1,1,1,3,3,3-hexafluoropropane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Using essentially the procedure as in Example 1, a mixture of perfluorobutyric acid fluorides (3.77 g with acyl fluoride content of 81%, 14 mmol), KF (1.02 g ,17 mmol), the ethoxyisobutene (4.56 g with purity 88%, 0.18 mmol) in 8.33 g diglyme was agitated at room temperature for four days. The reactor was vented to yield 0.67 g liquid which comprised (GC %): 88% starting acyl fluorides mixture and 8% C4F9OC2H5. The reaction solution remaining in the reactor was vacuum distilled to yield 3.0 g of a mixture which comprised (GC %): 75% C4F9OC2H5, 1.5% C2H5C(CF3)2C(O)F and 7.6% starting vinyl ether. After decarboxylation by treatment with triethylamine, the remaining diglyme solution yielded 1.45 g CF3CH2CF3 (purity 98% contaminated with 1.5% C4F9OC2H5 and 0.5% (CF3)CC2H5C(O)F). Triethylamine recovery gave 2.5 g organic liquid material with b.p. up to 101° C., consisting of (GC %): 2.5% CF3CH2CF3, 42% triethylamine, 9% starting vinyl ether and 29% diglyme. Calculated yields were: C4F9OC2H5, 72% on the consumed acid fluoride mixture, CF3CH2CF3, 75% on consumed vinyl ether.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Using essentially the same procedure as in Example 1, an isomeric mixture of the perfluorobutyric acid fluorides (2.67 g with summary acyl fluorides content 81%, 10 mmol), potassium fluoride (0.78 g, 13 mmol), the 1-methoxyheptafluoro-1-isobutene (5.10 g, 96% purity, 23 mmol) was combined in 8.54 g diglyme and agitated at room temperature for 34 hours. The reactor was vented and 5.44 g of material collected in the trap. The material consisted of (GC %): 4.0% starting C4 acyl fluoride, 35.3% C4F9OCH3, 58.5% hexafluoropivaloyl fluoride (C5 acid fluoride) and a trace (0.4%) of diglyme. To the diglyme residue was added 8.64 g H2O and 1.76 g triethylamine to yield 1.38 g CF3CH2CF3 (after recondensation), and 95.5 % purity. The products yields were calculated based on the weight of obtained mixtures, their GC % content and purity of starting compounds. Yield of C4F9OCH3 is 77% (from perfluorobutyric acid fluorides and 85% on the consumed fluorides). Yield of CF3CH2CF3 is 39% and C5 acid fluoride -65%. 5.44 g of material collected in the trap To the diglyme residue was added 8.64 g H2O and 1.76 g triethylamine

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A reaction was conducted as described in Example 6 except that benzoic acid was replaced with 105 mmol of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and the amount of PGE was 200 mmol. Desired 2,2-bis[4-(2-hydroxy-3-phenoxypropyloxy)phenyl[-1,1,1,3,3,3-hexafluoropropane was formed in analytical yield of 89% and isolated in a yield of 83%.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The present process produces a 1:1 molar mixture of HF and CF3CH═CF2 in the reactor exit stream. The reactor exit stream can also contain unconverted reactant, CF3CH2CF3. The components of the reactor exit stream can be separated by conventional means, such as distillation. Hydrogen fluoride and CF3CH═CF2 form a homogenous low-boiling azeotrope containing about 60 mole percent CF3CH═CF2. The present process reactor exit stream can be distilled and the low-boiling HF and CF3CH═CF2 azeotrope taken off as a distillation column overhead stream, leaving substantially pure CF3CH2CF3 as a distillation column bottom stream. Recovered CF3CH2CF3 reactant may be recycled to the reactor. CF3CH═CF2 can be separated from its azeotrope with HF by conventional procedures, such as pressure swing distillation or by neutralization of the HF with caustic. The present process produces a 1 The components of the reactor exit stream can be separated by conventional means, such as distillation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 100 g mixture containing 59.0% (CF3)2CHCF2OCH3 (ether A), 20% (CF3)2C=CFOCH3 (ether B), 15.9% toluene and 150 mL water was heated in a Hastelloy™ nickel alloy tube for 3 hours at 135° C. and 6 hours at 200° C. The volatiles were bubbled through a solution of aqueous NaOH and a CaSO4 drying column, and condensed in a dry ice cooled trap to give 12.9 g HFC-236fa identified by its infrared spectrum. The liquid contents of the tube contained two layers. The upper layer, 14.9 g, was shown by 1H and 19F NMR spectroscopy to contain 16.5 wt. percent HFC-236fa and toluene. The combined HFC-236fa from the volatiles and the toluene corresponded to a yield of 15.4 g, 29.0% based on the starting ethers. The volatiles were bubbled through a solution of aqueous NaOH a CaSO4 drying column, and condensed in a dry ice cooled trap

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Using essentially the procedure as in Example 1, a mixture of perfluorobutyric acid fluorides (3.77 g with acyl fluoride content of 81%, 14 mmol), KF (1.02 g ,17 mmol), the ethoxyisobutene (4.56 g with purity 88%, 0.18 mmol) in 8.33 g diglyme was agitated at room temperature for four days. The reactor was vented to yield 0.67 g liquid which comprised (GC %): 88% starting acyl fluorides mixture and 8% C4F9OC2H5. The reaction solution remaining in the reactor was vacuum distilled to yield 3.0 g of a mixture which comprised (GC %): 75% C4F9OC2H5, 1.5% C2H5C(CF3)2C(O)F and 7.6% starting vinyl ether. After decarboxylation by treatment with triethylamine, the remaining diglyme solution yielded 1.45 g CF3CH2CF3 (purity 98% contaminated with 1.5% C4F9OC2H5 and 0.5% (CF3)CC2H5C(O)F). Triethylamine recovery gave 2.5 g organic liquid material with b.p. up to 101° C., consisting of (GC %): 2.5% CF3CH2CF3, 42% triethylamine, 9% starting vinyl ether and 29% diglyme. Calculated yields were: C4F9OC2H5, 72% on the consumed acid fluoride mixture, CF3CH2CF3, 75% on consumed vinyl ether.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Using essentially the procedure as in Example 1, a mixture of perfluorobutyric acid fluorides (3.77 g with acyl fluoride content of 81%, 14 mmol), KF (1.02 g ,17 mmol), the ethoxyisobutene (4.56 g with purity 88%, 0.18 mmol) in 8.33 g diglyme was agitated at room temperature for four days. The reactor was vented to yield 0.67 g liquid which comprised (GC %): 88% starting acyl fluorides mixture and 8% C4F9OC2H5. The reaction solution remaining in the reactor was vacuum distilled to yield 3.0 g of a mixture which comprised (GC %): 75% C4F9OC2H5, 1.5% C2H5C(CF3)2C(O)F and 7.6% starting vinyl ether. After decarboxylation by treatment with triethylamine, the remaining diglyme solution yielded 1.45 g CF3CH2CF3 (purity 98% contaminated with 1.5% C4F9OC2H5 and 0.5% (CF3)CC2H5C(O)F). Triethylamine recovery gave 2.5 g organic liquid material with b.p. up to 101° C., consisting of (GC %): 2.5% CF3CH2CF3, 42% triethylamine, 9% starting vinyl ether and 29% diglyme. Calculated yields were: C4F9OC2H5, 72% on the consumed acid fluoride mixture, CF3CH2CF3, 75% on consumed vinyl ether.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Using essentially the same procedure as in Example 1, an isomeric mixture of the perfluorobutyric acid fluorides (2.67 g with summary acyl fluorides content 81%, 10 mmol), potassium fluoride (0.78 g, 13 mmol), the 1-methoxyheptafluoro-1-isobutene (5.10 g, 96% purity, 23 mmol) was combined in 8.54 g diglyme and agitated at room temperature for 34 hours. The reactor was vented and 5.44 g of material collected in the trap. The material consisted of (GC %): 4.0% starting C4 acyl fluoride, 35.3% C4F9OCH3, 58.5% hexafluoropivaloyl fluoride (C5 acid fluoride) and a trace (0.4%) of diglyme. To the diglyme residue was added 8.64 g H2O and 1.76 g triethylamine to yield 1.38 g CF3CH2CF3 (after recondensation), and 95.5 % purity. The products yields were calculated based on the weight of obtained mixtures, their GC % content and purity of starting compounds. Yield of C4F9OCH3 is 77% (from perfluorobutyric acid fluorides and 85% on the consumed fluorides). Yield of CF3CH2CF3 is 39% and C5 acid fluoride -65%. 5.44 g of material collected in the trap To the diglyme residue was added 8.64 g H2O and 1.76 g triethylamine

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A reaction was conducted as described in Example 6 except that benzoic acid was replaced with 105 mmol of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and the amount of PGE was 200 mmol. Desired 2,2-bis[4-(2-hydroxy-3-phenoxypropyloxy)phenyl[-1,1,1,3,3,3-hexafluoropropane was formed in analytical yield of 89% and isolated in a yield of 83%.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A reaction was conducted as described in Example 6 except that benzoic acid was replaced with 105 mmol of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and the amount of PGE was 200 mmol. Desired 2,2-bis[4-(2-hydroxy-3-phenoxypropyloxy)phenyl[-1,1,1,3,3,3-hexafluoropropane was formed in analytical yield of 89% and isolated in a yield of 83%.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 100 g mixture containing 59.0% (CF3)2CHCF2OCH3 (ether A), 20% (CF3)2C=CFOCH3 (ether B), 15.9% toluene and 150 mL water was heated in a Hastelloy™ nickel alloy tube for 3 hours at 135° C. and 6 hours at 200° C. The volatiles were bubbled through a solution of aqueous NaOH and a CaSO4 drying column, and condensed in a dry ice cooled trap to give 12.9 g HFC-236fa identified by its infrared spectrum. The liquid contents of the tube contained two layers. The upper layer, 14.9 g, was shown by 1H and 19F NMR spectroscopy to contain 16.5 wt. percent HFC-236fa and toluene. The combined HFC-236fa from the volatiles and the toluene corresponded to a yield of 15.4 g, 29.0% based on the starting ethers. The volatiles were bubbled through a solution of aqueous NaOH a CaSO4 drying column, and condensed in a dry ice cooled trap

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 600 mL, magnetically stirred, model autoclave fitted with a condenser (maintained at -10° C.), was evacuated, cooled to about -40° C., and charged with 0.6.9 g (0.036 mol) TiCl4 followed by 64 g (0.255 mol) CCl3CH2CCl3, and 102.5 g (5 mol) HF. The temperature was increased to 120° C. and maintained at that temperature for a total of 22 h. During the heating period, pressure in excess of 400 psig was periodically vented to an aqueous KOH scrubber which was attached to two -78° C. cold traps. At the end of the heating period, the remainder of the autoclave contents were slowly vented. The cold traps contained 36.1 g material which by GC analysis, contained 14.5% CF3CH2CF3 and 84.0% CF3CH2 CF2Cl, corresponding to a yield for CF3CH2CF2Cl of 69%. model autoclave fitted with a condenser was evacuated cooled to about -40° C. The temperature was increased to 120° C. maintained at that temperature for a total of 22 h was attached to two -78° C.