CA1137104A

CA1137104A - Carbonylation process

Info

Publication number: CA1137104A
Application number: CA000342000A
Authority: CA
Inventors: John E. Hallgren; William E. Smith
Original assignee: General Electric Co
Current assignee: General Electric Co
Priority date: 1978-12-15
Filing date: 1979-12-14
Publication date: 1982-12-07
Also published as: NL7908995A; DE2950096A1; JPS55102541A

Abstract

RD-10,733 ABSTRACT OF THE DISCLOSURE
A carbonylation process which comprises contacting a .beta.-fluoralkanol 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 .beta.-fluoroaliphatic carbonates can be employed in combination with alkanols and/or phenols to prepare aliphatic and aromatic mono-and polycarbonates. The resulting carbonates are useful in a wide variety of applications, especially polycarbonates which can be molded or formed into films, sheets, fibers, laminates, or reinforced plastics by conventional techniques.

Description

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:

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

CF3CH2OH , (CF3 )2CHOH , CF3CH-OH , and 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 ~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.

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 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 ~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 ` 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.

Claims

RD-10,733 The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A process for the preparation of an aliphatic .beta.-fluorocarbonate, which comprises contacting an aliphatic .beta.-fluoroalkanol, carbon monoxide and a Group VIIIB element selected from ruthenium, rhodium, palladium, osmium, iridium or platinum and having an oxidation state greater than zero.

2. The claim 1 process, further comprising a base.

3. The claim 2 process, further comprising a solvent.

4. The claim 1, 2 or 3 process, wherein said element is present in an ionic form.

5. The claim 1, 2 or 3 process, wherein said element has an oxidation state of at least +1.

6. The claim 2 or 3 process, wherein said base is present in the form of a sterically hindered amine.

7. The claim 1, 2 or 3 process, wherein said element is associated with a carbonyl group.

8. The claim 1, 2 or 3 process, wherein said element is associated with a halide.

9. The claim 1, 2 or 3 process, wherein said element is coordinated with a ligand selected from an arsine, a stibene, a phosphine, a nitrile or a halide.

10. The claim 1, 2 or 3 process, wherein said element is associated with an inorganic halide compound.

11. A process for the preparation of an aliphatic .beta.-fluorocarbonate, which comprises contacting an aliphatic .beta.-fluoroalkanol, carbon monoxide, a Group VIIIB element selected from ruthenium, rhodium, palladium, osmium, iridium or platinum, and an oxidant having an oxidation potential greater than the oxidation state of the Group VIIIB element.

12. The claim 11 process, further comprising a base.

13. The claim 12 process, further comprising a solvent.

RD-10,733

14. The claim 11, 12 or 13 process, wherein said element is present in an ionic form.

15. The claim 11, 12 or 13 process, wherein said element has an oxidation state of at least +1.

16. The claim 12 or 13 process, wherein said base is present in the form of a sterically hindered amine.

17. The claim 11, 12 or 13 process, wherein said element is associated with a carbonyl group.

18. The claim 11, 12 or 13 process, wherein said element is associated with a halide.

19. The claim 11, 12 or 13 process, wherein said element is coordinated with a ligand selected from an arsine, a stibene, a phosphine, a nitrile or a halide.

20. The claim 11, 12 or 13 process, wherein said element is associated with an inorganic halide compound.

21. The claim 11, 12 or 13 process, further comprising a redox co-catalyst.

22. The claim 13 process, further comprising substantially anhydrous reaction conditions.

23. The claim 13 process, further comprising a phase transfer agent.

24. The claim 22 process, further comprising a drying agent.

25. The claim 24 process, wherein the drying agent is a molecular sieve.

26. The claim 23 process, wherein the phase transfer agent is an onium halide.

27. The claim 25 process, wherein the solvent is methylene chloride, the base is 1,2,2,6,6-pentamethylpiperidine, the .beta.-fluoroalkanol is 2,2,2-trifluoroethanol, the Group VIIIB
element is palladium in the form of palladium(II) dibromide and the oxidant is air.

RD-10,733

28. The claim 27 process, further comprising manganese (III) tris(acetylacetonate) as a redox co-catalyst.

29. The claim 25 process, wherein the base is 1,2,2,6,6-pentamethylpiperidine, the .beta.-fluoroalkanol is 2,2,2-trifluoroethanol, and the Group VIIIB element is palladium in theform of palladium(II) dibromide.

30. The claim 29 process, further comprising manganese-(III) tris(acetylacetonate) as a redox co-catalyst.

31. The claim 11 process, wherein the .beta.-fluoroalkanol is 2,2,2-trifluoroethanol and the Group VIIIB element is palladium in the form of palladium(II) dibromide, and further comprising a redox co-catalyst, a molecular sieve and a solvent.

32. The claim 31 process, wherein the redox co-catalyst is manganese(III) tris(acetylacetonate), the solvent is methylene chloride and the oxidant is air.

33. The claim 11 process, wherein the .beta.-fluoroalkanol is 2,2,2-trifluoroethanol and the Group VIIIB element is palladium in the form of palladium(II) dibromide, and further comprising a base, a phase transfer agent, a molecular sieve, a solvent and a redox co-catalyst.

34. The claim 33 process, wherein the base is aqueous caustic, the phase transfer agent is tetrabutylammonium bromide, the solvent is methylene chloride and the redox co-catalyst is manganese(II) bis(acetylacetonate).

35. The claim 11 process, wherein the .beta.-fluoroalkanol is 2,2,2-trifluoroethanol, the Group VIIIB element is palladium in the form of palladium(I) bromide and the oxidant is oxygen, and further comprising a base, a molecular sieve and a redox co-catalyst.

36. The claim 35 process, wherein the base is an aqueous caustic solution and the redox co-catalyst is manganese(II) bis(acetylacetonate).