1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Iron metal (5.0 g, 99.95% purity) lumps were suspended in water (50 mL) and hydrogen bis-triflimide (HNTf2) (10 g) was added. This mixture was heated under reflux for 72 hours. The resultant slurry was cooled, filtered and concentrated on a rotary evaporator to give a pale yellow solution that crystalised on standing. The pale yellow crystals were heated at 150° C. at 1 mmHg to remove the residual water and hydrogen bis-triflimide. This mixture was heated under reflux for 72 hours The resultant slurry was cooled filtered concentrated on a rotary evaporator to give a pale yellow solution that crystalised to remove the residual water and hydrogen bis-triflimide

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Tungsten metal (1.0 g, 99% purity) filings were suspended in water (20 mL) and hydrogen bis-triflimide (HNTf2) (5 g) was added. This mixture was heated under reflux for 144 hours. The resultant slurry was cooled, filtered and concentrated on a rotary evaporator to give a colourless solution that crystalised on standing. The crystals were heated at 150° C. at 1 mmHg to remove the residual water and hydrogen bis-triflimide. The precise structure of the catalyst is not known, but it was found to be the best of all isolated metal bis-triflimide catalysts tested in the reaction of benzoyl chloride with toluene. This mixture was heated under reflux for 144 hours The resultant slurry was cooled filtered concentrated on a rotary evaporator to give a colourless solution that crystalised to remove the residual water and hydrogen bis-triflimide tested in the reaction of benzoyl chloride with toluene

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Tungsten metal (1.0 g, 99% purity) filings were suspended in water (20 mL) and hydrogen bis-triflimide (HNTf2) (5 g) was added. This mixture was heated under reflux for 144 hours. The resultant slurry was cooled, filtered and concentrated on a rotary evaporator to give a colourless solution that crystalised on standing. The crystals were heated at 150° C. at 1 mmHg to remove the residual water and hydrogen bis-triflimide. The precise structure of the catalyst is not known, but it was found to be the best of all isolated metal bis-triflimide catalysts tested in the reaction of benzoyl chloride with toluene. This mixture was heated under reflux for 144 hours The resultant slurry was cooled filtered concentrated on a rotary evaporator to give a colourless solution that crystalised to remove the residual water and hydrogen bis-triflimide tested in the reaction of benzoyl chloride with toluene

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Chromium metal (1.0 g, 99.95% purity) pieces were suspended in water (20 mL) and hydrogen bis-triflimide (HNTf2) (5 g) was added. This mixture was heated under reflux for 144 hours. The resultant mixture was cooled, filtered and concentrated on a rotary evaporator to give a green solid. The solid were heated at 150° C. at 1 mmHg to remove the residual water and hydrogen bis-triflimide. The solid was thought to contain an oxo chromium bis-triflimide species CrO(NTf2) from the mass of HNTf2 produced in drying process. The unpurified chromium(III) bis-triflimide was found to display catalytic activity in Friedel-Crafts reactions, and was similar in activity to Zn(NTf2)2. This mixture was heated under reflux for 144 hours filtered concentrated on a rotary evaporator to give a green solid to remove the residual water and hydrogen bis-triflimide produced in drying process

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

実験手順: 1.0 g of Barium(II) carbonate was suspended in 50 mL of water, to which freshly prepared HNTf2 (2.8 g) was added and stirred at room temperature for 24 hours. The reaction mixture was filtered and the filtrate was concentrated on a rotary evaporator and dried under vacuum (1 mmHg) for 4 hours at 150° C. The unpurified barium(II) bis-triflimide was found to display some catalytic activity in Friedel-Crafts reactions, and was more active than the calcium and strontium analogues. was added The reaction mixture was filtered the filtrate was concentrated on a rotary evaporator dried under vacuum (1 mmHg) for 4 hours at 150° C

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

実験手順: 1.0 g of calcium(II) carbonate was suspended in 50 mL of water, to which freshly prepared HNTf2 (5.6 g) was added and stirred at room temperature for 24 hours. The reaction mixture was filtered and the filtrate was concentrated on a rotary evaporator and dried under vacuum (1 mmHg) for 4 hours at 150° C. The unpurified calcium bis-triflimide was found to display poor catalytic activity in Friedel-Crafts reactions. was added The reaction mixture was filtered the filtrate was concentrated on a rotary evaporator dried under vacuum (1 mmHg) for 4 hours at 150° C

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

実験手順: 1.0 g of calcium(II) carbonate was suspended in 50 mL of water, to which freshly prepared HNTf2 (5.6 g) was added and stirred at room temperature for 24 hours. The reaction mixture was filtered and the filtrate was concentrated on a rotary evaporator and dried under vacuum (1 mmHg) for 4 hours at 150° C. The unpurified calcium bis-triflimide was found to display poor catalytic activity in Friedel-Crafts reactions. was added The reaction mixture was filtered the filtrate was concentrated on a rotary evaporator dried under vacuum (1 mmHg) for 4 hours at 150° C

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

実験手順: 5.0 g of Indium (III) hydroxide was dissolved in 50 ml of water and to which 27.0 g of HNTf2 was added and stirred at room temperature for 24 hours. The reaction mixture was filtered and the filtrate was concentrated on a rotary evaporator and dried under vacuum (1 mmHg) for 3 days at 120° C. The unpurified indium(III) bis-triflimide was found to be an excellent Friedel-Crafts catalyst for the reaction of toluene, anisole and xylene with benzoyl chloride or benzoic anhydride. was added The reaction mixture was filtered the filtrate was concentrated on a rotary evaporator dried under vacuum (1 mmHg) for 3 days at 120° C for the reaction of toluene, anisole and xylene with benzoyl chloride or benzoic anhydride

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

実験手順: A solution (2.0 ml) of the mixture of 4-tert-butylcyclohexanone (1b) (77.1 mg, 0.500 mmol, 0.250 M) and trimethyl(2-phenylallyl)silane (2d) (85.2 mg, 0.500 mmol, 0.250 M) in toluene/dichloromethane (1:1, volume ratio), solution (2.0 ml) of Tf2NH (1.41 mg, 5.00 μmol, 2.50 mM) in toluene/dichloromethane (1:1, volume ratio), and a solution (5.0 ml) of NEt3 (2.53 mg, 25.0 μmol, 5.00 mM) in toluene/dichloromethane (1:1, volume ratio) were used as solution A, solution B and solution C, respectively. The three kinds of solutions were each loaded in a gas tight syringe, and set on a syringe pump as shown in the above-mentioned schematic diagram. Using a microreactor (manufactured by Techno Applications Co., Ltd., COMET-X01) at room temperature, solution A and solution B were continuously supplied at a flow rate of 150 μl/min, and solution C was supplied at a flow rate of 300 μl/min. A micromixer was set at a place where solution A and solution B were mixed, and a micromixer was also set at a place where mixture A-B and solution C were mixed. A flask containing ice-cooled aqueous sodium hydrogen carbonate solution was set at the outlet of the reaction mixture, and the mixture of A, B and C was collected there. After completion of the reaction, the recovered product was extracted with hexane and the organic layer was dried over sodium sulfate. After filtration, the solvent was evaporated under reduced pressure to give the object product, 4-tert-butyl-1-trimethylsilyloxy-1-cyclohexene (3b) (yield 90%). The time necessary for mixing solution A and solution B (calculated from distance between the two micromixers and flow rate) was 145 sec, and the time necessary for mixing mixture A-B and solution C (calculated from distance from the second micromixer to reaction mixture outlet and flow rate) was 40 sec. each loaded in a gas tight syringe set on a syringe at room temperature were mixed were mixed A flask containing ice- the mixture of A, B and C was collected there After completion of the reaction the recovered product was extracted with hexane the organic layer was dried over sodium sulfate After filtration the solvent was evaporated under reduced pressure

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

実験手順: The fluorination reaction was carried out in a 10 mm NMR tube. To 0.28 mmol of the estratrien methyl ether were added 2.5 ml of CDCl3 by vacuum transfer. The mixture was warmed to room temperature forming a colorless solution. This solution was cooled to -196° C. and 0.28 mmol each of FN(SO2CF3)2 and CFCl3 were added by vacuum transfer. The tube was sealed and warmed to -74° C. and then to 22° C. over a 2 hour period. Near -65° C. the colorless solution began to turn to a pale yellow color. After reaching 22° C. 19F NMR indicated a quantitative amount of (CF3SO2)2NH was formed. Two other fluorine resonances are observed in the ratio of 1:1 with a total area equal to the internal CFCl3 standard. These resonances at -140.2 (m) and -168.6 (m) ppm relative to CFCl3 are assignable to an equimolar mixture of the two monofluoro derivatives of the estratrien, 2-fluoro-1,3,5(10)estratrien-3ol-17one methyl ether and 4-fluoro-1,3,5(10)estratrien-3ol-17one methyl ether, respectively. The fluorination reaction forming a colorless solution This solution was cooled to -196° C. The tube was sealed warmed to -74° C. Near -65° C. After reaching 22° C was formed