Methods for preparing partially fluorinated esters

Abstract

A method for preparing a partially fluorinated ester comprising acyl and alkoxy groups wherein the acyl group comprises a branched or linear fluorine containing C.sub.3-C.sub.8 group with one of the structures: (Formulae (I), (II)) wherein X and Y are independently selected from: H, CH.sub.3, F, Cl, CH.sub.2F, CF.sub.3OCF.sub.3, OCH.sub.2CF.sub.3, OCH.sub.2CF.sub.2CHF.sub.2 and CH.sub.2CF.sub.3 (wherein both X and Y cannot be H) comprising reacting an unsaturated halocarbon: (Formula (III)) wherein A and B are independently selected from the group comprising H, CH.sub.3, F, Cl, CH.sub.2F, CF.sub.3, OCF.sub.3, OCH.sub.2CF.sub.3, OCH.sub.2CF.sub.2CHF.sub.2 and CH.sub.2CF.sub.3 (wherein both A and B cannot be H) with carbon monoxide and an alcohol, in the presence of a catalyst methods. ##STR00001##

Claims

1. A method for preparing a partially fluorinated ester comprising acyl and alkoxy groups wherein the acyl group comprises a branched or linear fluorine containing C.sub.4-C.sub.8 group with one of the structures: ##STR00020## wherein X and Y are independently selected from: H, CH.sub.3, F, Cl, CH.sub.2F, CF.sub.3, OCF.sub.3, OCH.sub.2CF.sub.3, OCH.sub.2CF.sub.2CHF.sub.2 and CH.sub.2CF.sub.3, wherein both X and Y cannot be H, comprising (wherein both X and Y cannot be H) comprising reacting an unsaturated halocarbon: ##STR00021## wherein A and B are independently selected from the group comprising H, CH.sub.3, F, Cl, CH.sub.2F, CF.sub.3, OCF.sub.3, OCH.sub.2CF.sub.3, OCH.sub.2CF.sub.2CHF.sub.2 and CH.sub.2CF.sub.3, wherein both X and Y cannot be H, with with carbon monoxide and an alcohol, in the presence of a catalyst.

2. A method according to claim 1, where the acyl group has 3 to 7 carbon atoms.

3. A method according to claim 1, wherein the acyl group comprises CF.sub.3C.sub.2H.sub.3FCO, CF.sub.3CH.sub.2CH(F)CO, CF.sub.3CH(CH.sub.2F)CO, CF.sub.3CF(CH.sub.3)CO, CF.sub.3C.sub.3H.sub.3F.sub.3CO, or CF.sub.3CH.sub.2CH(CF.sub.3)CO.

4. A method according to claim 1, comprising reacting 2,3,3,3-Tetrafluoropropene (1234yf) with carbon monoxide and an alcohol of formula ROH to form CF.sub.3CF(CH.sub.3)CO.sub.2R and/or CF.sub.3CHFCH.sub.2CO.sub.2R; or reacting 2-chloro-3,3,3-trifluoropropene (1233xf) with carbon monoxide and an alcohol to form CF.sub.3CCl(CH.sub.3)CO.sub.2R and/or CF.sub.3CHClCH.sub.2CO.sub.2R.

5. A method according to claim 1, comprising reacting 1,3,3,3-Tetrafluoropropene (1234ze) with carbon monoxide and an alcohol of formula ROH to form to form CF.sub.3CH(CH.sub.2F)CO.sub.2R and/or CF.sub.3CH.sub.2CHFCO.sub.2R.

6. A method according to claim 1, comprising reacting 1,1,1,4,4,4-hexafluoro-2-butene (1336mzz) with carbon monoxide and an alcohol of formula ROH to form CF.sub.3CH.sub.2CH(CF.sub.3)CO.sub.2R.

7. A method according to claim 1, wherein the alkoxy group is derived from a branched or linear monohydric alcohol with the formula HOC.sub.nH.sub.2n+1?xF.sub.x, wherein n is from 1 to 10 and x has a value from 0 to 2n+1.

8. A method according to claim 1, wherein the catalyst comprises a group 8-12 metallic compound, and comprising a halogen ligand and a phosphorous-containing ligand or comprising a carbonyl ligand.

9. A method according to claim 8, wherein the group 8-12 metallic compound is selected from the group consisting of iron, ruthenium, osmium, cobalt rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, and mercury.

10. A method according to claim 8, wherein when the catalyst comprises the halogen ligand and the phosphorous-containing ligand, the halogen ligand is selected from the group consisting of fluorine, chlorine, bromine and iodine, and the phosphorous-containing ligand is selected from the group consisting of PH.sub.3 and PPh.sub.3.

11. A method according to claim 8, wherein when the catalyst comprises the carbonyl ligand, the catalyst comprises another ligand selected from the group consisting of halogen, alkyl, and phosphorous-containing compounds.

Description

EXAMPLES

Example 1AEsterification of HFO with Alcohol Using Bis(Triphenylphoshine)Palladium (II) Chloride Catalyst

(1) The following steps were followed. The reactor was charged with catalyst (bis(triphenylphoshine)palladium (II) chloride), solvent and alcohol, inside a nitrogen purged glovebox. Then sealed and removed from the glovebox. The HFO substrate was then added from a pre-loaded and weighed sample bomb. The reactor was then pressurised with CO to c.a. 37 barg and the reactor contents heated to the desired reaction temperature with stirring. At the end of the experiment the reactor contents were cooled, and any residual pressure vented before the crude product was recovered. The recovered crude product was analysed by GC-MS and NMR spectroscopy.

(2) TABLE-US-00001 Expt. EM1** EM2 EM8 EM5 EM3 EM7 EM4 HFO (g) 1243zf 1234ze-E 1234ze-E 1234ze-E 1234ze-Z 1336mzz-E 1336mzz-Z 9 7.4 10.8 3 10.1 5.5 5 Catalyst (g) 0.38 0.31 0.3 0.13 0.33 0.31 0.31 Solvent (g) ACN ACN ACN ACN ACN ACN ACN 20.41 22.4 29.16 15.74 23.05 28.86 22.85 Alcohol (g) EtOH EtOH EtOH EtOH EtOH EtOH EtOH 6.73 7.06 8.91 4.5 8.15 9.76 8.9 Temperature 100 100 100 100 110 100 100 (? C.) Pressure (barg) 47.8 46.4 46.4 49.4 45 47 46.2 Pressure drop 29.2 4.8 7 1.6 4.4 2 5.8 (barg) Duration (hrs) 50 71 70.5 73 50 47 71 Ester yield ND ND 33.7 36.8 51.6 41.3 100 (%) Regioselectivity 1:0.7 100% n-isomer Only 1 isomer n-:iso- possible Expt. EM6 EM9 EM10 EM11 EM12 EM13 EM14 EM15 HFO (g) 1234yf 1234yf 1234yf 1234yf 1234yf 1234yf 1234yf 1233xf 5.2 10.6 8.8 10.1 10.5 11.2 10.7 9.0 Catalyst (g) 0.3 0.6 0.27 0.58 0.62 0.6 0.6 0.58 Solvent (g) ACN ACN ACN ACN ACN Toluene THF ACN 25 29.71 28.77 28.8 28.6 29.7 29.1 29.7 Alcohol (g) EtOH EtOH EtOH EtOH MeOH EtOH EtOH EtOH 10.71 9.66 8.9 9.3 10.5 9.3 9.3 9.4 Temperature 100 100 120 120 120 120 120 120 (? C.) Pressure (berg) 44.4 48.4 51.2 52.6 49.2 55.2 50 51 Pressure drop 5.6 17.2 13.6 23 9 31.8 26 3.5 (berg) Duration (hrs) 66 72 70 92 46 48 73 71 Ester yield 100 72.4 73.2 91.7 48.9 56.2 ND 26.3 (%) Regioselectivity 1:100 1:10.8 n-:iso- **comparative example.

Example 1BEsterification of 1234yf with Ethanol in Acetonitrile Using Bis(Di-(Tert Butyl)(4-Trifluoromethyl)Phenyl(Phosphine) Palladium (II) Chloride or Bis(Dicyclohexyl)(4-Dimethylaminophenylphosphine) Palladium (II) Chloride Catalyst

(3) The same basic procedure as example 1A was used. The catalyst was selected from bis(di-(tert butyl)(4-trifluoromethyl)phenyl(phosphine) palladium (II) chloride (A) or bis(dicyclohexyl)(4-dimethylaminophenylphosphine) palladium (II) chloride (B)

(4) TABLE-US-00002 Pressure Catalyst 1234yf Ethanol Time Temperature CO drop Yield (g) (g) (g) (hrs) (? C.) (Barg) (Barg) (%) n:i A (0.50) 10.5 9.35 66 120 47.5 28.5 99.4 1:1.49 B (0.52) 11.2 9.49 46 120 54 8 33.5 1:5.8

Example 2Esterification of HFO with Alcohol

(5) The same basic procedure as example 1A was used. The experiments were repeated in a larger scale reactor (450 ml).

(6) TABLE-US-00003 Expt. Parr1 ** Parr2 Parr3 Parr4 HFO (g) 1243ze-E E-1234ze-E 1234yf 1234yf 39.2 36.9 35.1 36 Catalyst (g) A B B B 1.27 1.3 1.26 1.2 Solvent (g) ACN ACN ACN ACN 133.1 131.1 127.66 137 Alcohol (g) EtOH EtOH EtOH EtOH 34.5 34.3 37.86 35 Temperature 100 100 100 100 (? C.) Pressure 78 80 79 102* (barg) Pressure 6 6 11 20 drop (barg) Duration 72 72 69 72 (hrs) Ester yield 24.6 25.0 89.6 94.4 (%) *80 bar CO and 22 bar nitrogen. ** comparative example.

Example 3Esterification of 1243zf with Diol

(7) The following steps were followed. The reactor was charged with catalyst (bis(triphenylphoshine)palladium (II) chloride (2.26 g)), solvent (acetonitrile, 133 g) and alcohol (2,2-dimethyl propane diol, 36.4 g), inside a nitrogen purged glovebox. Then sealed and removed from the glovebox. The reactor contents were stirred. The HFO substrate (1243zf, 39 g) was then added from a pre-loaded and weighed sample bomb. The reactor was then pressurised with CO to c.a. 110 barg and the reactor contents heated to the desired reaction temperature (120? C.) with stirring. After 22 hours the pressure had dropped to 62 barg. The reactor contents were cooled and any residual pressure vented. A second portion of HFO substrate (1243zf, 43 g) was then added from a pre-loaded and weighed sample bomb. The reactor was then pressurised with CO to c.a. 108 barg and the reactor contents heated to the desired reaction temperature (120? C.) with stirring. After 72 hours the pressure had dropped to 80 barg. At the end of the experiment the reactor contents were cooled, and any residual pressure vented before the crude product was recovered.

(8) The recovered crude product was analysed by GC-MS and NMR spectroscopy. GC-MS analysis of the crude reaction mixture showed that the reaction mixture comprised all 5 possible ester products:

(9) TABLE-US-00004 Product GC-MS Area % 12.6 0 7.2 20.4 40.6 19.2 .sup.19F NMR (56 MHz) analysis of the crude reaction mixture confirmed the presence of: Iso-ester functions (R-OCOCH(CH.sub.3)CF.sub.3) ? ?70.95 ppm (vs C.sub.6F.sub.6, doublet, J = 8.7 Hz) n-esters functions (ROCOCH.sub.2CH.sub.2CF.sub.3) ? ?68.14 ppm (vs C.sub.6F.sub.6, triplet, J = 10.6 Hz)

Example 4Esterification of 1234yf with Diol

(10) The following steps were followed. The reactor was charged with catalyst (bis(triphenylphoshine)palladium (11) chloride (2.22 g)), solvent (acetonitrile, 131.7 g) and alcohol (2,2-dimethyl propane diol, 34.9 g), inside a nitrogen purged glovebox. Then sealed and removed from the glovebox. The reactor contents were stirred. The HFO substrate (1234yf; 104 g) was then added from a pre-loaded and weighed sample bomb. The reactor was then pressurised with CO to c.a. 107 berg and the reactor contents heated to the desired reaction temperature (120? C.) with stirring. After 66 hours the pressure had dropped to 57 barg. At the end of the experiment the reactor contents were cooled, and any residual pressure vented before the crude product was recovered. The recovered crude product was analysed by GC-MS and NMR spectroscopy.

(11) GC-MS analysis of the crude reaction mixture showed that the reaction mixture comprised all 5 possible ester products:

(12) TABLE-US-00005 Product GC-MS Area % 63.7 2.0 29.4 1.6 3.3 .sup.19F NMR (56 MHz) analysis of the crude reaction mixture confirmed the presence of: Iso-ester functions (R-OCOCF(CH.sub.3)CF.sub.3) ? (vs C.sub.6F.sub.6): CF.sub.3 ?80.6 ppm, CF ?169 (multiplet) n-esters functions (ROCOCH.sub.2CHFCF.sub.3) ? (vs C.sub.6F.sub.6): CF.sub.3 ?80.6 ppm, CHF ?201 (multiplet)

Example 5Esterification of 1234yf with Triol

(13) The following steps were followed. The reactor was charged with catalyst (bis(triphenylphoshine)palladium (II) chloride (1.91 g)), solvent (acetonitrile, 130.54 g) and alcohol (1,1,1-Tris(hydroxylmethyl)propane, 29.44 g), inside a nitrogen purged glovebox. Then sealed and removed from the glovebox. The reactor contents were stirred. The HFO substrate (1234yf, 92 g) was then added from a pre-loaded and weighed sample bomb. The reactor was then pressurised with CO to c.a. 107 barg and the reactor contents heated to the desired reaction temperature (120? C.) with stirring. As the pressure dropped in the reactor it was re-pressurised to 107 barg with CO twice After 79 hours the final pressure was 68 barg. At the end of the experiment the reactor contents were cooled, and any residual pressure vented before the crude product was recovered. The recovered crude product was analysed by GC-MS.

(14) A complex mixture of esters was produced, and the yield of these esters was estimated to be 104 g.

Example 6Esterification of a Propenyl Ether

(15) The following steps were followed. The reactor was charged with catalyst (bis(di(tert butyl)(4 trifluoromethyl)phenyl(phosphine) palladium chloride (0.37)), solvent (acetonitrile, 29.1 g) and alcohol (ethanol, 10.16 g) and the propenyl ether (3,3,3-trifluoro-1(2,2,2-trifluoroethoxy)prop-1-ene (13.3 g), inside a nitrogen purged glovebox. Then sealed and removed from the glovebox. The reactor contents were stirred. The reactor was then pressurised with CO to c.a. 107 barg and the reactor contents heated to the desired reaction temperature (120? C.) with stirring (300 rpm). After 90 hours the pressure had dropped by 7.2 barg. At the end of the experiment the reactor contents were cooled, and any residual pressure vented before the crude product was recovered.

(16) The recovered reaction mixture was analysed by .sup.19F NMR, which showed signals at ?60.93 and ?64.96 ppm corresponding to the CF.sub.3 (highlighted and underlined) groups in the acyl fragments of the products. These signals were in a ratio of 1:1 with the overlapping signals centred on ?75.74 of the CF.sub.3 groups in the ether functional group OCH.sub.2CF.sub.3 of both of the isomeric products.

(17) ##STR00019##

(18) Analysis of the crude reaction mixture by GC-MS showed that (excluding solvent and excess ethanol) the crude product comprised a mixture of these esters (84.7%) and unconverted feedstock (11.4%).

FIGURES

(19) FIGS. 1-11 illustrate the results of various spectroscopic analytical techniques carried out on some of the reaction products from the Examples.

(20) FIG. 1 shows MS data for product of 1234ze carbonylation with ethanol C.sub.6H.sub.8O.sub.2F.sub.4 MW 188. In the figure the following peaks have been assigned; m/z: 187 [M.sup.+?1H], 173 [M.sup.+?15 (CH.sub.3)], 161 [M.sup.+?27 (C.sub.2H.sub.3)], 143 [M.sup.+?45 (OCH.sub.2CH.sub.3)], 121 [C.sub.4H.sub.3F.sub.2O.sub.2.sup.+], 115 [M.sup.+?73 (CO.sub.2CH.sub.2CH.sub.3)], 95 [C.sub.3F.sub.3H.sub.2.sup.+], 69 [CF.sub.3.sup.+], 51 [CHF.sub.2.sup.+], 45 [OCH.sub.2CH.sub.3.sup.+].

(21) FIG. 2 shows MS data for product of 1234yf carbonylation with ethanol. C.sub.6H.sub.8O.sub.2F.sub.4 MW 188. In the figure the following peaks have been assigned; m/z: 187 [M.sup.+?1 H], 173 [M.sup.+?15 (CH.sub.3)], 161 [M.sup.+?27 (C.sub.2H.sub.3)], 143 [M.sup.+?45 (OCH.sub.2CH.sub.3)], 115 [M.sup.+?73 (CO.sub.2CH.sub.2CH.sub.3)], 96 [C.sub.3F.sub.3H.sub.3+], 94 [C.sub.3F.sub.3H.sup.+], 69 [CF.sub.3.sup.+], 65 [C.sub.2H.sub.3F.sub.2.sup.+], 51 [CHF.sub.2.sup.+], 45 [OCH.sub.2CH.sub.3.sup.+].

(22) FIG. 3 shows MS data for product of 1336mzz carbonylation with ethanol. C.sub.7H.sub.8O.sub.2F.sub.6 MW 238. In the figure the following peaks have been assigned; m/z: 238 [M.sup.+], 218 [M.sup.+?20 (HF)], 210 [M.sup.+?28 (C.sub.2H.sub.4)], 193 [M.sup.+?45 (OCH.sub.2CH.sub.3)], 165 [M.sup.+?73 (CO.sub.2CH.sub.2CH.sub.3)], 151 [C.sub.3HF.sub.6.sup.+], 145 [C.sub.4H.sub.2F.sub.5.sup.+], 123 [C.sub.4F.sub.2H.sub.5O.sub.2.sup.+], 95 [C.sub.3F.sub.3H.sub.2.sup.+], 77[C.sub.3H.sub.3F.sub.2.sup.+], 69 [CF.sub.3.sup.+], 51 [CHF.sub.2.sup.+], 45 [OCH.sub.2CH.sub.3+].

(23) FIG. 4 shows a .sup.19F NMR spectrum of a 1234ze ethoxy-carbonylation reaction product.

(24) FIG. 5 shows a .sup.19F COSY NMR spectrum of a 1234ze ethoxy-carbonylation reaction product.

(25) FIG. 6 shows .sup.13C CPD (red) and DEPT135 (blue) NMR spectra of a 1234ze ethoxy-carbonylation reaction product.

(26) FIG. 7 shows a .sup.19F NMR spectrum of a 1234yf ethoxy-carbonylation reaction product.

(27) FIG. 8 shows a .sup.19F COSY NMR spectrum of a 1234yf ethoxy-carbonylation reaction product.

(28) FIG. 9 shows .sup.13C CPD (red) and DEPT135 (blue) NMR spectra of a 1234yf ethoxy-carbonylation reaction product.

(29) FIG. 10 shows .sup.19F NMR spectrum of a 1336mzz ethoxy-carbonylation reaction product.

(30) FIG. 11 shows .sup.13C CPD (red) and DEPT135 (blue) NMR spectra of a 1336mzz ethoxy-carbonylation reaction product.