1,1,2,2,3,3,4,4,4-nonafluoro-N-methylbutane-1-sulfonamide

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: C4F9SO2N(CH3)(CH2)11OH was prepared using a procedure similar to that described above for preparing C4F9SO2N(CH3)(CH2)4OH. 175.9 g C4F9SO2NHCH3 and 121.4 g 25% NaOCH3 were reacted to produce a solution of C4F9SO2NNaCH3 in about 100 mL diglyme. This solution was treated with 141 g 11-bromoundecanol (available from Aldrich) and heated at 100° C. for 20 hr to form a heavy precipitate. The reaction was quenched in about 600 mL warm water and the resulting lower layer was stripped at 50° C./0.5 mTorr to leave 269.9 g of C4F9SO2N(CH3)(CH2)11OH, a low-melting solid. C4F9SO2N(CH3)(CH2)11OH was prepared to form a heavy precipitate The reaction was quenched in about 600 mL warm water was stripped at 50° C.

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: C4F9SO2—N(CH3)CH2CH2—NH2 was prepared by the following procedure: N-Methylnonafluorobutanesulfonamide (626 g, 2 moles, 3M Company, St. Paul, Minn.), 2-ethyl-2-oxazoline (198 g, 2 moles, Alfa Aesar, Ward Hill, Mass.), and sodium carbonate (17 g, 0.16 mole, EMD Chemicals, Gibbstown, N.J.) were combined and heated for 16 hours at 140° C. to form N-(2-(N-methylnonafluorobutanesulfonamido)ethyl)propionamide. This amide was twice extracted with 250 mL deionized water, heated for 18 hours at 100° C. with a mixture of 250 mL concentrated hydrochloric acid and 100 mL deionized water, extracted with 925 mL of 24 weight percent aqueous sodium hydroxide solution, extracted with 250 mL 10 weight percent aqueous sodium hydroxide solution, and distilled to provide N-(2-aminoethyl)-N-methylnonafluorobutanesulfonamide (538 g; 75 percent recovery; 94 percent pure by gas chromatography (GC); distilled at 104-109° C. under 2 mm Hg pressure).

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: C4F9SO2—N(CH3)CH2CH2—NH2 was prepared by the following procedure: N-Methylnonafluorobutanesulfonamide (626 g, 2 moles, 3M Company, St. Paul, Minn.), 2-ethyl-2-oxazoline (198 g, 2 moles, Alfa Aesar, Ward Hill, Mass.), and sodium carbonate (17 g, 0.16 mole, EMD Chemicals, Gibbstown, N.J.) were combined and heated for 16 hours at 140° C. to form N-(2-(N-methylnonafluorobutanesulfonamido)ethyl)propionamide. This amide was twice extracted with 250 mL deionized water, heated for 18 hours at 100° C. with a mixture of 250 mL concentrated hydrochloric acid and 100 mL deionized water, extracted with 925 mL of 24 weight percent aqueous sodium hydroxide solution, extracted with 250 mL 10 weight percent aqueous sodium hydroxide solution, and distilled to provide N-(2-aminoethyl)-N-methylnonafluorobutanesulfonamide (538 g; 75 percent recovery; 94 percent pure by gas chromatography (GC); distilled at 104-109° C. under 2 mm Hg pressure).

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

Procedure: N-Methylperfluorobutanesulfonamide (MeFBSA, 313 g, 1.0 mol; preparation described in U.S. Pat. No. 6,664,354, Savu et al., Example 1, Part A) was added to a stirred mixture of 220 g NaOCH3 (1.02 mol; 25% NaOMe in MeOH). The solvent was removed under vacuum (pot temperature about 80° C.; 50 mm Hg). The resulting paste was dissolved in 250 mL THF and treated with 473 g (5.11 mol) epichlorohydrin and stirred at reflux for 4 hr. GLC analysis showed complete conversion of MeFBSA. The slurry was cooled, washed with water (300 mL) and the resulting lower layer was taken up in methylene chloride, rewashed with water (300 mL), and dried over MgSO4. The product was stripped and one-plate distilled to a main cut of MeFBSG as a colorless liquid (260.8 g, bp 95-105° C./0.3 mmHg). preparation The solvent was removed under vacuum (pot temperature about 80° C.; 50 mm Hg) The resulting paste was dissolved in 250 mL THF at reflux for 4 hr The slurry was cooled washed with water (300 mL) dried over MgSO4 one-plate distilled to a main cut of MeFBSG as a colorless liquid (260.8 g, bp 95-105° C./0.3 mmHg)

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

Procedure: N-Methylperfluorobutanesulfonamide (MeFBSA, 313 g, 1.0 mol; preparation described in U.S. Pat. No. 6,664,354, Savu et al., Example 1, Part A) was added to a stirred mixture of 220 g NaOCH3 (1.02 mol; 25% NaOMe in MeOH). The solvent was removed under vacuum (pot temperature about 80° C.; 50 mm Hg). The resulting paste was dissolved in 250 mL THF and treated with 473 g (5.11 mol) epichlorohydrin and stirred at reflux for 4 hr. GLC analysis showed complete conversion of MeFBSA. The slurry was cooled, washed with water (300 mL) and the resulting lower layer was taken up in methylene chloride, rewashed with water (300 mL), and dried over MgSO4. The product was stripped and one-plate distilled to a main cut of MeFBSG as a colorless liquid (260.8 g, bp 95-105° C./0.3 mmHg). preparation The solvent was removed under vacuum (pot temperature about 80° C.; 50 mm Hg) The resulting paste was dissolved in 250 mL THF at reflux for 4 hr The slurry was cooled washed with water (300 mL) dried over MgSO4 one-plate distilled to a main cut of MeFBSG as a colorless liquid (260.8 g, bp 95-105° C./0.3 mmHg)

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

Procedure: A 250 mL three-neck round-bottom flask equipped with thermometer, magnetic stirring, and addition funnel was charged with a solution of 75 g of C4F9SO2NHCH3 in 80 g of dimethyl sulfoxide. The solution was stirred while a solution of 17.1 g potassium hydroxide in 20 g of water was added in 2 mL aliquots via pipette. The solution turned cloudy during the addition, then cleared with additional stirring. Allyl bromide (31.9 g) was charged to the addition funnel, and added dropwise to the reaction mixture. A rise in temperature of the reaction mixture to 75° C. was noted during the addition. The reaction mixture turned cloudy shortly after the addition was begun, and stirring was continued overnight at room temperature. The reaction mixture was poured into a separatory funnel and allowed to stand until the liquid layers had separated. A few mL water were added to the mixture to facilitate phase separation. The lower layer was drawn off, washed with water and brine, and dried over anhydrous magnesium sulfate, leaving 76.0 g of a clear, colorless crude liquid product which was vacuum distilled to yield 68.7 g C4F9SO2N(CH3)CH2CH═CH2, b.p. 97-101° C. at 19 torr (2.5 kPa). A 250 mL three-neck round-bottom flask equipped with thermometer, magnetic stirring, and addition funnel was added in 2 mL aliquots via pipette The solution turned cloudy during the addition added dropwise to the reaction mixture A rise in temperature of the reaction mixture to 75° C. was noted during the addition after the addition The reaction mixture was poured into a separatory funnel had separated A few mL water were added to the mixture phase separation washed with water and brine dried over anhydrous magnesium sulfate leaving 76.0 g of a clear, colorless crude liquid product which distilled

Conditions: temp:64.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of C4F9SO2NHCH3 (313 g, 1.00 mol), generally made as described in U.S. Pat. No. 6,664,354, Example 1, Part A, and sodium methoxide (216 g of a 25% solution in methanol) was concentrated to a solid, which was dissolved in dry THF (500 mL). Epichlorohydrin (120.2 g, 1.3 mol) was rapidly added to the resulting solution, and the mixture was stirred at reflux (64° C.) for 20 hours. The cooled mixture was washed with about 1 L of water, and dichloromethane was used to help transfer the organic fraction. The organic fraction was dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure. The residue was purified by one-plate distillation [bp 90° C./0.06 mmHg (8 Pa)] to provide 155.2 g of N-methyl-N-(oxiran-2-ylmethyl)perfluorobutane-1-sulfonamide, which was 98% pure by GLC. 6,664,354, Example 1, Part A, and sodium methoxide (216 g of a 25% solution in methanol) was concentrated to a solid, which was dissolved in dry THF (500 mL) The cooled mixture was washed with about 1 L of water, and dichloromethane The organic fraction was dried over anhydrous MgSO4 filtered concentrated under reduced pressure The residue was purified by one-plate distillation [bp 90° C./0.06 mmHg (8 Pa)]

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 mL three-necked round-bottom flask equipped with magnetic stirring, oil bath heat, and connection to a nitrogen bubbler was charged with 17.2 g of N-methylperfluorobutanesulfonamide (C4F9SO2NHCH3) and 250 mL dimethyl sulfoxide. Stirring was begun, and the solid dissolved within a few minutes. A solution of 4.0 g of potassium hydroxide in 5 mL of water was added via pipette, and stirring was continued for another 30 min while the oil bath was heated to 80° C. By the end of this period most of the potassium hydroxide had dissolved. 11-Bromo-1-undecene, obtained from Aldrich Chemical Co. (95 percent purity, 12.3 g) was then added to the flask via pipette, and the reaction mixture was left to stir for 19 hr at 80° C. The oil bath was then removed to allow the mixture to cool, and the flask contents were poured into a separatory funnel. The mixture separated into two liquid phases, and the lower layer was drawn off. The upper phase was diluted with an equal volume of water, causing separation of a small amount of lower phase. This was also drawn off and combined with the first batch. The combined crude product (18.0 g) was dissolved in 150 ml dichloromethane and washed successively with 100 ml portions of water, 10 weight percent aqueous potassium hydroxide solution, water, and brine. The dichloromethane solution was dried over anhydrous magnesium sulfate and filtered, then solvent was removed on a rotary evaporator at water aspirator pressure. This left 17.9 g light straw-colored liquid product. Bulb-to-bulb vacuum distillation of 17.3 g crude product at 160-180° C. and 0.3 torr (4 Pa) gave 16.2 g of N-(10-undecenyl)-N-methylperfluorobutanesulfonamide as a clear, colorless liquid distillate. A 500 mL three-necked round-bottom flask equipped with magnetic stirring, oil bath heat the solid dissolved within a few minutes stirring (95 percent purity, 12.3 g) was then added to the flask via pipette the reaction mixture was left to stir for 19 hr at 80° C The oil bath was then removed to cool the flask contents were poured into a separatory funnel The mixture separated into two liquid phases The upper phase was diluted with an equal volume of water separation of a small amount of lower phase was dissolved in 150 ml dichloromethane washed successively with 100 ml portions of water, 10 weight percent aqueous potassium hydroxide solution, water, and brine The dichloromethane solution was dried over anhydrous magnesium sulfate filtered solvent was removed on a rotary evaporator at water aspirator pressure vacuum distillation of 17.3 g crude product at 160-180° C.

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 313 g (1 mol) N-methylnonafluorobutanesulfonamide (3M Co., U.S. Pat. No. 6,664,354, Savu), 216 g (1 mol) 25% sodium methoxide in methanol (Aldrich), and 100 mL THF (EMD) was stirred at 50° C. for one hour and stripped. The residue was diluted with 600 mL THF and treated with 100 mL (1.15 mol) allyl bromide (Aldrich). The mixture was stirred at 40° C. for about 8 hr and then diluted with water. Extraction with methylene chloride and distillation yielded 321.7 g colorless liquid, by 75-80° C./1.1 mm Hg. Extraction with methylene chloride and distillation

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: C4F9SO2—N(CH3)CH2CH2—NH2 was prepared by the following procedure: N-Methylnonafluorobutanesulfonamide (626 g, 2 moles, 3M Company, St. Paul, Minn.), 2-ethyl-2-oxazoline (198 g, 2 moles, Alfa Aesar, Ward Hill, Mass.), and sodium carbonate (17 g, 0.16 mole, EMD Chemicals, Gibbstown, N.J.) were combined and heated for 16 hours at 140° C. to form N-(2-(N-methylnonafluorobutanesulfonamido)ethyl)propionamide. This amide was twice extracted with 250 mL deionized water, heated for 18 hours at 100° C. with a mixture of 250 mL concentrated hydrochloric acid and 100 mL deionized water, extracted with 925 mL of 24 weight percent aqueous sodium hydroxide solution, extracted with 250 mL 10 weight percent aqueous sodium hydroxide solution, and distilled to provide N-(2-aminoethyl)-N-methylnonafluorobutanesulfonamide (538 g; 75 percent recovery; 94 percent pure by gas chromatography (GC); distilled at 104-109° C. under 2 mm Hg pressure).

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: C4F9SO2N(CH3)(CH2)11OH was prepared using a procedure similar to that described above for preparing C4F9SO2N(CH3)(CH2)4OH. 175.9 g C4F9SO2NHCH3 and 121.4 g 25% NaOCH3 were reacted to produce a solution of C4F9SO2NNaCH3 in about 100 mL diglyme. This solution was treated with 141 g 11-bromoundecanol (available from Aldrich) and heated at 100° C. for 20 hr to form a heavy precipitate. The reaction was quenched in about 600 mL warm water and the resulting lower layer was stripped at 50° C./0.5 mTorr to leave 269.9 g of C4F9SO2N(CH3)(CH2)11OH, a low-melting solid. C4F9SO2N(CH3)(CH2)11OH was prepared to form a heavy precipitate The reaction was quenched in about 600 mL warm water was stripped at 50° C.

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: C4F9SO2—N(CH3)CH2CH2—NH2 was prepared by the following procedure: N-Methylnonafluorobutanesulfonamide (626 g, 2 moles, 3M Company, St. Paul, Minn.), 2-ethyl-2-oxazoline (198 g, 2 moles, Alfa Aesar, Ward Hill, Mass.), and sodium carbonate (17 g, 0.16 mole, EMD Chemicals, Gibbstown, N.J.) were combined and heated for 16 hours at 140° C. to form N-(2-(N-methylnonafluorobutanesulfonamido)ethyl)propionamide. This amide was twice extracted with 250 mL deionized water, heated for 18 hours at 100° C. with a mixture of 250 mL concentrated hydrochloric acid and 100 mL deionized water, extracted with 925 mL of 24 weight percent aqueous sodium hydroxide solution, extracted with 250 mL 10 weight percent aqueous sodium hydroxide solution, and distilled to provide N-(2-aminoethyl)-N-methylnonafluorobutanesulfonamide (538 g; 75 percent recovery; 94 percent pure by gas chromatography (GC); distilled at 104-109° C. under 2 mm Hg pressure).