methyl sulfate;trimethylsulfanium

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Synthesis of trimethysulfonium hydrogen sulfate: To dimethyl sulfate (10.0 mL, 1.05×10−1 mol) at 0° C. was added dimethyl sulfide (10.4 mL, 1.42×10−1 mol). After rapidly stirring at 0° C. for 30 minutes, the reaction was slowly warmed to room temperature yielding a crystalline solid, trimethylsulfonium methyl sulfate. After 3 hours, distilled water (20 mL) was added to form a clear solution of trimethylsulfonium sulfate. the reaction was slowly warmed to room temperature

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

Procedure: 3-Butyryl-4-(2-methylphenylamino)quinoline-8-carbaldehyde (0.5 q, 1.5 mmol) was dissolved in dichloromethane (5 ml) and trimethylsulphonium methylsulphate (0.34 g, 1.8 mmol) and 50% aqueous sodium hydroxide (0.75 ml) added. The mixture was stirred vigorously for 2.5 hours, when a further addition of trimethylsulphonium methylsulphate (0.23 g, 1.2 mmol) and 50% aqueous sodium hydroxide (0.5 ml) was made. After stirring for a further 2 hours the mixture was diluted with water and extracted with dichloromethane. The dried extracts were evaporated to an oil, which was purified by flash chromatography (silica gel, ethyl acetate/chloroform). The product crystallised on trituration with petroleum ether to give 3-butyryl-4-(2-methylphenylamino)-8-oxiranylquinoline (0.28 g, 54%), m.p. 114°-116°. After stirring for a further 2 hours the mixture extracted with dichloromethane The dried extracts were evaporated to an oil, which was purified by flash chromatography (silica gel, ethyl acetate/chloroform) The product crystallised on trituration with petroleum ether

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

Procedure: 3-Butyryl-4-(2-methylphenylamino)quinoline-8-carbaldehyde (0.5 q, 1.5 mmol) was dissolved in dichloromethane (5 ml) and trimethylsulphonium methylsulphate (0.34 g, 1.8 mmol) and 50% aqueous sodium hydroxide (0.75 ml) added. The mixture was stirred vigorously for 2.5 hours, when a further addition of trimethylsulphonium methylsulphate (0.23 g, 1.2 mmol) and 50% aqueous sodium hydroxide (0.5 ml) was made. After stirring for a further 2 hours the mixture was diluted with water and extracted with dichloromethane. The dried extracts were evaporated to an oil, which was purified by flash chromatography (silica gel, ethyl acetate/chloroform). The product crystallised on trituration with petroleum ether to give 3-butyryl-4-(2-methylphenylamino)-8-oxiranylquinoline (0.28 g, 54%), m.p. 114°-116°. After stirring for a further 2 hours the mixture extracted with dichloromethane The dried extracts were evaporated to an oil, which was purified by flash chromatography (silica gel, ethyl acetate/chloroform) The product crystallised on trituration with petroleum ether

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

Procedure: The procedure was based on methods described by Brandes and Jacobsen, (Tetrahedron Asym. 8:3927, 1997); and Kaufman (Syn. Commun. 23:473, 1993). A solution of trimethylsulfonium methylsulfate (3.95 g, 0.021 mol) in 8 mL water was added slowly to a biphasic mixture of 50% NaOH (20 mL), 3,4-dimethyl-benzaldehyde (1.34 g, 0.01 mmol), tetrabutylammonium bromide (0.025 g, 0.0782 mmol), and CH2Cl2 (26 mL). The reaction was heated at 50° C. for 13 hours and then cooled to room temperature. The reaction was diluted carefully with brine (50 mL) and diethyl ether (3×70 mL), then filtered to remove the solids. The aqueous layer was extracted with diethyl ether (3×70 mL), and the combined organic layers were washed with brine (50 mL) and dried over Na2SO4, filtered, and concentrated in vacuo to afford the product 3,4-dimethylphenyl oxirane as a light yellow oil (1.15 g, yield 78%). TLC Rf=0.9 (1:2 EtOAc/Hexane); 1H NMR (300 MHz, CDCl3) δ 7.39 (s, 1 H), 7.21 (d, 1 H), 7.19 (s, 1 H), 3.80 (m, 1 H), 3.17 (m, 1 H), 2.80 (m, 1 H), 2.23 (s, 6 H). cooled to room temperature filtered to remove the solids The aqueous layer was extracted with diethyl ether (3×70 mL) the combined organic layers were washed with brine (50 mL) dried over Na2SO4 filtered concentrated in vacuo

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

Procedure: The procedure was based on methods described by Brandes and Jacobsen, (Tetrahedron Asym. 8:3927, 1997); and Kaufman (Syn. Commun. 23:473, 1993). A solution of trimethylsulfonium methylsulfate (3.95 g, 0.021 mol) in 8 mL water was added slowly to a biphasic mixture of 50% NaOH (20 mL), 3,4-dimethyl-benzaldehyde (1.34 g, 0.01 mmol), tetrabutylammonium bromide (0.025 g, 0.0782 mmol), and CH2Cl2 (26 mL). The reaction was heated at 50° C. for 13 hours and then cooled to room temperature. The reaction was diluted carefully with brine (50 mL) and diethyl ether (3×70 mL), then filtered to remove the solids. The aqueous layer was extracted with diethyl ether (3×70 mL), and the combined organic layers were washed with brine (50 mL) and dried over Na2SO4, filtered, and concentrated in vacuo to afford the product 3,4-dimethylphenyl oxirane as a light yellow oil (1.15 g, yield 78%). TLC Rf=0.9 (1:2 EtOAc/Hexane); 1H NMR (300 MHz, CDCl3) δ 7.39 (s, 1 H), 7.21 (d, 1 H), 7.19 (s, 1 H), 3.80 (m, 1 H), 3.17 (m, 1 H), 2.80 (m, 1 H), 2.23 (s, 6 H). cooled to room temperature filtered to remove the solids The aqueous layer was extracted with diethyl ether (3×70 mL) the combined organic layers were washed with brine (50 mL) dried over Na2SO4 filtered concentrated in vacuo

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

Procedure: 2.4 g (0.044 mol) of sodium methoxide are added to the solution of 30 ml (0.04 mol) of a 1.36-molar solution of trimethylsulphonium methylsulphate in acetonitrile, and the mixture is stirred at room temperature for 30 minutes. 5.8 g (0.022 mol) of 1-(4-chlorophenoxyacetyl)-1-methyl-2,2-difluorocyclopropane are then added, and the mixture is stirred for 16 hours at 20° C. The reaction mixture is poured into 200 ml of water and extracted using methylene chloride, and the organic phase is washed with water and concentrated. 4.3 g (GC content of 73%; 71.6% of theory) of 2-(4-chlorophenoxymethyl)-2-(2,2-difluoro-1-methylcyclopropyl)-oxirane are obtained as a viscous resin which is reacted further directly. ##STR79## the mixture is stirred for 16 hours at 20° C extracted the organic phase is washed with water concentrated

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

Procedure: A mixture of 1,4-benzodioxanecarboxaldehyde [RN 29668-44-8](1.5 g, 9.14 mmol), trimethylsulfonium methyl sulfate (2.24 g, 11.9 mmol), dichloromethane (35 ml) and 50% aqueous sodium hydroxide (5 ml) were vigorously stirred for 70 hours. The mixture was partitioned between water and diethyl ether and the layers separated. The aqueous phase was extracted with diethyl ether. The combined organic phases were washed with water, brine, then dried over magnesium sulfate and evaporated to give crude 6-oxiranyl-2,3-dihydro-benzo[1,4]dioxine (1.64 g, 100%). The mixture was partitioned between water and diethyl ether the layers separated The aqueous phase was extracted with diethyl ether The combined organic phases were washed with water, brine dried over magnesium sulfate evaporated

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

Procedure: A mixture of 1,4-benzodioxanecarboxaldehyde [RN 29668-44-8](1.5 g, 9.14 mmol), trimethylsulfonium methyl sulfate (2.24 g, 11.9 mmol), dichloromethane (35 ml) and 50% aqueous sodium hydroxide (5 ml) were vigorously stirred for 70 hours. The mixture was partitioned between water and diethyl ether and the layers separated. The aqueous phase was extracted with diethyl ether. The combined organic phases were washed with water, brine, then dried over magnesium sulfate and evaporated to give crude 6-oxiranyl-2,3-dihydro-benzo[1,4]dioxine (1.64 g, 100%). The mixture was partitioned between water and diethyl ether the layers separated The aqueous phase was extracted with diethyl ether The combined organic phases were washed with water, brine dried over magnesium sulfate evaporated

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

Procedure: 12.00 g (76.83 mmol, 1.0 equiv.) of 1,4 Cyclohexanedione ethylene ketal was added to 120 ml methylene chloride along with 18.8 g (99.88 mmol, 1.3 equiv.) of trimethyl sulfonium methyl sulfate. 40 ml 50% sodium hydroxide (NaOH) was added last and the reaction was refluxed for 24 hours. The methylene chloride was removed, 200 ml ether was added and the ether layer was washed with water. The organic layer was dried with sodium sulfate and concentrated down, leaving a yellow oil, 1,7,10-trioxa-dispiro[2.2.4.2]dodecane. (12.13 g, 93% yield). No further purification was necessary. the reaction was refluxed for 24 hours The methylene chloride was removed 200 ml ether was added the ether layer was washed with water The organic layer was dried with sodium sulfate concentrated down

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

Procedure: 12.00 g (76.83 mmol, 1.0 equiv.) of 1,4 Cyclohexanedione ethylene ketal was added to 120 ml methylene chloride along with 18.8 g (99.88 mmol, 1.3 equiv.) of trimethyl sulfonium methyl sulfate. 40 ml 50% sodium hydroxide (NaOH) was added last and the reaction was refluxed for 24 hours. The methylene chloride was removed, 200 ml ether was added and the ether layer was washed with water. The organic layer was dried with sodium sulfate and concentrated down, leaving a yellow oil, 1,7,10-trioxa-dispiro[2.2.4.2]dodecane. (12.13 g, 93% yield). No further purification was necessary. the reaction was refluxed for 24 hours The methylene chloride was removed 200 ml ether was added the ether layer was washed with water The organic layer was dried with sodium sulfate concentrated down

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

Procedure: The procedure was based on methods described by Brandes and Jacobsen, (Tetrahedron Asym. 8:3927, 1997); and Kaufman (Syn. Commun. 23:473, 1993). A solution of trimethylsulfonium methylsulfate (3.95 g, 0.021 mol) in 8 mL water was added slowly to a biphasic mixture of 50% NaOH (20 mL), 3,4-dimethyl-benzaldehyde (1.34 g, 0.01 mmol), tetrabutylammonium bromide (0.025 g, 0.0782 mmol), and CH2Cl2 (26 mL). The reaction was heated at 50° C. for 13 hours and then cooled to room temperature. The reaction was diluted carefully with brine (50 mL) and diethyl ether (3×70 mL), then filtered to remove the solids. The aqueous layer was extracted with diethyl ether (3×70 mL), and the combined organic layers were washed with brine (50 mL) and dried over Na2SO4, filtered, and concentrated in vacuo to afford the product 3,4-dimethylphenyl oxirane as a light yellow oil (1.15 g, yield 78%). TLC Rf=0.9 (1:2 EtOAc/Hexane); 1H NMR (300 MHz, CDCl3) δ 7.39 (s, 1H), 7.21 (d, 1H), 7.19 (s, 1H), 3.80 (m, 1H), 3.17 (m, 1H), 2.80 (m, 1H), 2.23 (s, 6H). cooled to room temperature filtered to remove the solids The aqueous layer was extracted with diethyl ether (3×70 mL) the combined organic layers were washed with brine (50 mL) dried over Na2SO4 filtered concentrated in vacuo

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Synthesis of trimethysulfonium hydrogen sulfate: To dimethyl sulfate (10.0 mL, 1.05×10−1 mol) at 0° C. was added dimethyl sulfide (10.4 mL, 1.42×10−1 mol). After rapidly stirring at 0° C. for 30 minutes, the reaction was slowly warmed to room temperature yielding a crystalline solid, trimethylsulfonium methyl sulfate. After 3 hours, distilled water (20 mL) was added to form a clear solution of trimethylsulfonium sulfate. the reaction was slowly warmed to room temperature