Synthetic method of polyfluoroalkyl alcohol

Abstract

The invention discloses a synthesis method of polyfluoroalkyl alcohol, and relates to the technical field of organic fluorine chemical synthesis. The method comprises the following steps: by taking perfluoroalkyl ethylene as a substrate, pinacol borane as an electrophilic reagent, cobalt acetylacetonate as a catalyst and 1, 1 '-bis (diphenylphosphine) ferrocene as a ligand, selectively adding a small amount of sodium tert-butoxide as alkali, reacting in a solvent to synthesize perfluoroalkyl boric acid ester, adding an oxidizing agent, and reacting to obtain the perfluoroalkyl boric acid ester. And reacting in a solution of water and methanol to synthesize the perfluoroalkyl ethanol. The synthesis method has the advantages of simplicity and convenience in operation, product diversification, high-efficiency synthesis of products which are not easily obtained by other methods, and the like.

Description

Technical Field

[0001] The invention relates to the technical field of organic fluorine chemical synthesis, in particular to a method for synthesizing polyfluoroalkyl alcohol. Background Art

[0002] Organic borate compounds are an important class of molecules that have been widely used in organic synthesis, medicinal chemistry and drug discovery. In particular, due to their low toxicity and high functional group compatibility, organic borate compounds are important synthetic intermediates that can be easily cross-coupled with electrophiles (Suzuki-Miyaura reaction) to obtain structurally diverse organic molecules by forming CC bonds. Due to their great influence, various strategies for constructing organic borate compounds have been developed over the decades. Among them, the hydroboration of olefins is considered to be one of the powerful reactions for producing these value-added organic borate compounds. Therefore, the present invention proposes a method for synthesizing perfluoroalkyl borate intermediates using pinacol borane as an electrophile and perfluoroalkyl olefins, and synthesizing perfluoroalkyl alcohols under the action of an oxidant.

[0003] The above information disclosed in this background technology is only used to increase the understanding of the background technology of the present invention and therefore, it may include information that does not constitute the prior art known to ordinary technicians in this field. Summary of the invention

[0004] The object of the present invention is to provide a method for synthesizing polyfluoroalkyl alcohols, which has the advantages of simple operation, diversified products, and efficient synthesis of products that are not easily obtained by other methods.

[0005] To achieve the above object, the present invention provides the following technical solution: a method for synthesizing polyfluoroalkyl alcohol, comprising the following steps:

[0006] Using perfluoroalkylethylene as a substrate, pinacol borane as an electrophilic reagent, cobalt acetylacetonate as a catalyst, 1,1'-bis(diphenylphosphino)ferrocene as a ligand, and optionally adding a small amount of sodium tert-butoxide as a base, reacting in a solvent to synthesize perfluoroalkyl borate, and then adding an oxidant to react in a solution of water and methanol to synthesize perfluoroalkylethanol;

[0007] The perfluoroalkylethylene is any one of the following formulas 1 to 8:

[0008]

[0009] Preferably, when the electrophilic reagent is pinacol borane, a perfluoroalkyl borate is obtained, specifically any one of the following formulas 1 to 8:

[0010]

[0011] Preferably, when the oxidant is sodium perborate, a perfluoroalkylethanol is obtained, specifically any one of the following formulas 1 to 8:

[0012]

[0013] Preferably, the synthesis method is to mix perfluoroalkylethylene, pinacol borane, cobalt acetylacetonate and 1,1'-bis(diphenylphosphino)ferrocene in a solvent, and sodium tert-butoxide is added as a base in formula 5 and formula 6. After reacting at 70°C for 18h under magnetic stirring, the reaction mixture is first diluted with ethyl acetate, then washed with saturated brine, and the obtained organic phase is filtered through anhydrous MgSO 4 After drying, the mixture is filtered and the solvent is removed by rotary evaporation, and then purified by a silica gel column to obtain the perfluoroalkyl borate ester. An oxidant is then added, and the mixture is reacted in a mixed solution of water and methanol at room temperature for 12 hours to obtain the perfluoroalkyl ethanol.

[0014] Preferably, the molar ratio of perfluoroalkylethylene, pinacol borane, cobalt acetylacetonate, 1,1'-bis(diphenylphosphino)ferrocene, and oxidant used in Formulas 1 to 4 is 1:2:0.03:0.03:3; the molar ratio of perfluoroalkylethylene, pinacol borane, cobalt acetylacetonate, 1,1'-bis(diphenylphosphino)ferrocene, sodium tert-butoxide, and oxidant used in Formulas 5 to 6 is 1:2:0.03:0.03:0.3:3; the molar ratio of perfluoroalkylethylene, pinacol borane, cobalt acetylacetonate, 1,1'-bis(diphenylphosphino)ferrocene, and oxidant used in Formulas 7 and 8 is 1:3:0.09:0.09:5.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] The invention uses perfluoroalkylethylene which is easy to obtain as a substrate, pinacol borane as an electrophilic reagent, cobalt acetylacetonate as a catalyst, 1,1'-bis(diphenylphosphino)ferrocene as a ligand, and in some cases, a small amount of sodium tert-butoxide as a base, reacts in a solvent to synthesize perfluoroalkyl borate, then adds an oxidant, reacts in a solution of water and methanol to synthesize perfluoroalkylethanol, and the prepared perfluoroalkylethanol is extremely widely and diversified in industrial application. The synthesis method of the invention has the advantages of simple operation, diversified products, efficient synthesis of products which are not easily obtained by other methods, and the like.

[0017] The above summary is for illustrative purposes only and is not intended to be limiting in any way. In addition to the illustrative aspects, embodiments and features described above, further aspects, embodiments and features of the present invention will be readily apparent by reference to the accompanying drawings and the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1The figure is a schematic diagram of the synthesis method of the present invention. DETAILED DESCRIPTION

[0019] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] Substrate formula 1: CAS No. 19430-93-4.

[0021] Substrate formula 2: CAS No. 25291-17-2.

[0022] Substrate formula 3: CAS No. 21652-58-4.

[0023] Substrate formula 4: CAS No. 30389-25-4.

[0024] Substrate formula 5: CAS number 18599-22-9.

[0025] Substrate formula 6: CAS No. 374-25-4.

[0026] Substrate formula 7: CAS No. 170804-07-6.

[0027] Substrate formula 8: CAS No. 1800-91-5.

[0028] Example 1

[0029]

[0030] In a 10mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 2mmol of perfluorobutylethylene, 4mmol of pinacol borane, 60μmol of cobalt acetylacetonate, 60μmol of 1,1'-bis(diphenylphosphino)ferrocene, and finally 6mL of dimethylacetamide solvent were added. The mixture was stirred in a closed system at 70℃ metal bath for 18h and then cooled to room temperature. After the reaction was completed, the mixture was diluted with 20mL of ethyl acetate and then washed with 40mL of saturated sodium chloride solution. The organic phase was washed with anhydrous MgSO 4 After drying, the mixture was filtered and the solvent was removed by rotary evaporation. Perfluorobutyl ethyl borate (isolation yield 63%) was obtained by silica gel column chromatography using petroleum ether and ethyl acetate (30:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400 MHz, CDCl 3)δ2.29–2.07(m,2H),1.25(s,12H),1.07–0.95(m,2H). 19 F NMR (376 MHz, CDCl 3 )δ-81.0–-81.1(m,3F),-115.9–-117.0(m,2F),-124.5(q,J=9.5Hz,2F),-125.8–-126.6(m,2F). 13 C NMR (101 MHz, CDCl 3 )δ122.1–120.2(m),119.3–117.3(m),116.9–115.1(m),112.4–109.4(m),83.6(s),25.6(t,J=22.9Hz),24.7(s),1.5(br s).

[0031] Example 2

[0032]

[0033] In a 10mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 2mmol perfluorohexylethylene, 4mmol pinacol borane, 60μmol cobalt acetylacetonate, 60μmol 1,1'-bis(diphenylphosphino)ferrocene, and finally 6mL of dimethylacetamide solvent were added. The mixture was stirred in a closed system at 70℃ metal bath for 18h and then cooled to room temperature. After the reaction was completed, the mixture was diluted with 20mL ethyl acetate and then washed with 40mL saturated sodium chloride solution. The organic phase was washed with anhydrous MgSO 4 After drying, the mixture was filtered and the solvent was removed by rotary evaporation. Perfluorohexyl ethyl borate (isolation yield 90%) was obtained by silica gel column chromatography using petroleum ether and ethyl acetate (30:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 )δ2.28–2.08(m,2H),1.25(s,12H),1.12–0.93(m,2H). 19 F NMR (376 MHz, CDCl 3 )δ-80.9(t,J=9.9Hz,3F),-116.2(p,J=16.2,15.8Hz,2F),-122.0(s,2F),-122.9(s,2F),-123.6(s,2F),-126.2(td,J=14.7,6.4Hz,2F). 13 C NMR (101MHz, CDC l3)δ122.9–120.1(m),119.5–117.5(m),116.5–115.1(m),114.7–112.3(m),112 .2–109.6(m),109.9–107.0(m),83.6(s),25.7(t,J=23.0Hz),24.7(s),1.3(br s).

[0034] Example 3

[0035]

[0036] In a 10mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, 2mmol of perfluorooctylethylene, 4mmol of pinacol borane, 60μmol of cobalt acetylacetonate, 60μmol of 1,1'-bis(diphenylphosphino)ferrocene, and finally 6mL of dimethylacetamide solvent were added. The mixture was stirred in a closed system at 70℃ metal bath for 18h and then cooled to room temperature. After the reaction was completed, the mixture was diluted with 20mL of ethyl acetate and then washed with 40mL of saturated sodium chloride solution. The organic phase was washed with anhydrous MgSO 4 After drying, the mixture was filtered and the solvent was removed by rotary evaporation. Perfluorooctyl ethyl borate (isolation yield 88%) was obtained by silica gel column chromatography using petroleum ether and ethyl acetate (30:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400 MHz, DMSO-d 6 )δ2.28–2.07(m,2H),1.23(s,12H),1.08–0.88(m,2H). 19 F NMR (376 MHz, DMSO-d 6 )δ-81.2(t,J=10.0Hz,3F),-116.4(m,2F),-121.9–-122.1(m,2F),-122.1–-122.4( m,4F),-122.6–-123.4(m,2F),-123.7(s,2F),-126.4(td,J=12.7,10.9,5.1Hz,2F). 13 CNMR (101MHz, DMSO-d 6 )δ125.4–123.2(m),121.9–119.8(m),119.7–117.6(m),116.7–115.0(m),115.0–112.2(m),112 .2–109.5(m),109.4–106.7(m),106.6–104.9(m),83.5(s),25.6(t,J=23.0Hz),24.5(s),1.2(br s).

[0037] Example 4

[0038]

[0039] In a 10mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, add 2mmol perfluorodecylethylene, 4mmol pinacol borane, 60μmol cobalt acetylacetonate, 60μmol 1,1'-bis(diphenylphosphino)ferrocene, and finally add 6mL of dimethylacetamide solvent. Stir the reaction in a closed system at 70℃ metal bath for 18h and then cool to room temperature. After the reaction is completed, the mixture is diluted with 20mL ethyl acetate and washed with 40mL saturated sodium chloride solution. The organic phase is washed with anhydrous MgSO 4 After drying, the mixture was filtered and the solvent was removed by rotary evaporation. Perfluorodecyl ethyl borate (isolation yield 86%) was obtained by silica gel column chromatography using petroleum ether and ethyl acetate (30:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 )δ2.28–2.07(m,2H),1.24(s,12H),1.10–0.90(m,2H). 19 F NMR (376 MHz, CDCl 3 )δ-81.1(s,3F),-114.1–-117.3(m,2F),-121.9(s,10F),-122.9(s,2F),-123.7(s,2F),-126.4(s,2F). 13 C NMR (101 MHz, CDCl 3 )δ138.8(d,J=9.8Hz),133.4(d,J=19.4Hz),129.8–126.5(m),121.9–120.1(m),119.1–117.7(m),116.5–114.8(m),1 14.6–112.1(m),111.9–109.3(m),109.4–106.7(m),106.8–104.4(m),83.5(s),25.6(t,J=23.0Hz),24.6(s),1.3(br s).

[0040] Example 5

[0041]

[0042] In a 10mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, add 2mmol of 4-bromo-3,3,4,4-tetrafluorobutene, 4mmol of pinacol borane, 60μmol of cobalt acetylacetonate, 60μmol of 1,1'-bis(diphenylphosphino)ferrocene, 0.6mmol of sodium tert-butoxide, and finally add 6mL of toluene solvent. Stir the reaction in a closed system at 70℃ metal bath for 18h and then cool to room temperature. After the reaction is completed, the mixture is diluted with 20mL of ethyl acetate and then washed with 40mL of saturated sodium chloride solution. The resulting organic phase is washed with anhydrous MgSO 4 After drying, the mixture was filtered and the solvent was removed by rotary evaporation. 4-bromo-3,3,4,4-tetrafluorobutyl borate (isolation yield 89%) was separated by silica gel column chromatography using petroleum ether and ethyl acetate (30:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 )δ2.28–2.08(m,2H),1.24(s,12H),1.06–0.99(m,2H). 19 F NMR (376 MHz, CDCl 3 )δ-65.2(s,2F),-112.8–-114.4(m,2F). 13 C NMR (101 MHz, CDCl 3 )δ138.8(d,J=9.9Hz),133.3(d,J=19.4Hz),128.7–127.3(m),121.7–119.4(m),1 18.5–117.0(m),115.5–114.2(m),83.5(s),25.2(t,J=23.4Hz),24.7(s),2.0(br s).

[0043] Example 6

[0044]

[0045] In a 10mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, add 2mmol of 1-bromo-2-chloro-1,1,2-trifluoro-3-butene, 4mmol of pinacol borane, 60μmol of cobalt acetylacetonate, 60μmol of 1,1'-bis(diphenylphosphino)ferrocene, 0.6mmol of sodium tert-butoxide, and finally add 6mL of toluene solvent. Stir the reaction in a closed system at 70℃ metal bath for 18h and then cool to room temperature. After the reaction is completed, the mixture is diluted with 20mL of ethyl acetate and then washed with 40mL of saturated sodium chloride solution. The resulting organic phase is washed with anhydrous MgSO 4After drying, the mixture was filtered and the solvent was removed by rotary evaporation. 1-bromo-2-chloro-1,1,2-trifluoro-3-butyl borate (isolation yield 84%) was obtained by silica gel column chromatography using petroleum ether and ethyl acetate (30:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400 MHz, DMSO-d 6 )δ2.48–2.35(m,1H),2.32–2.11(m,1H),1.20(s,12H),1.08–0.93(m,2H). 19 F NMR (376 MHz, DMSO-d 6 )δ-61.5–-62.7(m,2F),-118.9–-119.4(m,1F). 13 C NMR (101 MHz, DMSO-d 6 )δ129.5(s),123.0(d,J=35.4Hz),119.9(d,J=35.2Hz),116.8(d,J=35.3Hz),114.5(t ,J=28.6Hz),112.8–111.2(m),83.7(s),31.4(d,J=21.5Hz),25.0(d,J=3.8Hz),4.3(br s).

[0046] Example 7

[0047]

[0048] In a 10mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, add 2mmol of 1,4-divinylperfluorobutane, 6mmol of pinacol borane, 180μmol of cobalt acetylacetonate, 180μmol of 1,1'-bis(diphenylphosphino)ferrocene, and finally add 6mL of dimethylacetamide solvent. Stir the reaction in a closed system at 70℃ metal bath for 18h and then cool to room temperature. After the reaction is completed, the mixture is diluted with 20mL of ethyl acetate and then washed with 40mL of saturated sodium chloride solution. The resulting organic phase is washed with anhydrous MgSO 4 After drying, the product was filtered and the solvent was removed by rotary evaporation. 3,3,4,4,5,5,6,6-octafluorooctane-1,8-diboronate (isolation yield 61%) was obtained by silica gel column chromatography using petroleum ether and ethyl acetate (5:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 )δ2.28–2.04(m,4H),1.23(s,24H),1.04–0.96(m,4H). 19 F NMR (376 MHz, CDCl3 )δ-116.2–-116.5(m,4F),-123.7(t,J=13.0Hz,4F). 13 CNMR (101MHz, CDCl 3 )δ125.6–122.9(m),122.0–119.9(m),119.3–117.6(m),116.8–115.0(m),115.0–113.3 (m),112.6–111.9(m),110.1–108.2(m),83.5(s),25.8(t,J=23.1Hz),24.7(s),1.4(br s).

[0049] Example 8

[0050]

[0051] In a 10mL reaction tube equipped with a polytetrafluoroethylene magnetic stirrer, add 2mmol of 3,3,4,4,5,5,6,6,7,7,8,8-twelve fluoro-1,9-decadiene, 6mmol of pinacol borane, 180μmol of cobalt acetylacetonate, 180μmol of 1,1'-bis(diphenylphosphino)ferrocene, and finally add 6mL of dimethylacetamide solvent. Stir the reaction in a closed system at 70℃ metal bath for 18h and then cool to room temperature. After the reaction is completed, the mixture is diluted with 20mL of ethyl acetate and washed with 40mL of saturated sodium chloride solution. The organic phase is washed with anhydrous MgSO 4 After drying, the product was filtered and the solvent was removed by rotary evaporation. 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorodecane-1,10-diborate (isolation yield 54%) was obtained by silica gel column chromatography using petroleum ether and ethyl acetate (5:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 )δ2.28–2.06(m,4H),1.23(s,24H),1.10–0.88(m,4H). 19 F NMR (376 MHz, CDCl 3 )δ-116.1(tt,J=17.5,10.4Hz,4F),-121.9(s,4F),-123.7(dt,J=19.4,10.0Hz,4F). 13 C NMR (101 MHz, CDCl 3)δ125.5–123.0(m),121.0(t,J=31.5Hz),118.5(t,J=31.4Hz),116.0(t,J=31.0Hz),113.9(dd,J= 37.5,31.0Hz),112.6–110.1(m),109.8–107.1(m),83.5(s),25.7(t,J=23.0Hz),24.6(s),1.3(br s).

[0052] Example 9

[0053]

[0054] In a 50 mL round-bottom flask equipped with a polytetrafluoroethylene magnetic stirrer, 1.5 mmol of perfluorobutyl ethyl borate, 4.5 mmol of sodium perborate tetrahydrate, and finally a mixed solvent of 10 mL of water and 10 mL of methanol were added, and the mixture was stirred at room temperature for 12 h. After the reaction, the mixture was diluted with 10 mL of ethyl acetate and then washed with 20 mL of saturated sodium chloride solution. The organic phase was washed with anhydrous MgSO 4 After drying, the mixture was filtered and the solvent was removed by rotary evaporation. Perfluorobutyl ethanol (isolation yield 87%) was separated by silica gel column chromatography using petroleum ether and ethyl acetate (10:1, v / v) as eluents. The characterization data are as follows: 1 HNMR (400MHz, CDCl 3 )δ3.91(q,J=5.8Hz,2H),3.43(t,J=4.9Hz,1H),2.32(tt,J=18.9,6.4Hz,2H). 19 F NMR (376 MHz, CDCl 3 )δ-81.9(tt,J=9.7,2.7Hz,3F),-114.4(pd,J=15.1,4.5Hz,2F),-124.1–-125.9(m,2F),-126.7(td,J=12.1,11.3,3.1Hz,2F). 13 CNMR (101MHz, CDCl 3)δ121.5(t,J=33.4Hz),120.4(t,J=31.8Hz),118.7(t,J=33.3Hz),117.9(t,J=31.8Hz),115.6(dt,J=48.2,32.3Hz),114.2–112.3( m),112.1–110.6(m),110.8–109.7(m),109.6–108.0(m),107.9–107.2(m),107.1–104.8(m),54.6(t,J=4.8Hz),33.4(t,J=21.2Hz).

[0055] Example 10

[0056]

[0057] In a 50mL round-bottom flask equipped with a polytetrafluoroethylene magnetic stirrer, 1.5mmol of perfluorohexyl ethyl borate and 4.5mmol of sodium perborate tetrahydrate were added, and finally a mixed solvent of 10mL of water and 10mL of methanol was added, and the reaction was stirred at room temperature for 12h. After the reaction was completed, the mixture was diluted with 10mL of ethyl acetate and then washed with 20mL of saturated sodium chloride solution. The organic phase was washed with anhydrous MgSO 4 After drying, the mixture was filtered and the solvent was removed by rotary evaporation. Perfluorohexylethanol was separated by silica gel column chromatography using petroleum ether and ethyl acetate (10:1, v / v) as eluent (isolation yield 90%). The characterization data are as follows: 1 HNMR (400MHz, CDCl 3 )δ3.94(q,J=5.5Hz,2H),2.81(s,1H),2.44–2.24(m,2H). 19 F NMR (376 MHz, CDCl 3 )δ-81.5(t,J=10.0Hz,3F),-112.8–-114.5(m,2F),-122.3(s,2F),-123.3(s,2F),-124.2(s,2F),-126.7(tt,J=18.5,15.0,5.7Hz,2F). 13 C NMR (101 MHz, CDCl 3)δ122.0–119.9(m),119.1–117.5(m),116.7–114.8(m),114.4–112.2(m),112.1–109.3(m),109.5–106.7(m),106.7–104.8 (m),54.9(t,J=4.8Hz),33.6(t,J=21.2Hz).IR(ATR):ν3357,2952,1435,1397,1203,1141,1055,1013,931,858,803,767cm -1 .

[0058] Embodiment 11

[0059]

[0060] In a 50 mL round-bottom flask equipped with a polytetrafluoroethylene magnetic stirrer, 1.5 mmol of perfluorooctyl ethyl borate and 4.5 mmol of sodium perborate tetrahydrate were added, and finally a mixed solvent of 10 mL of water and 10 mL of methanol was added, and the mixture was stirred at room temperature for 12 h. After the reaction, the mixture was diluted with 10 mL of ethyl acetate and then washed with 20 mL of saturated sodium chloride solution. The organic phase was washed with anhydrous MgSO 4 After drying, the mixture was filtered and the solvent was removed by rotary evaporation. Perfluorooctylethanol was separated by silica gel column chromatography using petroleum ether and ethyl acetate (10:1, v / v) as eluent (isolation yield 88%). The characterization data are as follows: 1 HNMR (400 MHz, DMSO-d 6 )δ4.85(t,J=5.4Hz,1H),3.66(q,J=6.3Hz,2H),2.32–2.10(m,2H). 19 F NMR (376 MHz, DMSO-d 6 )δ-82.9(t,J=10.0Hz,3F),-114.2(p,J=17.5Hz,2F),-122.8(s,2F),-123.0–-123.4(m,4F),-124.1(s,2F),-124.6(s,2F),-127.8(s,2F). 13 CNMR (101MHz, DMSO-d 6 )δ121.8–120.3(m),118.9–117.7(m),116.5–114.6(m),114.6–111.9(m),111.9–10 9.2(m),109.2–106.4(m),106.8–104.5(m),53.3(t,J=4.5Hz),33.5(t,J=21.0Hz).

[0061] Example 12

[0062]

[0063] In a 50 mL round-bottom flask equipped with a polytetrafluoroethylene magnetic stirrer, 1.5 mmol of perfluorodecyl ethyl borate and 4.5 mmol of sodium perborate tetrahydrate were added, and finally a mixed solvent of 10 mL of water and 10 mL of methanol was added, and the mixture was stirred at room temperature for 12 h. After the reaction was completed, the mixture was diluted with 10 mL of ethyl acetate and then washed with 20 mL of saturated sodium chloride solution. The resulting organic phase was washed with anhydrous MgSO 4 After drying, the mixture was filtered and the solvent was removed by rotary evaporation. Perfluorodecylethanol was separated by silica gel column chromatography using petroleum ether and ethyl acetate (10:1, v / v) as eluents (isolation yield 93%). The characterization data are as follows: 1 HNMR (400MHz,methanol-d 4 )δ3.86(t,J=6.6Hz,2H),2.39(tt,J=19.2,6.5Hz,2H),OHwas not observed. 19 F NMR (376MHz,methanol-d 4 )δ-82.6(t,J=10.2Hz,3F),-114.8(s,2F),-122.8(s,10F),-123.9(s,2F),-124.9(s,2F),-127.5(s,2F). 13 C NMR (101MHz,methanol-d 4 )δ122.5–119.9(m),119.7–117.0(m),116.4–114.8(m),114.7–112.0(m),112.3–109.3(m),109.3–107.0(m),106.5–104.5 (m),53.6(t,J=4.8Hz),33.4(t,J=21.2Hz).IR(ATR):ν3356,2950,1434,1398,1205,1141,1055,1014,932,857,802,765cm -1 .

[0064] Example 13

[0065]

[0066] In a 50 mL round-bottom flask equipped with a polytetrafluoroethylene magnetic stirrer, 1.5 mmol of 4-bromo-3,3,4,4-tetrafluorobutyl borate and 4.5 mmol of sodium perborate tetrahydrate were added, and finally a mixed solvent of 10 mL of water and 10 mL of methanol was added, and the reaction was stirred at room temperature for 12 h. After the reaction was completed, the mixture was diluted with 10 mL of ethyl acetate and then washed with 20 mL of saturated sodium chloride solution. The organic phase was washed with anhydrous MgSO 4 After drying, the mixture was filtered and the solvent was removed by rotary evaporation. 4-bromo-3,3,4,4-tetrafluorobutanol (isolation yield 87%) was obtained by silica gel column chromatography using petroleum ether and ethyl acetate (10:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400 MHz, CDCl 3 )δ3.96(t,J=6.4Hz,2H),2.72(s,1H),2.48–2.28(m,2H). 19 F NMR (376 MHz, CDCl 3 )δ-66.4(t,J=3.4Hz,2F),-111.3(tt,J=18.3,3.7Hz,2F). 13 C NMR (101 MHz, CDCl 3 )δ121.0–119.0(m),117.9–116.6(m),114.9–113.7(m),55.3(t,J=4.2Hz),33.2(t,J=21.6Hz).

[0067] Embodiment 14

[0068]

[0069] In a 50 mL round-bottom flask equipped with a polytetrafluoroethylene magnetic stirrer, add 1.5 mmol of 1-bromo-2-chloro-1,1,2-trifluoro-3-butyl borate, 4.5 mmol of sodium perborate tetrahydrate, and finally add a mixed solvent of 10 mL of water and 10 mL of methanol, and stir at room temperature for 12 hours. After the reaction is completed, the mixture is diluted with 10 mL of ethyl acetate and then washed with 20 mL of saturated sodium chloride solution. The resulting organic phase is washed with anhydrous MgSO 4 After drying, the mixture was filtered and the solvent was removed by rotary evaporation. 1-bromo-2-chloro-1,1,2-trifluoro-3-butanol (isolation yield 85%) was obtained by silica gel column chromatography using petroleum ether and ethyl acetate (10:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400 MHz, CDCl 3)δ4.04(t,J=6.1Hz,2H),2.73–2.58(m,1H),2.54–2.34(m,1H),2.30(s,1H). 19 F NMR (376 MHz, CDCl 3 )δ-62.1–-61.1(m,2F),-117.19(dq,J=29.9,10.2Hz,1F). 13 C NMR (101 MHz, CDCl 3 )δ122.7(d,J=34.9Hz), 119.6(d,J=34.9Hz), 116.5(d,J=35.2Hz), 111.9(t,J=29.8Hz), 109.3(t,J=29.8Hz), 57.1(d,J=3.1Hz), 38.9(d,J=20.0Hz).

[0070] Embodiment 15

[0071]

[0072] In a 50 mL round-bottom flask equipped with a polytetrafluoroethylene magnetic stirrer, 1.5 mmol of 3,3,4,4,5,5,6,6-octafluorooctane-1,8-diborate and 4.5 mmol of sodium perborate tetrahydrate were added, and finally a mixed solvent of 10 mL of water and 10 mL of methanol was added, and the reaction was stirred at room temperature for 12 h. After the reaction was completed, the mixture was diluted with 10 mL of ethyl acetate and then washed with 20 mL of saturated sodium chloride solution. The organic phase was washed with anhydrous MgSO 4 After drying, the product was filtered and the solvent was removed by rotary evaporation. 3,3,4,4,5,5,6,6-octafluorooctane-1,8-diol (isolation yield 89%) was separated by silica gel column chromatography using petroleum ether and ethyl acetate (5:1, v / v) as eluents. The characterization data are as follows: 1 H NMR (400MHz,methanol-d 4 )δ3.85(t,J=6.7Hz,4H),2.48–2.28(m,4H),OHwas not observed. 19 F NMR (376MHz,methanol-d 4 )δ-111.9–-117.9(m,4F),-125.0(t,J=14.0Hz,4F). 13 C NMR (101MHz,methanol-d 4)δ122.0–120.1(m),119.6–117.2(m),116.7–115.0(m),114.5–112.3(m),112.1–109.3(m),109.3–106.8(m),53. 6(t,J=4.9Hz),33.4(t,J=21.2Hz).IR(ATR):ν3358,2952,1435,1397,1202,1142,1053,1021,934,856,807,765cm -1 .

[0073] Example 16

[0074]

[0075] In a 50 mL round-bottom flask equipped with a polytetrafluoroethylene magnetic stirrer, add 1.5 mmol of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorodecane-1,10-diborate, 4.5 mmol of sodium perborate tetrahydrate, and finally add a mixed solvent of 10 mL of water and 10 mL of methanol, and stir at room temperature for 12 hours. After the reaction is completed, the mixture is diluted with 10 mL of ethyl acetate and then washed with 20 mL of saturated sodium chloride solution. The resulting organic phase is washed with anhydrous MgSO 4 After drying, the product was filtered and the solvent was removed by rotary evaporation. 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorodecane-1,10-diol was separated by silica gel column chromatography using petroleum ether and ethyl acetate (5:1, v / v) as eluent (isolation yield 90%). The characterization data are as follows: 1 H NMR (400MHz,methanol-d 4 )δ3.86(t,J=6.6Hz,4H),2.48–2.28(m,4H),OHwas not observed. 19 F NMR (376MHz,methanol-d 4 )δ-114.8(ddt,J=25.6,18.2,11.2Hz,4F),-122.9(q,J=17.7,16.2Hz,4F),-124.9(dt,J=19.4,9.7Hz,4F). 13 C NMR (101MHz,methanol-d 4)δ122.1–119.4(m),119.1–117.1(m),116.2–115.1(m),114.9–112.7(m), 112.4–109.8(m), 110.0–106.9(m), 53.7(t,J=4.9Hz), 33.5(t,J=21.2Hz).

[0076] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example" or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, unless they are contradictory.

[0077] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A method for synthesizing a polyfluoroalkyl alcohol, characterized in that: The steps include: Using perfluoroalkylethylene as a substrate, pinacol borane as an electrophilic reagent, cobalt acetylacetonate as a catalyst, 1,1'-bis(diphenylphosphino)ferrocene as a ligand, and optionally adding a small amount of sodium tert-butoxide as a base, reacting in a solvent to synthesize perfluoroalkyl borate, and then adding an oxidant to react in a solution of water and methanol to synthesize perfluoroalkylethanol; The perfluoroalkylethylene is any one of the following formulas 1 to 8:

2. The method for synthesizing a polyfluoroalkyl alcohol according to claim 1, characterized in that: When the electrophilic reagent is pinacol borane, a perfluoroalkyl borate is obtained, which is specifically any one of the following formulas 1 to 8:

3. The method for synthesizing a polyfluoroalkyl alcohol according to claim 1, characterized in that: When the oxidant is sodium perborate, a perfluoroalkylethanol is obtained, which is specifically any one of the following formulas 1 to 8:

4. The method for synthesizing a polyfluoroalkyl alcohol according to claim 1, characterized in that: The synthesis method specifically comprises the following steps: mixing perfluoroalkylethylene, pinacol borane, cobalt acetylacetonate and 1,1'-bis(diphenylphosphino)ferrocene in a solvent; sodium tert-butoxide needs to be added as a base to Formula 5 and Formula 6; reacting at 70°C for 18 hours under magnetic stirring; diluting the reaction mixture with ethyl acetate and then washing with saturated brine; drying the obtained organic phase over anhydrous MgSO4, filtering and removing the solvent by rotary evaporation; and purifying the mixture with a silica gel column to obtain the perfluoroalkyl borate; then adding an oxidant; and reacting the mixture in a mixed solution of water and methanol at room temperature for 12 hours to obtain the perfluoroalkylethanol.

5. The method for synthesizing a polyfluoroalkyl alcohol according to claim 4, characterized in that: The molar ratio of perfluoroalkylethylene, pinacol borane, cobalt acetylacetonate, 1,1'-bis(diphenylphosphino)ferrocene, and oxidant used in formulas 1 to 4 is 1:2:0.03:0.03:3; the molar ratio of perfluoroalkylethylene, pinacol borane, cobalt acetylacetonate, 1,1'-bis(diphenylphosphino)ferrocene, sodium tert-butoxide, and oxidant used in formulas 5 to 6 is 1:2:0.03:0.03:0.3:3; the molar ratio of perfluoroalkylethylene, pinacol borane, cobalt acetylacetonate, 1,1'-bis(diphenylphosphino)ferrocene, and oxidant used in formulas 7 and 8 is 1:3:0.09:0.09:5.

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