Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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O1 POLYALKYLPHENOXYAMINOALKANES
02 AND FUEL COMPOSITIONS CONTAINING THE SAME
03
04 BACKGROUND OF THE INVENTION
05
06 Field of the Invention
07
Og This invention relates to novel
Og polyalkylphenoxyaminoalkanes. In a further aspect,
this invention relates to the use of these compounds
il in fuel compositions to prevent and control engine deposits.
12
13 Description of the Related Art
14
It is well known that automobile engines tend to form
16 deposits on the surface of engine components, such as
1~ carburetor parts, throttle bodies, fuel injectors, intake
18 ports and intake valves, due to the oxidation and
1g polymerization of hydrocarbon fuel. These deposits, even
when present in relatively minor amounts, often cause
21 noticeable driveability problems, such as stalling and poor
22 acceleration. Moreover, engine deposits can significantly
23 increase an automobile's fuel consumption and production of
24 exhaust pollutants. Therefore, the development of effective
fuel detergents or "deposit control" additives to prevent or
26 control such deposits is of considerable importance and
2~ numerous such materials are known in the art.
28
2g For example, aliphatic hydrocarbon-substituted phenols are
known to reduce engine deposits when used in fuel
31 compositions. U.S. Patent No. 3,849,085, issued
32 November 19, 1974 to Kreuz et al., discloses a motor fuel
33 composition comprising a mixture of hydrocarbons in the
34 gasoline boiling range containing about 0.01 to 0.25 volume
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O1 percent of a high molecular weight aliphatic
02 hydrocarbon-substituted phenol in which the aliphatic
03 hydrocarbon radical has an average molecular weight in the ~
04 range of about 500 to 3,500. This patent teaches that
05 gasoline compositions containing minor amounts of an
06 aliphatic hydrocarbon-substituted phenol not only prevent or ~
07 inhibit the formation of intake valve and port deposits in a
Og gasoline engine, but also enhance the performance of the
pg fuel composition in engines designed to operate at higher
operating temperatures with a minimum of decomposition and
11 deposit formation in the manifold of the engine.
12
13 U.S. Patent No. 4,259,086, issued March 31, 1981 to
14 Machleder et al., discloses a detergent additive for fuels
and lubricating oils which comprises the reaction product of
16 an aliphatic hydrocarbon-substituted phenol, epichlorohydrin
17 and a primary or secondary monoamine or polyamine. In
ig addition, U.S. Patent No. 4,048,081, issued September 13,
ig. 1977 to Machleder et al., discloses a detergent additive for
gasoline which is the reaction product of a polyisobutene
21 phenol with epichlorohydrin, followed by amination with
22 ethylene diamine or other polyamine.
23 .
24 Similarly, U.S. Patent No. 4,134,846, issued January 16,
19'19 to Machleder et al., discloses a fuel additive
26 composition comprising a mixture of (1) the reaction product
27 of an aliphatic hydrocarbon-substituted phenol,
2g epichlorohydrin and a primary or secondary mono- or
2g polyamine, and (2) a polyalkylene phenol. This.patent
teaches that such compositions show excellent carburetor,
31 induction system and combustion chamber detergency and, in
32 addition, provide effective rust inhibition when used in
33 hydrocarbon fuels at low concentrations.
34
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O1 wino phenols are also known to function as
02 detergents/dispersants, antioxidants and anti-corrosion
~ 03 agents when used in fuel compositions. U.S. Patent
04 No. 4,320,021, issued March 16, 1982 to R. M. Lange, for
z 05 example, discloses amino phenols having at least one
06 substantially saturated hydrocarbon-based substituent of at
07 least 30 carbon atoms. The amino phenols of this patent are
Og taught to impart useful and desirable properties to
Og oil-based lubricants and normally liquid fuels.
11 In addition, polybutlyamines have been taught to be useful
12 for preventing deposits in the intake system of internal
13 combustion engines. For example, U.S. Patent No. 4,832,702,
14 issued May 23, 1989 to Kummer et al., discloses fuel and
lubricant compositions containing polybutly or
16 Poiyisobutylamine additives prepared by hydroformulating a
17 polybutene or polyisobutene and then subjecting the
1g resulting oxo product to a Mannich reaction or amination
19 under hydrogenating conditions.
21 Polyether amine fuel additives are also well known in the
22 art for the prevention and control of engine deposits.
23 These polyether additives have a polyoxyalkylene "backbone",
24 i.e., the polyether portion of the molecule consists of
repeating oxyalkylene units. U.S. Patent No. 4,191,537,
26 issued March 4, 1980 to Lewis et al., for example, discloses
27 a fuel composition comprising a major portion of
2g hydrocarbons boiling in the gasoline range and from 30 to
2g 2,000 ppm of a hydrocarbyl polyoxyalkylene aminocarbamate
having a molecular weight from about 600 to 10,000, and at
31 least one basic nitrogen atom. The hydrocarbyl
32 polyoxyalkylene moiety is composed of oxyalkylene units
33 having from 2 to 5 carbon atoms in each oxyalkylene unit.
34 These fuel compositions are taught to maintain the
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O1 cleanliness of intake systems without contributing to
02 combustion chamber deposits.
03
04 Aromatic compounds containing a poly(oxyalkylene) moiety are
05 also known in the art. For example, the above-mentioned U.S.
06 Patent No. 4,191,537, discloses alkylphenyl
07 poly(oxyalkylene) polymers which are useful as intermediates
Og in the preparation of alkylphenyl poly(oxyalkylene)
Og aminocarbamates.
11 Similarly, U.S. Patent No. 4,881,945, issued November 21,
12 1989 to Buckley, discloses a fuel composition comprising a
13 hydrocarbon boiling in the gasoline or diesel range and from
14 about 3o to about 5,000 parts per million of a fuel soluble
alkylphenyl polyoxyalkylene aminocarbamate having at least
16 one basic nitrogen and an average molecular weight of about
17 800 to 6,000 and wherein the alkyl group contains at least
1g 40 carbon atoms.
19
U.S. Patent No. 5,112,364, issued May 12, 1992 to Rath et
21 al., discloses gasoline-engine fuels which contain small
22 amounts of a polyetheramine and/or a polyetheramine
23 derivative, wherein the polyetheramine is prepared by
24 reductive amination of a phenol-initiated or alkylphenol-
initiated polyether alcohol with ammonia or a primary amine.
26
27 European Patent Application Publication No. 310,875,
2g published April 12, 1989 discloses fuels for spark ignition
2g engines containing a polyetheramine additive prepared by
first propoxylating and/or butoxylating an alkanol or
31 primary or secondary alkylmonoamine and then aminating the
32 resulting polyether with ammonia or a primary aliphatic
33 amine.
34
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01 French Patent No. 2,105,539, published April 28, 1972,
02 discloses carburetor detergent additives which are
03 phenoxypropylamines which may be substituted with up to five
04 hydrocarbon radicals of 1 to 30 carbon atoms on the aromatic
05 ring. This patent also discloses additives obtained by
06 reacting such phenoxypropylamines with alkylphosphoric
07 acids.
08
Og SUNadARY OF THE INVENTTON
il I have now discovered certain polyalkylphenoxyaminoalkanes
12 which provide excellent control of engine deposits,
13 especially intake valve deposits, when employed as fuel
14 additives in fuel compositions.
16 The compounds of the present invention include those having
17 the following formula and fuel soluble salts thereof:
18
19
, i 1 ~2
21 R O-CH-CH-A (I)
22
23 .
24 wherein R is a polyalkyl group having an average molecular
weight in the range of about 600 to 5,000;
26
27 Rl and R2 are independently hydrogen or lower alkyl having 1
2g to 6 carbon atoms; and
29
A is amino, N-alkyl amino having about 1 to about 20 carbon
31 atoms in the alkyl group, N,N-dialkyl amino having about 1
' 32 to about 20 carbon atoms in each alkyl group, or a polyamine
33 moiety having about 2 to about 12 amine nitrogen atoms and
' 34 about 2 to about 40 carbon atoms.
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01 The present invention further provides a fuel composition
02 comprising a major amount of hydrocarbons boiling in the
03 gasoline or diesel range and a deposit-controlling effective
04 amount of a compound of the present invention.
05
06 The present invention additionally provides a fuel
07 concentrate comprising an inert stable oleophilic organic
Og solvent boiling in the range of from about 150°F. to
400°F.
p9 and from about 10 to 70 weight percent of a compound of the
present invention.
11
Z2 Among other factors, the present invention is
13 based on the surprising discovery that certain
14 polyalkylphenoxyaminoalkanes provide excellent
y5 control of engine deposits, especially on intake valves,
16 when employed as additives in fuel compositions.
17
18 DETAILED DESCRIPTION OF THE INVENTION
19
The polyalkylphenoxyaminoalkanes of the present invention
21 have the general formula:
22
23 ~ f z i2
24 R O-CH-CH-A (I)
26
27 wherein R, R~, R2 and A are as defined above.
28
29 preferably, R is a polyalkyl group having an average
molecular weight in the range of about 600 to 3,000, more
31 preferably about 700 to 3,000, and most preferably about 900
32 to 2,500.
33
34
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O1 ~'referably, one of R2 and RZ is hydrogen or lower alkyl of 1
02 to 4 carbon atoms, and the other is hydrogen. More
- 03 preferably, one of Rl and R2 is hydrogen, methyl or ethyl,
04 and the other is hydrogen. Most preferably, R2 is hydrogen,
05 methyl or ethyl, and Rl is hydrogen.
06
07 In general, A is amino, N-alkyl amino having from about 1 to
Og about 20 carbon atoms in the alkyl group, preferably about 1
Og to about 6 carbon atoms, more preferably about 1 to about 4
carbon atoms; N,N-dialkyl amino having from about 1 to about
11 20 carbon atoms in each alkyl group, preferably about 1 to
12 about 6 carbon atoms, more preferably about 1 to about 4
13 carbon atoms; or a polyamine moiety having from about 2 to
14 about 12 amine nitrogen atoms and from about 2 to about 40
carbon atoms, preferably about 2 to 12 amine nitrogen atoms
16 and about 2 to 24 carbon atoms. More preferably, A is amino
17 or a polyamine moiety derived from a polyalkylene polyamine,
lg including alkylene diamine. Most preferably, A is amino or
19 a polyamine moiety derived from ethylene diamine or
diethylene triamine.
21
22 It is preferred that the R substituent is located at the
23 mete or, more preferably, the pare position on the aromatic
24 ring, i.e., pare or mete relative to the ether group.
26 The compounds of the present invention will generally have a
27 sufficient molecular weight so as to be non-volatile at
2g normal engine intake valve operating temperatures (about
29 200°-250°C.). Typically, the molecular weight of the
compounds of this invention will range from about 70o to
31 about 3,500, preferably from about 700 to about 2,500.
32
33
34
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_g_
O1 Fuel-soluble salts of the compounds of formula I can be
02 readily prepared for those compounds containing an amino or
03 substituted amino group and such salts are contemplated to ,
04 be useful for preventing or controlling engine deposits.
05 Suitable salts include, for example, those obtained by
06 protonating the amino moiety with a strong organic acid,
p7 such as an alkyl- or arylsulfonic acid. Preferred salts are
Og derived from toluenesulfonic acid and methanesulfonic acid.
09
Definitions
11
12 As used herein, the following terms have the following
13 meanings unless expressly stated to the contrary.
14
The term "amino" refers to the group: -NH2.
16
17 The term "N-alkylamino" refers to the group: -NHRa wherein
lg Ra is an alkyl group. The term "N,N-dialkylamino'° refers to
19 the group: -ilRbR~, wherein Rb and R~ are alkyl groups.
21 The term "hydrocarbyl" refers to an organic radical
22 primarily composed of carbon and hydrogen which may be
23 aliphatic, alicyclic, aromatic or combinations thereof,
24 e.g., aralkyl or alkaryl. Such hydrocarbyl groups are
generally free of aliphatic unsaturation, i.e., olefinic or
26 acetylenic unsaturation, but may contain minor amounts of
27 heteroatoms, such as oxygen or nitrogen, or halogens, such
28 as chlorine.
29
The term '°alkyl" refers to both straight- and branched-chain
31 alkyl groups.
32
33
34
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01 The term "lower alkyl" refers to alkyl groups having 1 to
02 about 6 carbon atoms and includes primary, secondary and
03 tertiary alkyl groups. Typical lower alkyl groups include,
04 for example, methyl, ethyl, n-propyl, isopropyl, n-butyl,
05 sec-butyl, t-butyl, n-pentyl, n-hexyl and the like.
06
The term "polyalkyl" refers to an alkyl group which is
Og generally derived from polyolefins which are polymers or
Og copolymers of mono-olefins, particularly 1-mono-olefins,
lp such as ethylene, propylene, butylene, and the like.
11 Preferably, the mono-olefin employed will have 2 to about
12 24 carbon atoms, and more preferably, about 3 to 12 carbon
13 atoms. More preferred mono-olefins include propylene,
14 butyiene, particularly isobutylene, 1-octene and 1-decene.
15 Polyolefins prepared from such mono-olefins include
16 polypropylene, polybutene, especially polyisobutene, and the
1~ polyalphaolefins produced from 1-octene and 1-decene.
18
lg The term "fuel" or "hydrocarbon fuel" refers to normally
20 liquid hydrocarbons having boiling points in the range of
21 gasoline and diesel fuels.
22
23 General Synthetic Procedures
24
25 The polyalkylphenoxyaminoalkanes of this invention may be
26 prepared by the following general methods and procedures.
2~ It should be appreciated that where typical or preferred
2g process conditions (e. g., reaction temperatures, times, mole
2g ratios of reactants, solvents, pressures, etc.}. are given,
30 other process conditions may also be used unless otherwise
31 stated. Optimum reaction conditions may vary with the
32 particular reactants or solvents used, but such conditions
33 can be determined by one skilled in the art by routine
' 34 optimization procedures.
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O1 Those skilled in the art will also recognize that it may be
02 necessary to block or protect certain functional groups
03 while conducting the following synthetic procedures. In
04 such cases, the protecting group will serve to protect the
05 functional group from undesired reactions or to block its
06 undesired reaction with other functional groups or with the
07 reagents used to carry out the desired chemical
Og transformations. The proper choice of a protecting group
O9 for a particular functional group will be readily apparent
to one skilled in the art. Various protecting groups and
11 their introduction and removal are described, for example,
12 in T. W. Greene and P. G. M. Wuts, Protective Groups in
13 Organic Synthesis, Second Edition, Wiley, New York, 1991,
14 and references cited therein.
16 Synthesis
17
lg The polyalkylphenoxyaminoalkanes of the present invention
lg may be prepared by a process which initially involves
hydroxyalkylation of a polyalkylphenol of the formula:
21
22
23 . R OH (II)
24
26 wherein R is as defined herein, with an alkylene carbonate
2~ of the formula:
28
O
29
31 (III)
32
33 Rl R2
34
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O1 wherein Rl and RZ
are as defined herein,
in the presence
of
02 a catalytic amount
of an alkali metal
hydride or hydroxide,
03 or alkali metal salt,
to provide a polyalkylphenoxyalkanol
04 of the formula:
_ 05
06 i 1 12
R O-C
C
O
IV
07 )
H-
H-
H (
08
09
wherein R, R1 and
R2 are as defined
herein.
11
The polyalkylphenols
of formula II are
well known materials
12
and are typically
prepared by the
alkylation of phenol
with
13
the desired polyolefin
or chlorinated polyolefin.
A further
14
discussion of polyalkylphenols
can be found, for
example, in
US. Patent No. 4,744,921
and U.S. Patent
No. 5,300,701.
16
17
Accordingly, the
polyalkylphenols
of formula II may
be
18
prepared from the
corresponding olefins
by conventional
19
procedures. For example,
the polyalkylphenols
of formula II
above may be prepared
by reacting the
appropriate olefin
or
21
olefin mixture with
phenol in the presence
of an alkylating
22
catalyst at a temperature
of from about 25C.
to 150C., and
23
preferably 30C. to
100C. either neat
or in an essentially
24
inert solvent at
atmospheric pressure.
A preferred
alkylating catalyst
is boron trifluoride.
Molar ratios of
26
reactants may be
used. Alternatively,
molar excesses of
27
phenol can be employed,
i.e., 2 to 3 equivalents
of phenol
28
for each equivalent
of olefin with unreacted
phenol
29
recycled. The latter
process maximizes
monoalkylphenol.
Examples of inert
solvents include
heptane, benzene,
31
toluene, chlorobenzene
and 250 thinner
which is a mixture
of
32
aromatics, paraffins
and naphthenes.
33
34
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1 The polyalkyl substituent on the polyalkylphenols employed in
2 the invention is generally derived from polyolefins which are
3 polymers or copolymers of mono-olefins, particularly 1-mono-
4 olefins, such as ethylene, propylene, butylene, and the like.
Preferably, the mono-olefin employed will have 2 to about 24
6 carbon atoms, and more preferably, about 3 to 12 carbon atoms.
7 More preferred mono-olefins include propylene, butylene,
8 particularly isobutylene, 1-octene and 1-decene. Polyolefins
9 prepared from such mono-olefins include polypropylene,
polybutene, especially polyisobutene, and the polyalphaolefins
11 produced from 1-octene and 1-decene.
12
13 The preferred polyisobutenes used to prepare the presently
14 employed polyalkylphenols are polyisobutenes which comprise at
least about 20% of the more reactive methylvinylidene isomer,
16 preferably at least 50% and more preferably at least 70%.
17 Suitable polyisobutenes include those prepared using BF3
18 catalysts. The preparation of such polyisobutenes in which the
19 methylvinylidene isomer comprises a high percentage of the
total composition is described in U.S. Patent Nos. 4,152,499
21 and 4,605,808. Such polyisobutenes, known as "reactive"
22 polyisobutenes, yield high molecular weight alcohols in which
23 the hydroxyl group is at or near the end of the hydrocarbon
24 chain. Examples of suitable polyisobutenes having a high
alkylvinylidene content include Ultravis 30, a polyisobutene
26 having a number average molecular weight of about 1300 and a
27 methylvinylidene content of about 74%, and UltravisTM 10, a
28 polyisobutene having a number average molecular weight of
29 about 950 and a methylvinylidene content of about 76%, both
available from British Petroleum.
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01 The alkylene carbonates of formula III are known compounds
02 which are available commercially or can be readily prepared
03 using conventional procedures. Suitable alkylene carbonates
04 include ethylene carbonate, propylene carbonate, 1,2-
05 butylene carbonate, 2,3-butylene carbonate, and the like. A
06 preferred alkylene carbonate is ethylene carbonate.
07
Og The catalyst employed in the reaction of the polyaklyphenol
Og and alkylene carbonate may be any of the well known
hydroxyalkylation catalysts. Typical hydroxyalkylation
11 catalysts include alkali metal hydrides, such as lithium
12 hydride, sodium hydride and potassium hydride, alkali metal
13 hydroxides, such as sodium hydroxide and potassium
14 hydroxide, and alkali metal salts, for example, alkali metal
halides, such as sodium chloride and potassium chloride, and
16 alkali metal carbonates, such as sodium carbonate and
17 potassium carbonate. The amount of catalyst employed will
lg generally range from about 0.01 to 1.0 equivalent,
1g. preferably from about 0.05 to 0.3 equivalent.
21 The polyalkylphenol and alkylene carbonate are generally
22 reacted in essentially equivalent amounts in the presence of
23 the hydroxyalkylation catalyst at a temperature in the range
24 of about 100°C. to 210°C., and preferably from about
150°C.
to about 170°C. The reaction may take place in the presence
26 or absence of an inert solvent.
27
2g The time of reaction will vary depending on the particular
2g alkylphenol and alkylene carbonate reactants, the catalyst
used and the reaction temperature. Generally, the reaction
31 time will range from about two hours to about five hours.
32 The progress of the reaction is typically monitored by the
33 evolution of carbon dioxide. At the completion of the
3 4 -
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O1 reaction, the polyalkylphenoxyalkanol product is isolated
02 using conventional techniques.
03 _
04 The hydroxyalkylation reaction of phenols with alkylene
05 carbonates is well known in the art and is described, for -
06 example, in U.S. Patent Nos. 2,987,555; 2,967,892; 3,283,030
and 4,341,905.
OS
Og Alternatively, the polyalkylphenoxyalkanol product of
formula IV may be prepared by reacting the polyalkylphenol
11 of formula II with an alkylene oxide of the formula:
12
13 ~O
14
R1-CH CH-R2 (V)
16
1~ wherein R1 and R2 are as defined herein, in the presence of
ig a hydroxyalkylation catalyst as described above.
19
Suitable alkylene oxides of formula V include ethylene
21 oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene
22 oxide, and the like. A preferred alkylene oxide is ethylene
23 oxide.
24
In a manner similar to the reaction with alkylene carbonate,
26 the polyalkylphenol and alkylene oxide are reacted in
2-7 essentially equivalent or equimolar amounts in the presence
2g of 0.01 to 1.0 equivalent of a hydroxyalkylation catalyst,
2g such as sodium or potassium hydride, at a temperature in the
range of about 30°C. to about 150°C., for about 2 to about
31 24 hours. The reaction may be conducted in the presence or
32 absence of a substantially anhydrous inert solvent. '
33 Suitable solvents include toluene, xylene, and the like.
34 Generally, the reaction is conducted at a pressure
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O1 sufficient to contain the reactants and any solvent present,
02 typically at atmospheric or higher pressure. Upon
03 completion of the reaction, the polyalkylphenoxyalkanol is
04 isolated by conventional procedures.
05
06 The polyalkylphenoxyalkanol of formula IV is subsequently
07 reacted, either directly or through an intermediate, with an
Og appropriate amine to provide the desired
Og polyalkylphenoxyaminoalkanes of formula T. Suitable amine
reactants which may be employed to form the amine component,
11 i.e., substituent A, of the polyalkylphenoxyaminoalkanes of
12 the present invention are discussed more fully below.
13
lg The Amine Component
16 In general, the amine component of the present
17 polyalkylphenoxyaminoalkanes will contain an average of at
lg least about one basic nitrogen atom per molecule. A "basic
19 nitrogen atom" is one that is titratable by a strong acid,
for example, a primary, secondary, or tertiary amine
21 nitrogen; as distinguished from, for example, an carbamyl
22 nitrogen, e.g., -OC(O)NH-, which is not titratable with a
23 strong acid. Preferably, at least one of the basic nitrogen
24 atoms of the amine component will be primary or secondary
amine nitrogen, more preferably, at least one will be a
26 primary amine nitrogen.
27
2g The amine component of the polyalkylphenoxyaminoalkanes of
2g this invention is preferably derived from ammonia, a primary
alkyl or secondary dialkyl monoamine, or a polyamine having
31 a terminal amino nitrogen atom.
32
33 Primary alkyl monoamines useful in preparing compounds of
' 34 the present invention contain 1 nitrogen atom and from about
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O1 1 to about 20 carbon atoms, more preferably about 1 to 6
02 carbon atoms, most preferably 1 to 4 carbon atoms. Examples
03 of suitable monoamines include N-methylamine, N-ethylamine,
04 N-n-propylamine, N-isopropylamine, N-n-butylamine, N-
05 isobutylamine, N-sec-butylamine, N-tert-butylamine, N-n-
06 pentylamine, N-cyclopentylamine, N-n-hexylamine, N-
O~ cyclohexylamine, N-octylamine, N-decylamine, N-dodecylamine,
pg N-octadecylamine, N-benzylamine, N-(2-phenylethyl)amine, 2-
Og aminoethanol, 3-amino-1-propanol, 2-(2-aminoethoxy)ethanol,
N-(2-methoxyethyl)amine, N-(2-ethoxyethyl)amine and the
i1 like. Preferred primary amines are N-methylamine,
12 N-ethylamine and N-n-propylamine.
13
14 The amine component of the present
polyalkylphenoxyaminoalkanes may also be derived from a
16 secondary dialkyl monoamine. The alkyl groups of the
1~ secondary amine may be the same or different and will
lg generally each contain about 1 to about 20 carbon atoms,
ig more preferably about 1 to about 6 carbon atoms, most
preferably about 1 to about 4 carbon atoms. One or both of
21 the alkyl groups may also contain one or more oxygen atoms.
22
23 Preferably, the alkyl groups of the secondary amine are
24 independently selected from the group consisting of methyl,
ethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl and 2-
26 methoxyethyl. More preferably, the alkyl groups are methyl,
2~ ethyl or propyl.
28
2g Typical secondary amines which may be used in this invention
include N,N-dimethylamine, N,N-diethylamine, N,N-di-n-
31 propylamine, N,N-diisopropylamine, N,N-di-n-butylamine,
32 N,N-di-sec-butylamine, N,N-di-n-pentylamine, N,N-di-n- "
33 hexylamine, N,N-dicyclohexylamine, N,N-dioctylamine,
34 N-ethyl-N-methylamine, N-methyl-N-n-propylamine, N-n-butyl- -
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01 N-methylamine, N-methyl-N-octylamine, N-ethyl-N-
02 isopropylamine, N-ethyl-N-octylamine, N,N-di(2-
03 hydroxyethyl)amine, N,N-di(3-hydroxypropyl)amine,
04 N,N-di(ethoxyethyl)amine, N,N-di(propoxyethyl)amine and the
. 05 like. Preferred secondary amines are N,N-dimethylamine,
06 N,N-diethylamine and N,N-di-n-propylamine.
07
pg Cyclic secondary amines may also be employed to form the
Og additives of this invention. In such cyclic compounds, the
alkyl groups, when taken together, form one or more 5- or
12 6-membered rings containing up to about 20 carbon atoms.
12 The ring containing the amine nitrogen atom is generally
13 saturated, but may be fused to one or more saturated or
14 unsaturated rings. The rings may be substituted with
hydrocarbyl groups of from 1 to about 10 carbon atoms and
16 may contain one or more oxygen atoms.
17
1g Suitable cyclic secondary amines include piperidine,
19 4-methylpiperidine, pyrrolidine, morpholine,
2,6-dimethylmorpholine and the like.
21
22 Suitable polyamines can have a straight- or branched-chain
23 structure and may be cyclic or acyclic or combinations
24 thereof. Generally, the amine nitrogen atoms of such
polyamines will be separated from one another by at least
26 two carbon atoms, i.e., polyamines having an aminal
2~ structure are not suitable. The polyamine may also contain
2g one or more oxygen atoms, typically present as an ether or a
2g hydroxyl group. Polyamines having a carbon-to-nitrogen ratio
of from about 1:1 to about 10:1 are particularly preferred.
31
' 32 In preparing the compounds of this invention using a
33 polyamine where the various nitrogen atoms of the polyamine
34 are not geometrically equivalent, several substitutional
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O1 isomers are possible and each of these possible isomers is
02 encompassed within this invention.
03 _
04 A particularly preferred group of polyamines for use in the
05 present invention are polyalkylene polyamines, including
06 alkylene diamines. Such polyalkylene polyamines will
07 typically contain from about 2 to about 12 nitrogen atoms
08 and from about 2 to about 40 carbon atoms, preferably about
Og 2 to 24 carbon atoms. Preferably, the alkylene groups of
such polyalkylene polyamines will contain from about 2 to
11 about 6 carbon atoms, more preferably from about 2 to about
12 4 carbon atoms.
13
14 examples of suitable polyalkylene polyamines include
ethylenediamine, propylenediamine, isopropylenediamine,
16 butylenediamine, pentylenediamine, hexylenediamine,
17 diethylenetriamine, dipropylenetriamine,
lg dimethylaminopropylamine, diisopropylenetriamine,
lg dibutylenetriamine, di-sec-butylenetriamine,
triethylenetetraamine, tripropylenetetraamine,
21 triisobutylenetetraamine, tetraethylenepentamine,
22 pentaethylenehexamine, dimethylaminopropylamine, and
23 mixtures thereof..
24
Particularly suitable polyalkylene polyamines are those
26 having the formula:
27
28 H2N-(Rg-NH)Z-H
29
wherein Rg is a straight- or branched-chain alkylene group
31 having from about 2 to about 6 carbon atoms, preferably from
32 about 2 to about 4 carbon atoms, most preferably about 2 -
33 carbon atoms, i.e., ethylene {-CH2CH2-); and z is an integer
34 from about 1 to about 4, preferably about 1 or about 2. -
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O1 Particularly preferred polyalkylene polyamines are
02 ethylenediamine, diethylenetriamine, triethylenetetraamine,
03 and tetraethylenepentamine. Most preferred are
04 ethylenediamine and diethylenetriamine, especially
05 ethylenediamine.
06
07 Also contemplated for use in the present invention are
Og cyclic polyamines having one or more 5- to 6-membered rings.
Og Such cyclic polyamines compounds include piperazine,
2-methylpiperazine, N-(2-aminoethyl)piperazine,
11 N-(2-hydroxyethyl)piperazine, 1,2-bis-(N-piperazinyl)ethane,
12 3-aminopyrrolidine, N-(2-aminoethyl)pyrrolidine, and the
13 like. Among the cyclic polyamines, the piperazines are
14 preferred.
16 Many of the polyamines suitable for use in the present
17 invention are commercially available and others may be
1g prepared by methods which are well known in the art. For
1g example, methods for preparing amines and their reactions
are detailed in Sidgewick's 'The Organic Chemistry of
21 Nitrogen", Clarendon Press, Oxford, 1966; Noller's
22 "Chemistry of Organic Compounds", Saunders, Philadelphia,
23 2nd Ed., 1957; and Kirk-Othmer's "Encyclopedia of Chemical
24 Technology", 2nd Ed., especially Volume 2, pp. 99-116.
26 Preparation of the Polyalkylphenoxyaminoalkane
27
2g As noted above, the polyalkylphenoxyaminoalkanes of the
2g present invention may be conveniently prepared by reacting
the polyalkylphenoxyalkanol of formula IV, either directly
31 or through an intermediate, with a nitrogen-containing
' 32 compound, such as ammonia, a primary or secondary alkyl
33 monoamine, or a polyamine, as described herein.
' 34
CA 02226982 2005-08-03
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1 Accordingly, the polyalkylphenoxyalkanol of formula IV may be
2 converted to the desired polyalkylphenoxyaminoalkane by a
3 variety of procedures known in the art.
4
For example, the terminal hydroxy group on the
6 polyalkylphenoxyalkanol may first be converted to a suitable
7 leaving group, such as a mesylate, chloride or bromide, and
8 the like, by reaction with a suitable reagent, such as
9 methanesulfonyl chloride. The resulting polyalkylphenoxyalkyl
mesylate or equivalent intermediate may then be converted to a
11 phthalimide derivative by reaction with potassium phthalimide
12 in the presence of a suitable solvent, such as N,N-
13 dimethylforamide. The polyalkylphenoxyalkyl phthalimide
14 derivative is subsequently converted to the desired
polyalkylphenoxyaminoalkane by reaction with a suitable amine,
16 such as hydrazine. Alternatively, the leaving group can be
17 converted to an azide, as described, for example, in Turnbull
18 Scriven, Chemical Reviews, Volume 88, pages 297-368, 1988. The
19 azide is subsequently converted to the desired
polyalkylphenoxyaminoalkane by reduction with hydrogen and a
21 catalyst, such as palladium on carbon or a Lindlar catalyst.
22
23 The polyalkylphenoxyalkanol of formula IV may also be
24 converted to the corresponding polyyalkylphenoxyalkyl chloride
by reaction with a suitable halogenating agent, such as HCl,
26 thionyl chloride, or epichlorohydrin, followed by displacement
27 of the chloride with a suitable amine, such as ammonia, a
28 primary or secondary alkyl monoamine, or a polyamine, as
29 described, for example, in U.S. Patent No. 4,247,301 to
Honnen.
, CA 02226982 2005-11-28
-21-
1 Alternatively, the polyalkylphenoxyaminoalkanes of the
2 present invention may be prepared from the corresponding
3 polyalkylphenoxyalkanol by a process commonly referred to
4 as reductive amination, such as described in U.S. Patent
No. 5,112,364 to Rath et al. and U.S. Patent No.
6 4,332,595 to Herbstman et al.
7
8 In the reductive amination procedure, the
9 polyalkylphenoxyalkanol is aminated with an appropriate
amine, such as ammonia or a primary alkyl monoamine, in
11 the presence of hydrogen and a hydrogenation-
12 dehydrogenation catalyst. The amination reaction is
13 typically carried out at temperatures in the range of
14 about 160°C to about 250°C and pressures of about 1,000 to
about 5,000 psig, preferably about 1,500 to about 3,000
16 psig. Suitable hydrogenation-dehydrogenation catalysts
17 include those containing platinum, palladium, cobalt,
18 nickel, copper, or chromium, or mixtures thereof.
19 Generally, an excess of the ammonia or amine reactant is
used, such as about a 5-fold to about 60-fold molar
21 excess, and preferably about a 10-fold to about 40-fold
22 molar excess, of ammonia or amine.
23
24 When the reductive amination is carried out with a
polyamine reactant, the amination is preferably conducted
26 using a two-step procedure as described in commonly-
27 assigned copending European Patent Application No.
28 0781793 and titled "Reductive Amination Process for
29 Manufacturing a Fuel Additive From Polyoxybutylene
Alcohol with Ethylene Diamine". According to this
31 procedure, an appropriate alcohol is first contacted with
32 a hydrogenation-dehydrogenation catalyst at a temperature
33 of at least 230°C to provide a carbonyl-
CA 02226982 1998-O1-13
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-22-
01 containing intermediate, which is subsequently reacted with
02 a polyamine at a temperature below about 190°C in the
03 presence of hydrogen and a hydrogenation catalyst to produce
04 the desired polyamine adduct.
05
06 In an alternative procedure for preparing the
07 polyalkylphenoxyaminoalkanes of the present invention, the
Og polyalkylphenol of formula II may be reacted with an
Og aziridine of the formula:
11 R4
I2
13
14
R1-CH- H-R2 (VI)
16 wherein RI and R2 are as defined herein, and R4 is hydrogen
17 or alkyl of 1 to 20 carbon atoms. A preferred aziridine is
18 one wherein R~ is hydrogen, R2 is hydrogen, methyl or ethyl,
19 and R4 is hydrogen.
21 The reaction of aziridines with alcohols to produce beta-
22 amino ethers is well known in the art and is discussed, for
23 example, in Ham and Dermer, "Ethyleneimine and Other
24 Aziridines", Academia Press, New York, 1969, pages 224-227
and 256-257.
26
27 Fuel Compositions
28
29 The compounds of the present invention are useful as
additives in hydrocarbon fuels to prevent and control engine
31 deposits, particularly intake valve deposits. The proper
32 concentration of additive necessary to achieve the desired -
33 deposit control varies depending upon the type of fuel
34
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-23-
01 employed, the type of engine, and the presence of other fuel
02 additives.
03
04 In general, the concentration of the compounds of this
05 invention in hydrocarbon fuel will range from about 50 to
~ 06 about 2500 parts per million (ppm) by weight, preferably
07 from 75 to 1,000 ppm. When other deposit control additives
Og are present, a lesser amount of the present additive may be
Og used.
11 The compounds of the present invention may be formulated as
12 a concentrate using an inert stable oleophilic (i.e.,
13 dissolves in gasoline) organic solvent boiling in the range
14 of about 150°F. to 400°F. (about 65°C. to
205°C.).
Preferably, an aliphatic or an aromatic hydrocarbon solvent
16 is used, such as benzene, toluene, xylene or higher-boiling
17 aromatics or aromatic thinners. Aliphatic alcohols
1g containing about 3 to 8 carbon atoms, such as isopropanol,
1g isobutylcarbinol, n-butanol and the like, in combination
with hydrocarbon solvents are also suitable for use with the
21 present additives. Tn the concentrate, the amount of the
22 additive will generally range from about 10 to about
23 70 weight percent, preferably 10 to 50 weight percent, more
24 preferably from 20 to 40 weight percent.
in gasoline fuels, other fuel additives may be employed with
26 the additives of the present invention, including, for
27 example, oxygenates, such as t-butyl methyl ether, antiknock
2g agents, such as methylcyclopentadienyl manganese
2g tricarbonyl, and other dispersants/detergents, such as
hydrocarbyl amines, hydrocarbyl poly(oxyalkylene) amines,
31 hydrocarbyl poly(oxyalkylene) aminocarbamates, or
- 32 succinimides. Additionally, antioxidants, metal
33 deactivators and demulsifiers may be present.
~ 34
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01 In diesel fuels, other well-known additives can be employed,
02 such as pour point depressants, flow improvers, cetane
03 improvers, and the like.
04
05 A fuel-soluble, nonvolatile carrier fluid or oil may also be ,
06 used with the compounds of this invention. The carrier
07 fluid is a chemically inert hydrocarbon-soluble liquid
Og vehicle which substantially increases the nonvolatile
Og residue (NVR), or solvent-free liquid fraction of the fuel
additive composition while not overwhelmingly contributing
11 to octane requirement increase. The carrier fluid may be a
12 natural or synthetic oil, such as mineral oil, refined
13 petroleum oils, synthetic polyalkanes and alkenes, including
14 hydrogenated and unhydrogenated polyalphaolefins, and
synthetic polyoxyalkylene-derived oils, such as those
16 described, for example, in U.S. Patent No. 4,191,537 to
17 Lewis, and polyesters, such as those described, for example,
ig in U.S. Patent Nos. 3,756,793 to Robinson and 5,004,478 to
ig Vogel et al., and in European Patent Application
Nos. 356,726, published March 7, 1990, and 382,159,
21 published August 16, 1990.
22
23 These carrier fluids are believed to act as a carrier for
24 the fuel additives of the present invention and to assist in
removing and retarding deposits. The carrier fluid may also
26 exhibit synergistic deposit control properties when used in
27 combination with a compound of this invention.
28
29 The carrier fluids are typically employed in amounts ranging
from about 100 to about 5000 ppm by weight of the
31 hydrocarbon fuel, preferably from 400 to 3000 ppm of the
32 fuel. Preferably, the ratio of carrier fluid to deposit
33 control additive will range from about 0.5:1 to about lo: l,
34 more preferably from 1:1 to 4:1, most preferably about 2:1. '
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-25-
O1 When employed in a fuel concentrate, carrier fluids will
02 generally be present in amounts ranging from about 2o to
- 03 about 60 weight percent, preferably from 30 to 50 weight
04 percent.
05
06 PREPARATIONS AND EXAMPLES
07
Og A further understanding of the invention can be had in the
09 following nonlimiting Examples. Wherein unless expressly
stated to the contrary, all temperatures and temperature
11 ranges refer to the Centigrade system and the term "ambient"
12 or "room temperature" refers to about 20°C.-25°C. The term
13 "percent" or "%" refers to weight percent and the term
14 "mole" or "moles" refers to gram moles. The term
"equivalent" refers to a quantity of reagent equal in moles,
16 to the moles of the preceding or succeeding reactant recited
17 in that example in terms of finite moles or finite weight or
lg volume. Where given, proton-magnetic resonance spectrum
19 (p~m~r. or n.m.r.) were determined at 300 mHz, signals are
assigned as singlets (s), broad singlets (bs), doublets (d),
21 double doublets (dd), triplets (t), double triplets (dt),
22 quartets (q), and multiplets (m), and cps refers to cycles
23 per second.
24
Example 1
26
27 Preparation of Polyisobutyl Phenol
28
2g To a flask equipped with a magnetic stirrer, reflux
condenser, thermometer, addition funnel and nitrogen inlet
31 was added 203.2 grams of phenol. The phenol was warmed to
32 40°C. and the heat source was removed. Then, 73.5
33
' 34
CA 02226982 1998-O1-13
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-26-
O1 milliliters of boron trifluoride etherate was added
O2 dropwise. 1040 grams of Ultravis 10 Polyisobutene
03 (molecular weight 950, 76% methylvinylidene, available from
04 British Petroleum) was dissolved in 1,863 milliliters of
05 hexane. The polyisobutene was added to the reaction at a
06 rate to maintain the temperature between 22°C-27°C. The
07 reaction mixture was stirred far 16 hours at room
08 temperature. Then, 400 milliliters of concentrated ammonium
09 hydroxide was added, followed by 2,000 milliliters of
to hexane. The reaction mixture was washed with water (3 X
21 2,000 milliliters), dried over magnesium sulfate, filtered
12 and the solvents removed under vacuum to yield 1,056.5 grams
13 of a crude reaction product. The crude reaction product was
14 determined to contain 80% of the desired product by proton
15 NMR and chromatography on silica gel eluting with hexane,
16 followed by hexane: ethylacetate: ethanol (93:5:2).
17
18 Example 2
19
20 Preparation of
21
2 2 ~~H
23
24
26
2~ P1B {molecular weight - 950)
28
29
Potassium hydride (1.1 grams of a 35 weight percent
dispersion of in mineral oil) and 4- polyisobutyl phenol
31
32 (9g'7 grams, prepared as in Example 1) were added to a ,
flask equipped with a magnetic stirrer, reflux condensor,
33
nitrogen inlet and thermometer. The reaction was heated at
34
CA 02226982 1998-O1-13
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-27-
O1 130°C for one hour and then cooled to 100°C. Ethylene
02 carbonate (8.6 grams) was added and the mixture was heated
03 at 160°C far 16 hours. The reaction was cooled to room
04 temperature and one milliliter of isopropanol was added.
05 The reaction was diluted with one liter of hexane, washed
three times with water and once with brine. The organic
07 layer was dried over anhydrous magnesium sulfate, filtered
Og and the solvents removed in vacuo to yield 98.0 grams of the
Og desired product as a yellow oil.
to
11 Example 3
12
13 Preparation of
14
15 O~~S ~2C H3
16
17
18
19
2 0 P IB (molecular weight ~ 950)
21
22
The alcohol from Example 2 (20.0 grams), triethylamine (2.9
23
mL), and anhydrous dichloromethane (200 mL) were combined.
24
The solution was cooled to 0°C and methanesulfonyl chloride
(1.5 mL) was added dropwise. The reaction was stirred at
26
room temperture under nitrogen for 16 hours. The solution
27
was diluted with dichloromethane (600 mL) and was washed
28
twice with saturated aqueous sodium bicarbonate solution and
29
once with brine. The organic layer was dried over anhydrous
sodium sulfate, filtered and the solvents removed in vacuo
31
to yield 20.4 grams as a yellow oil.
32
33
34
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_2g_
O1 Example 4
02
03 Preparation of
04
05 H
06 O~N~NH2
07
o8
09
11 P IB (molecular weigf~t ~ 950)
12
13 Ethylenediamine (12.3 mL) and anhydrous toluene (100 mL)
14 were combined under nitrogen. The product from Example 3
(20.4 grams, dissolved in 100 mL of anhydrous toluene) was
16 added dropwise. The resulting solution was refluxed for 16
17 hours. The solution was diluted with hexane (600 mL) and was
18 washed once with saturated aqueous sodium bicarbonate
19 solution , three times with water and once with brine. The
organic layer was dried over anhydrous sodium sulfate,
21 filtered and the solvents removed in vacuo to yield 15.3.
22 grams as a yellow oil. The oil was chromatographed on silica
23 gels eluting with~hexane / diethyl ether _(50:50) then hexane
24 / diethyl ether / methanol / isopropylamine ( 40:40:15:5) to
yield 10.3 grams of the desired product as a yellow oil. 1H
26 ~ (CDCLg) d 7.25 (d, 2H), 6.8 {d, 2H), 4.1 (t, 2H), 3.0
27 (t, 2H), 2.85 (t, 2H), 2.75 {t, 2H ), 1.95 (bs, 3H), 1.5-0.7
28 {m~ 137H).
29
31
32 '
33
34 '
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-2 9-
O1 Example 5
02
03 Preparation of
04
05
06 O/~N3
07
08
09
11 P IB (molecular weight ~ 950)
12
13 A mesylate prepared as described in Example 3 (406.5 grams),
14 sodium azide (198.2 grams ), Adogen 464, a methyltrialltyl
(C8_C~o) ammonium chloride available from Ashland Chemical
16 (g.p mL ), N,N - dimethyformamide (800 mL ) and toluene (1.2
17 L ) were combined. The reaction was refluxed for sixteen
18 hours and cooled to room temperature. The mixture was
i9 filtered and the solvent was removed in vacuo . The residue
was diluted with hexane (3.0 L ) and washed three times with
21 water and once with brine. The organic layer was dried over
22 anhydrous magnesium sulfate, filtered and the solvents
23 removed in vacuo to yield 334.3 grams of the desired azide
24 ~as a yellow oil.
26
27
28
29
31
32
33
34
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-30-
01 Example 6
02
03 Preparation of
04
05
o s O~NH2
07
os /
09
11 P IB (molecular weight ~ 950)
12
13 p, solution of the product from Example 5 ( 334.3 grams ) in
14 ethyl acetate (750 mL j and toluene (750 mL ), containing
10~ palladium on charcoal ( 7.0 grams j was hydrogenolyzed
16 at 35-40 psi for 16 hours on a Parr low pressure
17 hydrogenator. Catalyst filtration and removal of the
18 solvent in vacuo yielded 322.3 grams of the desired
19 product as a yellow oil. 1H NMR (CDClg) d 7.25 (d, 2H), 6.8
(d, 2H ), 4.0 (t, 1H), 3.1 (t, 2H), 2.35 (bs, 2Hj, 0.7-1.6
21 (m, 137H).
22
23
24
26
27
28
29 -
31
32 '
33
34 '
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-31-
O1 Examble 7
02
03 Preparation of
04
05 OH
06
07
08
09
to P IB (molecular weight ~ 950)
11
12
Potassium hydride (15.1 grams of a 35 weight percent
13
dispersion of in mineral oil) and 4- polyisobutyl phenol
14
(1378.5 grams, prepared as in Example 1) were added to a
flask equipped with a mechanical stirrer, reflux condensor,
16
nitrogen inlet and thermometer. The reaction was heated at
17
130°C for one hour and then cooled to 100°C. Propylene
18
carbonate (115.7 milliliters) was added and the mixture was
19
heated at 160°C for 16 hours. The reaction was cooled to
room temperature and ten milliliters of isopropanol were
21
added. The reaction was diluted with ten liters of hexane,
22
washed three times with water and once with brine. The
23
organic layer was dried over anhydrous magnesium sulfate,
24
filtered and the solvents removed in vacuo to yield 1301.7
grams of the desired product as a yellow oil.
26
27
28
29
31
32
33
' 34
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-32-
01 Example 8
02
03 Pr~aration of
04
05
06 O OSO2CH3
07
08 /
09
11 P IB (molecular weight ~ 950)
12
13 The alcohol from Example 7 (50.0 grams), triethylamine (7.0
14 mL), and anhydrous dichioromethane (500 mL) were combined.
The solution was cooled to 0°C and methanesulfonyl chloride
16 (3.7 mL) was added dropwise. The reaction was stirred at
17 room temperture under nitrogen for 16 hours. The solution
18 was diluted with dichloromethane (1.5L ) and was washed
19 three times with saturated aqueous sodium bicarbonate
solution and once with brine. The organic layer was dried
21 over anhydrous sodium sulfate, filtered and the solvents
22 removed in vacuo to field 57.7 rams as a
y g yellow oil.
23
24
26
27
28
29
31
32
33
34 -
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-33-
O1 Example 9
02
O3 Preparation of
04
05
06 O N3
07
Os
09
11 PiB (molecuia~weight ~ 950)
12
13 The mesylate from Example 8 (57.7 grams ), sodium azide
14 (27.1 grams ), Adogen 464 {1.0 mL ), N,N - dimethyformamide
(400 mL ) and. toluene (600 mL ) were combined. The reaction
16 was refluxed for sixteen hours and cooled to room
17 temperature. The mixture was filtered and the solvent was
18 removed in vacuo . The residue was diluted with hexane (1.5
19 ~, ) and washed three times with water and once with brine.
The organic layer was dried over anhydrous magnesium
21 sulfate, filtered and the solvents removed in vacuo to yield
22 43.1 grams of the desired azide as a yellow oil.
23
24
26
27
28
29
31
32
33
- 34
CA 02226982 2005-08-03
-34-
1 Example 10
2
3 Preparation of
4
NH2
6 0
8 ~ ~
P ~ (molecular weight ~ 950)
11 A solution of the product from Example 9 ( 43.1 grams ) in
12 ethyl acetate (100 mL ) and toluene (100 mL ), containing 10%
13 palladium on charcoal ( 2.O grams ) was hydrogenolyzed at 35-
14 40 psi for 16 hours on a Parr low pressure hydrogenator.
Catalyst filtration and removal of the solvent in vacuo
16 yielded 41.5 grams of the desired product as a yellow oil. 1H
17 NMR (CDC13) d 7.25 (d, 2H) , 6. 85 (d, 2H) , 3 .9 (abq, 1H) , 3 .65
18 (abq, 1H), 3.35 (m, 1H), 1.9 (bs, 2H), 0.7-1.6 (m, 140H).
19
Example 11
21
22 Single-Cylinder Engine Test
23
24 The test compounds were blended in gasoline and their deposit
reducing capacity determined in an ASTM~CFR single-cylinder
26 engine test.
27
28 A WaukeshaT"" CFR single-cylinder engine was used. Each run was
29 carried out for 15 hours, at the end of which time the intake
valve was removed, washed with hexane and weighed.
CA 02226982 1998-O1-13
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_35_
01 The previously determined weight of the clean valve was
02 subtracted from the weight of the value at the end of the
03 run. The differences between the two weights is the weight
04 of the deposit. A lesser amount of deposit indicates a
05 superior additive. The operating conditions of the test
06 were as follows: water jacket temperature Zoo°F; vacuum of
07 12 in Hg, air-fuel ratio of 12, ignition spark timing of
Og 400 BTC; engine speed is 1800 rpm; the crankcase oil is a
Og commercial 30W oil.
11 The amount of carbonaceous deposit in milligrams on the
12 intake valves is reported for each of the test compounds in
13 Table I and Table II.
14
TABLE I
16
17 Intake Valve Deposit Weight
18 (in milligrams)
19 Sampler Run 1 Run 2 Average
Base Fuel 333.5 354.9 344.2
21 Example 4 22.5 22.7 22.6
22
23 rAt 150 parts per million actives (ppma).
24
TABLE II
26
27 Intake Valve Deposit Weight
28 (in milligrams)
29 Sampler Run 1 Run 2 Average
Base Fuel 323.8 312.1 318.0
31 Example 6 12.1 21.0 16.6
' 32
33 rAt 125 parts per million actives (ppma).
' 34
CA 02226982 1998-O1-13
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-36-
01 The base fuel employed in the above single-cylinder engine
O2 tests was a regular octane unleaded gasoline containing no
03 fuel detergent. The test compounds were admixed with the .
04 base fuel to give the concentrations indicated in the
05 tables.
06
07 The data in Table I and Table II illustrates the significant
Og reduction in intake valve deposits provided by the
Og polyalkylphenoxyaminoalkanes of the present invention
(Examples 4 and 6) compared to the base fuel.
21
12
13
14
Z6
17
18
19
21
22
23
24
26
27
28
29
31
32 '
33
34 '
