Note: Descriptions are shown in the official language in which they were submitted.
11371~i~ RD-10,733
This invention relates to a carbonylation process
which comprises contacting a ~-fluoroalkanol with carbon
monoxide and a Group VIIIB element selected from ruthenium,
rhodium, palladium, osmium, iridium or platinum having an
oxidation state greater than zero. The resulting ~-
fluoroaliphatic carbonates can be employed in situ or
isolated from the reaction mixture in the preparation of
mono- or polycarbonates.
The synthesis of bis(2,2,2-trifluoroethyl)carbonate
by the reaction of ~ -trifluoroethanol with phosgene is
described by Aldrich & Shepard (J. Org. Chem. 29, 11 (1964).
This invention embodies a carbonylation process
comprising contacting a ~ -fluoroalkanol with carbon
monoxide and a Group VIIIB element selected from ruthenium,
rhodium, palladium, osmium, iridium or platinum having an
oxidation state greater than zero to form a ~ -fluoroaliphatic
carbonate.
The reactants and the resulting reaction products
of the process can be illustrated by the following
equations which are furnished for illustrative purposes only
since the reactants, reaction products, reaction mechanisms,
etc., involved in the preparation of ~ -fluoroaliphatic
carbonates can be different and/or more complex:
(I) 2CF3CH20H + 2Pd(CO)Cl ~ (CF3CH20 ~ CO + 2Pd + 2HCl ,
(II~ 2CF3CH2OH + CO + 1/2 2V ~ (CF3CH2O - CO + H2O ,
Any ~ -fluoroalkanol can be used in our process and
is defined herein in the appended claims as a
"~ -fluoroalkanol". Illustratively, the ~ -fluoroalXanol
reactants can be described by the generic formula:
-- 1 --
RD-10,733
113710~
(III) -C--C--OH ,
~ a
which describes the essential features of a ~ -fluoroalkanol
reactant, i.e. alkanols of the class wherein at least one
hydroxyl group is separated from a fluorinated carbon atom
by at least two carbon atoms. Further, illustratively with
primary alkanols a fluorine atom is at least located on a
single ~ carbon, with secondary alkanols a fluorine atom is
at least located on either or both ~ carbon atoms and with
tertiary alkanols a fluorine atom is at least located on any
of three ~ -carbon atoms. The fluorine atoms, as
illustrated by the specific examples set out hereafter, can
be associated with any ~ carbon atom as well as other
carbon atoms -- subject to the above class requirement. In
a presently preferred embodiment primary or secondary
fluorinated alkanols, more preferred in that order, are
employed since the reactivity of ~ -fluorinated primary
alkanols is generally greater than ~ -fluorinated secondary
alkanols, whose reactivity is generally greater than
~-fluorinated tertiary alkanols. Further, the alkanols
can be mono- and polyhydroxy-functional. Broadly, the
~-fluoroalkanols can be carbo or heteromonocyclic,
polycyclic or fused polycyclic and can have two or more
cyclic systems (monocyclic, polycyclic or fused polycyclic
systems) which are connected to each other by single or
double valence bonds or multivalent radials. ~urther,
presently preferred are ~ -tri-fluoroalkanol reactants which
contain from 2-10 carbon atoms, and more preferably from
2-4 carbon atoms. Illustrative of commercially important
~ -fluoroalkanols include the following:
113~ i RD-10,733
CH2FcH2oH
CHF2CH20H
CF3CH2OH ,
(CF3 )2CHOH ,
CF3CF2 2
CF3CH-OH , and
CH3
CF3cF2cF2cH2oH
Any Group VIIIB element, defined herein and in
the appended claims as "the Group VIIIB element" can be
employed subject to the proviso that the element be selected
from ruthenium, rhodium, palladium, osmium, iridium, or
latinum. The Group VIIIB elements can be present in ionic,
inorganic or organic compound or complex, etc., forms.
The Group VIIIB elements can be employed in oxide, halide,
nitrate, sulfate, oxalate, acetate, carbonate, propionate,
hydroxide, tartrate, etc., forms. Group VIIIB elements in
complex form, e.g., with ligands, such as carbon monoxide,
nitriles, tertiary amines, phosphines, arsines, or stibines,
etc., can be employed and illustratively are often
represented by those skilled in the art as mono-, di-, or
poly-nuclear Group VIIIB element forms. Generally, the
dimeric or polymeric forms are considered to contain Group
VIIIB atoms bridged by ligands, halogens, etc. Preferred
Group VIIIB elements form homogeneous mixtures when
combined with the reactants, especially when the process is
carried out under liquid phase reaction conditions.
The Group VIIIB elements can be employed in any of
their oxidation states including zero, as well as any
oxidation state greater than zero including plus one, plus
two, etc.
Illustrative of the Group VIIIB elements,
113~ RD-10,733
compounds, or complexes are as follows: Ru,
Ru(CO)Cl,Cu(CO)Br, Ru(CO)I, RuClrP(C2H5)3]3 RuC12,RuBr2,
RuI2,Ru(CO)2C12, Ru(CO)2I2, Ru(CO)4C12, Ru(CO)4Br2,
Ru(CO)4I2, RuC13, RuBr3, RuI3, etc., Rh,RhCl(CO)tP(C2H5)3~2
3 6 4)2~ [Rh(CNCH3OC6H4)4~Clr rP~h(CNClC H4) ]Cl
LRh(CO) C~ , Rh2C12(CO)2, Rh2(CO)4 2' 2 4 2
Rh2(CO)4I2, Rh(CO)C12,Rh(CO)Br2, Rh(CO)I2, Rh2C12(CO)2,
Rh2 (CO~ 4cl2 Rh2 (cO) 4sr2 Rh2 (Co) 4I2 rRh (CO~ 2C1]2~ RhC13,
- r~hBr3, RhI3, etc., Os, Os(CO)3C12, Os(CO)3Br2, OS(co)3I2~
Os(CO)4C12, Os(CO)4Br2~ Os(CO)~I2' OS(CO)8C12, ~(CO)8Br2'
Os(CO)8I2, OsC12, OsC13, OsI2, OsI3, Os(CO)2Cl, Os(CO)2Br,
Os(CO)2I, Os(CO)4C1, Os(CO)4Br, Os(CO)4I, OsBr3, OsBr4 and
OsC14, etc., Pd, PdC12, PdBr2, PdI2, LPd(CO)C12~2,
L ( ) 2~2' ~Pd(C)I2]2' (C6H5cN)2pdcl2~ PdC14, Pd(OH)2-
(CNC4H9)2' PdI2(CNC6H5)2' Pd(OH)2(CNCH3OC6H5~2,
Pd(CNC4Hg)4, Pd(CO)C1, Pd(CO)Br, Pd(CO)I, PdH(CO)Cl,
6 6) (H2O)C1O4, Pd2(CO)2Cl~[(HgC ) N] PdBr
K2Pd2(CO)2C14, Na2Pd2(CO)2Br4, etc. Ir,
Ir~CO)2C1, Ir(CO)2Br, Ir(CO)2I, Ir(CO)3Cl, Ir(CO)3Br,
Ir(CO) I, Ircl(co)~p(c6Hs)3~2~ Ircl3~ IrC13(C)~ 2 8
IrC13, IrBr3, IrC13, IrBr4, IrI4, etc., Pt, PtC12, PtBr2,
PtI2, Pt(CO)2C12, Pt(CO)2Br2, Pt(CO)2I2, Pt(CO)2C14,
Pt(CO)2Br4, Pt(CO)2I4, Pt(CO)3C14, Pt(CO)3Br4, Pt(CO)3I4,
PtC12(CNC6H5)2, Pt(CO)Cl, Pt(CO)Br, Pt(CO)I, Na2Pt2(CO)2C14,
2 2(CO~2Br4~ K2Pt2(CO)I4, etc.
Further illustrative of other Group VIIIB complexes
which also can be employed are the following:
2rP(C6H5)3~4' LRh(C~2cl]2, trans L(C2H5)3p] ,
[P(C4Hg)3~2Pdcl4, L(C6H5~3p]3Ircl3(co)~ L(C6H5) 3As~3IrC13(CO),
6 5 3 ]3 3(CO~, L(C6H5~ 3P]2PtC12~ L(C6H5) 3P~2PtF ~
6 5 3 2 2 2' r(C6H5)3P~2(CO)2, etc. The Group
-- 4 --
~1371Q~ RD-10,733
VIIIB element, compounds and/or complexes can be prepared
by any method well-known to those skilled in the art
including the methods referenced in Reactions of
Transition-Metal Complexes, J.P. Candlin, K.A. Taylor and
D.T.Thompson, Elsevier Publishing Co. (1968) Library of
Congress Catalog Card No. 67-19855.
To enhance the rate of reaction and to reduce the
quantity of the Group VIIIB element employed, an oxidant
can be employed in our process subject to the proviso that
the oxidant has an oxidation potential greater than or more
positive than the Group VIIIB element employed as the
catalytic species. Preferred oxidants comprise any
element, compound or complex of a periodic Group IIIA, IVA,
VA, VIA, VIIA, IB, IIB, IVB, VB, VIB, VIIB, VIIIB,
lanthanides or actinide having an oxidation potential
greater than or more positive than "the Group VIIIB element".
Typical well-known oxidants of "the Group VIIIB elements"
are compounds or complexes of copper, iron, manganese,
cobalt, mercury, lead, cerium, vanadium, uraniuml bismuth,
chromium, etc. Wherein-
the oxidant is employed in salt form, the anion portion of
the salt may be a Cl 20 carboxylate, halide, nitrate,
sulfate, etc., and preferably is a halide, e.g. chloride,
bromide, iodide, or fluoride. Illustrative of typical
oxidants are cupric chloride, cupric bromide, cupric nitrate,
cupric sulfate, cupric acetate, etc. In addition to the
compounds described above, elements commonly employed as
oxidants in elemental form, e.g. oxygen, ozone, chlorine,
bromine, fluorine, etc., may be employed as the sole oxidant
in the herein claimed process. Frequently, compounds or
complexes of a periodic Group IIIA, IVA, VA, VIA, VIIA, IB,
IIB, IVB, VB, VIB, VIIB, VIIIB, lanthanide or actinide are
1~37~Q'~ RD-10,733
preferably employed as a redox co-catalyst of a
periodic Group VIA or VIIA element, e.g. oxygen, sulfur,
selenium, fluorine, chlorine, bromine, iodine, etc.,
including mixtures thereof, in order to enhance the rate of
oxidation of "the Group VIIIB element".
Any periodic Group element, compound or complex
redox co-catalyst can be employed and comprises any element,
compound or complex which catalyzes the oxidation of "the
Group VIIIB element", i.e. ruthenium, rhodium, palladium,
osmium, iridium or platinum, in the presence of any oxidant
from a lower oxidation state to a higher oxidation state.
In a presently preferred embodiment oxygen is employed as a
sole oxidant in combination with a redox co-catalyst
selected from "a periodic Group" element, compound or
complex. Any source of oxygen can be employed, i.e.
air, gaseous oxygen, liquid oxygen, etc. Preferably either
air or gaseous oxygen is employed.
A presently preferred redox co-catalyst is
selected from manganese or cobalt chelates. Illustrative of
manganese or cobalt redox co-catalysts are manganese and/or
cobalt chelates containing ligands selected from
omega (~)-hydroxyoximes, ortho(o)-hydroxy-
areneoximes, alpha (Q) -diketone or beta (B ) -diketone
ligands including combinations thereof. Illustrative of
well-known commercially available redox co-catalysts include
manganese (II) bis(acetylacetonate), manganese(II)bis-
(benzoinoxime), etc. The redox co-catalysts are well known
to those of ordinary skill in the art and are readily
prepared as described in U.S. Patent No. 3,972,851 -
August 3, 1976 - Olander; U.S. Patent No. 3,965,069 -
dated June 22, 1976 - Olander; U.S. Patent No. 3,956,242 -
dated May 11, 1976 - Olander; U.S. Patent No. 3,781,382 -
dated December 25, 1973 - Izawa et al; U.S. Patent No.
-- 6 --
l l~7 1Q~a RD-10,733
3,455,880 - dated July 15, 1969 - Kobayashi; and
U.S~ Patent No. 3,444,133 - dated May 13, 1969 - Behr;
etc.
As used herein and in the appended claims, the
expression "complexes" includes coordination or complex
compounds well-known to those skilled in the art such as
those described in Mechanisms of Inorganic Reactions,
Fred Basolo and Ralph G. Pearson, 2nd Edition, John Wiley
and Sons, Inc. (1968). These compounds are generally
defined herein as containing a central ion or atom, i.e.
"a periodic Group" IIIA, IVA, VA, VIA, VIIA, IB, IIB,
IVB, VB, VIB, VIIB, VIIIB, Lanthanide or actinide element
and a cluster of atoms or molecules surrounding a periodic
Group element. The complexes may be nonionic, cationic or
anionic, depending on the charges carried by the central
atom and the coordinated groups. The coordinated groups
are defined herein as ligandsl and the total number of
attachments to the central atom is defined herein as the
coordination number. Other common names for these complexes
include complex ions (if electrically charged), Werner
complexes, coordination complexes or, simply, complexes.
The process can be carried out in the absence of
any solvent, e.g. where the ~-fluoroalkanol reactant acts
as both solvent and reactant. Representative of solvent
species which can be employed are the following: methylene
chloride, ethylene dichloride, chloroform,
carbontetrachloride, tetrachloroethylene, nitromethane,
hexane, 3-methylpentane, heptane, cyclohexane,
methylcyclohexane, cyclohexane, isooctane, p-cymene, decalin,
toluene, benzene, diphenylether, dioxane, thiophene,
dimethylsulfide, ethylacetate, tetrahydrofuran,
chlorobenzene, anisol, bromobenzene, o-dichlorobenzene,
1137~ RD-10,733
methylformate, iodobenzene, acetone, acetophenone, etc.,
and mixtures thereof.
Although not required and accordingly --
optionally, the process can be carried out under basic
reaction conditions. Representative of basic species
which can be employed are the following: elemental alkali
and alkaline earth metals, basic quaternary ammonium,
quaternary phosphonium or tertiary sulfonium compounds;
alkali or alkaline earth metal hydroxides; salts of strong
bases and ~eak organic acids; primary, secondary or tertiary
amines; etc. Specific examples of the aforementioned are
sodium, potassium, magnesium metals, etc; quaternary
ammonium hydroxide, tetraethyl phosphonium hydroxide, etc.;
sodium, potassium, lithium, and calcium hydroxide;
quaternary phosphonium, tertiary sulfonium, sodium, lithium
and barium carbonate, sodium acetate, sodium benzoate,
sodium methylate, sodium thiosulfate; sodium compounds, e.g.
sulfide, tetrasulfide, cyanide, hydride and borohydride;
potassium fluoride, methylamine, isopropylamine,
methylethylamine, allylethylamine, ditertbutylamine,
dicyclohexylamine, dibenzylamine, tertbutylamine,
allyldiethylamine, benzyldimethylamine,
diactylchlorobenzylamine, dimethylphenethylamine,
l-dimethylamino-2-phenylpropane, propanediamine, ethyl-
enediamine, N-methylethylenediamine, N,N'-dimethylethylene-
diamine, N,N,N'-tritertbutylpropanediamine, N, N',N',N''-
tetramethyldiethylenetriamine, pyridine, aminomethylpyridines,
pyrrole, pyrrolidine, piperidine, 1,2,2,6,6-pentamethyl-
pipexidine, imidazole, etc. Especially preferred bases are
the hydroxides of lithium, sodium, potassium, calcium or
barium; sodium, lithium or baxium carbonate; sodium acetate,
sodium benzoate, sodium methylate, etc., including mixtures
1~371~ RD-10,733
thereof.
Although not required and accordingly -- optionally,
the process can be carried out in the presence of an organic
phase transfer agent (PTA) including any onium phase transfer
agent, e.g. quaternary ammonium hydroxide, tetraethyl
phosphonium hydroxide, etc., as described by C.M. Starks,
J.A.C.A. 93, 195 (1971); any crown ether phase transfer
agent, e.g. Aldrichimica ACTA 9, Issue #1 (1976) Crown Ether
Chemistry: Principles and Applications, G.W. Gokel and H.D.
Durst, as well as C.J. Pederson in U.S. Patent No. 3,622,577 -
dated November 23, 1971 - Pedersen, etc.; any chelated
cationic salt, e.g. alkaline or alkali earth metal diamine
halides; cryptates, etc., i.e. any agent which is soluble
in the organic phase and which enhances the transfer,
maintenance, or retentlon of a cation, e.g. a halide.
In a preferred embodiment, the process is carried
out in a reaction environment which contains or provides at
least one of the following groups or conditions: (A) a
base, (B) an oxidant, (C) a manganese redox co-catalyst of
any ¢-diketone or ~ diketone, or mixture thereof, and
(D) substantially anhydrous reaction conditions.
Any amount of ~-fluoroalkanol, Group VIIIB
element, oxidant - including redox co-catalyst, base,
ligand associated with a Group VIIIB element, solvent, phase
transfer agent, drying agent, carbon monoxide, etc., can
be employed.
Illustratively, unless otherwise stated, on a mole
ratio basis relative to a ~ -fluoroalkanol, the following
reaction parameters can be employed:
Any amount of Group VIIIB element can be employed.
For example, Group ~IIIB element to ~ -fluoroalkanol mole
proportions within the range of from about about 0.001:1 or
~1371Q4 RD-10,733
lower to about 1000.1 or higher are effective, however,
preferably ratios of from 0.1:1 to 10:1, and more
preferably at least 1:1 are employed in order to insure
that optimum conversion of ~-fluoroalkanol to ~ -fluoro-
aliphatic carbonate occurs.
As stated before, although not required, base can
be employed. In general, any amount can be employed.
Generally effective mole ratios of base to Group VIIIB
elements are within the range of from about 0.000001:1 to
about 100:1 or higher, preferably from 0.5:1 to about 10:1,
and more preferably from 1:1 to 2:1.
Any amount of the oxidant can be employed. For
example, oxidant to ~ -fluoroalkanol mole proportions within
the range of from about 0.001:1 or lower to about 1000:1 or
higher are effective: however, preferably ratios from 0.1:1
to 10:1 are employed to insure an optimum conversion of
B-fluoroalkanol to ~ -fluoroaliphatic carbonate.
Any amount of redox co-catalyst component can be
employed. For example, redox catalyst to ~ -fluoroalkanol
mole proportions within the range of from about 0.0001:1 or
lower to about 1000:1 or higher are effective; however,
preferably ratios of from 0.0001:1 to 1:1, and more
preferably 0.001:1 to 0.01:1 are employed.
As stated before, although not required, a phase
transfer agent can be employed. Any amount can be employed.
Generally effective mole ratios of phase transfer agents to
"the Group YIIIB element" are within the range of from about
0.00001:1 about 1000:1 or higher, preferably from about 0.05:1
to about 100:1 and more preferably from about 10:1 to 20:1.
As stated before, although not required, a solvent,
preferably inert, can be employed. Any amount can be employed.
Generally optimum solvent to ~ -fluoroalkanol reactant mole
-- 10 --
1137~ RD-10,733
proportions are from 0.5:99.5 to 99.5:0.5, preferably
from 50:50 to 99:1.
Any amount of carbon monoxide can be employed.
Preferably the process is carried out under positive carbon
monoxide pressure. i.e., where carbon monoxide is present
in at least amounts sufficient to form the desired
~ -fluoroaliphatic carbonate. In general, carbon monoxide
pressures within the range of from about 1/2 to about 500
atmospheres, or even higher, can be employed with good
results. Presently preferred are CO pressures within the
range of from 1 to 200 atmospheres.
Any reaction time period can be employed.
Generally optimum reaction time periods are about 0.1 hour
or even less to about 10 hours or even more.
Any reaction temperature can be employed. In
general, optimum reaction temperatures are 0 C. or even
lower to 200C. or even higher and more often 0 C. to 50 C.
Although the foregoing generally describes
reactions involving e -fluoroalkanols to form fluorinated
aliphatic carbonates, this invention also includes a
carbonylation process wherein ~-fluoroalkanols plus other
alcohols and/or phenols react in accordance with the process
parameters described herein to form ~-fluoroaliphatic -
carbonates. Accordingly, the scope of the reaction products
of this invention include compounds of the generaic formula:
(IV~ l C-C-O t C O R~
wherein the ~ -fluoroaliphatic carbonate is formed having
at least two oxy groups both of which are independently and
directly bonded to the same carbonyl carbon atom subject
to the proviso that at least one of the oxy groups is
-- 11 --
~37~Q4 RD- 1 o, 733
separated from any ~-fluorine atoms by at least two
~-aliphatic carbon atoms R being a ~C-C- ~ group,
~ a
or an alkyll a cycloalkyl, or aryl radical, including
combinations thereof.
In order that those skilled in the art may better
understand my invention, the following examples are given
which are illustrative of the best mode of this invention,
however, these examples are not intended to limit the
invention in any manner whatsoever. Unless otherwise
specified, all parts are by weight and all reaction products
were verified by gas chromotography - mass spectrometry
(gc-ms).
EX~PLE I
A 50 ml three-neck flask equipped with subsurface
air and CO inlets was charged with 1.0 g (10.0 mmol.) of
CF3CH2OH2,2,2-trifluoroethanol, 0.027 g. (0.1 mmol.) of
PdBr2 -- palladium (II)dibromide, 0.106 g. (0.3 mmol.) of
Mn(acac)3 -- manganese tris(acetylacetonate), 0.23 g.
(1.5 mmol.) of 1,2,2,6,6-pentamethylpiperidine, 2 g. of
Linde 3A molecular sieves, and 25 ml. of methylene chloride.
100.0 of toluene as an internal standard and CO and air
were bubbled through the mixture for 16 hr. at 25 C. Vapor
phase chromotography (vpc) showed the presence of 0.74 g.
(67~ conversion) of bis (2,2,2-trifluoroethyl) carbonate of
the formula: (CF3CH2O ~ CO.
EXAMPLE II
A 50 ml. three-neck flask equipped ~ith subsurface
air and CO inlets was charged with 32.2g. (0.322 mmol.) of
CF3CH2OH, 0.027 g. (0.1 mmol.) of Pd~r2, 0.106 g.
(0.3 mmol.~ of Mn(acac)3, 0.232 g. (1.5 mmol.) of
1,2,2,6,6-pentamethylpiperidine, 2 g. of Linde 3A molecular
` 11371~ RD-10,733
sieves. CO and air were bubbled through the mixture for
16 hr. Vpc showed the presence of 0.44 g. of bis(2,2,2-
trifluoroethyl) carbonate.
EXAMPLE III
A 100 ml. three-neck flask equipped with
subsurface air and CO inlets was charged with 3.8 g. (38 mmol.)
of CF3CH20H, 0.027 g. (0.1 mmol.~ of PdBr2, 0.106 g.
(0.3 mmol.) of Mn(acac)3, 2 g. of Linde 3A molecular sieves,
and 50 ml. of methylene chloride. CO and air were bubbled
through the mixture for 42 hr. Vpc showed the presence of
0.26 g. of bis (2,2,2-trifluoroethyl) carbonate.
EXAMPLE IV
A 100 ml. three-neck flask equipped with a CO
inlet and air inlet, exit tube, and spin bar was charged
with 1.28 g. (12.8 mmol.) of CF3CH2CH, 0.104 g.
~1.3 mmol.) of 50% aqueous caustic ~NaOH), 0.37 g.
(1.6 mmol.) of tetrabutylammonium bromide (Bu4N Br ),
2.0 g. of mol. sieves, and 70 ml. of methylene chloride.
The mixture was stirred at room temperature for one hour,
then 0.076 g. (0.3 mmol.) of Mn(acac)2 and 0.027 g.
(O.1 mmol.) of PdBr2 were added. CO and air were bubbled
through the mixture at room temperature an additional 18
hrs. Vpc showed 0.94 g. (73% conversion) of bis
(2,2,2-trifluoroethyl carbonate.
EXAMPLE V
A 100 ml. three-neck flask equipped with a CO
inlet, air inlet, exit tube, spin bar was charged with 40
ml. of CF CH2OH, 0.104g. (1.3 mmol.) of 50% aqueous caustic,
3.0 g. of mol. slie~es. The mixture was stirred at room
temperature for one hour, then 0.027 g. (0.1 mmol.~ of
PdBr~ and 0.076 g. (0.3 mmol.~ of Mn(acac~2 were added. CO
and air were bubbled slowly through the reaction mixture
- 13 -
` 113710~ RD-10,733
for an additional 18 hrs. VPc showed 8.45 g.
(16.4~ conversion) to bis(trifluoroethyl) carbonate.
Although the above examples have illustrated
various modifications and changes that can be made in
carrying out my process, it will be apparent to those
skilled in the art that other changes and modifications
can be made in the particular embodiments of the invention
described which are within the full intended scope of the
invention as defined by the appended claims.
