, sodium rhodium cyanide, sodium selenide,
sodium selenite, sodium selenocynate, sodium selenocyanoplatinate)
sodium disilicate, sodium metasilicate, lithium sodium carbonate,
lithium sodium ferricyanide, sodium hydroxostannate, sodium disufide,
sodium hydrosulfide, sodium pentasulfide, sodium tetrasulfide, sodium
trisulfide, sodium telluride, sodium thioarsenate, sodium thioar- senite,
sodium trithiocarbonate, sodium thiocyanate, sodium amide, sodium
salt (E,E)-2,4-hexadienoic acid, disodium fluorophosphate, disodium
fluorophosphite, trisodium phosphate, trisodium phosphite, sodium
perchlorate, propanoic acid sodium salt, sodium formate, sodium
cyanate, sodium hexacyanocobaltate (III), sodium hypo- phosphite,
sodium hexaflurorsilicate, sodium nitroprusside, sodium phenoxide,
sodium phosphate (dibasic, monobasic, tribasic), sodium salicylate,
sodium selenide, sodium tetracyanonickeiate (11), sodium
tetrafluoroborate) sodium xanthogenate, sodium -p-aminoben- zoate,
sodium copper ferrocynanide, sodium cupric ferrocyanide, sodium
hexafluorophosphate, sodium hexanitricobaltate III, sodium
naphthenate, sodium -B-naphthoxide, sodium polysulfide, lithium -
sodium phosphate, sodium stearate, sodium sulfide, sodium sulfite,
sodium sulfate, sodium thiocyanate, sodium xanthate, sodium
fluorosilicate, N-sodiumethylenediamine, oxalic acid disodium salt,
sodium beta-hydropyruvic acid, sodium 1,1-dimethyfurea, sodium 1,1-
diethylurea, sodium 1,1-diepropylurea, sodium xanthate, sodium
ethylxanthate, sodium methylxanthate, sodium salt thio- phenol, sodium
triphenylmethylsodium, methylsodium, ethylsodium,
sodiumethynyl(acetylide), propylsodium, isopropylsodium, butyl-
sodium, isobutylsodium, secbutylsodium, tertbutylsodium, pen-
tasodium, hexylsodium, heptasodium, amylsodium, isoamylsodium,
benzylsodium) dimethylbenzylsodium, tolylsodium, dodecylsodium,
cyclopentadienylsodium, methylcyclopentadienylsodium, cyclohexyl-
sodium) sodiumheptyl, sodiumdodecyl, sodium tetradecyl, sodium
hexadecyl, sodium octadecyl, phenylsodium) sodium o-tolyl, sodium m-
tolyl, sodium p-tolyl, sodium-p-chiorophenyl, sodium p-bromo- phenyl,
sodium sodium o- anisyl, sodium m-anisyl, sodium p-anisyl, sodium
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diethoxyphenyl, sodium dimethoxyphenol, sodium m-cumyl, sodium p-
ethoxyphenyl, sodium m-dimethylaminophenyl, sodium 9- flourene,
sodium a-napthyl, sodium b-napthyl, sodium p-phenyl- phenyl, sodium
9-phenylanthryl, sodium 9-anthryl, sodium 9- methylphenanthryl,
sodium pyridyl) sodium 2-pyridyl, sodium 3- pyridyl, sodium 6-bromo-2-
pyridyl, sodium 5-bromo-2-pyridyl, sodium dibenzofuryl, sodium 3-
quinoyl) sodium 2-lepidyl, sodium triphenyl- methyl, sodium 2,4,6-
trimethylphenyl) sodium 2,4,6-triisopropyl- phenyl, sodium 2,3,5,6-
tetraisopropylphenyl, sodium tetrabutyl- phenyl, thiophenedisodium,
toluenedisodium, diphenylethylenedi- sodium, sodiumamylethynyl,
sodiumphenylethynyl, sodium- methoxybromophenyl, sodium
phenylisopropyl, sodium tetraphenyl- boron, sodium tetramethylboron,
sodium a-thienyl, sodium m- trifluoromethylphenyl,
phenylethynylsodium, 3-furylsodium, phenylisopropylsodium,
dibenzofuranylsodium, sodium dimethylbenzyl, sodium selenocyanate,
sodium trimethylsilanolate, diphenyl- phosphide, sodium benzoate,
sodium tert-butyl carbonate, sodium azide, di-sodiumcyanamide,
sodium cyanide, sodium dicyanamide, cyclohexanebutyric acid sodium
salt, cyclohexane acid sodium salt, cyclopentadientylsodium, sodium
tri-tert-butoxyaluminurn hydride, sodiurnaluminum-tri-tert-butoxide,
sodium triethylborohydride, sodium trimethylborohydride, sodium
tripropylborohydride, sodium triisopropylborohydride, sodium
tributylborohydride, sodium triisobutylborohydride, sodium tri-sec-
butylborohydride, sodium tri-tert-butylborohydride, sodium
trisiamylborohydride, sodium chlorate, sodium tert-butoxide, sodium
sec-butoxide, iso-butoxide, sodium antimonate, sodium
diphenylphosphide, sodium bis(trismethyl- silyl) amide, trisodium
phosphite, sodium selenocyanate, sodium tri-sec-butylborohydride,
sodium triethylsilanolate, sodium thiocyanate, sodium acetylide,
sodium chlorate, sodium salicylate, sodium di-sodium
tetracarbonylferrate, sodium tetraphenylborate, sodium
triethylborohydride, sodium triacetoxyborohydride, sodium
triphenylborane, sodium hydroxide, sodium diphenylphosphide, sodium
methoxide, sodium ethoxide, sodium tri-sec-butylborohydride, tri- tert-
butylborohydride, sodium triethylborohydride, sodium tri-
phenylborohydride, sodium trisiamyfborohydride, sodium meta-
vanadate, sodium cyclohexanebutyrate, sodium hexachloroplatinate,
sodium thiocyanate, sodium selenocyanate, sodium cyanate, sodium
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floride, sodium hexafluoroantimonate, sodium hexafluoroaluminate,
sodium hexafluoroarsenate, sodium hexafluorosilicate, sodium
hexacyanocobalt(II)ferrate(II), disodiumhexacyanocobalt(II)- ferrate(Il))
sodium hexafluorotitanate, sodium hexafluorozirconate, sodium
hexahydroxyantimonate, sodium hexachlororuthenate, sodium
hexachloropalladate, sodium formate, sodium tetracyanonickelate,
sodium tetrafluoroaluminate, sodium tetrafluoroborate, sodium
thioacetate, L-glutamic acid monosodium salt, fumaric acid sodium salt,
oxamic acid sodium salt, sodium salt diphenyl-phospane, P-
aminobenzoic sodium salt, aminobenzole acid sodium salt, alpha-
napthaleneacetic acid sodium salt, disodium salt 2,6-naphth-
alenedicarboxlic acid, sodium cyclcohexanetherate, sodium phthali-
mide, P-aminosalicylic acid sodium salt) sodium salt 3,5-dimethyl-
cyclohexyl sulfate, indolebutyric acid sodium salt,indole-3-butyric acid
sodium salt, diphenylphosphide, sodium dimethylsilanolate, sodium
triethylborohydride, sodium propoxide, sodium isopropoxide, sodium
butoxide, sodium sec-butoxide, sodium pentoxide, sodium tert-
pentoxide, sodium hydrogenphthalate, sodium oxalate) sodium
hydrogensulfate, monosodium acetyienedicarboxylic acid, sodium
pyrophosphate, sodium dihydrogenphosphate, sodium hexoate (sodium
salt hexoic acid), sodium diphenylphosphide, sodium trimethyl-
silonalate, sodium phthalic acid, P-aminobenzoic acid sodium salt,
monosodium L-aspartic acid, tetraphenyldisodium (C6H5)2-
CLi2C(C6H5)2, sodiurnethylphenyi (LiCH2C6H5), sodium bromate,
sodium hydrogenphospate, monsodium salt D-shaccharic acid) DI-
asparatic sodium salt, (R)-alpha-hyroxymethylaspartic acid sodium salt,
sodium fluoride, sodium iodate, sodium salt ethyl malonate, sodium
thioacetate, sodium phenol, sodium salt aminobenzoic acid) sodium
aminophenol salt, sodium cyclohexenol, sodium methylcyclohexenol,
sodium cyclopropanol, sodium methylcyclopropanol, sodium cyclo-
butanol, sodium methylcyclobutanol, sodium methylcyclopentanol,
sodium cyclopentanol, sodium cyclohexenol, sodium methyl-
cyclohexenol, sodium dimethylcyclohexenols (e.g. sodium 3,5-
dimethylcyclohexanol, sodium 2,3-dimethylcyclohexanol) sodium 2,6-
dimethylcyclohexanol, sodium 2,5-dimethylcyclohexanol, 3,5-
dimethyicyclohexanol), sodium o-ethylxanthic acid, monosodium salt 2-
ketoglutaric acid, disodium salt, ketomalonic acid) sodium salt lactic
acid, disodium thiosulfate, sodium antimony tartrate, sodium
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dichloroacetate, sodium dimethylacetate, sodium diethyiacetate,
sodium dipropylacetate, sodium metaborate, sodium tetraborate,
sodium tetrachlorocuprate, sodium acetoacetate, sodium diisopro-
pylamide) sodium diethylamide, sodium dimethylamide, sodium
bis(dimethylsilyl)amide, disodium phthalocyanine, disodium-
tetrabromocuprate, disodium tetrabromonickelate, disodium-
tetrachloromanganate, disodiumbutadiyne, sodium cyclopentadienide,
sodium dicyclohexylamide, sodium diethylamide, sodium dimethyl-
amide, sodium dipropylamide, sodium diisopropylamide, sodium
thexylborohydride, sodium tri-tert-butoxyaluminohydride, sodium
trimethylsilyl)acetylide, sodium triethylsilyl)acetylide) sodium tris[{3-
ethyl-3-pentyl)oxy]aluminohydride, (phenylethynyl)sodium, 2-
thienylsodium, sodium diethyldihydroaluminate, sodium dimethyl-
dihydroaluminate, sodium aluminum hydride, sodium bifluoride, sodium
biphenyl, sodium biselenite, sodium bis(2-methoxyethoxy)- aluminum
hydride, sodium bismuthate, sodium borate, sodium chlorite, sodium
cobaltnitrite, sodium cyanoborohydride, sodium cyclopentadienide,
sodium dicyanamide, sodium hexametaphosphate, sodium
hexanitrocolbaltate) sodium hydrogenphosphite, sodium
hydrogenselenite, sodium hydrogensulfite, sodium hydrosulfite, sodium
hypochloride, sodium metaarsenite, sodium metabisulfide, sodium
metaperiodate, sodium methacrylate, sodium nitro- ferricyanide,
oxybate, sodium pentamethylcyclopentadienide, sodium phenolate,
polyphosphate, sodium polyphosphite, sodium propionate, sodium
pyrophosphate, sodium selenate, sodium selenite, sodium
tetrachloroaluminate, sodium thiomethoxide, sodium thiosulfate,
sodium thiosulfide, sodium thiosulfite, sodium tri- actoxyborohydride,
sodium sodium trimethylsilonate, sodium triethylsilonate, sodium tris(1-
pyrazoly)borohydride, including analogues, homologues, isomers and
derivatives thereof.
The non limiting examples of aluminum derivative compounds of
this invention include: diisobutylaluminum hydride, dimethylaluminum
hydride, dimethylaluminum hydride, dipropylaluminumhydride,
diisopropylaluminumhydride) dibutylaluminumhydride, di-tert-
butylaluminum hydride, di-sec-butylafuminum hydride, di-
isobutylaluminum chloride, ethyialuminum sesquichloride, lithium
aluminum hydride, lithium tri-tert-butoxyaluminum hydride, lithium-
aluminum alloy, aluminum triethoxide, aluminum trimethoxide,
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aluminum tripropoxide, aluminum triisopropoxide, aluminum tri-tert-
butoxide, aluminum tri-sec-butoxide (aluminum sec-butoxide),
aluminum tri-isobutoxide) aluminum tributoxide, aluminum pentoxide,
diethylaluminum ethoxide, aluminum phosphate, diethylaluminum
chloride, diethylaluminum cyanide, diethylaluminum ethoxide,
diethylaluminum methoxide) diisobutylaluminum hydride, diisobutyl-
aluminum chloride, diisobutyalumnum fluoride, tetraisobutyi-
dialuminoxane, triethylaluminum, trimethylaluminum, tributyl- aluminum,
triisobutylaiuminum, tri-sec-butylaluminum, tri-tert- butylaluminum,
tripentaluminum, triphenylaluminum, triamylaluminum,
triisoamylaluminum, tripropylaluminum, triisopropylaluminum,
triisobutylaluminum, triisobutyldialuminoxane, trioctylaluminum, sodium
aluminum hydride, bis(2-methoxyethoxy)aluminum hydride, aluminum
borohydride) aluminum hydride, dimethlylberyllium, potassium tri-tert-
butoxyaluminum hydride, sodium tri-tert- butoxyaluminum hydride,
lithium tri-tert-butoxyaluminum hydride, aluminum sec butoxide,
aluminum tert-butoxide) aluminum acetyl- acetone, aluminum ethoxide)
aluminum meth oxide, aluminum propoxide, aluminum isopropoxide)
aluminum butoxide, aluminum isobutoxide, aluminum pentoxide,
aluminum metaphosphate, aluminum hydroxide, aluminum
metaphosphite, aluminum monostearate, aluminum hydroxys- tearate,
aluminum nitrate, aluminum fluoride, aluminum fluoride trihydrate,
sodium diethyldihydroaluminate) sodium hexafluoro- aluminate,
aluminum hexafluorosilicate, lithium aluminum hydride, lithium
aluminum hydride bis(tetrahydrofuran), lithium tris((3- thyl-3-
pentyl)oxy)aluminohydride, lithium tri-tert-aluminohydride, aluminum-
nickel catalyst) aluminum silicate, aluminum silicate hydroxide,
aluminum chloride hydrate, diethylaluminum chloride, sodium bis(2-
methoxyethoxy)aluminum dihydride, aluminum carbide, aluminum
phosphate, aluminum acetate (aluminum diacetate hydr- oxide),
dihydroaluminum acetate, aluminum formoacetate, lithium aluminate,
aluminum salt lactic acid, tetramethyllithiumaluminum salt (LiAI(CH3)4),
tetaethyllithiumaluminum salt, tetrapropyl- lithiumaluminum salt)
tetraisopropyllithiumaluminum salt, tetra- butyllithiumaluminum salt,
tetraisobutyllithiumaluminum salt, tetra-sec-butyllithiumaluminum salt)
tetra-tert-butyl- lithiumaiuminum salt) tetraphenyllithium aluminum salt,
aluminum tririconoleate, aluminum metaphosphate, sodium aluminum
hydride, aluminum dodecaboride, aluminum diboride, aluminum
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arsenide, aluminum lactate, aluminum titanium chloride, tri(N-nitroso-N-
phenylhydroxylaminoato)aluminum, aluminum acetyiacetonate,
methylaluminum dichloride, ethylaluminum dichloride) propylaluminum
dichloride, isopropylaluminum dichloride, butylaluminum dichloride ,
sec-butylaluminum dichloride, tert-butylaluminum dichloride,
isobutylaluminum dichloride, phenylaluminum dichloride, ethyl-
aluminum sesquichloride, methylaluminum sesquichioride, methyl-
aluminoxane, propylaluminum sesquichloride, ethylaluminoxane,
sodium bis(2-methoxyethoxy)aluminum, aluminum magnesium silicate,
aluminum hydroxychloride, aluminum phosphide, aluminum potassium
sulfide, aluminum stearate, aluminum octoate (aluminum ethyl-
hexonate), aluminum diformate, aluminum triformate, aluminum
chromate, aluminum napthenate, aluminum oleate, aluminum palmite,
aluminum pictrate, aluminum sodium silicate, aluminum sodium
chloride, aluminum isopropylate, aluminum magnesium ethoxide,
trimethyialuminum etherate, triethylaluminum etherate, including
analogues, homologues, isomers and derivatives thereof. Correspond-
ing compounds of gallium, indium, thallium are contemplated in the
practice of this invention.
The non-limiting examples of silicon derivative compounds of this
invention include: dimethoxymethylsilane, dimethoxyethylsilane,
diethoxymethylsilane, dipropoxyrnethylsilane, diisoprop-
oxymethylsilane, dibutoxymethylsilane, diisobutoxymethylsilane, di-
sec-butoxymethylsilane) di-sec-butoxymethylsilane, diethoxyethyl-
silane, dipropoxyethylsilane, diisopropoxyethylsilane, dibut-
oxyethylsilane, diisobutoxyethylsilane, di-sec-butoxyethylsilane, di-sec-
butoxyethylsilane, diethoxydimethylsilane, dimethoxydi- methylsifane,
dipropoxydimethylsilane, diisopropoxydimethylsilane,
dibutoxydimethylsilane, diisobutoxydimethylsilane, di-sec-butoxydi-
methylsilane, di-sec-butoxydimethylsilane, diethoxymethylethyl- silane,
ethoxytrimethylsilane, ethoxytriethylsilane, ethoxytri- propylsilane,
ethoxytriispropylsilane, methoxytrimethylsilane, propoxytrimethylsilane,
isopropoxytrimethylsilane, butoxytrimethyl- silane,
isobutoxytrimethylsilane, sec-butoxytrimethylsilane, sec-
butoxytrimethylsilane, phenoxytrimethyisilane, ethoxydiethylsilane,
isobutyldiethoxysilane, sec-butyldiethoxysilane, butyldiethoxy- silane,
tertbutyldiethoxysilane, pentyldiethoxysilane, isobutyl- dimethoxysilane,
secbutyldimethoxysilane, butyldimethoxysilane,
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tertbutyltrimethoxysilane, rnethyltrimethoxysilane, methyltriethoxy-
silane, pentyldimethoxysilane, diethylsilandiol, tripropylsilan- diol,
triisopropylsilandiol, tertbutyldimethylsilane, diethyl- silanediol
(C2H5Si(OH)2), methyl-tripropoxysilane, methyl-
tris(dimethylsiloxy)silane, 1,1-diphenylsilacyclohexane, pen-
tamethylsilanime, 1,1,1-trimethyl-N-phenyl-N-silanamine, hexa-
methyldisilazane, [1,1'-biphenyl]-4-yltrichlorosilane, (bromo-
methyl)chlorodimethylsilane, bromomethyltrimethylsilane, (4-
bromophenoxy)trimethylsilane, butylchlorodimethylsilane, trichloro-
butylsilane, trimethylbutylsilane, chloro(chloromethyl)dimethyl- sifane,
chloro(dichloromethyl)dimethylsilane, chlorodimethylphenyl- silane,
chlorodimethyl-2-propenylsilane, chloroethenyldimethyl- silane,
chloromethylsilane, (chloromethyl)dimethylphenylsilane,
chloromethyldiphenylsilane, chloromethylphenylsilane, (chloro-
methyl)trimethylsilane, (4-chloropehoxy)trimethylsilane, phenyl-
chlorosilane, (3-chlorophenyl)trimethylsilane, (3-chloropropyl)-
trimethylsilane, chlorotriethoxysilane, chlorotriethylsilane,
trimethylchlorosilane, dichloro(chloromethyl)methylsilane,
dichloro(dichioromethyl)methylsilane, dichlorodiethoxysilane,
dichlorodiethylsilane) dichlorodimethylsilane) dichlorodiphenyl- silane,
dichloroethenylmethylsilane, methylethyldichlorosilane,
dichloromethylsilane, dichloromethyl(1-methylethyl)silane,
dichloromethyl(4-rnethylphenyl)silane, dichloromethylphenylsilane,
dichloromethyl-2-propenylsiiane,dichlorophenyisilane, diethenyl-
diphenylsilane, diethoxydirnethylsilane, diphenyldiethoxysilane,
diethoxymethylphenylsilane, diethyloxymethyl-2-propenylsilane,
diethylsilane, diethyldifluorosilane, difluorodiphenylsiiane,
dimethyoxydimethylsilane, dirnethoxydiphenylsilane, dimethylsilane,
dimethyldiphenoxysilane, dimethyldiphenylsilane, dimethyl-2-
propenylsilane, dimethylphenylsilane, dirnethyl-diacetatesilane,
diphenylsilane, 1,2,-ethenediylbis[trimethyl-(E)]silane {C8H20Si2))
ethenyldiethoxymethyfsilane, ethenylethoxydimethylsilane, ethenyl-
triethoxysiiane, ethenyltrimethylsilane, ethenyltris(1-methyl- ethoxy)-
sifane, ethenyltris(2-propenyloxy)silane, ethoxytriethyl- silane,
ethoxytrifluorosilane, ethoxytrimethylsilane, ethoxytri- phenylsilane,
ethyltrifluorosilane, ethyltrimethoxysilane, 1,2,- ethynediylbis[trimethyl]-
silane, ethynylsilane, methoxysilane, methylsilane, methyidiphenyl-
silane) methylenebissilane, methyiene- bis[trichloro]silane, (2-methyl-
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phenoxy)triphenylsilane, methyl- phenylsitane, methyltriphenoxysitane,
methyltriphenylsilane, methyttri-p-toly-silane, phenylsilane, [1,3-
phenylenebis(oxy)]bis- [trimethyl]silane, phenyttripropylsilane, tetra-
ethenylsilane, tetraethylsilane, tetraethoxysilane, tetramethylsitane,
tetra- methoxysilane, tetrapropylsilane, tetrapropoxysilane, tetra-
isopropylsilane, tetraisopropoxysilane, tetrabutylsilane, tetra-butoxy-
sitane, tetra-sec-butylsilane, tetra-sec-butoxysilane, tetra- tert-butyl-
silane, tetra-tert-butoxysilane) tert-iso-butylsilane, tetra-iso-butoxy-
silane, tetraphenylsilane, tetraphenoxysilane, triethylsilane, triethoxy-
silane, trimethyfsilane, trimethoxysilane, tripropylsilane, tripropoxy-
silane, triisopropylsilane, triiso- propoxysilane, tributyfsilane,
tributoxysilane, tri-sec-butyl- silane, tri-sec-butoxysilane, tri-tert-
butylsilane, tri-tert- butoxysilane, tert-iso-butylsilane, tri-iso-butoxy-
silane, tripheny- Isilane, triphenoxysilane, triethylmethylsilane,
triethoxymethyl- silane, trimethoxymethylsilane, tripropylmethytsilane,
tripro- poxymethylsilane, triisopropytmethylsilane, triisoproxymethyl-
silane, tributylmethylsilane, tributoxymethylsiiane) tri-sec- butylmethyl-
silane, tri-sec-butoxymethylsilane, tri-tert-butyl- methylsilane, tri-tert-
butoxymethylsilane, tert-iso-butylmethyl- silane, tri-iso-butoxymethyl-
silane, triphenylmethyfsilane, triphenoxymethylsitane, diethylsilane,
diethoxysilane, dimethyl- silane, dimethoxysilane, dipropylsilane,
dipropoxysilane, di- isopropylsilane, diisopropoxysilane, dibutylsilane,
dibutoxysilane, di-sec-butylsilane, di-sec-butoxysilane, di-tert-
butylsilane, di- tert-butoxysilane, tert-iso-butylsilane, di-iso-
butoxysilane, diphenylsilane, diphenoxysilane, ethylsilane,
ethoxysilane, methylsilane, methoxysilane, propylsilane, propoxysilane,
iso- propylsilane, isoproxysitane, butylsilane, butoxysilane, sec-
butylsilane, sec-butoxysilane, tert-butylsilane, tert-butoxysilane, iso-
butylsilane, iso-butoxysilane, phenylsilane, phenoxysilane,
tribromomethylsilane, tributylsilane, tributylphenylsilane,
trichloro(chloromethyl)silane, trichloro(4-chlorophenyl)silane,
trichloro(3-chloropropyl)silane, trichloro(dichloromethyl)silane,
trichlorododecylsilane, trichloroethenylsilane, trichloroethoxy- silane,
trichloroethylsilane, trichlorohexylsilane, trichloromethy- Isilane,
trichloro(1-methylethyl)silane, trichloro(2-methyl- phenyl)sitane)
trichloro(3-methylphenyl)silane, trichloro(2- methylpropyl)silane,
trichlorootadectylsilane, trichlorooctyl- silane, trichloropentylsilane,
trichlorophenylsilane, trichloro(2- phenylethyl)silane, trichloro-2-
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propenylsilane, trichtoropropylsilane, triethoxysilane,
triethoxyethylsilane, triethoxyethylsilane, triethoxyphenylsilane,
triethoxypentylsilane, triethoxy-2-propenylsifane, triethylsilane,
triethylfluorosilane, triethylphenylsilane, trifluorophenylsilane,
trimethoxymethylsilane, trimethoxyethylsilane, trimethoxypropylsilane,
trimethoxyisopropylsilane) trimethoxybutylsilane, trimethoxyisobutyl-
silane,trimethoxy-sec-butylsilane, trimethoxy-tert-butylsilane,
trimethoxyphenylsilane, trimethylsilane, trimethyl(4-methylphenyl)-
silane, trimethyl(2-methylpropyl)silane, trimethylphenoxysilane,
trimethylphenylsilane, trimethyl(phenylmethyl)silane,
trimethyl(cyclohexylmethyl)silane, trimethyl-2-propenylsilane,
trimethylpropylsilane, trimethyl[4-[(trimethylsityl)oxy]phenyl]silane,
ethenyttriacetatesilanetriol, methyltriacetatesilantriol, tripropylsilane,
ethyfdimethylsilanol, methyldiphenylsilanol, triethylsilanol,
triphenylsilanol, tetrabutyl ester silicic acid (C16H3604Si), tetraethyl
ester silicic acid, tetrakis(2-ethylbutyl) ester silicic acid, methylsilicate
(C4H12Si04), tetraphenyl ester silicic acid, tetrapropyl ester silicic
acid, triethyl phenyl ester silicic acid, 1,2-dichloro-1,1,2,2-
tetramethyldisilane, 1,2,-diftuorotetramethyldisilane,
hexamethyldisilane, 1, 3-d iethenyl-1,1, 3, 3-tetramethyld isiloxa ne, 1, 3-
diethenyl-1,1,3,3-tetramethyldisilazane, bis-(methoxydimethylsilyl)-
oxide, 1,1,1,3,3,3-hexaethyldisiloxane, 1,1,1,3,3, 3-hexaethyldisilazane,
hexamethyldisiloxane, hexamethyl- disilazane, 1,1,3,3-
tetramethyldisiloxane, 1,1,3,3-tetra methyl- disilazane, 1,1,3,3-
tetramethyt-1,3-diphenyldisifoxane, 1,1,3,3- tetramethyl-1,3-
d iphenyldisilazane, 1,1,1-trimethyl-3,3, 3-tri- phenyldisiloxane, 1,1,1-
trimethyl-3,3,3-triphenyldisilazxane, docosamethyldecasiloxane,
docosamethyldecasilazane, ethenylhep- tamethylcyctetrasiloxane,
ethenylheptamethylcyctetrasilazane, heptamethyfcyclotetrasiloxane,
heptamethylcyclotetrasilazane, octaphenylcyclotetrasiloxane,
butylmethyl(cyclic tetramer)siloxane, 2,4,6,8-tetraethenyl-2,4,6,8-
tetramethylcyclotetrasiloxane (C12H2404Si4), 2,4,f,8-tetraethyl-
2,4,6,8-cyclotetrasiloxane, 2,4,6,8-tetraethyl-2,4,6,8-
cyclotetrasilazane, 2,4,6,8-tetraethyl- 2,4,6,8-cyclotetrasiloxane,
2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-
tetramethylcyctotetrasilazane, 2,4,6,8-tetramethyl-2,4,6,8-
tetraphenylcyclotetrasiloxane, 2,2,4,4,6,6-hexamethyl- cyclotrisilazane,
hexamethylcyclotrisiloxane, 2,4,6-triethyl-2,4,6-
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trimethylcyclotrisiloxane, 2,4,6-triethyl-2,4,6-trimethyl- cyclotrisiloxane,
2,4,6-triethyl-2,4,6-triphenyicyclotrisiloxane, 2,4,6-trimethyl-2,4,6-
tripehnylcyclotrisiloxane, decamethyl- cyclopentasiloxane)
decamethylcyciopentasilazane) 2,4,6,8,10-
pentamethylcyclopentasiloxane, 2,4,6,8,10-pentamethylcyclopen-
tasilazane, octademethylcyclononasiloxane) octademethyl-
cycfononasilazane, hexadecamethylcyclooctasiloxane,
hexadecamethyl- cyciooctasilazane, dodecamethylcyciohexasiloxane,
dodecamethyl- cyclohexasilazane, hexamethylcyclohexasiloxane,
tetradecamethyl- cycloheptasiloxane,
tetradecamethylcycloheptasilazane, decamethyl- tetrasiloxane,
1,1,1,3,5,7,7,7-octamethyltetrasiloxane, aminotri- silane,
benzyltriethoxysilane, butyltrifluorosilane, carboxyethyl- dimethylsilane,
chloromethylsilicane, chlorotriisocyanatesilane, dichloromethylsilicane,
diethoxydibutoxysilane, diethylaniiine- fluorosilicate,
diethyldichlorosilane, [2-(cyclohexenyl)ethyl]tri- ethoxysilane) [2-
(cyclohexenyl)ethyl]methyldiethoxysilane, [2-
(cyclohexenyl)ethyl]dimethylethoxysilane) (2-(cyclohexenyl)-
ethyl]trimethylsilane, [2-(cyclohexenyl)ethyl]triethylsilane)
cyclohexyldimethoxymethylsilane, cyclohexylmethoxydimethylsilane,
cyclohexyltrimethylsilane, cyclohexyltriethylsilane, dicyclohexyl-
dimethylsilane, cyclohexyldimethylsiiane, cyclohex-1-enyl-tri-
methylsilane) benzyltrimethylsilane, (1-cyclohexen-1-ylethynyl)tri-
methylsilane, 1-cyclohexenyltrimethylsilane, cyclohexenyloxytri-
methylsilane, cyclohexyltrichlorosilane, 1-cyclopropyl-1-(trimethy-
Isilyloxy)ethylene, phenyldimethylsilanol, phenylsilandiol,
cyclohexylsilandiol, cyclohexylethylsilandiol, tert-butylsilandiol,
cyclohexyldimethylsifanol, cyciohexyldiethylsilanol, benzyltri-
methylsilane, N-benzyltrimethylsifylamine, phenyl dimethylsilanol,
phenyl diethylsilanol, cyclohexylethylenetrimethylsilane, N-
cyclohexylethylenetrimethylsilylamine) cycloethylenetrimethyl- silane,
diphenyldiethoxysilane, diphenyldimethoxysilane, diphenyl- methyl-
ethoxysilane, diphenylmethylsilane, diphenylmethylsilandiol,
diphenylsilandiol, methyl-phenyl-diethoxysilane, methyl-phenyl-
dimethoxysilane, methyl-phenyl-dichlorosilane, octadecyltri-
methoxysilane, octyltriethoxysilane, octyltrimethoxysilane, 1,3- bis(3-
aminopropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(3- aminopropyl)-
1,1,3,3-tetramethyldisilazane, tertbutyldimethylsilan- diol,
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hydroxymethylenetrimethyisilane (CH3)3CH20H), hydro-
xyethylenetrimethylsilane, hydroxymethyltriethylsilane, hydroxy-
ethyltriethylsilane,diethylsiianediol, dimethylsilanediol)
dipropylsilanediol, diisopropylsilanediol, dibutylsilanediol, di- tert-
butylsilanediol, di-iso-butylsilanediol, di-sec-butyl- silanediol,
diphenylsilanediol, dicyclohexyisilanediol, cyclohexyl- methylsilanediol,
cyclohexylethylsilanediol, dimethoxydichloro- silane,
dimethylanilineflourosilicate, dimethyldi(B-chloroethoxy)- silane,
dimethylflourochlorosilane, dimethylsilicane, di-a-
napthylamineflourosilicate, di-b-napthylamineflourosilicate, di-m-
nitranilineflourosilicate, dinitrosodiphenylamine, diphenylar-
sinophenylenetriethylsilane, diphenyldichlorophenoxysilane, di-o-
toluidinefluorosilicate, di-m-toluidinefluorosilicate, di-p-
toluidinefluorosilicate, docosarnethyidecasiloxane) dodecamethyl-
cyclohexasiloxane, dodecamethylpentasiloxane, eicosamethyl-
nonasiloxane, silanesiianesilanedocosamethyldecasilazane, dode-
camethylcyclohexasilazane, dodecamethylpentasilazane, eicosamethyl-
nonasilazane, ethyldiethoxyacetoxysilane, ethyldiethoxychloro- silane,
ethylisocyanatesilane, ethyltriethoxysilane, ethyltri- phenylsilicane,
hexadacamethylcycfooctasiloxane, hexadacamethyl- cyclooctasilazane,
hexamethylsilicane (hexamethyldisilane), hexamethylmethylenedislane,
hydroxymethyltrimethylsilane, methyl- silicane, methyltriphenylsificane,
octadecamethylcotasiloxane, octamethylcyclotetrasiloxane,
octamethyltrisiloxane, octadeca- methylcotasilazane,
octamethylcyclotetrasilazane, octa- rnethyltrisilazane,
tetraphenylenesilane, phenylenediamineflouro- silicate,
phenylisocyanatesiiane, phenyitrichlorosilicane, silicobenzoic acid,
tetra-m-aminophenylsilane, tetrabenzylsiiicane, tetra-p-
biphenylylsilane, tetradecamethylcycfoheptasiioxane,
tetradecamethylcycloheptasilazane, tetradecamethylhexasiloxane,
tetradecamethylhexasilazane, tetraethylsiiane, tetraethyl- thiosilane,
tetrahexyloxysilane, tetraisopropyimercaptane silicon,
tetramethoxysilane, tetramethylmercaptanesilicon, tetramethyl- silane)
tetraphenoxysilane, tetraphenylsilane, tertapropoxysilane,
tetratriethylsiloxysilane, thioisocyanatotriethylsilane, tolidine-
fluorosilicate(o), tri-p-Biphenylylphenylsilane, trichloromethyl-
triethoxysilane, triethylbromosilane, triethylchlorosilane,
triethylfluorosilane, triethylphenylsilane, trimethylchloromethyl- silane,
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trimethylethoxysilane, triphenylacetoxysilane, vinyltri- phenoxysilane,
vinyitriethoxysilane, silicane cyanate, dibromo- silane,
dibromodichlorosilane, dichlorosilane, dichlorodifluoro- silane,
hexaoxocyclosilane) hexacyclosilazane, monooiodosilane, (tri-
)nitrilosilane (silicylamine), trichlorosilane, tri- fluorosilane, silicane
diimide (Si(NH)2), silicane tetramide, silicane isocyanate, silicon
tetracetate, tetrabromosilane, silicon hex(di-)bromide, silcon carbide,
tertachlorosilane, hexachlorodi- silane, tetrafluorosilane, hexa-
fluorodisilane, silicon hydride (SiH4), disilane (Si2H6), trisilanepropane,
tetrasilane butane, silicon nitride, silicon thiocyanate, disilicic acid,
silicon cyanate, allylchlorodimethylsilane, allylchloromethyldimethyl-
silane, allyldichlorodimethylsilane, allyl(diisoproprylamino)di-
methylsilane, allyloxy-tert-butyldimethylsilane, allyloxy-sec-
butyldimethylsiiane, allyloxy-iso-butyldimethylsilane, allylchloro-
diethylsilane, allylchloromethyldiethylsilane, allyldichloro- diethylsilane,
allyl(diisoproprylamino)diethylsilane, allyloxy- tert-butyldiethylsilane,
allyloxy-sec-butyldiethylsilane, allyloxy- iso-butyldiethylsilane,
allyloxybutyldimethylsilane, allyloxy- trimethylsiiane,
allyloxytriethylsilane, diallyloxydimethylsilane, triallyloxymethylsilane,
diallyloxydiethylsilane, triallyloxyethy!- silane,
diallyloxydimethoxyfsilane, triallyloxymethoxylsilane,
diallyloxydiethoxylsilane, triallyloxyethoxylsilane, allyltri- chlorosilane,
allyltriethoxysilane, allyltriisopropylsiiane, allyltripropylsilane,
allyltriisopropyloxysilane) allyl- tripropyloxysilane, allyltrimethoxysilane,
allyltrimethylsilane, allyltriethylsilane, allyltriphenylsilane, 3-
aminopropyltriethoxy- silane, 3-aminopropyltrimethoxysilane, 3-
aminoethyltriethoxysilane, 3-aminoethyltrimethoxysilane, 3-
aminomethyltriethoxysilane, 3- aminomethyltrimethoxysilane, 3-
aminotrimethoxysilane, 3-aminotri- ethoxysilane, 3-
amino(cyclohexyl)propyltriethoxysilane, 3-amino-
(cyclohexyl)propyltrimethoxysilane, 3-amino(cyclohexyl)ethyftri-
ethoxysilane, 3-amino(cyclohexyl)ethyltrimethoxysilane, 3-
amino(cyclohexyl)methyltriethoxysilane, 3-amino(cyclohexyl)-
methyltrimethoxysilane, 3-amino(cyclohexyl)trimethoxysilane, 3-
amino(cylcohexyl)triethoxysilane, trimethoxypropylsilane, trie-
thoxypropylsilane, trimethoxysilane, 3-aminopropyltrimethoxysilane, N-
[3-(trimethoxysilyl)propyl]aniline, N-[3-(triethoxysilyf)propyl]- aniline, N-
[3-(triethoxysilyl)ethyl]aniline, N'-[3-(trimethoxy-
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silyl)propyljdiethylenetriamine) N-[3-(trimethoxysilyl)propyl]-
ethylenediamine, N-[3-(triethoxysifyl)propyljethylenediamine) 3-
(trimethoxysilyl)propyl methacryfate, 3-(triethoxysilyl)propyl
methacrylate, aminotriphenylsifane, azidotrimethylsilane, azidotri-
ethylsilane, azidotripropylsilane, azidotributylsilane, azidotri-
methoxysilane, azidotriethoxysilane, azidotripropoxysilane,
azidotributoxysilane, bis[3-(trimethoxysilyl)propyljamine, N,O-
bis(trimethylsilyl)acetamide, bis(trimethylsilyl)acetylene,
bis(trimethylsilyl)cyclopentadiene, 1,4-bis(trimethylsilyl)benzene, N,O-
bis(trimethylsilyl)hydroxylamine, bis(trimethylsilyl)methane, 2,3-
bis(trimethylsilyloxy)-1,3-butadiene, 1,2-bis(trimethylsilyl-
oxy)cyclobutene, 1,2-bis(trimethylsilyl)cyclobutene, 1,2,3-
bis(trimethylsilyl)cyclobutene, 1,2,3,4-bis(trimethylsiiyl)cyclo- butene,
bis(trimethylsilyl)cycfobutene, 1,2-bis(trimethylsilyl- oxy)ethane, 2,3-
bis(trimethylsilyl)-1-propene, 2,4-bis(trimethyl- silyloxy)pyrimidine, 1,3-
bis(trimethylsilyl)urea) O,O'-bis(tri- methylsilyl)uracil,
bis(trimethylsilyl)trifluoroacetamide, (1- cyclohexenyl-1-
ethynyl)trimethylsilane, 1-cyclohexenyloxytrimethyl- silane, 1-
cyclohexyltrimethylsilane, cyclohexyldimethoxysilane,
cyclohexyltrimethoxysilane, cyclohexyldiethoxysilane, cyclohexyl-
triethoxysilane, cyclohexyldimethoxymethylsilane, cyclohexyltri-
methoxysilane, cyclohexyldiethoxymethylsilane, cyclohexyltri-
ethoxysilane, cyclohexyldimethoxysilandiol, cyclohexyl-
diethoxysilandiol, cyclohexyldipropxymethylsilane, cyclohexyl-
dipropxymethyfsilandiol, cyclohexyltrichlorosilane, [(1-cyclopro-
pyletheneyl)oxyjtrimethylsifane, diallyldimethylsilane,
diethoxymethyfphenylsilane, 3-(diethoxymethylsilyl)propylamine,
diethoxymethyfsilane, dimethyloctadecyfine, ethyltriacetoxysilane,
methyltriacetoxysilane, propyltriacetoxysilane, isopropyltriacet-
oxysilane, butyltriacetoxysilane, isobutyltriacetoxysilane) sec-
butyftriacetoxysilane, tert-butyltriacetoxysilane, benzyltri-
acetoxysilane, phenyltriacetoxysilane, cyclpentadienyltriacet-
oxysilane, cyclohexyltriacetoxysilane, isopropoxytrimethylsilane,
isopropylaminotrimethylsilane, lithium bis(trimethylsilyl)amide,
methoxydimethyfoctylsilane, methylbis(trimethylsilyloxy)vinyl- silane,
octyltriethoxysilane, octyltrimethoxysilane,
(phenylthiomethyl)trimethylsilane, phenyltriethoxysilane, phenyl-
trimethoxysilane, poly(dimethylsiloxane) silicon hexaboride, silicon
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nitride, silicon tetracetate, silicon tetrachloride) silicon tetraffuoride,
sodium bis(trimethyisifyl)amide, tetrakis- (trimethylsilyl)siiane)
tetravinylsilane, trichloro-3-chloropropyl- silane,
trichlorocyclopentysilane, cyclohexyltrichlorosilane, trichlorovinylsilane,
3-(triethoxysilyf)propionitrile, 3-(tri- methoxysilyl)propyfamine, 3-
(trimethoxysilyl)propyl isocyanate, 3- (trimethoxysilyl)propyl
thiocyanate) trihexylsilane, triisopropyl- silane,
(triisopropyfsilyl)acetyiene (chlorotriisopropylsilane),
triisopropylsilylchloride, 1-(triisopropylsilyl)pyrrole, trimethyl-
silylacetate, {trimethylsilyl)acetic acid, (trimethylsilyl)- acetylene,
trimethylsilyl cyanide, (trimethylsilyl)diazomethane, 5-(trimethylsilyl}-
1,3-cyclopentadiene, 1-(trimethylsilyl)imid- azofe, 1-
(trimethylsilyl)pyrrolidine, triphenylsilane, 1,1,1- triphenylsilylamine,
triphenylsifylchloride, tris(2-methoxyethoxy)- vinylsilane, 2,5,5-
tris(trimethylsilyl)-1,3-cylcopentadiene, tris(trimethylsilyl)borate,
tris(trimethylsilyl)amine, tris(tri- methylsilyl)germaniumhydride,
tris(trimethylsilyl)methane, tris(trimethylsilylmethyl)borane,
tris(trimethylsilyloxy)silane, vinyltrimethoxysilane, vinyltrimethylsilane,
trimethylsilyl N- (trimethylsilyf)-carbamate, triphenylsilylamine,
triethoxysilyl- amine, tributoxysilyamine, tripropoxysilylamine,
vinyltrichioro- silane, vinyltriethoxysilane, vinyl-triisopropoxsilane,
vinyitri- methoxysifane, vinyltriethoxysilane,
dimethoxymethylvinylsilane) diethoxymethylvinylsilane,
dimethoxyethylvinylsilane, diethoxy- ethylvinyisilane,
dimethylmethoxyvinylsilane, dimethylethoxyvinyl- silane,
dimethylpropoxyvinylsilane, dimethylisopropoxyvinylsilane,
diethylmethoxyvinylsilane, diethylethoxyvinylsilane, diethylpro-
poxyvinylsilane, diethylisopropoxyvinylsilane, dimethylethoxy-
(methylvinyl)silane, dimethoxymethyl(ethylvinyl)silane, diethoxy-
methyl(propylvinyl)silane, vinyltrimethylsilane, vinyltriethyl- silane,
vinyltriphenylsilane, vinyltris(2-butylidenaminooxy)silane, vinyltris(2-
methoxyethoxy)silane, vinyltris(2-methylethoxy)silane, vinyltris(2-
ethoxy)silane, vinyltris(trimethylsiloxy)silane, 3-(2-
aminoethylamino)propyltrimethoxysilane, 3-aminopropyl-methyl-
diethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimeth-
oxysilane, 3-aminomethyltriethoxysilane, 3-aminoethyltriethoxy- silane,
3-aminopropyltrimethoxysilane, 3-aminomethyltrimethoxy- silane, 3-
aminoethyltrimethoxysilane, (3-aminopropyl)tris[2-(2-
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methoxyethoxy)ethoxysifane, amyltriethoxysilane, 1,3-bis(chloro-
methyl)-1,1, 3,3-tetramethyldisilazane, 1, 3-bis(chloromethyl)- 1,1,3,3-
tetramethyldisiloxane, 1,2-bis(chlorodimethylsilyl)ethane, 1,3-bis(3-
cyanopropyl)tetramethyldisiloxane, 1,3-bis(3-cyano-
propyl)tetramethyldisilazane, bis(diethylamino)dimethylsilane)
bis(dimethylamino)dimethylsilane, bis(diethylamino)diethylsilane,
bis(dimethylamino)diethylsilane, 1,2-bis[(dimethylamino)dimethyl-
silyl]ethane, 1,2-bis(dimethylsilyl)benzene, 1,2-bis(dimethyl-
silyl)cyclohexene, 1,4-bis{dimethylsilyl)benzene, 1,4-bis(dimethyl-
silyl)cyclohexene, 1,3-bis(4-hydroxybutyl)-1,1, 3, 3-tetramethyl-
disiloxane, 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisilazane, bis(N-
methylbenzamido)methylethoxysilane, 1,4-bis(trimethyl- silyl)butadiyne,
N,O-bis(trimethylsilyl)acetimide, N,N-bis{tri- methylsilyl)methylamine,
N, N-bis(trimethylsilyl)amine, N, N-bis(tri- ethylsilyl)amine, N, N'-
bis(trimethylsilyl)urea, bis(trimethyl- silyl)phosphite, N,O-
bis(trimethylsilyl)trifluoroacetimide, tert- butyldimethylsilane, tert-
butyldimethylsilanol, (tert-butyldimeth- silyl)acetylene, tert-
butyldimethylsilyl cyanide, N-(tert-butyl- dimethyisilyl)dimethylamine,
butyldimethylchiorosilane, tert- butyldimethylchlorosilane, O-(tert-
butyldimethylsilyl)hydroxyl- amine, 1-(tert-butyldimethylsilyl)imidazole,
tert-butyldiphenyl- silyl cyanide, tert-butyldicyclohexylsilyl cyanide, N-
tert- butyltrimethylsilylamine, tert-butyl-trimethylsilyl peroxide, tert-
butyl-trimethylsilyl acetate, [2-(cyclohexenyl)ethyl]triethoxy- sifane,
N,N-diethyltrimethylsilylamine, N,N-diethyltriethyi- silylamine, N,N-
diethyl(trimethylsilylmethyl)amine, diethyl trimethylsilyl phosphite,
diphenylmethylsilane, dicyclohexylmethyl- silane, diphenylethylsilane,
dicyclohexylethylsilane, diphenylsilane) dicyclohexylsilane,
dicyclohexylsiladiol, 1, 3- diphenyl-1,1,3,3-tertamethyldisilazane, 1,3-
diphenyl-1,1,3,3- tertamethyldisiloxane, 1,3-dicyclohexyl-1,1,3,3-
tertamethyl- disilazane, 1,3-dicyclohexyl-1,1,3,3-tertamethyldisiloxane,
1,3- divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3-
tetramethyldisiloxane, dodecyltriethoxysilane, 1,1,3,3,5,5-
hexamethyltrisilazane, 1,1,3,3,5,5-hexamethyltrisiloxane, methyl-
triethoxysilane, ethyltriethoxysilane, propyltriethoxysilane,
isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxy- silane,
isobutyltriethoxysilane, sec-butyltriethoxysilane, tert-
butyltriethoxysilane, hexyltriethoxysilane, (3-isocyanatropropyl)-
triethoxysilane, (isopropenyloxy)trimethylsilane, isopropyl-
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dimethylchlorosilane, lithium bis(trimethylsilyl)amide, potassium
bis(trimethylsilyl)amide, (3-mercaptopropyl)methyldimethoxysilane, (3-
mercaptopropyl)triethoxysilane, (3-mercaptopropyl)trimethoxy- silane,
(methoxymethyl)trimethylsilane, methoxytrimethylsilane,
ethoxytrimethylsilane, [3-(methylamino)propyl]trimethoxysilane,
methyldiethoxysilane, 2-methylbenzosilylazole, methyl-octadecyl-
dichlorosilane, methyl-octyldimethoxysilane, methyl-octyldichloro-
silane, methyl-phenyl-chlorosilane, methyl-phenyl-dichlorosilane,
methyl-phenyl-diethoxysilane) methyl-phenyl-dimethoxysilane,
(methylthio)trimethylsilane, methyltriactoxysilane, methyltri-
chlorosilane, ethyltrichlorosilane, methylethoxysilane, ethyleth-
oxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrie-
thoxysilane, N-methyl-N-trimethylsilylacetamide, methylvinyl-
diethoxysilane, phenyltriethoxysilane, cyclohexyltriethoxysilane,
Phenyltrimethoxysilane, cyclohexyltrimethoxysilane, Phenyl(methy-
lene)triethoxysilane, cyclohexyl(methylene)triethoxysilane,
phenyl(methylene)trimethoxysilane, cyclohexyl(methylene)trimethoxy-
silane, Phenyl(ethylene)triethoxysilane, cyclohexyl(ethylene)tri-
ethoxysilane, phenyl(ethylene)trimethoxysilane, cyclohexyl(ethy-
lene}trimethoxysilane, phenyltrimethylsilane, phenyltriethylsilane,
phenyltripropylsilane, phenyltriisopropylsilane, phenyltributyl- silane,
phenyltri-sec-butylsilane, phenyltri-tert-butylsiiane)
phenyltriisobutylsilane, cyclohexyltrimethylsilane, cyclohexyltri-
ethylsilane, cyclohexyltripropylsilane, cyclohexyltriisopropyl- silane,
cyclohexyltributylsilane, cycfohexyltri-sec-butylsilane, cyclohexyltri-tert-
butylsiiane, cyclohexyltriisobutylsilane, Phenyltriethoxysilanediol,
cyclohexyltriethoxysilanediol, Phenyl- trimethoxysilanediol,
cyclohexyltrimethoxysilanediol, phenyltrimethylsilanediol,
phenyltriethylsilanediol, phenyltripro- pylsifanediol,
phenyltriisopropylsilanediol, phenyltributyl- silanediol, phenyltri-sec-
butylsilanediol, phenyltri-tent-butyl- silanediol,
phenyltriisobutylsilanediol, cyclohexyltrimethyl- silanediol,
cyclohexyltriethylsilanediol, cyclohexyltripropyl- silanediol,
cyclohexyltriisopropylsilanediol, cyciohexyltributyl- silanediol,
cyclohexyltri-sec-butylsilanediol, cyclohexyltri-tert- butylsilanediol,
cyclohexyltriisobutylsilanediol, propyltrimethoxy- silane,
tetramethylsilane, 2,4,6,8-tetramethylcyclotetrasilazane, 1,1,3,3-
tetramethyldisilazane, 1,1,3,3-tetramethyldisiloxane,
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tetramethyltetrasilylfulvalene, trimethylethoxysilane, N-
(trimethylsilyl)acetamide, trimethylphenoxylsilane, 1-(trimethy-
Isiloxy)cyclopentene, 1-(trimethylsiloxy)cyclohexene.
trimethoxylphenylsilane, 1-(trimethoxylsilyl)cyclopentene, 1-
(trimethoxylsilyl)cyclohexene) triethoxylphenylsilane, 1-(tri-
ethoxylsilyl)cyclopentene, 1-(triethoxylsilyl)cyclohexene,
trimethoxylcyclohexylsilane, (trimethoxylsilyl)cyclopentane,
(trimethoxylsilyl)cycfohexane) triethoxylcyclohexylsilane,
(triethoxylsilyl)cyclopentane, (triethoxylsilyl)cyclohexane, trimethylsilyl
azide, triethylsilyl azide, tripropylsiiyl azide, triisopropylsilyl azide,
tributyl azide) triisobutyl azide, tri- tert-butyl azide, tri-sec-butyl azide,
triphenyl azide, trimethoxylsilyl azide, triethoxylsilyl azide,
tripropoxylsilyl azide, triisopropoxylsilyl azide, tributoxyl azide,
triisobutoxyl azide, tri-tert-butoxyl azide, tri-sec-butoxyl azide,
(trimethylsilyl)cyclopentadiene, trimethylsilyl cyanide) (trimethy-
Isilyl)acetontrile, trans-3-(trimethylsilyl)allyl alcohol, 2-
(trimethylsilyl)methanol) 2-(triethylsilyl)ethanol, (trimethy-
Isilyl)methanol, (triethyisilyl)ethanol, triisobutylsilane, 2-
(trimethylsilyl)methanol, 2-(trimethylsilyl)ethanol, O-(trimethy-
lsilyl)hdroxylamine, 1-(trimethylsilyl)imidazole, trimethyl-
silylisocyanate, (trimethylsifyl)methyl acetate, trimethylsilyl
methacrylate, (trimethylsilyl)methylamine, N-(trimethylsily- Imethyl)urea,
4-(trimethylsilyl)morpholine, 4-(triethoxysilyl)- butyronitrile, 1-
(trimethylsilyl)pryrrolide, 1-trimethylsilyl- 1,2,4-triazole, triphenylsilane,
triphenylsilandiol, triphenyl- silylamine, tricyclohexylsilylamine,
phenyldimethoxysilylamine, methylphenyldimethoxysilane,
phenyldiethoxysilylamine, cyclohexyl- dimethoxysilylamine,
cyclohexyldiethoxysilylarnine, dipheny- Imethoxysilylamine,
diphenylethoxysilylamine, dicyclohexyl- methoxysilylamine)
dicyclohexylethoxysilylamine, cyclohexyl- silyltriamine,
cyclohexyl(ethyl)silyltriamine, cyclohexyl(methyl)- silyltriamine,
benzylsilyltriamine, benzyl(methyl)silyltriamine, diphenylsilyldiamine,
phenylethoxysilyldiarnine, cyclohexylethoxy- silyldiamine,
cyclohexyldiethoxysilylamine, cyclohexylmethoxysilyl- diamine,
cyclohexyl(ethyl}ethoxysilyldiamine, cyclohexyl(methyl)-
ethoxysilyldiamine, benzylmethoxysilyldiamine, benzyl-
dimethoxysilylamine, tris(trimethylsilyl)amine, tris(trimethoxyl-
silyl)amine, tris(triethoxylsilyl)amine, tris(trimethylsilyl)- borate,
CA 02274607 1999-06-09
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tris(trimethylsilyl)methane, tris(trimethylsilyl)ethane,
tris(trimethylsilyf)phosphate, tris(trimethylsilyl)phosphine,
tris(trimethylsilyl)silane, vinyltriethoxysilane, vinyltrichloro- silane,
vinyl-
triisopropylsilane) vinyltrimethylsilane, vinyltri- phenylsilane, vintris(2-
buytlidenaminooxy)silane, vinyitris(2- methoxyethoxysilane),
vinyltris(trimethylsiloxy)silane, allyldimethylsilane, allyldiethylsilane,
diallyldimethylsilane, diallyldiethylsilane, allyoxytrimethylsilane,
allyoxytriethyl- silane, allylphenylsilicon, tripropylsilane)
tris(trimethylsilyl)- silane, pentamethylcyclopentasiloxane, 2,4,6,8,10-
pentamethyl- cyclopentasiloxane, pentamethyldisiloxane,
amyltriethoxysilane) vinyltricholorsilane, vinyltriethylsilane,
vinyltrimethylsilane, vinyltriphenylsilane, vinyltriethoxysilane)
vinyltripropyoxysilane, vinyltrisopropyoxysilane, vinyltrimethoxylsilane,
vinyltriphenoxy- silane, vinyltributoxysilane, vinyltriisobutoxysilane,
vinyltrisec- butoxysilane, vinyltri-tert-butoxysilane, vinyltris(2-buty-
lidenaminooxy)silane, vinyltris(2-rnethoxyethoxy)silane, vinyltris-
(trimethoxysiloxy)silane, N,N-dimethyltrimethylsilyamine, N,N-
diethyltrimethylsilyamine, 3,3-dimethyl-1-trimethylsily-1-butyne, 3,3-
diethyl-1-trimethylsily-1-butyne, dimethyltrimethylsiiylmethyl-
phosphonate, dimethyltrimethylsilylphosphite, dimethyltritylbromo-
silanE, dimethyl-vinyl-ethoxysilane, dimethylvinylchlorosilane,
diphenylmethylchlorosilane, diphenylethylchlorosilane, phenyl-
dimethylchlorosilane, phenyldiethylchlorosilane, diphenyldi(M-
tolyl)silane, 1,2-dimethylsilane, 1,2-diethylsilane, 2,2,4,4,6,6-
hexamethylcyclotrisilazane, N-benzyltrimethylsilyiamine,
chlorodimethyloctylsilane, trimethyloctylsilane, disiloxane, silicon
nitride, disilane, dimethylsilanediol, trichlorocyclopen- tysilane,
tris(isopropylthio)silane, chlorotrimethylsilane, chlorodimethylsilane,
bis(chloromethyl)dimethylsilane, propyltri- chlorosilane,
trimethyl(pentafluorophenyl)silane, trichloro(1 H,1 H,- 2H,2H-
perfluorooctyl)silane, silicon tetraboride, silicon hexa- boride, trimethyl-
2-thienylsilane, (4-bromophenyl)trimethylsilane, 4-(trimethylsilyl)phenol,
5-(trimethylsilyl)-1,3-cyclopentadiene,
trimethylsilylmethylmagnesiumchloride, N,N-diisopropyltrimethyl-
silylamine, dicyclohexyl-methyl-silane, tetracyclohexysilane,
1,1,2,2,3,3,4,4,5,5-decaphenyl-6,6-dimethylcyclohexasilane)
trimethylsilylpolyphosphate, trimethylsilylpolyphosphite, including
analogues, homologues, isomers and derivatives thereof. Additional
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examples of acceptable silicon derivatives can be found in Silicon
Compounds, Register and Review, Petrarch Systems, Inc. (1984),
Frontiers of Organosilicon Chemistry, Bassindale, Gaspar, The Royal
Society of Chemistry, (1991), incorporated herein by reference.
Corresponding compounds of germanium, tin, titanium, zirconium,
selenium, tellurium, are contemplated in the practice of this invention.
Other non-limiting germanium derivative compounds include:
decamethylgermaniumocene (bis(pentamethylcyclopentadienyl)ger-
manium), tertbutylgermanium, tetrarnethylgermanium, tetraethylger-
manium, tetrapropylgermanium, tetraisopropylgermanium) tetrabutyl-
germanium, tetraisobutylgermanium, tetra-tert-butyigermanium, tetra-
sec-butylgermanium, tetra-phenylgermanium, phenylgermanium,
methylphenylgermanium, methylphenolgermanium, including
analogues, homologues, isomers and derivatives thereof.
Other non-limiting derivative tin compounds include: deca-
methylstannocene (bis(pentarnethylcyclopentadienyl)tin), dibutyltin
bis{2-ethylhexanoate), dibutyltin diacetate, dibutyloxo- tin (dibutyltin
oxide), dimethyltin, diethyltin, dipropyltin, diisopropyltin, dibutyltin,
diisobutyltin, di-tert-butyltin, di- sec-butyltin, di-phenyltin)
tetramethyltin, tetraethyltin, tetrapropyltin, tetraisopropyltin,
tetrabutyltin, tetraisobutyltin, tetra-tert-butyltin, tetra-sec-butyltin, .
tetraphenyltin, tetrameth- oxytin, tetraethoxytin, tetrapropoxytin,
tetraisopropoxytin, tetrabutoxytin, tetraisobutoxytin, tetra-tert-butoxytin,
tetra-sec- butoxytin, tetraphenoxytin, trimethoxyrnethyltin,
triethoxymethyl- tin, tripropoxymethyltin, triisopropoxymethyltin,
tributoxymethyl- tin, triisobutoxymethyltin) tri-tert-butoxymethyltin; tri-
sec- butoxymethyltin, triphenoxymethyltin, dibutyltin dichloride,
dibutyitin diiaurate, dibutyltin dirnethoxide, dibutyltin dieth- oxide,
dibutyltin methoxide) dibutyltin ethoxide, tetrabutyltin, tetramethyltin,
tetraethyltin, tetrapropyltin, tetra-tert-butyltin, allyldibutyltin,
allyldiphenyltin, allyldiphenylstannane, dichlorodiphenyltin, diphenyltin
acetate, tributyltineacetate, tributyltinechloride, tributyltincyanide,
tributyltin ethoxide, tributyltin meth oxide, tributyltinhydride,
tributylvinyltin, triphenyltinchloride, triphenyltinhydroxide,
triphenyltinhydride, tributyltin ethoxide, including analogue, homologue,
isomer, and derivative thereof. The non-limiting examples of
phosphorus derivative compounds of this invention include:
tetrabutylphosphonium hydroxide, allyldiphenylphospine,
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diphenylphosphine, phenyfphosphine, diphenyl phosphate,
diphenylphosphine, diphenylphosphinic acid, diphenylethoxyphospine,
diphenylmethoxyphospine, diphenylpropoxy- phospine,
diphenylisopropoxyphospine, diphenylbutoxyphospine, Biphenyl-sec-
butoxyphospine, Biphenyl-tert-butoxyphospine, Biphenyl-iso-
butoxyphospine, dicyclohexylethoxyphospine, dicyclo-
hexylmethoxyphospine, dicycfohexylpropoxyphospine, dicyclohexyliso-
propoxyphospine, dicyclohexylbutoxyphospine, dicycfohexyl-sec-
butoxyphospine, dicyclohexyl-tert-butoxyphospine, dicyclohexyl-iso-
butoxyphospine, dicyclopentylethoxyphospine, dicyclopentyl-
methoxyphospine, dicyclopentylpropoxyphospine, dicyclo-
pentyfisopropoxyphospine, dicyclopentylbutoxyphospine, dicyclopen-
tyl-sec-butoxyphospine, dicyclopentyl-tert-butoxyphospine,
dicycfopentyl-iso-butoxyphospine, dicyclohexyl(ethyl)ethoxy- phospine,
dicyclohexyl(ethyl)methoxyphospine, dicyclohexyl(ethyl}-
propoxyphospine, dicyclohexyl(ethyl)isopropoxyphospine,
dicyclohexyl(ethyl)butoxyphospine, dicyclohexyl(ethyl)-sec-
butoxyphospine, dicyclohexyl(ethyl)-tert-butoxyphospine, dicyclo-
hexyl(ethyl)-iso-butoxyphospine, phenyldiethoxyphospine {diethy-
Iphenylphosphonite), phenyldimethoxyphospine, phenyldipropoxyphos-
pine, phenyldiisopropoxyphospine, phenyldibutoxyphospine, phenyldi-
sec-butoxyphospine, phenyldi-tert-butoxyphospine, phenyldiisobut-
oxyphospine, cyclohexyldiethoxyphospine, cyclohexyl-
dimethoxyphospine, cyclohexyldipropoxyphospine, cyclohexyl-
diisopropoxyphospine, cyclohexyldibutoxyphospine, cyclohexyldi-sec-
butoxyphospine, cyclohexyldi-tent-butoxyphospine, cyclohexyldi-iso-
butoxyphospine, cycfopentyldiethoxyphospine, cyclopentyfdimethoxy-
phospine, cyclopentyldipropoxyphospine, cyclopentyldiisopropoxy-
phospine, cyclopentyldibutoxyphospine, cyclopentyldi-sec-butoxy-
phospine, cyclopentyldi-tert-butoxyphospine, cyclopentyldiiso-
butoxyphospine, cyclohexyl(ethyl)diethoxyphospine, cyclohexyl-
(ethyl)dimethoxyphospine) cycfohexyl(ethyl)dipropoxyphospine,
cyclohexyl(ethyl)diisopropoxyphospine, cyclohexyl(ethyl)dibutoxy-
phospine, cyclohexyl(ethyl)di-sec-butoxyphospine, cyclohexyf-
(ethyl)ditert-butoxyphospine, cyclohexyl(ethyl)diiso-butoxyphos- pine,
dimethylmethylphosphate, diethylmethylphosphate, diethylet-
hylphosphate, dimethylethylphosphate, ethylenebis(diphenylphos-
phine), methyldichlorophosphite, methyldichlorophosphate, methyl-
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dichlorophosphine, methyldiphenylphosphine, propylphosphonic
anhydride, dimethylphosphine, diethylphosphine, dimethylphosphine,
dipropylphosphine, diisopropylphosphine, dibutylphosphine,
diisobutylphosphine, disecbutylphosphine, di-t-butylphosphine,
diphenylphosphine, diphenylphosphate, diphenylphosphineoxide,
diphenylphosphine oxide, diphenylphosphineselenide) dis(diethyl-
amino)phosphine, dis(dimethylamino)phospine, dis(2-ethyl-
hexyl)phosphate) dis(dimethylsilyl)phosphate, dis{dirnethylsil-
yl)phosphite, di(toly)phosphine, di(o-toly)phosphine, di(m-
toly)phosphine, di(p-toly)phosphine) di(toly)phosphite, di(o-
toly)phosphite, di(m-toly)phosphite, di(p-toly)phosphite, di(toly)-
phosphate, di(toly)hydrophosphate, di{toly)phosphonic acid
[(CH3C6H4)2P(OH)], mono{toly)phosphonic acid [(CH3C6H4)P(OH)2],
diethylphenylphosphine, diethyiphenylphosphite, dipropylphosphite,
diisopropyiphosphite, dibutylphosophite, diisobutylphosophite, di- sec-
butylphosophite, di-tert-butyiphosophite, diphenylphosphite,
allydiphenylphosphonium, allydiphenylphosphonium hydride, al-
lydiphenylphosphonium hydroxide, allydiphenylphosphonium chloride,
dimethylphosphorarnidous dichloride, hexamethylphosphoramide,
hexamethylphosphorus diamide, hexamethylphosphorus triamide,
hexamethyiphospophorimidic triarnide, trimethylphosphine, trimethyl-
phospate, trirnethylphosphite, triethylyiphosphite, tripropyl- phosphate,
triisopropylphosphite, tri-butyl-phosphate, tri-iso- butylphosphite, tri-sec-
butylphosphite, tri-tert-butylphosphite, triphenylphosphite,
dimethylphosphite, diethylphosphite, dipropyl- phosphate,
diisopropylphosphite, dibutylphosphite, diisobutyl- phosphate, di-sec-
butylphosphite, di-tert-butylphosphite, Biphenyl- phosphate,
dimethylethylphosphine, dimethylethylphosphate,
dimethylethylphosphite, diethylmethyfphosphite, dipropylmethyl-
phosphite, diisopropylmethylphosphite, di-butyl-methylphosphite, di-iso-
butylmethylphosphite, di-sec-butylmethylphosphite, di-tert-
butylmethylphosphite, diphenylmethyl phosphate, dimethyl-
phosphonate, diethylphosphonate, dipropylphosphonate, diisopropyl-
phosphonate, di-butyl-phosphonate, di-iso-butylphosphonate, di-sec-
butylphosphonate, di-tert-butylphosphonate, diphenylphosphonate,
dimethylmethyiphosphonate, dimethylethylphosphonate, diethylmethyl-
phosphonate, dipropylmethylphosphonate, diisopropylmethyl-
phosphonate, di-butyl-methylphosphonate, di-iso-butylmethyl-
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phosphonate, di-sec-butylmethylphosphonate, di-tert-butylmethyl-
phosphonate, diphenyfmethy! phosphonate, diethylethylphosphonate,
dipropylethylphosphonate, diisopropylethylphosphonate, di-butyl-
ethylphosphonate, di-iso-butylethylphosphonate, di-sec-butylethyl-
phosphonate, di-tert-butylethylphosphonate, diphenylethyl phosphon-
ate, dimethylcarbophosphonate, diethylcarbophosphonate, dipropyl-
carbophosphonate, diisopropylcarbophosphonate, di-butyl-phosphon-
ate, di-iso-butylcarbophosphonate, di-sec-butylcarbophosphonate, di-
tert-butylcarbophosphonate, diphenylcarbophosphonate, dimethyl-
methylcarbophosphonate, dimethylethylcarbophosphonate, diethyl-
methylcarbophosphonate, dipropylmethylcarbophosphonate, diisopro-
pylmethylcarbophosphonate, di-butyl-methylcarbophosphonate) di-iso-
butylmethylcarbophosphonate, di-sec-butylmethylcarbophosphonate,
di-tert-butyimethylcarbophosphonate, diphenylmethyl phosphonate)
diethylethylcarbophosphonate, dipropylethylcarbophosphonate,
diisopropylethylcarbophosphonate, di-butyl-ethylcarbophosphonate, di-
iso-butylethylcarbophosphonate, di-sec-butylethylca r- bophosphonate,
di-tert-butylethylcarbophosphonate, diphenylethyl phosphonate,
dimethylphospite, dimethylphosphite, trimethyl phosphonoacetate,
trimethyl 2-phosphonoacrylate, trimethyl phosphonoformate,
trioctylphosphine oxide, triphenyl phospate, triphenylphosphine,
triphenylphosphine oxide, triphenyl- phosphine-copper hydride,
triphenylphosphine hydrobromide, triphenylphosphine dibromide,
triphenylphosphine oxide, triphenyl- phosphine selenide,
triphenylphosphine sulfide, tripiperidinophosphine oxide, tris(2-
ethylhexyl)phosphate, tris(dimethylamino)phosphine,
tris(hydroxymethyl)aminomethane phosphate,
tris(trimethylsilyl)phosphate, tris(trimethylsilyl)phos- phite,
tri(toly)phosphines (e.g. tri(o-toly)phosphine, trim- toly)phosphine,
trip-toly)phosphine), tri(toly)phosphite (e.g. tri{o-toly)phosphite, tri(m-
toly)phosphite, trip-toly)phosphite), tri(toly)phosphate,
tri(toly)hydrophosphate, tri(toly)phosphonic acid [(CH3C6H4)3P(OH)2],
bis(2-ethylhexel) phosphate, diallyphenyl- phosphine,
dibenzylphosphite, dibenzylphosphate, dibutyl phosphate, dimethyl
methylphosphonate, dimethyl methylphosphine, dimethyl
methylphosphonite, dimethylphenylphosphine, dimethylphenyl-
phosphonite, dimethylphenylphosphite, dimethylphosphinic acid,
dimethyl(trimethylsilylmethyl)phosphonate, dimethyl trimethylsilyl
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phosphate, dimethyl trimethylsilyl phosphonate) ethytdiphenyl-
phosphonite, diphenyl(2-methoxyphenyl)phosphine, manganese (II)
hydrogen phosphate, disodium fluorophosphate, disodium
fluorophosphite) disodiumhydrogenphosphite, trisodium phosphate,
trisodium phosphate, dipotassiium fluorophosphate, dipotassium
fluorophosphtte, tripotassium phosphate, tripotassium phosphate,
ethyldiphenylphosphine, ethyldiphenylphosphinite,
ethyldiphenylphosphonate, methyldiphenyfphosphine, methyldiphenyl-
phosphinite, methyldiphenylphosphonate, phenylphosphine, phenyl-
phosphonic acid, phenylphospate phosphorus acid, phosphoric acid,
phosphorus trichloride, phosurea, phosphorus trisulfide, tributyl
phosphate, tributylphosphine, tri-tert-butylphosphine, tributyl-
phosphine oxide, tributylphosphite, tris(2,4-di-tert-butyl-
phenyl)phosphite, tris(nonlphenyl)phosphite, phosphorous acid
triphenylester with propane 1,3-diol, tris(2,2,2-tri- fluoroethyl)phosphite,
tris(2-chtoroethyl)phosphite, tris(1- chloroethyl)phosphite)
trichlorophosphite, tris(tridecyl)phosphite) isooctyldiphenytphosphite,
diisodecylphenylphosphite, triethyl 4- phosphonocrotonate, trimethyl 4-
phosphonocrotonate, triethyl- phosphonoacetate,
trimethylphosphonoacetate, trimethyl 2-phosphono- butyrate, triethyl 2-
phosphonobutyrate, trimethylphosphonoforrnate,
triethylphosphonoformate) trimethytphosponopropionate, trimethyl-
phosponopropionate, tricyclohexylphosphite, tricyclohexylphophine,
triethylphosphine, triethylphosphite, trimethylphosphine, triethyl-
phosphate, trimethylphosphate, tripropylphosphate, triisopropyl-
phosphate, tributylphosphate, triisobutylphosphate, tri-sec-
butylphosphate, tri-tert-butytphosphate, triphenylphosphate,
dimethylphosphate, diethylphosphate, dipropylphosphate, diisopro-
pylphosphate, dibutylphosphate, diisobutylphosphate, di-sec-
butylphosphate, di-tert-butylphosphate, diphenylmethylphosphate,
diphenylethylphosphate, diphenytpropylphosphate, diphenylisopropyl-
phosphate, dirnethylethylphosphate, diethylmethylphosphate,
dipropytmethylphosphate, diisopropylmethylphosphate, di-butyl-
methylphosphate, di-iso-butylmethytphosphate, di-sec-butylmethyl-
phosphate, di-tert-butylmethylphosphate, diphenylmethyl phosphate,
triethylphosphoramide, trimethylphosphoramide, tripropylphosphor-
amide, triisopropylphosphoramide, tributylphosphoramide, tri-
isobutylphosphoramide, tri-sec-butylphosphoramide, tri-tert-
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butylphosphoramide, triphenylphosphoramide,. dimethoxyphosphorus-
amide (CH30)2PNH2), diethoxyphosphorusamide,
dipropoxyphosphorus- amide, diisopropoxyphosphorusamide,
dibutoxyphosphorusamide, diisobutoxyphosphorusamide, di-sec-
butoxyphosphorusamide) di-tert- butoxyphosphorusamide,
diphenoxyphosphorusamide, dimethyiphosphor- amide
(CH30)2PONH2), diethylphosphoramide, dipropylphosphoramide,
diisopropylphosphoramide, dibutylphosphoramide) diisobutylphosphor-
amide, di-sec-butylphosphoramide, di-tert-butylphosphoramide,
diphenylphosphoramide, dimethylethylphosphoramide, diethylmethyl-
phosphoramide, dipropylmethylphosphoramide, diisopropylmethyl-
phosphoramide, di-butyl-methylphosphoramide, di-iso-butyfmethyl-
phosphoramide, di-sec-butylmethylphosphoramide, di-tert-butyl-
methylphosphoramide, diphenylmethyl phosphoramide, triethylcar-
bophosphate, trimethylcarbophosphate, tripropylcarbophosphate,
triisopropylcarbophosphate, tri-butyl-phosphate, tri-iso-butyicar-
bophosphate, tri-sec-butylcarbophosphate, tri-tert-butylcar-
bophosphate, triphenylcarbophosphate, dimethylcarbophosphate)
diethylcarbophosphate, dipropylcarbophosphate, diisopropylcar-
bophosphate, dibutylcarbophosphate) diisobutylcarbophosphate, di-
sec-butylcarbophosphate, di-tert-butylcarbophosphate, diphenylcar-
bophosphate, dimethylethylcarbophosphate, diethylmethyl-
carbophosphate, dipropylmethylcarbophosphate, diisopropylmethylcar-
bophosphate, di-butyl-methylcarbophosphate, di-iso-butylmethylcar-
bophosphate, di-sec-butylmethylcarbophosphate, di-tert-butylmethyl-
carbophosphate, diphenylmethyl phosphate, dimethylvinylphosphate,
diethylvinylphosphate, dipropylvinylphosphate, diisopropylvinyl-
phosphate, dibutylvinylphosphate, diisobutylvinylphosphate, di-sec-
butylvinylphosphate, di-tert-butylvinylphosphate, diphenylvinyl-
phosphate, triisobutylphosphine, triisodecylphosphite, triisopro-
pylphosphite, dibenzyldiethylphosphoramidite, dibenzyldiisopropyl-
phosphoramidite, dibenzylphosphite, dibenzylphosphate, tris(tri-
decyl)phosphite, tritolylphosphate, tritolyphophine, tritolyphos- phite,
tricyclohexylphosphine, afiminum phosphate, 1,2-bis(di-
phenylphosphino)propane, trioctylphosphine oxide, trioctyl- phosphine,
dichloromethylphosphine, dichlorophosphineoxide (C12P0),
ethyldichlorophosphite, tetraethylpyrophosphite, benzyldiethyl-
phosphite, benzyldiethoxyphosphorus, cyclohexyldiethoxyphosphorus,
fit
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dibenzyldiisopropylphosphoramite (dissopropyl-phosphoraramidous
acid dibenyl ester), di-tert-butyl diisopropylphosphoramidite, tert-butyl
tetraisopropylphosphorodiamidite, (+/-)-1-amino-cis-3-
phosphonocyclopentanecarboxlic acid, diallyl diisopropyl-
phosphoramide, tert-butyl tetraisopropylphosphorodiamite, (1-amino-
butyl)-phosponic acid, 6-amino-1-hexyl phosphate, 1-aminoethyl-
phosponic acid) 2-aminoethyl dihydrogenphosphate, 2-aminoethyl-
phosponic acid, methyl N,N,N'-tetraisopropyiphosphordiamidite,
hexamethylphosphoramide [(CH3)2N]3P0,
hexamethylphosphortriamidite [(CH3)2N]3P, diethyl 4-
aminobenzylphosphonate, diethyl 4-aminoben- zylphosphite,
diethylbenzylphosphonate, diethylbenzylphosphite,
tetraethylbenzylphosphonate, diethyl (pyrrolidinomethyl)phos- phonate,
diethyloxyphosphinyl isocyanate, 6-amino-1-hexyfphosphate,
diethyloxyphinyl isocyanate, diethylcyanomethylphosphonate,
diethylveinylphosphonate, dioctylphenylphosphonate, ethylphenyl-
phosphinate, ethylphenylphosphonic acid, methylphosphonic acid,
ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic
acid, butylphosphonic acid, sec-butylphosphonic acid) tert-
butylphosphonic acid, isobutylphosphonic acid) phenylphosphonic acid,
phenylphosphoric acid) phenylphosphinic acid, methylphenyl-
phosphinate, methylphenylphosphine, aminomethylphosphonic acid,
vinylphosphonic acid, hypophosphorus acid) sodium hypophosphate,
sodium dihydrogenphosphate, fluorophosphoric acid, ammonium
hydrogenphosphate, ammonium hydrogenphosphite, ammonium
hydrogen- phosphine) lithiumdihydrogenphosphate,
triphenylphosphineselenide, phosphoric acid, phosphorus oxychloride,
phosphorus pentasulfide, metaphosphoric acid, phenylphosphate
disodium salt, nitrilotris(methylene)triphosphonic acid,
ethylenephosphite, ammonium salt benzylphosphite,
potassiumhexafluorophosphate, diethyltrimethylsilylphosphite,
diethyl(trichloroethyl)phosponate, dimethyl(trimethylsilyl)phosphite,
tris(trimethylsilyl)phosponate) 2-chloro-1,3,2-dioxaphospolane, 2-
chloro-1,3,2-dioxaphospholane-2- oxide, dimethylmethylphosphonate,
diethylmethylphosphonate, dimethylethylphosphonate,
diethylethyfphosphonate) ethylmethyl- phosphonate, 2-
carboxyehtylphosphonic acid, 2,2,2-trichloro-1,1-
dimethylethyldichiorophosphite, bis{2-chloroethyl)phosphoramidic
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dichloride, butyldichlorophosphite) butylphosphonic dichloride, tert-
butyiphosphonic dichloride, tert-butyldichlorophosphine,
trimethylphosphonoformate, trimethylpropionamide, trimethylpropion-
anilide, diethylchlorophosphate, diethylchlorophosphite, chlorodi-
ethylphosphine, diethylphosphoramidous dichloride, diethyl-
thiophosphate, sodium salt diethylthiophosphate, diethyl-
phosphoramidate, dimethylphosphoramidate, tetramethyl-
phosophorodiamidic chloride, tetramethylphosphonium chloride,
diethylcyanophosphate, diethylcyanophosphonate, diethylcyanomethyl-
phosphonate, diethoxyphosphinyl isocyanate, O,O'-diethylmethyl-
phosphonothioate, diethylmethylphosphonate, diethyl(hydroxymethyl)-
phosphonate, dimethyltrimethylsilylphosphite, 1-ethyl-3-methyl-1 H-
imidzoiium hexaflurophosphite, diethylcyanmethylphosphonate,
phosphorus napthenate, methylphenylphospholene, methylphenyl-
phosolenedichloride, (aminobenzyl)phosphonic acid (e.g. (4-
aminobenzyl)phosphonic acid), cyclophosphamide, pinacolylmethyl-
phosphonate) diethyl(ethylthiomethyl)phosphonate, 2-furyl tetra-
methylphosphorodiamidite, diisopropylcyanomethylphosphate, 1,3,5-
tris(2-hydroxyethyl)cyanuric acid, tris(2,4,-di-tert-butyl-
phenyl)phosphite, tris(tridecyl)phosphite, tris(nonylphenyi)phos- phite,
phosphorus anyhydride, phospham, phosphonium chloride,
phosphoniumsulfide, phosphoniumsulfate, phosphoramide, phor-
phoramidite, metaphosphoramide, phosphorus chloride(di)nitride,
phosphorus cyanide, phosphorus trifluoride, phosphorus penta-
ffuoride, phosphorus oxybromide, phosphorus pentaselenide,
phosphorus trioxide, phosphorus sesquioxide, phosphorus tri(tetra-
)selenide, phosphorus thiochloride, phosphorus thiocyanate)
hypophosphorus acid, metaphosphorus acid, orthophosphorus acid,
pyrophosphorus acid, phosphine, phosphorus nitride, phosphorus
sesquisulfide, including analogues, homologues, isomers and
derivatives thereof. The corresponding compounds of arsenic, antimony
and bismuth are contemplated.
Other non-limiting antimony derivative compounds include: alkyl
antimony compounds, triaikyl compounds, cyciomatic/ring system
compounds) including, trimethylantimony, triethylantimony,
tripropylantimony, triisopropylantimony, tributylantimony,
triisobutylantimony, tri-tert-butylantimony, tri-sec-butylantimony, tri-
phenylantimony, phenylantimony, tri(methylphenyl)antimony)
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triphenyiantimony oxide, tri(methylphenol)antimony, antimony ethoxide,
pentamethylantimony) phenyldimethylantimony, phenyl- stibinic acid,
tetramethyldistibyl) tributylstibene, triethylan- timony, triethylantimony
chloride, trimethylantimony, triphenylan- timony, triphenylantimony
dichloride, triphenylantimony sulfide, including analogue, homologue,
isomers and derivative thereof.
Non-limiting arsenic derivative compounds include: alkyl arsenic
compounds, dialkyl compounds, cyclomatic/ring system compounds
including, trimethylarsine, triethylarsine, tripropylar- sine,
triisopropylarsine, tributylarsine, triisobutylarsine, tri- tert-butylarsine,
tri-sec-butylarsine, tri-phenylarsine, phenylar- sine)
tri(methylphenyl)arsine, triphenylarsine oxide, tri(methyl- phenol)arsine,
phenylarsenic acid, phenylcyclotetramethylenearsine, arsenobenzene,
cacodyl oxide, cacodyl amide, dimethylarsine, dimethylchlorarsine,
dimethylcyanoarsine, diphenylarsinic acid, diphenylchloroarsine,
ethylarsonic acid, methylarsine, methyl- dichioroarsine, phenylarsine,
phenyldimethylarsine, tetraethyldiar- sine, tetramethylbiarsine,
tribenzylarsine, trimethylarsine, triethyiarsine, tributyl arsine, tri-
isobutyl
arsine, triphenyl arsine, including analogue, homologue, isomers and
derivative thereof. See Organo Arsenial Compounds, Raiziss, Gavron,
American Chemical Society (1923) and relatedlsubsequent editions,
volumes or supplements, incorporated by reference. Corresponding
compounds of phosporus, antimony, bismuth are also contemplated
herein and incorporated by reference.
Non-limiting bismuth derivative compounds include: alkyl bismuth
compounds, dialkyl compounds, cyclomatic/ring system compounds
including, triphenylbismuth, triphenylbismuth carbonate,
diphenylbismuthine, methylbismuthine, triethylbismthine, trimethyl-
bismthine, triphenylbismuthine, tri-n-propylbismuth, including analogue,
homologue, isomers and derivative thereof.
Non-limiting potassium derivative compounds of this invention
include: potassium bis(dimethylsilyl)amide, potassium acetamide,
potassium bis(trimethylsilyl)amide, oxamic acid, P-aminosaiicylic acid
potassium salt, potassium salt 5-nitroorotic acid, potassium D-
gluconate, potassium hexacyanoferrate(III) (K3Fe(CN)6), potassium
diphenylphosphide, potassiumetherate, potassium acetate, potassium
acetate acid, potassium salt acetic acid, potassiumbenzamide)
potassium azide, potassium antimonide) potassium orthoarsenate)
CA 02274607 1999-06-09
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potassium orthoarsenite, potassium meta-arsenate, potassium diborane,
potassium pentaborate, potassium dihydroxy diborane, potassium
borohydride, potassium anilide, potassium cadium iodide, potassium
chloride, potassium calcium chloride, potassium carbide, potassium
carbonate, potassium hydrogen carbonate, potassium carbonate,
potassium carbonyl, potassium cobalt (II) cyanide, potassium cobalt
(III) cyanide, potassium cobaltinitrite, potassium cynomanganate (II),
potassium cynomanganate (III), potassium citrate, potassium
ferricyanide, potassium ferrocyanide, potassium hydride, potassium
hydroxide, potassium manganate, potassium permanganate, potassium
methionate, potassium napthenate, potassium nitride, potassium
nitrate, potassium nitrite, potassium nitrophenoxide, potassium
nitrobenzene (e.g. potassium-p- nitrobenzene)potassium oleate,
potassium oxalate, potassium oxalatoferrate (II), potassium
oxalatoferrate (Ill), potassium monoxide, potassium oxide, potassium
peroxide, potassium mono- orthophosphate, potassium hypophosphite,
potassium orthophosphate, potassium hydroxoplumbate, potassium
rhodium cyanide, potassium selenide, potassium selenite, potassium
selenocynate, potassium selenocyanoplatinate, potassium disilicate)
potassium metasilicate, potassium sodium carbonate, potassium
sodium ferricyanide, potassium hydroxostannate, potassium disufide,
potassium hydrosulfide, potassium pentasulfide, potassium tetrasulfide,
potassium trisulfide, potassium telluride, potassium thioarsenate,
potassium thioarsenite, potassium trithiocarbonate, potassium
thiocyanate, potassium amide, potassium salt (E,E)-2,4-hexadienoic
acid, dipotassium fluorophosphate) dipotassium fluorophosphite,
tripotassium phosphate, tripotassium phosphate, potassium perchlorate,
propanoic acid potassium salt, potassium formate, potassium cyanate,
potassium hexacyanocobaltate (III), potassium hypophosphite,
potassium hexaflurorsilicate, potassium nitroprusside, potassium
phenoxide, potassium phosphate (dibasic, monobasic, tribasic),
potassium salicylate, potassium selenide, potassium
tetracyanonickelate (II), potassium tetrafluoroborate) potassium
xanthogenate, potassium -p-aminobenzoate, potassium copper
ferrocynanide, potassium cupric ferrocyanide, potassium
hexafluorophosphate, potassium hexanitricobaltate III, potassium
naphthenate, potassium-B-naphthoxide,potassium polysulfide,
potassium -sodium phosphate, potassium stearate, potassium sulfide)
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potassium sulfite, potassium sulfate, potassium thiocyanate, potassium
xanthate, potassium fluorosificate, N-potassiumethylene- diamine,
oxalic acid dipotassium salt, potassium beta-hydropyruvic acid,
potassium 1,1-dimethylurea, potassium 1,1-diethylurea, potassium 1,1-
diepropylurea, potassium xanthate, potassium ethylxanthate,
potassium methylxanthate, potassium salt thiophenol,
potassiurnaluminum-tri-tert-butoxide, potassium ferrosilicon,
triphenylmethylpotassium, methylpotassium, ethylpotassium,
potassiumethynyl(acetylide), propylpotassium, isopropylpotassium,
butylpotassium, isobutylpotassium, secbutylpotassium, tertbutyl-
potassium, pentapotassium, hexylpotassium, heptapotassium,
amylpotassium, isoamylpotassium, benzylpotassium, dimethylbenzyl-
potassium, tolylpotassium, dodecylpotassium, cyclopentadienylpotas-
sium, methylcyclopentadienylpotassium, cyclohexylpotassium,
potassiumheptyl, potassiumdodecyl, potassium tetradecyl, potassium
hexadecyl, potassium octadecyf, phenylpotassium, potassium o-tolyl,
potassium m-tolyl, potassium p-tolyl, potassium-p-chlorophenyl,
potassium p-bromophenyl, potassium potassium o- anisyl, potassium
m-anisyl, potassium p-anisyl, potassium diethoxyphenyl, potassium
dimethoxyphenol, potassium m-cumyl, potassium p-ethoxyphenyl,
potassium m-dimethylaminophenyl, potassium 9-flourene, potassium a-
napthyl, potassium b-napthyl) potassium p-phenylphenyl, potassium 9-
phenylanthryl, potassium 9-anthryl, potassium 9-methylphen- anthryl,
potassium pyridyl, potassium 2-pyridyl, potassium 3- pyridyl, potassium
6-bromo-2-pyridyl, potassium 5-bromo-2-pyridyl, potassium
dibenzofuryl, potassium 3-quinoyl, potassium 2-lepidyl, potassium
triphenylmethyl, potassium 2,4,6-trimethylphenyl, potassium 2,4,6-
triisopropylphenyl, potassium 2,3,5,6-tetraiso- propylphenyl, potassium
tetrabutylphenyl, thiophenedipotassium, toluenedipotassium,
diphenylethylenedipotassium, potassium- amylethynyf,
potassiumphenylethynyl, potassiummethoxybromophenyl, potassium
phenylisopropyl, potassium tetraphenylboron, potassium
tetramethylboron, potassium a-thienyl, potassium m-trifluoromethyl-
phenyl, phenylethynylpotassium, 3-furylpotassium, phenylisopropyl-
potassium, dibenzofuranylpotassium, potassium dimethylbenzyl,
potassium selenocyanate, potassium trimethylsilanolate, diphenyl-
phosphide, potassium benzoate, potassium tert-butyl carbonate)
potassium azide, di-potassiumcyanamide, potassium cyanide,
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potassium dicyanamide, cyclohexanebutyric acid potassium salt,
cyclohexane acid potassium salt, cyclopentadientylpotassium,
potassium tri-tert-butoxyaluminum hydride, potassium triethyl-
borohydride, potassium trimethylborohydride, potassium tripropyl-
borohydride, potassium triisopropylborohydride, potassium tributyl-
borohydride, potassium triisobutylborohydride, potassium tri-sec-
butylborohydride, potassium tri-tert-butylborohydride, potassium
trisiamylborohydride, potassium chlorate, potassium tert-butoxide,
potassium sec-butoxide, iso-butoxide, potassium antimonate,
potassium diphenylphosphide, potassium bis(trismethylsilyl) amide,
tripotassium phosphite, potassium selenocyanate, potassium tri-sec-
butylborohydride, potassium triethylsilanolate, potassium thiocyanate,
potassium acetylide, potassium chlorate, potassium saiicylate,
potassium di-potassium tetracarbonylferrate, potassium
tetraphenylborate, potassium triethylborohydride, potassium
triacetoxyborohydride, potassium triphenylborane, potassium
hydroxide, potassium diphenylphosphide, potassium methoxide,
potassium ethoxide, potassium tri-sec-butylborohydride, tri-tert-
butylborohydride, potassium triethylborohydride, potassium
triphenylborohydride, potassium trisiamylborohydride, potassium
metavanadate, potassium cyclohexanebutyrate, potassium hexachloro-
platinate, potassium thiocyanate, potassium selenocyanate, potassium
cyanate, potassium floride, potassium hexafluoroan- timonate,
potassium hexafluoroaiuminate) potassium hexafluoroar- senate,
potassium hexafluorosiiicate, potassium hexacyano-
cobalt(II)ferrate(II), dipotassiumhexacyanocobalt(II)ferrate(II),
potassium hexafluorotitanate, potassium hexafluorozirconate)
potassium hexahydroxyantimonate, potassium hexachlororuthenate)
potassium hexachloropalladate, potassium formate, potassium
tetracyanonickelate, potassium tetrafluoroaluminate) potassium
tetrafiuoroborate, potassium thioacetate, L-glutamic acid mono-
potassium salt, fumaric acid potassium salt, oxamic acid potassium
salt, potassium salt diphenyl-phospane, P-aminobenzoic potassium
salt, aminobenzole acid potassium salt, alpha-napthaleneacetic acid
potassium salt, dipotassium salt 2,6-naphthalenedicarboxlic acid,
potassium cyclcohexanetherate, potassium phthalimide, P-amino-
salicylic acid potassium salt, potassium salt 3,5-dimethylcyclo- hexyl
sulfate, indolebutyric acid potassium salt,indole-3-butyric acid
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potassium salt, potassium diphenylphosphide, potassium
dimethylsilanolate, potassium triethylborohydride, potassium propoxide,
potassium isopropoxide, potassium butoxide, potassium sec-butoxide,
potassium pentoxide, potassium tert-pentoxide, potassium
hydrogenphthalate, potassium oxalate, potassium hydrogen- sulfate,
monopotassium acetyienedicarboxylic acid, potassium pyrophosphate,
potassium dihydrogenphosphate, potassium hexoate (potassium salt
hexoic acid), potassium diphenylphosphide, potassium
trimethylsilonalate, potassium phthalic acid, P-aminoben- zoic acid
potassium salt, monopotassium L-aspartic acid, tetra-
phenyldipotassium (C6H5)2CK2C(C6H5)2, potassiumethylphenyl
(KCH2C6H5), potassium bromate, potassium chromate, potassium
hydrogenphospate, monpotassium salt D-shaccharic acid, DI-asparatic
potassium salt) (R)-alpha-hyroxymethylaspartic acid potassium salt,
potassium fluoride, potassium iodate, potassium salt ethyl malonate,
potassium thioacetate) potassium phenol, potassium salt aminobenzoic
acid, potassium aminophenol salt, potassium cyclo- hexenol, potassium
methyfcyclohexenol, potassium cyclopropanol, potassium
methylcyclopropanol, potassium cyclobutanol, potassium
methylcyclobutanol) potassium methylcyclopentanol, potassium
cyclopentanol, potassium cyclohexenol, potassium methyl-
cyclohexenol) potassium dimethylcyclohexenols (e.g. potassium 3,5-
dimethylcyclohexanol, potassium 2,3-dimethylcyclohexanol, potassium
2,6-dimethylcyclohexanol, potassium 2,5-dimethylcyclohexanol, 3,5-
dimethylcyclohexanol), potassium o-ethylxanthic acid, monopotassium
salt 2-ketoglutaric acid, dipotassium salt, ketomalonic acid, potassium
salt lactic acid, dipotassium thiosulfate, potassium antimony tartrate)
potassium dichloroacetate, potassium dimethyl- acetate, potassium
diethylacetate, potassium dipropylacetate, potassium metaborate,
potassium tetraborate, potassium tetrachloro- cuprate, potassium
acetoacetate, potassium diisopropylamide, potassium diethylamide,
potassium dimethylamide, potassium bis(dimethylsilyl)amide,
dipotassium phthalocyanine, dipotassium- tetrabromocuprate,
dipotassium tetrabromonickelate, dipotassium- tetrachloromanganate,
dipotassiumbutadiyne, potassium cyclopen- tadienide, potassium
dicyclohexylamide, potassium diethylamide, potassium dimethyiamide,
potassium dipropylamide, potassium diisopropylamide, potassium
thexylborohydride, potassium tri-tert- butoxyaluminohydride, potassium
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trimethylsilyl)acetylide, potassium triethylsilyl)acetylide, potassium
tris[(3-ethyl-3-pentyl)oxy]- aluminohydride, (phenylethynyl)potassium,
2-thienyipotassium, potassium diethyldihydroaluminate, potassium
dimethyldihydroalumin- ate, potassium aluminum hydride, potassium
bifluoride, potassium biphenyl, potassium biselenite, potassium bis(2-
methoxyethoxy)- aluminum hydride, potassium bismuthate, potassium
borate) potassium chlorite, potassium cobaltnitrite, potassium
cyanoborohydride, potassium cyclopentadienide, potassium
dicyanamide, potassium hexametaphosphate, potassium
hexanitrocolbaltate, potassium hydrogenphosphite, potassium
hydrogenselenite, potassium hydrogen- sulfite, potassium hydrosulfite,
potassium hypochloride, potassium metaarsenite, potassium
metabisulfide, potassium metaperiodate, potassium methacrylate,
potassium nitroferricyanide, oxybate, potassium
pentamethylcyclopentadienide, potassium phenolate, polyphosphate,
potassium polyphosphite, potassium propionate, potassium
pyrophosphate, potassium selenate, potassium selenite, potassium
tetrachloroaluminate, potassium thiomethoxide, potassium thiosulfate,
potassium thiosulfide, potassium thiosulfite, potassium
triactoxyborohydride, potassium trimethylsilonate, potassium
triethylsilonate, potassium tris(1-pyrazoly)borohydride, including
analogues, homologues, isomers and derivatives thereof.
Corresponding compounds of rubidium, caesium (cesium), francium are
contemplated in the practice of this invention.
Non-limiting derivative magnesium compounds contemplated by
this invention include: alkyl manganese compounds, dialkyl magnesium
compounds) magnesium ethylate (ethoxide), magnesium methoxide,
dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
diisopropylmagnesium, dibutylmagnesium, ditertbutylmagnesium, di-
iso-butylmagnesium, di-sec-butylmagnesium, diphenylmagnesium,
methylmagnesium chloride) methylmagnesium iodide, magnesium
methylcarbonate, magnesium hydroxide, magnesium anthracene
dianion, bromomagnesium isopropylcyclohexylamide,
methylmagnesium bromide, methylmagnesium chloride,
ethylmagnesium chloride, magnesium floride, magnesium chloride,
butyfmagnesium chloride, isopropylmag- nesium chloride,
cyclopentylmagnesiumhydride, cyclopentylmagnesium- hydroxide)
cyclopentylmagnesiumchloride, cyclopentylmagnesium- methyl,
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cyclopentylmagnesiumethyl, cyclopentylmagnesiummethylol,
cyclopentylmagnesiumethylol, cyclopentylmagnesiummethoxy,
cyclopen- tylmagnesiumethoxy,cyclohexylmagnesiumhydride,
cyclohexylmagnesiumhydroxide, cyclohexylmagnesiumchloride,
cyclohexylmagnesiummethyl) cyclohexylmagnesiumethyl,
cyclohexylmagnesiummethylol, cyclohexylmagnesiumethylol,
cyclohexyimagnesiummethoxy, cyclohexylmagnesiumethoxy, tert-
butylmagnesium chloride, isobutylmagnesium chloride, allymag- nesium
chloride, benzylmagnesium chloride, benzylmagnesium hydride,
benzylmagnesium ethylate, benzylmagnesium methylate, benzylmag-
nesium ethoxy, benzylmagnesium methoxy, magnesium acetate,
magnesium methyl carbonate, trimethylsilylmethyl magnesium chloride,
magnesium acetate tetrahydrate, methylmagnesium
isopropylcyclohexylamide, magnesium pyrophosphate,
phenylethynylmagnesium bromide, methylphenylmagnesiumchloride,
methylmagnesium, ethylmagnesium, propylmagnesium, isopropylmag-
nesium, butylmagnesium, isobutylmagnesium) tert-butylmagnesium,
sec-butylmagnesium, phenyimagnesium, magnesium acetate,
magnesium hydrogenphosphate, cyclopentylmagnesium,
cyclopentylmagnesium- hydroxide, cyclopentylmethylmagnesium,
methylcyclopentylmethylmag- nesium, allylmagnesium,
benzylmagnesium, pentylmagnesium, 1,1-
dimethylpropylmagnesiumhydroxide, 1,1-dimethylpropylmethylmag-
nesium, phenylmagnesium, phenolmagnesium, magnesium hydroxide,
magnesiumcarbonate, magnesiumsilicide, magnesium phosphate,
magnesium phosphite, magnesium bisulfite, L-aspartic acid mag-
nesium, DL-aspartic acid magnesium, including analogue, homologue)
isomer, and derivative thereof. Corresponding beryllium, calcium,
strontium, barium, radium and zinc compounds are contemplated in the
practice of this invention. See The Organic Compounds of Magnesium,
Beryllium, Calcium, Strontium, and Barium, loffe, Nesmeyanov,
Amsterdam (1967), Organomagnesium Methods in Organic Synthesis,
Wakefield, Academic Press, FL (1995), incorporated by reference. The
mixture of dialkyl magnesium compounds with pyrophoric metallics is
specifically contemplated.
Non-limiting selenium derivative compounds include: alkyl and
dialkyi selenium compounds, dimethyiselenium, dimethyl selenide,
diethylselenium, dipropylselenium, diaisopropylselenium, diabutyl-
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selenium, diaisobutylselenium, dia-tert-butylselenium, dia-sec-
butylselenium, di-phenylselenium) tetramethylselenium, tetraethyl-
selenium, tetrapropylselenium) tetraisopropylselenium, tetrabutyl-
selenium, tetraisobutylselenium, tetra-tert-butylselenium, tetra-sec-
butylselenium, tetra-phenylselenium, phenylselenium) methyl-
phenylselenium) methylphenylselenide, methylphenolselenium, zinc
selenite, di-n-butylphosphane selenide, selenanthrene, selenourea,
selenophene, allylphenylselenide, 1,3-dihydro-benzoimid, 2,3- dihydro-
3-methyl, 1,1-dimethyl-2-selenourea, diphenyl diselenide,
phenylselenyl chloride, benzeneseleninic acid, sodium selenite,
benzeneseninic anhydride, potassium selenocyanate, selenourea,
sodium hydrogenselenite, 4-chlorobenzeneseleninide, 4-
(methylseleno)butyrate, benzyl selenide, alkyl selenium, including
dimethylselenide, diethylselenide, dipropylselenide, etc., ally phenyl
selenide, benzeneselenol, benzyl selenide, (phenylselenomethyl)tri-
methylsilane, potassium selenate, potassium selenite, selenic acid,
dibenzyl diselenide, p-tolyl selenide, triphenylphosphine selenium,
seleno-DL-methionine) P-tolyl selenide, including analogue,
homologue, isomer, and derivative thereof. See Organoselenium
Chemistry, Liotta, John Wifey & Sons, N.Y. (1987), incorporated herein
by reference.
Non-limiting telluride derivative compounds include: di-n-
butylphosphane selenide, selenanthrene, selenourea, selenophene,
allylphenylselenide, dimethyltelluride, diethyltelluride, dipropyl-
telluride, diisopropyltelluride, dibutyltelluride, diaisobutyltel- luride, dia-
tert-butyltelluride, dia-sec-butyltelluride, di- phenyltelluride,
tetramethyltelluride, tetraethyltelluride, tetrapropyltelluride,
tetraisopropyltelluride, tetrabutyltelluride, tetraisobutyltelluride, tetra-
tert-butyltelluride, tetra-sec-butyltelluride, tetra-phenyltelluride,
phenyltelluride, methyl-phenyltelluride, methylphenoltelluride, zinc
selenite, di-n-butylphosphane telluride, diphenyl ditelluride,
dimethylteliuride, diethyltelluride, dipropyltelluride, diisopropyltelluride,
dibutyltelluride, diisobutyltelluride, di-tert-butyltelluride, di- sec-
butyltelluride, di-phenyltelluride, dimethylditelluride, diethylditelluride,
dipropylditelluride, diisopropylditelluride, dibutylditelluride,
diisobutylditelluride, di-tert-butylditelluride, di-sec-butylditelluride, di-
phenylditel- luride, including analogue, homologue, isomer, and
derivative thereof.
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Non-limiting iron derivative compounds include:
[cyclopentadienyl] methylcyclopentadienyl iron, ferrocene,
methylferrocene, and butadiene iron tricarbonyl, [butadiene iron
tricarbonyl,] dicyclopentadienyl iron and dicyclopentadienyl iron
compounds;ferrocene, methylferrocenes, decamethylferrocene
(bis(pentamethylcyclopentadienyl)iron)) 1,1'-diacetylferrocene,
ferrocenecarboxylic acid, 1,1'-ferrocenecarboxylic acid,
ferroceneacetic acid, ferroceneacetronitrile, 1,1'-ferrocene-
bis(diphenylphosphine), ferrocenecarbonxaldehyde,
ferrocenecarboxylic acid, 1,1'ferrocenedicarboxylic acid, 1,1-
'ferrocenedimethanol, ferrocenedimethanol, diiron nonacarbonyl, di-
irondodecacarbonyl, di-ironnonacarbonyl, ironpentacarbonyl, triiron
dodecacarbonyl, vinylferrocene, biscyclopentadienyl iron (ferrocene),
cyclopentadienyl methylcyclopentadienyl iron, bis(methyl-
cyclopentadienyl)iron, cyclopentadienyl ethylcyclopentadienyl iron,
bis{ethylcyclopentadienyl)iron, bis(dimethylcyclopentadienyl)iron,
bis(trimethyl- cyclopentadienyl)iron, cyclopentadienyl tert-
butyfcyclopentadienyl iron, bis(pentamethylcyclopentadienyl)iron,
methylcyclopentadienyl ethylcyclopentadienyl iron)
bis(hexylcyclopentadienyl)iron, bisindenyl iron, butadiene iron
tricarbonyl, dicyclopentadienyl iron, cyclopentadienyl iron (di carbonyl)
(iodide), cyclopen- tadienyl iron (carbonyl) (iodide)
(methyltetrahydrofuran), iron (III) ferrocyanide, ammonium
hexacyanoferrate (II) hydrate, cyclopentadienyliron dicarbonyl dimer,
cyclopentadienyliron dicarbonyl iodide, iron pentacarbonyl, diiron
nonacarbonyl, ferroceneacetic acid, ferroceneacetonitrile,
ferrocenemethanol, acetylferrocene, including analogue, homologue,
isomer, and derivative thereof. Other examples are set forth U.S.
Patents 2,680,; 2,804,468; 3,341,311, The Organic Chemistry of Iron,
Koerner, New York, Academic Press (1978), incorporated herein by
reference.
Non-limiting nickel derivative compounds include: alkyl, aryl,
alkyloxy, alkylanol, aryloxy, di/trialkyl, di/triaryl, di/trialkyloxy,
diltrialkylanol, diltriaryloxy, and/or cyclomatic complexes, including,
biscyclopentadienyl nickel, cyclopentadienyl methylcyclopentadienyl
nickel, bis(methyfcyclopentadienyl) nickel,
bis(triphenylphosphine)dicarbonyl nickel, bis(isopropylcyclopenta-
dienyl) nickel, bisindenyl nickel, cyclopentadienyl nickel nitrosyl,
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methylcyclopentadienyl nickel nitrosyl, including analogue, homologue)
isomer, and derivative thereof.
Non-limiting cobalt derivative compounds include: biscyciopen-
tadienyl cobalt, bis(methylcyclopentadienyl) cobalt, bis(dimethyl-
cyclopentadienyl) cobalt, cyciopentadienyl cobalt, dicarbonyl,
cobalt(ous) hexamethylenetetramine, cobalt(ous) hydroxyquinone,
cyclopentadienylcobalt dicarbonyl, including analogue, homologue,
isomer, and derivative thereof.
Non-limiting zinc derivative compounds include: alkyl zinc, aryl
zinc, alkyloxy zinc, aryloxy zinc, dialkyl zinc, diaryl zinc) dialkyloxy zinc,
diaryloxy zinc, cyclomatic zinc complexes, including, dimethyizinc,
diethylzinc, dipropylzinc, diisopropyl- zinc, dibutylzinc, diisobutylzinc,
di-tert-butylzinc, di-sec- butylzinc, di-phenylzinc, zinc acetate, zinc
ethoxide, zinc arsenide, zinc hydroxide, zinc seienide, zinc selenite,
zinc flouride, zinc chloride, zinc cyanide, zinc floride, zinc chloride, zinc
undecylenate, zinc nitrate, zinc acrylate, zinc methacrylate, methyl zinc
chloride, isobutylzinc chloride, zinc stearate, zinc
dimethyidiethiocarbamate, di-n-propylzinc, di-o-tolyzinc, isobutyl- zinc
chloride, methylzinc chloride, zinc methacrlate, zinc acrylate, zinc
hexaflourosilicate, zinc nitrate, zinc hydroxide, zinc undecylenate, zinc
selenite, zinc stearate, zinc cyanide, isobutylzinc chloride, methyl zinc
chloride, L(+)lactic acid hemizinc, including analogues, homologues,
isomers and derivatives thereof. Corresponding magnesium
compounds are contemplated. See Zinc, The Science and Technology
of the Metal, Its Alloys & Compounds, Mattewson, N.Y., Reinhoid
(1959), incorporated by reference.
Non-limiting examples of transition metal derivative compounds,
e.g. metals of scandium, titanium, vanadium, chromium, manganese,
iron, cobalt, nickel, and their respective chemical groups, include
transition metal alkyl, aryl, alkyloxy, aryloxy, andlor ring system type
compounds. Multiple alkyl, alkyloxy radicals per metal are contemplate.
Cyclomatic transition metal compounds are expressly contemplated.
See Organometaliic Chemistry of Transition Metals, 2 Ed, Crabtree,
John Wiley & Sons, N.Y. (1994), incorporated herein by reference.
Non-limiting examples of manganese compounds include
benzyleyelopentadienyl manganese tricarbonyl; 1.2-dipropyl 3-
cyclohexylcyclopentadienyl manganese tricarbonyl; 1.2-
diphenylcyclopentadienyl manganese tricarbonyl; 3-propenylienyl
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manganese tricarbonyl; 2-tolyindenyl manganese tricarbonyl; fluorenyl
manganese tricarbonyl; 2.3.4.7 - propyflourentyl manganese
tricarbonyl; 3-naphthylfiuorenyl manganese tricarbonyl; 4.5.6.7-
tetrahydroindenyl manganese tricarbonyl; 3-3ethenyl-4, 7-
dihydroindenyl manganese tricarbonyl; 2-ethyl 3 (a-phenylethenyl)
4,5,6,7 tetrahydroindenyl manganese tricarbonyl; 3 - (a-
cyclohexylenthenyl) -4.7 - dihydroindenyl manganese tricarbonyl;
1,2,3,4,5,6,7,8 - octahydrofluorenyl manganese tricarbonyl and the like.
A preferred cyclomatic manganese tricarbonyl is cyclopentadienyl
manganese tricarbonyl. A more preferred cyclomatic manganese
tricarbonyl is methyl cyclopentadienyl manganese (MMT). Non-limiting
examples of acceptable substitutes include the alkyl, aralkyl, aralkenyl,
cycloalkyl) cycloalkenyl, aryl and alkenyl groups. The above
compounds can be generally prepared by methods that are known in
the art. Corresponding compounds of technetium and rhenium (see
Canadian Patent #1073207) are contemplated.
Non-limiting nitrogen derivative compounds include: 2-
methoxybenzylamine, 2-methoxybenzylamine, 2-(4-methoxyben-
zylamino)pyridine, nitroanline, 1-nitroanline, 2-nitroanline, 3-
nitroanline) 4-nitroaniine, nitroanisole, 1-nitroanisole, 2- nitroanisole, 3-
nitroanisole, 4-nitroanisole, aniline, 2-anilino- ethanol, anisamide)
anisonitrile, acetonitrile) nitromethane, nitroethane, picoline, 1-picofine)
2-picoline, 3-picoline, 4- picoline, tetramethyiammoniumhydroxide,
tetraethylammoniumhydroxide, N,N,N',N'-tetramethylethylenediamine,
toluic hydazide, toluidine, m-toluidine, o-toluidine, p-toluidine,
tolunitrile, o-tolunitrile, p-tolunitrile) triazacyclononane, triazole, 1,2,4-
triazole, triazine, 1,3,5-triazine, tributylamine, triethanolamine,
trimethanolamine, tripropanolamine, trimethoxypyrimidine) 2,4,6-
trimethoxypyrimidine, tetramethylammonium, trimethylpyrazine, urea,
urazole, guanidine nitrate, guandine acetatic acid, thiophenol, sodium
salt thio- phenol, thiourea, cumidine, diphenylamine, m-xylidine,
monmel- thylanine) toluidine, amylaminobenzene, ethylaminobenzene,
aminophenyl, methyl-o-toluidine, n-butylaminobenzene, n-propyl-
aminobenzene, monoethylaniline, mon-n-propylaniline, ethyldiphenyl-
amine, mono-n-butylaniline, diethylamine, di-n-propylaniline, mono-
isoamyianiline, diethylaniline, dimethylaniline, ethylamine,
triethylamine, triphenylamine, isopropylnitrite, ammonia, including
analogues, homologues, isomers and derivatives thereof.
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Non-limiting titanium derivative compounds include: titanium
diisopropoxide bis(2,4-pentanedionate), titanium methoxide, titanium
ethoxide, titanium (IV) 2-ethylexoxide, titanium isopro- poxide,
tetraethylorthotitanate, including analogues, homologues, isomers and
derivatives thereof.
Non-limiting zirconium derivative compounds include: zirconium
carbide) zirconium propoxide, zirconium ethoxide, decamethylzir-
conocene, decamethylzirconocene dichloride, bis-cyclopentadienyl
zirconium, including analogues, homologues, isomers and derivatives
thereof.
Non-limiting molybdenum derivative compounds include: molyb-
denumcarbonyl, molybdenum hexacarbonyl, tripyridine tricarbonyl-
molybdenum, molybdenumoxytetrachloride, cyclopentadienyl
molybdenum carbonyls, including but not limited to
benzenemolybdenumtricar- bony(, bicycioheptadienemolybdenum
tetracarbonyl, cycloheptatrien- molybdenum tricarbonyl, bis-
cyclopentadienylbimolybdenum pentacar- bony(,
mesitylenemolybdenum tricarbonyl, tropeniummolybdenum tricarbonyl
fluoroborate, cyclopentadienylmolybdenum tricarbonyl dimer,
methylcyclopentadienylmolybdenum tricarbonyl dimer, anisole
molybdenum tricarbonyl) mesitylene molybdenum tricarbonyl, including
analogue, homologue, isomers and derivative thereof. See U.S.
Patents 3,272,606, and 3,718,444, incorporated by reference.
Corresponding chromium and tungsten compounds are contemplated in
the practice of this invention.
Non-limiting copper derivative compounds include: alkyl copper
compounds, bis(ethyienediamine)copper(ll) hydroxide, copper
carbonate, cyclopentadienyltriethylphosphine copper,
diazoaminobenzene (ous), copper acetate, copper acetylacetonate,
copper aminoacetate, copper ethylacetate, copper ferrocyanide, copper
potassium ferrocyanide, copper nathenate, copper nitrate, copper
phosphide, copper phthalate, including analogue, homologue, isomers
and derivative thereof. See Copper, The Science and Technology of
the Metal, Its Alloys & Compounds, Butts, N.Y., Reinhold (1954),
incorporated by reference.
Other contemplated organometallic compounds are
metalfocenes, non-limiting example compounds include, ferrocene,
cobaltocene, nickelocene, titanocene dichloride, zirconocene
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dichloride, uranocene, decamethylferrocene, decamethylsilicocene,
decamethyl-germaniumocene, decamethylstannocene,
decamethylphosocene, decamethylosmocene, decamethylruthenocene,
decamethylzirconocene, including analogue, homologue, isomers and
derivative thereof.
It is to be noted the above list is not exhaustive. The metals and
their derivative compounds of this invention include every metal,
metalloid, and/or non-metal (herein "metal" or "metallic") capable of
acheiving vapor phase combustion, individually or incombination with
DMC.
Applicant's invention contemplates wide variation in metal
substitution and mixing practice. Thus, it is expressly contemplated the
non-lead organo-metallics, non-lead inorganic metallics, and/or their
related high heat releasing compounds, including those set forth above
may be mixed in varying proportions, and/or substituted and/or
replaced by any non-lead metallic or non-metallic (organic or inorganic
[atom, molecule or compound, including those containing nitrogen,
sulfur) chlorine, fluorine, helium, neon, argon) krpton, xenon, or radon
atoms)) accomplishing the object of this invention.
Derivative compounds and combinations may be entirely or may
contain in part or whole non-metal atoms, e.g. nitrogen, sulfur, chlorine,
fluorine, helium, neon, argon, krpton, xenon, or radon, etc., so long as
primary object of vapor phase combustion is accomplished. It is
contemplated said non-metals will employed in varying proportions
within the compound or combination compounds to achieve synergistic
improvements in heat releases, burning velocity, thermal efficiency,
emissions, power generation, and the like. For example,
hexamethylphosphoric triamide, N,N,N',N'- hexamethylsilanediamine,
bis(diethylamono)-dimethyisilane may be added as a co-metallic in
minor amounts to the composition to further improve vapor phase
combustion (e.g further enhancing fuel ecomony or power, etc.).
Ranges vary depending upon the specific metallic, fuels, fuel
weight, regulations, advance applications, thermodynamics, and the
extent combustion systems are modified to enhance the accelerated
low temperature high energy nature of Applicant's invention. Thus,
metallic concentrations that maximize combustion velocity and/or the
vapor phase combustion object of this invention are expressly
contemplated.
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Thus, it is contemplated Applicant's metals are substitutents in
the fuel, itself, which may also contain certain non-metals and their
derivative compounds, including but not limited to nitrogen, sulfur,
fluorine, chlorine, helium, neon, argon, krpton, xenon, or radon, in
combination with dialkyl carbonates. These non-metals, and their
derivative compound, may be employed with or without any other
contemplated metals. It is further contemplated to substitute or mix
these non-metallics with non-metallics, with metaliics, or to mix
metallics with metallics, etc., to achieve synergistic improvements in
heat releases, burning velocity, thermal efficiency, emission reductions,
power generation) and the like. This is set forth below in the practice of
trimethoxymethylsilane. However, it is contemplated that Applicant's
fuel also be absent any metal or non-metal. That is, Applicant's
invention) by accelerating burning velocity and/or increasing latent heat
of vaporization, adn/or reducing combustion temperatures by fuel
substituent tailoring, chemical and/or mechanical means, as set forth
herein or in my co-pending Applications, said fuel can be employed
absent either DMC or a metallic or non-metallic.
in accordance with this invention, Applicant's fuels will contain
that amount of at least non-lead metallic) which constitutes a
combustion improving amount consistent with the fuel composition)
stoichiometry, combustion system, efficiencies, fuel economy and
power desired, as well as legal and/or environmental considerations.
It is expressly contemplated that Applicant's metallics be
incorporated into liquid fuel systems by means of mutual solvents,
mutual dispersents/solvents, colloidal media, suspension media, or
other known means, or being separately injected. Metallic's, which are
solid at ambiant temperatures may be introduced into the
combustor/combustion chamber by liquidification or gasification means.
It is preferred the metallics of this invention be relatively
inexpensive to manufacture on a mass production basis.
The metal and concentration amounts are to be optimized, such
that vapor phase combustion results. Thus, the metal and its optimum
concentration amount, is an amount that results in vapor phase
combustion, which is evidenced by improved fuel economy, emissions,
power, etc. In the practice of this invention, the ratio of dialkyl
carbonates (DMC) by weight to elemental metal weight concentration is
equal to or less than 10,000:1 (by parts) to 1:1, including from
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1, 000, 000:1, 100, 000:1, 50, 000:1, 25, 000:1, 15, 000:1, 10, 000:1,
5) 000:1, 1, 000:1, 500:1, 300:1, 200:1, 150:1, 100:1, 90:1, 80:1, 75:1,
70:1, 60:1, 50:1, 40:1, 30:1, 20:1, 10:1, 5:1 to 3:1, or interval ratio
contained therein (e.g. 50:1 to 30:1 ) and also 1:1 to 1:20, or other ratio
that maximizes vapor phase combustion.
Metallic salts may be employed in fuels at 0.01 to 4000.0 parts
metallic per million fuel, 1.0 to 150 ppm metallic being contemplated,
with concentrations equal or less than 50.0, 40.0, 30.0, 20.0, 16.0,
10.0, 5.0 ppm metallic also contemplated. Other salt concentrations
will vary from 0.10 to 75.0 ppm metal per million, from 30.0 to 2000.0
per million, from 25 to 750 parts metallic or salt per million fuel. In the
application of Applicant's invention elemental metal concentrations
from 3.0 to 500.0 ppm metal are expressly contemplated and desirable.
Concentrations outside these ranges are contemplated.
It has been found that higher oxygen weight concentrations in
fuel compositions, particularly with higher concentrations of enhanced
combustion properties, permit higher acceptable metallic
concentrations. Higher average fuel densities are also associated with
higher acceptable metallic concentrations and higher exhaust
velocities, and are preferred. Engine combustion thermal dynamics
and stoichiometry dictate upper metallic limits.
As noted above, elemental metallic concentrations will vary
substantially. Non-limiting examples include elemental metallic
concentrations equal to or greater than 1/64 grams/gal) preferably 1.0
or more grams/gal, more preferably 10 or more grams/gal, even up to
90 grams/gal. Indeed, in advance aviation, rocket and/or propellant
applications, elemental metal concentrations can be on the order of
100 to 1000 or more grams/gal, especially in hypergolic conditions.
Concentrations above these ranges are also contemplated. Ali
combustion improving or stoichiometric amounts of elemental metal are
contemplated, which maximize combustion so long as the resultant
fuel's burning velocity increases compared to fuel absent metallic.
Thus, metallic concentrations that maximize combustion velocity
and/or other objects of this invention are expressly contemplated.
Ranges will vary depending upon the specific metallic, its
concentration, concentration and type of dialkyl carbonate,
concentration and nature of hydrocarbon fuel composition, including its
density, the intended application, relevant thermodynamics, extent
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combustion systems are modified to enhance the accelerated low
temperature high energy nature of Applicant's invention, environmental
regulation, and the like. Metallics used in the fuel compositions of the
present invention should be fuel soluble generally having melting and
boiling ranges compatible with liquid hydrocarbons, or be incorporated
into liquid fuel systems by means of mutual solvents, dispersants, or
other means, as required. Alternatively, the metallics may be
introduced into the combustor/combustion chamber of liquide or
gaseous fuels (e.g. natural gas) by separate means, including separate
injection, liquidification or gasification, colloidal media, suspension
media. Metallics may be introduced into the combustor in an atomized,
vaporized, or gasified form, separately and/or in combination with the
other ingredients of the invention.
In solid fuel applications, the metallic may be introduced as a
solid. In hybrid applications, it may be introduced as either as solid,
liquid or gas, together with the balance of the invention's ingredients.
Most preferably, the metallic is employed as a propellant or co-
propellant, or jointly together with a propellant. Hydrogen content of
the metallic andlor metallic containing fuel should be maximized, to the
extent possible.
It is preferred practice that metals herein have oxides whose
heats of formation are negative, and should be equal or exceed (e.g.
be more negative) about -10,000 to -75,000 calories/mole. More
preferred are those equal or exceeding -100,000 to -400,000 gr
calories/mole, and greater (more negative). Acceptable simple oxides
containing one or two oxygens may have heats of formation equal or
exceeding -50,000 to -200,000, or greater, calories/mole.
It is also desirable the element metal employed in this invention
be of a low relative molecular weight. Acceptable metals have
molecular weights of 100 or less, preferably 79 or less, more preferably
40 or less, and most preferably 30 or less.
Applicant's fuel may include gaseous and solid metals and/or
their related compounds. It is preferred the combustion products of the
metals be environmentally friendly, e.g. low or no toxicity. Potassium,
sodium) magnesium, lithium) born, silicon, sodium, iron, copper)
calcium) aluminum, and phosphorus are acceptable. Potassium,
sodium, magnesium, lithium, born, silicon, sodium, iron, and
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phosphorus are also acceptable. The related high energy combustible
compounds of these metals are beleive to be environmentally friendly.
Applicant's metals also include a full range of combustion
catalysts including ferrous picrate, potassium salts, Li and LH
promoters. As presented below trimethoxymethyisilane has immediate
application in instant invention and is preferred.
As noted, Applicant's invention, by accelerating burning velocity
and/or reducing combustion temperatures by fuel substituent tailoring,
chemical and/or mechanical means as set forth in above PCT
Applications, can be employed absent a metallic.
Any example or disclosure of Mn may be substituted for any
metal or derivative compound set forth in herein, under proviso said
metallic causes vapor phase combustion. Likewise, wide latitude in
metal substitution is contemplated. Thus, any metal, metalloid, or non-
metal, may be substituted with any other in a particular metallic
compound. That is not to say substitution is blind, but rather if the
element is likely to be advantageously impacted, it may be substituted.
Thus, non-leaded elements and their compounds, may be freely
substituted for one another, herein.
It is preferred that metals in the fuel composition of the present
invention, including oxygenated metallic compounds, contribute to the
fuel's heat of vaporization, its burning velocity, post ignition and pre-
combustion temperatures which enhance generation and combustion of
free radicals, thermal stability at ambient temperature, and have high
heat and energy releasing characteristics, etc.
METALLIC CATALYST PRACTICE
!n the practice of this invention, it has been found that
combustion activity employing Applicant's dialkyl carbonates and
metallics, which together yield vapor phase combustion, can be
improved by the addition of trimethoxymethylsilane or substitute. As
contemplated herein any reference to trimethoxymethylsilane ("TMMS")
or metallic catalyst in the specification or examples herein
contemplates TMMS substitution, as set forth below.
Applicant has discovered TMMS to be a catalyst, when in
combination with a large population of metallics disclosed herein, and
acts to benefically improve the overall results of this invention.
TMMS is a desireable co-metallic of this invention. Its use is
contemplated with a majority of the metallics, which may be utilized in
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the practice of this invention, including cyclomatic metallics, alkali
metal alkanols, inorganic metallics such as the metallic hexacyanides,
etc. Thus, it is an embodiment herein that disclose to any metallic also
includes TMMS as a co-metallic.
Non-limiting examples of TMMS substitutes include those
compounds, including metallic and non-metallic organics, whose
structure is similar to TMMS's, thus including derivative, analogue,
homologue and isomers of TMMS. Other subsitutes are also
contemplated. Specific non-limiting examples include,
ethoxytrimethylsilane, isobutyltriethoxysilane, tetramethylsilane,
dimethoxy-methyl-vinyl- silane, methyltriethoxysilane, 3-aminopropyl-
triethoxysilane, 3- aminopropyl-trimethoxysilane, vinyltrimethoxysilane,
diethoxydimethylsilane, dimethoxydimethylsilane, vinyltris(2-
butyldenaminooxy)silane, tetraalkyloxysilanes (e.g. tetramethoxysilane)
tetraethoxysilane, tetrapropyloxysilane, tetraisopropylsilane,
tetraisobutylsilane, etc.), dialkylphosphites (e.g. dimethylphosphite,
dipropylphosphite, diethylphosphite, dibutylphosphite, di-tert-
butylphosphite, etc.), trialkylphosphites (e.g. trimethylphosphite,
triethylphosphite, triisopropylphosphite, tributylphosphite),
dimethylmethylphosphonate, diethylmethylphosphonate, potassium
pryophosphite, trimethylorthoacetate, triethylorthoacetate,
trimethylorthobutyrate, triethylorthobutyrate, trimethylorthovalerate,
trimethylorthoformate, including homolgues, analogues, isomers, and
derivatives thereof.
The examples of aforementioned PCT Applications are
incorporated herein and are optionally modified for pH limitation, non-
manganese metallics, and addition of a co-metallic catalyst. They are
also optionally modifed for the viscosity, burning velocity, and enthalpy
of vaporization limitations contained either therein or herein.
A vapor phase method of the present invention for combusting a
metallic includes the steps of introducing kinetic free radicals into a
combustor from a dialkyl carbonate (dimethyl carbonate); igniting and
combusting a flammable metallic or metal compound in presence of
said free radicals at temperature below said metal's oxide boiling point
and preferably above said metal or metallic compound's boiling point;
combusting said metal; whereby accelerated burning occurs, evidenced
by a brilliant luminous reaction zone extending some distance from the
metal's surface; and wherein metallic oxide particles resulting from
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combustion range in low to submicron range and/or remain in a
gaseous state. Contemplated metallics include ail non-lead metals and
their related compounds whose combustion product has negative high
heat of formation. As provided herein metals also refer to non-metals.
Contemplated compounds of said elemental metals are those with have
high heats of combustion. Metallics may be organo-metallics or
inorganic compounds.
By way of further example, a fuel composition of the present
invention may include a combustion improving amount of a lower
dialkyl carbonate; a combustion improving amount of at least one high
heating (exceeding 2,000 to 8,000 to 12,000, or more, Kcal/kg)
combustible compound containing at least one element selected from
the group consisting of aluminum, boron, bromine, bismuth, beryllium,
calcium, cesium, chromium, cobalt, copper, francium, gallium,
germanium, iodine, iron, indium, lithium, magnesium, manganese,
molybdenum, nickel, niobium, phosphorus, potassium, palladium,
rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon, vanadium,
strontium, barium, radium, scandium) yttrium, lanthanum, actinium,
cerium, thorium) titanium, zirconium, hafium, praseodymium,
protactinium, tantalum, neodyium) uranium, tungsten, promethium)
neptunium, samarium, plutonium, ruthenium, osmium, europium,
americium, rhodium, iridium, gadolinium, curium, platinum, terbium,
berkelium, silver) gold, dysprosium, californium, cadmium, mercury,
holmium, titanium, erbium) thulium, arsenic, antimony, ytterbium)
selenium, tellurium, polonium, lutetium, astatine, mixture thereof,
including organic and inorganic derivatives (as set forth above). Said
fuel optionally containing hydrogen or a viscous hydrocarbon base fuel,
an oxidizer, or a co-metallic catalyst (as set forth above). Said fuel
further characterized as having a pH of 10.5 or less. When this fuel
composition contains a hydrocarbon base, said base may have a
viscosity outside normal industry standards (as set forth above).
However, resultant fuel's viscosity is to be within industry standards.
Said result fuel is characterized as being a vapor phase composition
wherein a luminous reaction zone extends from surface of said
element) typically evidenced by increased fuel economy, range, thrust,
emissions, or power, as compared to the hydrocarbon base alone.
By further example, a method is contemplated for minimizing
hydrolysis of a fuel compositions comprising the steps of: providing or
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introducing a symmetrical lower dialkyl carbonate to a combustion
improving amount of at one least metal or non-metal as set forth above
(combustible compound) containing at least one element selected from
the group consisting of aluminum, boron, bromine, bismuth, beryllium,
calcium, cesium, chromium) cobalt, copper, francium, gallium,
germanium, iodine, iron, indium, lithium, magnesium, manganese,
molybdenum, nickel, niobium, phosphorus, potassium, palladium,
rubidium, sodium, tin, zinc, praseodymium) rhenium, silicon, vanadium,
strontium, barium, radium, scandium, yttrium, lanthanum, actinium,
cerium, thorium, titanium, zirconium, hafium, praseodymium,
protactinium, tantalum, neodyium, uranium, tungsten, promethium,
neptunium, samarium, plutonium, ruthenium, osmium, europium,
americium, rhodium, iridium, gadolinium, curium, platinum, terbium,
berkelium, silver, gold, dysprosium, californium, cadmium, mercury,
holmium, titanium, erbium, thulium, arsenic, antimony, ytterbium,
selenium, tellurium, polonium, lutetium, astatine, mixture thereof,
including their organic and inorganic derivative compounds, then
adding a hydrocarbon, including those whose viscosity is greater than
acceptable industry standards; mixing said carbonate, said combustible
compound, and said hydrocarbon so as to produce a fuel composition
having a pH of less than 11 (more preferrable ranges set forth above),
which has acceptable viscosities, can be stored at average
temperatures of 95°F or 65°F for up to 6 or 9 months, absent
hydrolysis, and which is a vapor phase composition having upon
combustion a luminous reaction zone that extends from surface of said
combustible compound/element.
Those skilled in the art will appreciate that many variations and
modifications of the invention disclosed herein may be made without
departing from the spirit and scope thereof.
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