3,4,4-trifluoro-3-(trifluoromethyl)oxathietane 2,2-dioxide

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using essentially the procedure of Example 1, the reactor was charged with 44.7 g hexafluoropropene, 45.9 g of 67 wt. % oleum and 41.5 g Fluorinert FC-77™. The reaction mixture was heated at 50° C. for 6 hours. The reactor was vented of excess HFP and the sultone layer (95.0 g) was separated and distilled to provide the HFP sultone (45 g, b.p. 48°-52° C., purity 93% by gc). The yield was 65% based on consumed HFP. the sultone layer (95.0 g) was separated distilled

Conditions: temp:43.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using essentially the procedure of Example 1, the reactor was charged with 33.8 g of 67 wt. % oleum (0.28 mole SO3) and 58.0 g hexafluoropropene. After the initial exotherm (max. pressure 896 kPa at 39° C.) the mixture was heated for 13 hours at 43° C. The reactor was vented of excess hexafluoropropene (16.0 g recovered including HFP collected during followed distillation). There was consumed 42.0 g (0.28 mole) HFP. The two phase reaction solution (70.1 g) was distilled using a concentric tube column to yield HFP sultone (39.8 g, 62% yield based on HFP consumed, b.p. 47° C.). The distillation residue was then distilled using a mini-lab apparatus to give 5.4 g of an intermediate fraction with a b.p. of 56°-155° C., 20 g of a fraction with a b.p. of 156°-167° C., and 1.3 g ofundistilled residue. The fraction with b.p. 156°-167° C. was analyzed by 19F and 1H NMR to reveal a complex mixture of primarily fluorosulfonic acid and several acid fluorides, sulfonyl fluorides, and at least three tetrafluoropropionic acid derivatives of the structure CF3CHFCOX, where X=F, OSO2F and possibly OCOCHFCF3. The molar ratio of HSO3F to all CHF compounds was 88:35. There was consumed 42.0 g (0.28 mole) HFP was distilled

Conditions: temp:-45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 100 mL Parr™ reactor was charged with 63.8 g of 65% oleum (0.52 mole SO3), cooled to -45° C., evacuated, and then charged with 62 grams (0.44 mole) liquid hexafluoropropene from a cold trap (-78° C.). The reaction mixture was allowed to warm to room temperature. At 20° C. a slight exotherm was observed which increased to a maximum temperature of 56° C. and a pressure of 965 kPa over a 9 minute period. Following the exotherm the reactor was held at 42° C. for 6 hours while the mixture was agitated. The reactor was then vented of excess HFP (with the recovery of 0.7 g HFP) and the contents of the reactor were decanted to yield 103.8 grams (g) of a two phase reaction product. The upper layer (90.6 g) was separated from the lower layer, washed with concentrated sulfuric acid to remove residual SO3 and then distilled to give 63.3 grams of HFP suitone (66% yield with respect to the consumed olefln) with boiling point (b.p.) 45°-50° C. NMR analysis of a higher boiling fraction (b.p. 50°-167° C., yield 25 g) revealed a mixture oftetrafluoropropionic acid derivatives and fluorosulfonic acid. A small portion of this fraction was refluxed in methanol for one hour to give tetrafluoropropionic acid methyl ester (yield 12% based on hexafluoropropene consumed). HFP sultone, after heating with concentrated sulfuric acid for 17 hours at 40° C., was recovered by distillation with 95% yield. evacuated to warm to room temperature At 20° C. increased to a maximum temperature of 56° C. was held at 42° C. for 6 hours while the mixture were decanted to yield The upper layer (90.6 g) was separated from the lower layer washed with concentrated sulfuric acid to remove residual SO3 distilled

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using essentially the procedure of Example 1, the reactor was charged with 44.7 g hexafluoropropene, 45.9 g of 67 wt. % oleum and 41.5 g Fluorinert FC-77™. The reaction mixture was heated at 50° C. for 6 hours. The reactor was vented of excess HFP and the sultone layer (95.0 g) was separated and distilled to provide the HFP sultone (45 g, b.p. 48°-52° C., purity 93% by gc). The yield was 65% based on consumed HFP. the sultone layer (95.0 g) was separated distilled

Conditions: temp:43.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using essentially the procedure of Example 1, the reactor was charged with 33.8 g of 67 wt. % oleum (0.28 mole SO3) and 58.0 g hexafluoropropene. After the initial exotherm (max. pressure 896 kPa at 39° C.) the mixture was heated for 13 hours at 43° C. The reactor was vented of excess hexafluoropropene (16.0 g recovered including HFP collected during followed distillation). There was consumed 42.0 g (0.28 mole) HFP. The two phase reaction solution (70.1 g) was distilled using a concentric tube column to yield HFP sultone (39.8 g, 62% yield based on HFP consumed, b.p. 47° C.). The distillation residue was then distilled using a mini-lab apparatus to give 5.4 g of an intermediate fraction with a b.p. of 56°-155° C., 20 g of a fraction with a b.p. of 156°-167° C., and 1.3 g ofundistilled residue. The fraction with b.p. 156°-167° C. was analyzed by 19F and 1H NMR to reveal a complex mixture of primarily fluorosulfonic acid and several acid fluorides, sulfonyl fluorides, and at least three tetrafluoropropionic acid derivatives of the structure CF3CHFCOX, where X=F, OSO2F and possibly OCOCHFCF3. The molar ratio of HSO3F to all CHF compounds was 88:35. There was consumed 42.0 g (0.28 mole) HFP was distilled

Conditions: temp:-45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 100 mL Parr™ reactor was charged with 63.8 g of 65% oleum (0.52 mole SO3), cooled to -45° C., evacuated, and then charged with 62 grams (0.44 mole) liquid hexafluoropropene from a cold trap (-78° C.). The reaction mixture was allowed to warm to room temperature. At 20° C. a slight exotherm was observed which increased to a maximum temperature of 56° C. and a pressure of 965 kPa over a 9 minute period. Following the exotherm the reactor was held at 42° C. for 6 hours while the mixture was agitated. The reactor was then vented of excess HFP (with the recovery of 0.7 g HFP) and the contents of the reactor were decanted to yield 103.8 grams (g) of a two phase reaction product. The upper layer (90.6 g) was separated from the lower layer, washed with concentrated sulfuric acid to remove residual SO3 and then distilled to give 63.3 grams of HFP suitone (66% yield with respect to the consumed olefln) with boiling point (b.p.) 45°-50° C. NMR analysis of a higher boiling fraction (b.p. 50°-167° C., yield 25 g) revealed a mixture oftetrafluoropropionic acid derivatives and fluorosulfonic acid. A small portion of this fraction was refluxed in methanol for one hour to give tetrafluoropropionic acid methyl ester (yield 12% based on hexafluoropropene consumed). HFP sultone, after heating with concentrated sulfuric acid for 17 hours at 40° C., was recovered by distillation with 95% yield. evacuated to warm to room temperature At 20° C. increased to a maximum temperature of 56° C. was held at 42° C. for 6 hours while the mixture were decanted to yield The upper layer (90.6 g) was separated from the lower layer washed with concentrated sulfuric acid to remove residual SO3 distilled

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of commercial liquid sulfur trioxide (10 ml) and hexafluoropropene (45 g, 0.30 mol) was sealed in a Carius tube at liquid nitrogen temperature, mixed well at 25° C., allowed to stand for 4 days at 25° C., and finally heated in a steam bath for 6 hours. From two such tubes, there was obtained by distillation, 3-(trifluoromethyl)-3,4,4-trifluoro-1-oxa-2-thiacyclobutane 2,2-dioxide (2-hydroxy-1-trifluoromethyl-1,2,2-trifluoroethane sulfonic acid sultone, D. C. England, M. A. Dietrich and R. V. Lindsey, Jr., J. Amer. Chem. Soc., 82, 6181 (1960)) (25 g, 22%) bp 44° C., and pentafluoro-2-propenyl fluorosulfate (hereinafter referred to as perfluoroallyl fluorosulfate) (73 g, 63%), bp 58°-60° C. was sealed in a Carius tube at liquid nitrogen temperature mixed well at 25° C. finally heated in a steam bath for 6 hours

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of commercial liquid sulfur trioxide (10 ml) and hexafluoropropene (45 g, 0.30 mol) was sealed in a Carius tube at liquid nitrogen temperature, mixed well at 25° C., allowed to stand for 4 days at 25° C., and finally heated in a steam bath for 6 hours. From two such tubes, there was obtained by distillation, 3-(trifluoromethyl)-3,4,4-trifluoro-1-oxa-2-thiacyclobutane 2,2-dioxide (2-hydroxy-1-trifluoromethyl-1,2,2,-trifluoroethane sulfonic acid sultone, D. C. England, M. A. Dietrich and R. V. Lindsey, Jr., J. Amer. Chem. Soc., 82 6181 (1960)) (25 g, 22%) bp 44° C., and pentafluoro-2-propenyl fluorosulfate (hereinafter referred to as perfluoroallyl fluorosulfate) (73 g, 63%), bp 58°-60° C. was sealed in a Carius tube at liquid nitrogen temperature mixed well at 25° C. finally heated in a steam bath for 6 hours

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of commercial liquid sulfur trioxide (10 ml) and hexafluoropropene (45 g, 0.30 mol) was sealed in a Carius tube at liquid nitrogen temperature, mixed well at 25° C., allowed to stand for 4 days at 25° C., and finally heated in a steam bath for 6 hours. From two such tubes, there was obtained by distillation, 3-(trifluoromethyl)-3,4,4-trifluoro-1-oxa-2-thiacyclobutane 2,2-dioxide (2-hydroxy-1-trifluoromethyl-1,2,2-trifluoroethane sulfonic acid sultone, D. C. England, M. A. Dietrich and R. V. Lindsey, Jr., J. Amer. Chem. Soc., 82, 6181 (1960)) (25 g, 22%) bp 44° C., and pentafluoro-2-propenyl fluorosulfate (hereinafter referred to as perfluoroallyl fluorosulfate) (73 g, 63%), bp 58°-60° C. was sealed in a Carius tube at liquid nitrogen temperature mixed well at 25° C. finally heated in a steam bath for 6 hours

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using essentially the procedure of Example 1, the reactor was charged with 44.7 g hexafluoropropene, 45.9 g of 67 wt. % oleum and 41.5 g Fluorinert FC-77™. The reaction mixture was heated at 50° C. for 6 hours. The reactor was vented of excess HFP and the sultone layer (95.0 g) was separated and distilled to provide the HFP sultone (45 g, b.p. 48°-52° C., purity 93% by gc). The yield was 65% based on consumed HFP. the sultone layer (95.0 g) was separated distilled

Conditions: temp:43.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using essentially the procedure of Example 1, the reactor was charged with 33.8 g of 67 wt. % oleum (0.28 mole SO3) and 58.0 g hexafluoropropene. After the initial exotherm (max. pressure 896 kPa at 39° C.) the mixture was heated for 13 hours at 43° C. The reactor was vented of excess hexafluoropropene (16.0 g recovered including HFP collected during followed distillation). There was consumed 42.0 g (0.28 mole) HFP. The two phase reaction solution (70.1 g) was distilled using a concentric tube column to yield HFP sultone (39.8 g, 62% yield based on HFP consumed, b.p. 47° C.). The distillation residue was then distilled using a mini-lab apparatus to give 5.4 g of an intermediate fraction with a b.p. of 56°-155° C., 20 g of a fraction with a b.p. of 156°-167° C., and 1.3 g ofundistilled residue. The fraction with b.p. 156°-167° C. was analyzed by 19F and 1H NMR to reveal a complex mixture of primarily fluorosulfonic acid and several acid fluorides, sulfonyl fluorides, and at least three tetrafluoropropionic acid derivatives of the structure CF3CHFCOX, where X=F, OSO2F and possibly OCOCHFCF3. The molar ratio of HSO3F to all CHF compounds was 88:35. There was consumed 42.0 g (0.28 mole) HFP was distilled

Conditions: temp:-45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 100 mL Parr™ reactor was charged with 63.8 g of 65% oleum (0.52 mole SO3), cooled to -45° C., evacuated, and then charged with 62 grams (0.44 mole) liquid hexafluoropropene from a cold trap (-78° C.). The reaction mixture was allowed to warm to room temperature. At 20° C. a slight exotherm was observed which increased to a maximum temperature of 56° C. and a pressure of 965 kPa over a 9 minute period. Following the exotherm the reactor was held at 42° C. for 6 hours while the mixture was agitated. The reactor was then vented of excess HFP (with the recovery of 0.7 g HFP) and the contents of the reactor were decanted to yield 103.8 grams (g) of a two phase reaction product. The upper layer (90.6 g) was separated from the lower layer, washed with concentrated sulfuric acid to remove residual SO3 and then distilled to give 63.3 grams of HFP suitone (66% yield with respect to the consumed olefln) with boiling point (b.p.) 45°-50° C. NMR analysis of a higher boiling fraction (b.p. 50°-167° C., yield 25 g) revealed a mixture oftetrafluoropropionic acid derivatives and fluorosulfonic acid. A small portion of this fraction was refluxed in methanol for one hour to give tetrafluoropropionic acid methyl ester (yield 12% based on hexafluoropropene consumed). HFP sultone, after heating with concentrated sulfuric acid for 17 hours at 40° C., was recovered by distillation with 95% yield. evacuated to warm to room temperature At 20° C. increased to a maximum temperature of 56° C. was held at 42° C. for 6 hours while the mixture were decanted to yield The upper layer (90.6 g) was separated from the lower layer washed with concentrated sulfuric acid to remove residual SO3 distilled