METHOD FOR PREPARING PARTIALLY FLUORINATED ALCOHOL

Abstract

A method for preparing a partially fluorinated alcohol. comprises reacting an epoxide: wherrein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from the group comprising H, F, Cl, Br, I, CF.sub.3, alkyl, fluoroalkyl, haloalkyl with a fluorinating agent.

##STR00001##

Claims

1.-8. (canceled)

9. Compounds with either of the following structures ##STR00025## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from the group consisting of H, F, Cl, Br, I, CF.sub.3, alkyl, fluoroalkyl, and haloalkyl, with the provision that the compound is not 1,1,1,3-tetrafluoropropan-2-ol.

10. A compound of claim 9, formed by the process comprising reacting an epoxide: ##STR00026## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from the group consisting of H, F, Cl, Br, I, CF.sub.3, alkyl, fluoroalkyl, and haloalkyl; with a fluorinating agent.

11. A method for preparing a partially fluorinated carbonate ester with the structure ##STR00027## comprising reacting a fluorohydrin having either of the following structures ##STR00028## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from the group consisting of H, F, Cl, Br, I, CF.sup.3, alkyl, fluoroalkyl, and haloalkyl with COX.sub.2, wherein X is selected from the group consisting of fluorohydrin F, Cl, OCH.sub.3, OCCl.sub.3, imidazole, and succinimidyl.

12. A compound with the structure ##STR00029## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from the group consisting of H, F, Cl, Br, I, CF.sub.3, alkyl, fluoroalkyl, and haloalkyl.

13. A composition comprising the compound with the structure according to claim 12 ##STR00030##

14. A solvent composition comprising the compound according to claim 12.

15. A solvent composition comprising the composition according to claim 13.

16. A solvent composition according to claim 14, wherein the composition comprises an electrolyte comprising a lithium salt, selected from the group comprising lithium hexafluorophosphate (LiPF.sub.6), lithium triflate (LiSO.sub.3CF.sub.3), lithium bis(fluorosulfonyl)imide (Li(FSO.sub.2).sub.2N) and lithium bis(trifluoromethanesulfonyl)imide (Li(CF.sub.3SO.sub.2).sub.2N).

17. A method for preparing a fluorinated compound, comprising reacting a compound having either of the following structures: ##STR00031## wherein at least 2 of R.sup.1 to R.sup.4 independently comprise H, Cl, Br, or l; with a fluorinating agent.

18. The method according to claim 17, wherein in the fluorinated compound at least 2 of R.sup.1 to R.sup.4 independently comprise F, CF.sub.3 or a fluoroalkyl.

19. The method according to claim 17, wherein in the fluorinated compound at least 1 of R.sup.1 to R.sup.4 comprises H.

20. The method according to claim 17, wherein the fluorinated compound comprises hexafluoroisopropanol.

21. A method for preparing a partially fluorinated epoxide, comprising reacting a partially fluorinated alkene: ##STR00032## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from the group consisting of H, F, Cl, Br, I, CF.sub.3, alkyl, fluoroalkyl, and haloalkyl; with an oxidising agent.

22. The method according to claim 21, wherein the oxidising agent is selected from the group consisting of air, oxygen and oxygen containing compounds.

23. The method according to claim 21, wherein the oxidising agent comprises a hypohalite.

23. (canceled)

24. The method for preparing a partially fluorinated alcohol, comprising a method for preparing a partially fluorinated epoxide according to claim 21 and reacting the partially fluorinated epoxide with a fluorinating agent.

25. The method for preparing a partially fluorinated alcohol, comprising a method for preparing a partially fluorinated epoxide according to claim 21, reacting the partially fluorinated epoxide with a first fluorinating agent to form a compound having at least either of the following structures: ##STR00033## wherein at least 2 of R.sup.1 to R.sup.4 independently are H, Cl, Br, or l; and reacting the compound having the at least either of the above structures with a second fluorinating agent.

26. A method for preparing a partially fluorinated ether with the structure ##STR00034## comprising reacting a fluorohydrin having either of the following structures ##STR00035## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from the group consisting of H, F, Cl, Br, I, CF.sub.3, alkyl, fluoroalkyl, or haloalkyl.

27. A compound with the structure ##STR00036## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from the group consisting of H, F, Cl, Br, I, CF.sub.3, alkyl, fluoroalkyl, and haloalkyl.

28. A composition comprising the compound with the structure according to claim 27 ##STR00037##

29. A solvent composition comprising the compound according to claim 27.

30. A coolant composition comprising the composition according to claim 28.

31. A method for preparing a partially fluorinated ether with the structure ##STR00038## comprising reacting a fluorohydrin having either of the following structures ##STR00039## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 are independently selected from the group comprising H, F, Cl, Br, I, CF.sub.3, alkyl, fluoroalkyl, haloalkyl and R.sup.5 is independently selected from the group consisting of CF.sub.3, alkyl, fluoroalkyl, perfluoroalkyl, haloalkyl and perfluorohaloalkyl.

32. A compound with the structure ##STR00040## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 are independently selected from the group comprising H, F, Cl, Br, I, CF.sub.3, alkyl, fluoroalkyl, haloalkyl and R.sup.5 is independently selected from the group consisting of CF.sub.3, alkyl, fluoroalkyl, perfluoroalkyl, haloalkyl and perfluorohaloalkyl.

33. A composition comprising the compound with the structure according to claim 32 ##STR00041##

34. A solvent composition comprising the compound according to claim 32.

35. A coolant composition comprising the composition according to claim 33.

36. A method according to claim 21, wherein the alkene comprises: a tetrafluoropropene from the group consisting of 1,3,3,3-Tetrafluoropropene (1234ze) and 2,3,3,3-Tetrafluoropropene (1234yf); or a pentafluoropropene consisting of 1,1,3,3,3-Pentafluoropropene (1225zc).

Description

EXAMPLES

Example 1Ring Opening of an Epoxide with Olah's Reagent

[0055] The following steps were followed. [0056] The reactor was charged with Olah's reagent (70% HF:Pyridine, 5 ml) and cooled in an ice batch with stirring. [0057] 2,3-epoxyl,1,1-trifluoropropane (TFPO) (3.4 g) was then added dropwise. [0058] At the end of the addition the reaction mixture was allowed to warm up to room temperature; stirring was continued for 48 hours. [0059] After 48 hours the reaction mixture was quenched with ice. [0060] Salt was added, and the product extracted with diethyl ether (3?5 ml). The diethyl ether extracts were combined, washed with saturated potassium bicarbonate solution and water before being dried over anhydrous sodium sulphate. Diethyl ether was removed in vacuo to yield the desired product as a clear, colourless liquid boiling point 91-93? C. The identity of this product was confirmed by NMR spectroscopy.

Example 2Ring Opening of 2,3-epoxy-1,1,1,3-tetrafluoropropane with Olah's Reagent

[0061] ##STR00022##

[0062] 2,3-epoxy-1,1,1,3-tetrafluoropropane was ring opened using the following procedure: [0063] A 100 ml Hastalloy C pressure reactor was charged with Olah's reagent (70% HF:Pyridine, 25 g). [0064] After sealing, the contents of the reactor were cooled to 20? C. with stirring. [0065] 2,3-epoxy-1,1,1,3-tetrafluoropropane (11 g) was then added. [0066] After this addition was complete the reaction mixture was heated to 50? C. and stirred for 168 hours. [0067] After 168 hours the reaction mixture was quenched with ice and saturated sodium chloride solution (22 ml) added. [0068] The product was extracted from this mixture with diethyl ether. [0069] The diethyl ether extracts were combined, washed with saturated potassium bicarbonate solution and then water before being dried over anhydrous sodium sulphate. The identity of the product was confirmed by NMR spectroscopy.

Example 2aRing Opening of 2,3-epoxy-1,1,1,3-tetrafluoropropane with Olah's Reagent

[0070] ##STR00023##

[0071] 2,3-epoxy-1,1,1,3-tetrafluoropropane was ring opened using the following procedure: [0072] A 100 ml Hastalloy C pressure reactor was charged with Olah's reagent (70% HF:Pyridine, 25 g). [0073] After sealing, the contents of the reactor were cooled to 20? C. with stirring. [0074] 2,3-epoxy-1,1,1,3-tetrafluoropropane (10.6 g) was then added. [0075] After this addition was complete the reaction mixture was heated to 80? C. and stirred for 43 hours. [0076] After 43 hours a sample of the reaction mixture was analysed by GCMS and it was found that all the feed epoxide had reacted. [0077] After cooling the reaction mixture was quenched with ice and saturated sodium chloride solution (22 ml) added. [0078] The product was extracted from this mixture with diethyl ether. [0079] The diethyl ether extracts were combined, washed with saturated potassium bicarbonate solution and then water before being dried over anhydrous sodium sulphate. The identity of the product was confirmed by NMR spectroscopy.

Example 3Ring Opening of 2,3-epoxy-1,1,1-trifluoro-2-(trifluoromethyl)Propane with Olah's Reagent

[0080] ##STR00024##

[0081] 2,3-epoxy-1,1,1-trifluoro-2-(trifluoromethyl)propane was ring opened using the following procedure: [0082] A 100 ml Hastalloy C pressure reactor was charged with Olah's reagent (70% HF:Pyridine, 16.5 g). [0083] After sealing, the contents of the reactor were cooled to 20? C. with stirring. [0084] 2,3-epoxy-1,1,1-trifluoro-2-(trifluoromethyl)propane (10 g) was then added. [0085] After this addition was complete the reaction mixture was heated to 50? C. and stirred for 160 hours. [0086] After 160 hours the reaction mixture was quenched with ice and saturated sodium chloride solution (22 ml) added. [0087] The product was extracted from this mixture with diethyl ether. [0088] The diethyl ether extracts were combined, washed with saturated potassium bicarbonate solution and then water before being dried over anhydrous sodium sulphate. The identity of the product was confirmed by NMR spectroscopy.

Example 4Preparation of di-(1,1,1,3-tetrafluoropropyl) Carbonate with Phosgene

[0089] Di-(1,1,1,3-tetrafluoropropyl) carbonate was synthesised using the following procedure: [0090] A three necked round bottom flask was cooled to 0? C. under an inert atmosphere. [0091] Phosgene solution (15% by weight in toluene, 50 mL of solution) was added and stirred. [0092] A mixture of 1,1,1,3-tetrafluoropropan-2-ol (18.42 g) and pyridine (11.02 g) was added to the solution dropwise, and the temperature of the solution was monitored to ensure it did not rise above 10? C. [0093] The solution was allowed to warm to room temperature and stirred for 48 hours. [0094] The product was filtered to remove pyridinium salts and the solvent was removed in vacuo to yield the crude product. [0095] The crude product was distilled under atmospheric conditions to yield di-(1,1,1,3-tetrafluoropropyl) carbonate as a yellow oil (7.08 g, 35% yield).

FIGURES

[0096] The Figures illustrates the results of various spectroscopic analytical techniques carried out on some of the reaction products from the Examples.

[0097] FIG. 1 shows a .sup.19F NMR spectrum of the reaction product of 2,3-epoxyl, 1,1-trifluoropropane (TFPO) with Olah's reagent.

[0098] FIG. 2a shows a .sup.19F NMR spectrum of the reaction product of 2,3-epoxy-1,1,1,3-tetrafluoropropane ring opening with Olah's reagent.

[0099] FIG. 2b shows a proton coupled .sup.19F NMR spectrum of the reaction product of 2,3-epoxy-1,1,1,3-tetrafluoropropane ring opening with Olah's reagent.

[0100] FIG. 2c shows a proton decoupled .sup.19F NMR spectrum of the reaction product of 2,3-epoxy-1,1,1,3- tetrafluoropropane ring opening with Olah's reagent.

[0101] FIG. 3 shows a .sup.19F NMR spectrum of the reaction product of 2,3-epoxy-1,1,1-trifluoro-2-(trifluoromethyl)propane) ring opening with Olah's reagent.

[0102] FIG. 4 shows a .sup.19F NMR spectrum of the reaction product of 1,1,1,3-tetrafluoropropan-2-ol with phosgene, consistent with that of the product di-(1,1,1,3-tetrafluoropropyl) carbonate.