Method for preparing fluorinated alcohol

Abstract

To provide a method for preparing a partially fluorinated alcohol.SOLUTION: The method comprises reacting an epoxide represented by the formula in the figure (where R1, R2, R3 and R4 are independently selected from the group comprising H, F, Cl, Br, I, CF3, alkyl, fluoroalkyl, haloalkyl) with a fluorinating agent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a process for preparing partially fluorinated alcohols (fluorohydrins) from fluorinated epoxides, and to a process for preparing fluorinated carbonates from fluorohydrins. [Background technology]

[0002] Fluorohydrins are useful as solvents and as synthetic building blocks from which a variety of species such as esters, ethers, ketones, aldehydes, and acids can be prepared. Of particular interest is their utility in the preparation of fluorinated carbonates, an important class of materials with significant commercial value. Fluorinated carbonates are commonly used without modification as synthetic intermediates and as solvents in electronic devices such as batteries (e.g., lithium ion batteries), and to manufacture products such as lubricants, sealants, and coatings.

[0003] The production of fluorohydrins from epoxides is known in the art. For example, Olah describes a general method for preparing fluorohydrins by ring-opening epoxides with a nucleophilic source of fluoride (GA Olah et al, Israel Jr. Chem., 17 (1978), 148-149). However, Olah did not extend this work to the preparation of fluorohydrins from fluorinated epoxides.

[0004] The ring-opening of the fluorinated epoxide, 2,3-epoxy 1,1,1-trifluoropropane (TFPO), with various nucleophiles to form fluorohydrins was reviewed in a discussion of the chemical reactions of TFPO by Uneyama in Jr. Fluorine Chem., 105 (2000) 285-293. However, this discussion did not address the possibility or possible results of attempting the ring-opening of TFPO, or indeed any other fluorinated epoxide, with the nucleophilic fluorinating agents taught by Olah.

[0005] General methods for producing carbonates from alcohols and carboxylating agents are known in the art and are described, for example, in "March's Advanced Organic Chemistry", M.B. Smith and J. March, 6 th See, e.g., U.S. Pat. No. 5,333,393, issued Dec. 19, 1999, page 1276. However, the formation of a fluorinated carbonate from a fluorohydrin and a carboxylating agent as a product of such a reaction is not known. DISCLOSURE OF THEINVENTION

[0006] According to a first aspect of the present invention, there is provided a process for preparing a partially fluorinated alcohol, comprising: [ka] (In the formula, R 1 , R 2 , R 3 , and R 4 is independently selected from the group consisting of H, F, Cl, Br, I, CF3, alkyl, fluoroalkyl, haloalkyl) with a fluorinating agent.

[0007] Preferably, R 1 ~R 4 At least one of contains F, CF3, or fluoroalkyl.

[0008] Preferably, the fluorinating agent comprises a nucleophilic fluorinating agent, examples of which include HF and complexes of HF with nitrogen-containing species such as Oller's reagent (HF:pyridine complex), complexes of HF with urea, or complexes of HF with tertiary amines.

[0009] The method can include reacting an epoxide of 3,3,3-trifluoropropene (1243zf) with HF and / or Oller's reagent to form CF3CH(OH)CH2F. [ka]

[0010] The method can include reacting an epoxide of 1,3,3,3-tetrafluoropropene (1234ze) with HF and / or Oller's reagent to form CF3CH(OH)CHF2. [ka]

[0011] The method can include reacting the epoxide of 1,1,1,4,4,4-hexafluoro-2-butene (1336mzz) with HF and / or Oller's reagent to form CF3CH(OH)CHF(CF3). [ka]

[0012] The method can include reacting an epoxide of 1,1,3,3,3-pentafluoropropene (1225zc) with HF and / or Oller's reagent to form CF3CH(OH)CF3. [ka]

[0013] Compounds and Compositions of the Invention According to a second aspect of the present invention, a structure [ka] (In the formula, R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of H, F, Cl, Br, I, CF3, alkyl, fluoroalkyl, haloalkyl), with the proviso that the compound is not 1,1,1,3-tetrafluoropropan-2-ol.

[0014] The compounds of the second aspect of the invention may be used in the preparation of carbonate esters.

[0015] According to a third aspect of the present invention, there is provided a process for preparing a partially fluorinated carbonate having the structure: [ka] Fluorohydrin [ka] (In the formula, R 1 , R 2 , R 3 , and R 4 is independently selected from the group including H, F, Cl, Br, I, CF3, alkyl, fluoroalkyl, haloalkyl) with COX2, where X is selected from the group including -F, -Cl, -OCH3, -OCCl3, imidazole, succinimidyl.

[0016] Preferably, 2 equivalents of fluorohydrin are used per equivalent of COX2 (on a molar basis).

[0017] Alternatively, one equivalent of a fluorohydrin of the present invention can be used with one equivalent of an alcohol species (branched or linear mono / polyhydric alcohol) to prepare an asymmetric carbonate.

[0018] Compounds produced by the method according to the third aspect of the invention are covered by the fourth aspect of the invention. According to the fourth aspect of the invention, [ka] (In the formula, R 1 , R 2 , R 3 , and R 4 are independently selected from the group including H, F, Cl, Br, I, CF3, alkyl, fluoroalkyl, haloalkyl.

[0019] The compounds of the fourth aspect of the present invention can also be used as battery solvent components (e.g., in lithium-ion batteries).The compounds herein have been found to be beneficial as a result of their physical properties, electrochemical stability, compatibility with battery components such as carbon- and silicon-containing electrodes, lithium-containing electrolyte salts, separators, binders, battery electrodes (cathode and anode) including current collectors, and low flammability.

[0020] The compounds of the fourth aspect of the invention may also be used with other solvents and additives, such as other linear and cyclic carbonates.

[0021] Preferably, when used as a solvent, the composition comprises an electrolyte salt. Preferred examples of electrolyte salts include lithium-type electrolytes such as those selected from the group including lithium hexafluorophosphate (LiPF6), lithium triflate (LiSO3CF3), lithium bis(fluorosulfonyl)imide (Li(FSO2)2N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CF3SO2)2N).

[0022] The compounds of the second aspect of the present invention can be used to prepare (higher) fluorinated derivatives. One or more of the R groups may be substituted with fluorine. The R groups modified by fluorination in this process are preferably selected from the group including H, Cl, Br, I.

[0023] The preparation process for fluorinated derivatives may include a multi-step process, preferably a two-step process, depending on the nature of the R group to be modified. In a preferred two-step process, the first step is to modify the target R group to a (different) halogen group, preferably a chlorine group (using a suitable chlorinating agent such as chlorine), and in the second step, the chlorine group is modified to a fluorine group (using a suitable fluorinating agent such as HF, or a metal fluoride salt such as NaF, KF). It will be understood that if the target R group already contains a halogen other than fluorine, the two-step process of replacing the halogen with chlorine may not be necessary.

[0024] Therefore, the compound [ka] (In the formula, R 1 ~R 4 at least two of which independently contain H, Cl, Br, I) can be converted to (more highly) fluorinated derivatives.

[0025] R in fluorinated derivatives 1 ~R 4 Preferably at least two, more preferably at least three of R independently comprise F, CF, or fluoroalkyl. 1 ~R 4 and more preferably at least one of R 1 ~R 4 and R 1 ~R 4 One of the groups contains CF3 and R 1 ~R 4 Two of them contain F and R 1 ~R 4 One of the groups comprises H. Most preferably, the fluorinated derivative comprises hexfluroroisopropanol.

[0026] compound [ka] (The preferred alternative is ·R 1 is -CF3, R 2 is H and R 3 and R 4 Both are H. ·R 1 is -CF3, R 2 is H and R 3 and R 4 One of the groups is H and the other is R 3 and R 4The preferred reaction pathway occurs when one of the

[0027] This preferred route is shown below. [ka] X is either F or Cl.

[0028] Epoxides useful in the first aspect of the invention can be prepared from fluorinated alkenes. According to a fifth aspect of the invention, there is provided a process for preparing partially fluorinated epoxides comprising: [ka] (In the formula, R 1 , R 2 , R 3 , and R 4 is independently selected from the group including H, F, Cl, Br, I, CF3, alkyl, fluoroalkyl, haloalkyl) with an oxidizing agent.

[0029] Preferably, R 1 ~R 4 At least one of contains F, CF3, or fluoroalkyl.

[0030] Preferred examples of oxidizing agents include air, oxygen, and oxygen-containing compounds such as peroxides, persalts, and compounds of oxygen and other elements such as hypohalites. Preferably, the oxidizing agent comprises a hypohalite such as chlorite.

[0031] Preferably, the compound reacted with the oxidizing agent is tetrafluoropropene. Most preferably, R 1 and R 2 One of the groups is -CF3, and R 3 and R 4One of the is -F. Thus, the tetrafluoropropene is 1,3,3,3-tetrafluoropropene (1234ze) or 2,3,3,3-tetrafluoropropene (1234yf).

[0032] According to a sixth aspect of the present invention, there is provided a process for preparing a fluorohydrin comprising the fifth and first aspects of the present invention.

[0033] According to a seventh aspect of the present invention, there is provided a process for preparing a partially fluorinated ether having the structure: [ka] structure [ka] (In the formula, R 1 , R 2 , R 3 , and R 4 is independently selected from the group including H, F, Cl, Br, I, CF3, alkyl, fluoroalkyl, haloalkyl.

[0034] According to an eighth aspect of the present invention, a structure [ka] (In the formula, R 1 , R 2 , R 3 , and R 4 are independently selected from the group including H, F, Cl, Br, I, CF3, alkyl, fluoroalkyl, haloalkyl.

[0035] According to a ninth aspect of the present invention there is provided a composition comprising a compound according to the eighth aspect of the present invention.

[0036] The compound of the eighth aspect of the invention or the composition according to the ninth aspect of the invention may be used as a solvent, for example in battery applications.

[0037] The compound of the eighth aspect of the invention or the composition according to the ninth aspect of the invention may be used as a coolant, for example an immersion coolant.

[0038] Also provided is a method for preparing a partially fluorinated ether having the structure: [ka] structure [ka] (In the formula, R 1 , R 2 , R 3 , R 4 is independently selected from the group consisting of H, F, Cl, Br, I, CF3, alkyl, fluoroalkyl, and haloalkyl; R 5 is independently selected from the group CF3, alkyl, fluoroalkyl, perfluoroalkyl, haloalkyl, perfluorohaloalkyl.

[0039] Preferably, the ether synthesis occurs via the acid catalyzed dehydration of a fluorohydrin.

[0040] Alternatively, ether synthesis occurs via one or more of the following techniques: i. Alkoxy dehalogenation - reaction of an alkyl halide with a fluorohydrin, preferably under basic conditions; ii. Alkoxydesulfonyloxy substitution - reaction of a fluorohydrin sulfate with an alkoxide or a fluorohydrin alkoxide; iii. Hydro, alkoxy dediazodisubstitution - reaction of fluorohydrins with diazo compounds; iv. Alkoxy dehydroxylation - dehydration of two alcohols to give an ether, for example using concentrated sulfuric acid; v. Transesterification of hydroxy or alkoxy dealkoxylated-(fluorohydrin) ethers with alcohols or fluorohydrins, and / or vi. Alkoxy dehydroxylation - reaction of alcohols or fluorohydrins with oxonium compounds.

[0041] Additionally provided is a compound having the structure: [ka]

[0042] Also provided is a composition comprising a compound having the structure: [ka] The compound or composition may be used, for example, as a solvent in battery applications.

[0043] The compound or composition may be used as a coolant, for example an immersion coolant.

[0044] The invention will now be described with reference to the following non-limiting examples. EXAMPLES

[0045] Example 1 - Ring opening of epoxides using Oller's reagent The following steps were followed: The reactor was charged with Oller's Reagent (70% HF:pyridine, 5 ml) and cooled with an ice batch while stirring. Then 2,3-epoxy 1,1,1-trifluoropropane (TFPO) (3.4 g) was added dropwise. At the end of the addition, the reaction mixture was allowed to warm to room temperature and stirring was continued for 48 h. After 48 hours, the reaction mixture was quenched with ice. Salt was added and the product was extracted with diethyl ether (3 x 5 ml). The diethyl ether extracts were combined, washed with saturated potassium bicarbonate solution and water, and then dried over anhydrous sodium sulfate. The diethyl ether was removed in vacuo to give the desired product as a clear, colorless liquid boiling at 91-93°C. The identity of the product was confirmed by NMR spectroscopy.

[0046] Example 2 - Ring opening of 2,3-epoxy-1,1,1,3-tetrafluoropropane using Oller's reagent [ka] The following procedure was used to ring open 2,3-epoxy-1,1,1,3-tetrafluoropropane. A 100 ml Hastalloy C pressure reactor was charged with Oller's reagent (70% HF:pyridine, 25 g). After sealing, the reactor contents were cooled to 20°C with stirring. Then 2,3-epoxy-1,1,1,3-tetrafluoropropane (11 g) was added. After this addition was complete, the reaction mixture was heated to 50° C. and stirred for 168 hours. After 168 hours, the reaction mixture was quenched with ice and saturated sodium chloride solution (22 ml) was added. The product was extracted from this mixture using diethyl ether. The diethyl ether extracts were combined, washed with saturated potassium bicarbonate solution and then with water, and then dried over anhydrous sodium sulfate. The identity of the product was confirmed by NMR spectroscopy.

[0047] Example 2a - Ring opening of 2,3-epoxy-1,1,1,3-tetrafluoropropane with Oller's reagent [ka] The following procedure was used to ring open 2,3-epoxy-1,1,1,3-tetrafluoropropane. A 100 ml Hastalloy C pressure reactor was charged with Oller's reagent (70% HF:pyridine, 25 g). After sealing, the reactor contents were cooled to 20°C with stirring. Then 2,3-epoxy-1,1,1,3-tetrafluoropropane (10.6 g) was added. After the addition was complete, the reaction mixture was heated to 80° C. and stirred for 43 hours. After 43 hours, a sample of the reaction mixture was analyzed by GCMS and it was found that all the feed epoxide had reacted. After cooling, the reaction mixture was quenched with ice and saturated sodium chloride solution (22 ml) was added. The product was extracted from this mixture using diethyl ether. The diethyl ether extracts were combined, washed with saturated potassium bicarbonate solution and then with water, and then dried over anhydrous sodium sulfate. The identity of the product was confirmed by NMR spectroscopy.

[0048] Example 3 - Ring opening of 2,3-epoxy-1,1,1-trifluoro-2-(trifluoromethyl)propane with Oller's reagent [ka] The following procedure was used to ring open 2,3-epoxy-1,1,1-trifluoro-2-(trifluoromethyl)propane. A 100ml Hastalloy C pressure reactor was charged with Oller's reagent (70% HF:pyridine, 16.5g). After sealing, the reactor contents were cooled to 20°C with stirring. Then 2,3-epoxy-1,1,1-trifluoro-2-(trifluoromethyl)propane (10 g) was added. After the addition was complete, the reaction mixture was heated to 50° C. and stirred for 160 hours. After 160 hours, the reaction mixture was quenched with ice and saturated sodium chloride solution (22 ml) was added. The product was extracted from this mixture using diethyl ether. The diethyl ether extracts were combined, washed with saturated potassium bicarbonate solution and then with water, and then dried over anhydrous sodium sulfate. The identity of the product was confirmed by NMR spectroscopy.

[0049] Example 4 - Preparation of di-(1,1,1,3-tetrafluoropropyl)carbonate using phosgene Di-(1,1,1,3-tetrafluoropropyl)carbonate was synthesized using the following procedure. Under an inert atmosphere, a three-neck round-bottom flask was cooled to 0°C. Phosgene solution (15 wt% in toluene, 50 mL of solution) was added and stirred. A mixture of 1,1,1,3-tetrafluoropropan-2-ol (18.42 g) and pyridine (11.02 g) was added dropwise to the solution, monitoring to ensure that the temperature of the solution did not rise above 10°C. The solution was warmed to room temperature and stirred for 48 hours. The product was filtered to remove the pyridinium salt and the solvent was removed in vacuo to give the crude product. The crude product was distilled under atmospheric pressure to give di-(1,1,1,3-tetrafluoropropyl)carbonate as a yellow oil (7.08 g, 35% yield). [Brief description of the drawings]

[0050] The figures show the results of various spectroscopic techniques performed on some of the reaction products from the examples.

[0051] [Figure 1] 1 shows the 19F NMR spectrum of the reaction product of 2,3-epoxy 1,1,1-trifluoropropane (TFPO) with Oller's reagent. [Diagram 2] 19F NMR spectrum of the reaction product of 2,3-epoxy-1,1,1,3-trifluoropropane ring-opened with Oller's reagent. [Figure 2a-1]1 shows a proton coupled 19F NMR spectrum of the reaction product of 2,3-epoxy-1,1,1,3-tetrafluoropropane ring-opened with Oller's reagent. [Figure 2a-2] 1 shows a proton decoupled 19F NMR spectrum of the reaction product of 2,3-epoxy-1,1,1,3-tetrafluoropropane ring-opened with Oller's reagent. [Diagram 3] 19F NMR spectrum of the reaction product of 2,3-epoxy-1,1,1-trifluoro-2-(trifluoromethyl)propane ring-opened with Oller's reagent. [Figure 4] 1 shows the 19F NMR spectrum of the reaction product of 1,1,1,3-tetrafluoropropan-2-ol with phosgene, which matches the spectrum of the product di-(1,1,1,3-tetrafluoropropyl)carbonate.

Claims

1. 1. A process for preparing a partially fluorinated alcohol, comprising: 【Chemistry 1】 (In the formula, R １ , R ２ , R ３ , and R ４ But H, F, Cl, Br, I, CF ３ , alkyl, fluoroalkyl, haloalkyl) with a fluorinating agent.

2. The method of claim 1 , wherein the fluorinating agent comprises a nucleophilic fluorinating agent.

3. 3. The method of claim 1 or 2, wherein the fluorinating agent is selected from HF and complexes of HF with nitrogen-containing species such as Oller's reagent (HF:pyridine complex), complexes of HF with urea, or complexes of HF with tertiary amines.

4. 4. The method of claim 3, wherein the ratio of HF to pyridine is 7:3 by weight.

5. R １ ~R ４ One of the groups is -CF ３ and R １ ~R ４ is -F, and R １ ~R ４ Two of R are -H, preferably １ is -F, and R ３ But -CF ３ and R ２ and R ４ is —H or preferably, R １ is -F, and R ２ But -CF ３ and R ３ and R ４ The method of any one of claims 1 to 4, wherein is -H.

6. R １ ~R ４ Two of them are -CF ３ and R １ ~R ４ Two of R are -H, preferably １ But -CF ３ and R ３ But -CF ３ and R ２ is -H and R ４ The method of any one of claims 1 to 4, wherein is -H.

7. R １ ~R ４ One of the groups is -CF ３ and R １ ~R ４ Three of R are -H, preferably １ But -CF ３ , R ２ , R ３ , and R ４ The method of any one of claims 1 to 4, wherein is -H.

8. R １ ~R ４ One of the groups is -CF ３ and R １ ~R ４ is -Cl, and R １ ~R ４ Two of R are -H, preferably １ is -Cl, and R ３ But -CF ３ and R ２ and R ４ is —H or preferably, R １ is -Cl, and R ２ But -CF ３ and R ３ and R ４ The method of any one of claims 1 to 4, wherein is -H.

9. structure 【Chemistry 2】 (In the formula, R １ , R ２ , R ３ , and R ４ But H, F, Cl, Br, I, CF ３ , alkyl, fluoroalkyl, haloalkyl), with the proviso that said compound is not 1,1,1,3-tetrafluoropropan-2-ol.

10. A compound according to claim 9, formed by the process according to any one of claims 1 to 8.

11. 1. A process for preparing a partially fluorinated carbonate ester having the structure: 【Chemistry 3】 structure 【Chemistry 4】 (In the formula, R １ , R ２ , R ３ , and R ４ But H, F, Cl, Br, I, CF ３ , alkyl, fluoroalkyl, haloalkyl) with COX ２ (Wherein, X is —F, —Cl, —OCH ３ , -OCCl ３ , imidazole, succinimidyl)。

12. A compound having the following structure: 【Chemistry 5】

13. A composition comprising a compound having the structure: 【Chemistry 6】

14. 14. Use of a compound according to claim 12 or a composition according to claim 13 as a solvent, for example in battery applications.

15. A solvent composition comprising the compound of claim 12 or the composition of claim 13.

16. The composition comprises lithium hexafluorophosphate (LiPF ６ ), lithium triflate (LiSO ３ CF ３ ), lithium bis(fluorosulfonyl)imide (Li(FSO ２ ) ２ N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CF ３ SO ２ ) ２ 16. The solvent composition of claim 15, comprising an electrolyte comprising a lithium salt selected from the group consisting of:

17. 1. A method for preparing a fluorinated compound, comprising the steps of: 【Chemistry 7】 (In the formula, R １ ~R ４ wherein at least two of independently comprise H, Cl, Br, I) with a fluorinating agent.

18. R in the fluorinated compound １ ~R ４ At least two of the following are F, CF ３ or fluoroalkyl.

19. R in the fluorinated compound １ ~R ４ The method of claim 17 or 18, wherein at least one of comprises H.

20. 20. The method of claim 17, 18, or 19, wherein the fluorinated compound comprises hexfluoroisopropanol.

21. 1. A process for preparing a partially fluorinated epoxide, comprising: 【Chemistry 8】 (In the formula, R １ , R ２ , R ３ , and R ４ But H, F, Cl, Br, I, CF ３ , alkyl, fluoroalkyl, haloalkyl) with an oxidizing agent.

22. 22. The method of claim 21, wherein the oxidizing agent is selected from the group including air, oxygen, and oxygen-containing compounds such as peroxides, persalts, and compounds of oxygen and other elements such as hypohalites.

23. 23. The method of claim 21 or 22, wherein the oxidizing agent comprises a hypohalite, such as chlorite.

23. 23. The method of claim 20, 21, or 22, wherein the alkene comprises a tetrafluoropropene, such as 1,3,3,3-tetrafluoropropene (1234ze) or 2,3,3,3-tetrafluoropropene (1234yf), or a pentafluoropropene, such as 1,1,3,3,3-pentafluoropropene (1225zc).

24. A process for preparing a partially fluorinated alcohol comprising a process for preparing a partially fluorinated epoxide according to any one of claims 20 to 23 and a process comprising reacting an epoxide according to any one of claims 1 to 7.

25. A process for preparing a partially fluorinated alcohol comprising a process for preparing a partially fluorinated epoxide according to any one of claims 20 to 23, a process comprising reacting an epoxide according to any one of claims 1 to 7, and a process for preparing a fluorinated compound according to any one of claims 16 to 19.

26. 1. A process for preparing a partially fluorinated ether having the structure: 【Chemistry 9】 structure 【Chemistry 10】 (In the formula, R １ , R ２ , R ３ , and R ４ But H, F, Cl, Br, I, CF ３ , alkyl, fluoroalkyl, haloalkyl)。 Reacting a fluorohydrin with an alkyl group (independently selected from the group consisting of alkyl, alkyl, fluoroalkyl, haloalkyl).

27. A compound having the following structure: 【Chemistry 11】

28. A composition comprising a compound having the structure: 【Chemistry 12】

29. 29. Use of a compound according to claim 27 or a composition according to claim 28 as a solvent, for example in battery applications.

30. 29. Use of a compound according to claim 27 or a composition according to claim 28 as a coolant, for example as an immersion coolant.

31. 1. A process for preparing a partially fluorinated ether having the structure: 【Chemistry 13】 structure 【Chemistry 14】 (In the formula, R １ , R ２ , R ３ , R ４ But H, F, Cl, Br, I, CF ３ , alkyl, fluoroalkyl, haloalkyl; R ５ But group CF ３ , alkyl, fluoroalkyl, perfluoroalkyl, haloalkyl, perfluorohaloalkyl) with a fluorohydrin having an alkyl group selected from the group consisting of aryl, alkyl, fluoroalkyl, perfluoroalkyl, haloalkyl, perfluorohaloalkyl, and aryl.

32. A compound having the following structure: 【Chemistry 15】

33. A composition comprising a compound having the structure: 【Chemistry 16】

34. 34. Use of a compound according to claim 32 or a composition according to claim 33 as a solvent, for example in battery applications.

35. 34. Use of a compound according to claim 32 or a composition according to claim 33 as a coolant, for example as an immersion coolant.

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