2,2,4-trimethylpentane

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: The title compound was prepared from (-)-N-ethyl-2-(3,5-dichloro-2,6-dimethoxybenzamidomethyl)pyrrolidine by dealkylation in the same manner as described in Example 2. Yield 37%. M.p. 48°-49° C. (i-octane). [α]D25 =-64° C. (c=1.26; CHCl3).

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

実験手順: To a stirred solution of [4-[4-(aminosulfonyl)phenyl]-3-phenylisoxazol-5-yl]acetic acid (Step 1) (0.85 g, 2.37 mmol) in THF (25 mL) was added borane dimethylsulfide (0.47 mL of 10.0M solution, 4.74 mmol). After stirring at room temperature for 2 days, the reaction was quenched with aqueous KHSO4 (0.25M) and extracted with ethyl acetate. The combined ethyl acetate phases were washed with saturated NaHCO3 solution, brine, dried over MgSO4, filtered and concentrated in vacuo yielding a pale yellow solid. The crude product was dissolved in hot dichloromethane and isooctane was added to induce crystallization. Vacuum filtration of the resulting suspension yielded 4-[5-(2-hydroxyethyl)-3-phenylisoxazol-4-yl]benzenesulfonamide (0.276 g, 34%) as a pale yellow solid: mp 186°-190° C. 1H NMR (DMSO d6 /300 MHz) 7.81 (d, 2H, J=8.0 Hz), 7.48-7.28 (m, 9H), 4.95 (t, 1H, J=5.0 Hz), 3.70 (q, 2H, J=5.6 Hz), 2.92 (t, 2H, J=6.2 Hz). FABLRMS m/z 345 (M+H). FABHRMS m/z 345.0923 (M+H, C17H17N2O4S requires 345.0909). Anal. Calc'd for C17H17N2O4S.1.66 wt % H2O: C. 58.30; H, 4.79; N, 8.00. Found: C, 58.37; H, 4.89; N, 7.60. the reaction was quenched with aqueous KHSO4 (0.25M) extracted with ethyl acetate The combined ethyl acetate phases were washed with saturated NaHCO3 solution, brine dried over MgSO4 filtered concentrated in vacuo yielding a pale yellow solid crystallization Vacuum filtration of the resulting suspension

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

実験手順: A 0.3% solution of 0.2 g of poly(isobutylene-co-isoprene) was prepared in 99.7% of a 1:2 mixture of 2,2,4-trimethylpentane and CCl4. The solution was purged with N2, heated to 75 C., 0.09 g of azobisisobutyronitrile was added, followed by 5 g of methylmethacrylate, added over a period of one half hour. The polymerization was carried out for 8 hours with constant mechanical stirring, under a N2 atmosphere. After cooling the reaction mixture to room temperature, the cleaning procedure used was identical to that of Example 1. The solution was purged with N2 heated to 75 C , 0.09 g of azobisisobutyronitrile was added added over a period of one half hour

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

実験手順: A solution of 1,1,4,4-tetramethyl-6-ethyl-1,2,3,4-tetrahydronaphthalene (528 grams) and acetyl chloride (234 grams) is added over a 31/2 hour period at 70° C. to a well stirred slurry of aluminum chloride (534 grams), 1,1,4,4-tetramethyl-6-ethyl-1,2,3,4-tetrahydronaphthalene (1200 grams) and isooctane (432 grams). The reaction is worked up as in Example I to afford 689 grams of 1,1,4,4-tetramethyl-6-ethyl-7-acetyl-1,2,3,4-tetrahydronaphthalene (89% based on consumed 1,1,4,4-tetramethyl-6-ethyl-1,2,3,4-tetrahydronaphthalene) and 1106 grams of recovered 1,1,4,4-tetramethyl-6-ethyl-1,2,3,4-tetrahydronaphthalene.

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

実験手順: The title compound was prepared from (-)-N-ethyl-2-(3,5-dichloro-2,6-dimethoxybenzamidomethyl)pyrrolidine by dealkylation in the same manner as described in Example 2. Yield 37%. M.p. 48°-49° C. (i-octane). [α]D25 =-64° C. (c=1.26; CHCl3).

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

実験手順: To a stirred solution of [4-[4-(aminosulfonyl)phenyl]-3-phenylisoxazol-5-yl]acetic acid (Step 1) (0.85 g, 2.37 mmol) in THF (25 mL) was added borane dimethylsulfide (0.47 mL of 10.0M solution, 4.74 mmol). After stirring at room temperature for 2 days, the reaction was quenched with aqueous KHSO4 (0.25M) and extracted with ethyl acetate. The combined ethyl acetate phases were washed with saturated NaHCO3 solution, brine, dried over MgSO4, filtered and concentrated in vacuo yielding a pale yellow solid. The crude product was dissolved in hot dichloromethane and isooctane was added to induce crystallization. Vacuum filtration of the resulting suspension yielded 4-[5-(2-hydroxyethyl)-3-phenylisoxazol-4-yl]benzenesulfonamide (0.276 g, 34%) as a pale yellow solid: mp 186°-190° C. 1H NMR (DMSO d6 /300 MHz) 7.81 (d, 2H, J=8.0 Hz), 7.48-7.28 (m, 9H), 4.95 (t, 1H, J=5.0 Hz), 3.70 (q, 2H, J=5.6 Hz), 2.92 (t, 2H, J=6.2 Hz). FABLRMS m/z 345 (M+H). FABHRMS m/z 345.0923 (M+H, C17H17N2O4S requires 345.0909). Anal. Calc'd for C17H17N2O4S.1.66 wt % H2O: C. 58.30; H, 4.79; N, 8.00. Found: C, 58.37; H, 4.89; N, 7.60. the reaction was quenched with aqueous KHSO4 (0.25M) extracted with ethyl acetate The combined ethyl acetate phases were washed with saturated NaHCO3 solution, brine dried over MgSO4 filtered concentrated in vacuo yielding a pale yellow solid crystallization Vacuum filtration of the resulting suspension

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

実験手順: To a stirred solution of [4-[4-(aminosulfonyl)phenyl]-3-phenylisoxazol-5-yl]acetic acid (Step 1) (0.85 g, 2.37 mmol) in THF (25 mL) was added borane dimethylsulfide (0.47 mL of 10.0M solution, 4.74 mmol). After stirring at room temperature for 2 days, the reaction was quenched with aqueous KHSO4 (0.25M) and extracted with ethyl acetate. The combined ethyl acetate phases were washed with saturated NaHCO3 solution, brine, dried over MgSO4, filtered and concentrated in vacuo yielding a pale yellow solid. The crude product was dissolved in hot dichloromethane and isooctane was added to induce crystallization. Vacuum filtration of the resulting suspension yielded 4-[5-(2-hydroxyethyl)-3-phenylisoxazol-4-yl]benzenesulfonamide (0.276 g, 34%) as a pale yellow solid: mp 186°-190° C. 1H NMR (DMSO d6 /300 MHz) 7.81 (d, 2H, J=8.0 Hz), 7.48-7.28 (m, 9H), 4.95 (t, 1H, J=5.0 Hz), 3.70 (q, 2H, J=5.6 Hz), 2.92 (t, 2H, J=6.2 Hz). FABLRMS m/z 345 (M+H). FABHRMS m/z 345.0923 (M+H, C17H17N2O4S requires 345.0909). Anal. Calc'd for C17H17N2O4S.1.66 wt % H2O: C. 58.30; H, 4.79; N, 8.00. Found: C, 58.37; H, 4.89; N, 7.60. the reaction was quenched with aqueous KHSO4 (0.25M) extracted with ethyl acetate The combined ethyl acetate phases were washed with saturated NaHCO3 solution, brine dried over MgSO4 filtered concentrated in vacuo yielding a pale yellow solid crystallization Vacuum filtration of the resulting suspension

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

実験手順: A 0.3% solution of 0.2 g of poly(isobutylene-co-isoprene) was prepared in 99.7% of a 1:2 mixture of 2,2,4-trimethylpentane and CCl4. The solution was purged with N2, heated to 75 C., 0.09 g of azobisisobutyronitrile was added, followed by 5 g of methylmethacrylate, added over a period of one half hour. The polymerization was carried out for 8 hours with constant mechanical stirring, under a N2 atmosphere. After cooling the reaction mixture to room temperature, the cleaning procedure used was identical to that of Example 1. The solution was purged with N2 heated to 75 C , 0.09 g of azobisisobutyronitrile was added added over a period of one half hour

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

実験手順: To a stirred solution of 42.5 g (0.25 mol) of phenyl ether in 200 mL of dichloromethane at −20° C. under argon was slowly added 23.3 g (0.20 mol) of chlorosulfonic acid. After the addition was complete, the reaction was allowed to slowly warm to room temperature. After 16 hours, 150 mL of isooctane was added and the solution was concentrated to an oily residue. Redissolution in 200 mL of 1:3 dichloromethane/isooctane and reconcentration with cooling to about 100 mL gave a solid. The supernatant was decanted, and the solid triturated with additional isooctane and then dried in vacuo to give 55.2 g of crude 4-phenoxybenzene sulfonic acid. The crude acid was dissolved in 200 mL of dichloromethane, and 34 g (0.25 mol) of oxalyl chloride was added, followed by 2.5 mL of DMF. After 2 days, the reaction solution was poured into 200 mL of ice water, and extracted with 400 mL of hexane. The organic layer was washed with 100 mL of water and 100 mL of brine, dried over magnesium sulfate, and concentrated. Recrystallization of the residue from dichloromethane/isooctane gave 38.5 g of 4-phenoxybenzenesulfonyl chloride as a white solid: mp 41.5° C. at −20° C. After the addition the solution was concentrated to an oily residue Redissolution in 200 mL of 1:3 dichloromethane/isooctane and reconcentration with cooling to about 100 mL gave a solid The supernatant was decanted the solid triturated with additional isooctane dried in vacuo

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

実験手順: To a stirred solution of 42.5 g (0.25 mol) of phenyl ether in 200 mL of dichloromethane at −20° C. under argon was slowly added 23.3 g (0.20 mol) of chlorosulfonic acid. After the addition was complete, the reaction was allowed to slowly warm to room temperature. After 16 hours, 150 mL of isooctane was added and the solution was concentrated to an oily residue. Redissolution in 200 mL of 1:3 dichloromethane/isooctane and reconcentration with cooling to about 100 mL gave a solid. The supernatant was decanted, and the solid triturated with additional isooctane and then dried in vacuo to give 55.2 g of crude 4-phenoxybenzene sulfonic acid. The crude acid was dissolved in 200 mL of dichloromethane, and 22 mL (32 g, 0.25 mol) of oxalyl chloride was added, followed by 2.5 mL of N,N-dimethylformamide. After 2 days, the reaction solution was poured into 200 mL of ice water, and extracted with 400 mL of hexane. The organic layer was washed with 100 mL of water and 100 mL of brine, dried over magnesium sulfate, and concentrated. Recrystallization of the residue from dichloromethane/isooctane gave 38.5 g of 4-phenoxybenzenesulfonyl chloride as a white solid: mp 41.5° C.; 1H-NMR (CDCl3) δ 7.10 (apparent t, 4H, J=7 Hz), 7.28 (t, 1H, J=7 Hz), 7.46 (t, 2H, J=8 Hz), 7.98 (d, 2H, J=8.8 Hz). at −20° C. After the addition the solution was concentrated to an oily residue Redissolution in 200 mL of 1:3 dichloromethane/isooctane and reconcentration with cooling to about 100 mL gave a solid The supernatant was decanted the solid triturated with additional isooctane dried in vacuo

反応条件: temp:0.00; pressure:0.00; stir: