nitrosomethylurea

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: Nitrosomethylurea (99.5 mmol) is added in portions to a cold (0° C.) mixture of aqueous 50% KOH (50 ml) and diethylether (150 ml) at 0° C. The yellow ether solution of diazomethane (Note: explosive) is separated, is washed with water, and is added in portions to a solution of 5-fluoro-2-methylindene-3-acetic acid (90 mmol) in dichloromethane (200 ml). When the evolution of N2 ceases, the reaction is complete. After evaporation of the solvents, the residue is recrystallized from hexane to give methyl 5-fluoro-2-methyl-3-indenylacetate (yield 93%; m.p. 53° C.). The yellow ether solution of diazomethane (Note: explosive) is separated is washed with water After evaporation of the solvents the residue is recrystallized from hexane

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

Procedure: With cooling and stirring, an ethereal diazomethane solution prepared by reaction of 5.34 g of N-nitrosomethylurea with aqueous sodium hydroxide solution in ether is added dropwise to a solution of 5 g of 4,4'-dichlorobenzil in 50 ml of dioxane. When the dropwise addition is complete, stirring is continued for 16 hours at room temperature, and the reaction solution is then concentrated by evaporation. The residual oil is crude 2-(4-chlorobenzoyl)-2-(4-chlorophenyl)oxirane which is purified by high vacuum distillation. With cooling When the dropwise addition stirring the reaction solution is then concentrated by evaporation is purified by high vacuum distillation

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

Procedure: With cooling and stirring, an ethereal diazomethane solution prepared from 3.1 g of nitrosomethylurea and aqueous sodium hydroxide solution in ether is added dropwise to a solution of 3.4 g of 2,2',4,4'-tetrachlorobenzil in 50 ml of dioxane. When the dropwise addition is complete, stirring is continued for 16 hours at room temperature, and the reaction mixture is then concentrated to dryness. The residual oil is crude 2-(2,4-dichlorobenzoyl)-2-(2,4-dichlorophenyl)oxirane which is purified by high vacuum distillation. With cooling When the dropwise addition stirring the reaction mixture is then concentrated to dryness is purified by high vacuum distillation

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

Procedure: Compound 7 was dissolved in tetrahydrofuran (120 ml) and cooled in an ice bath. Diazomethane was generated by addition of N-nitrosomethylurea to an ice cold, equivolume mixture of ether and 40% aqueous potassium hydroxide. The diazomethane solution was added without purification to the stirred solution of the amino acid derivative. The reaction was complete when N2 was no longer evolved upon addition of diazomethane. Excess diazomethane was consumed by the addition of acetic acid. The solution was extracted successively with saturated saline, 1M sodium bicarbonate, 0.1M HCl, and again with saline and dried (MgSO4). Evaporation left 3.56 g (88.4%) of a solid melting at 110°-112° C. which was pure by TLC (chloroform/methanol acid: 85/10/5). [α]D25 =-13.8 (c=2.1, ethanol) cooled in an ice bath Excess diazomethane was consumed by the addition of acetic acid The solution was extracted successively with saturated saline, 1M sodium bicarbonate, 0.1M HCl again with saline and dried (MgSO4) Evaporation left 3.56 g (88.4%) of a solid melting at 110°-112° C. which

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

Procedure: Compound 7 was dissolved in tetrahydrofuran (120 ml) and cooled in an ice bath. Diazomethane was generated by addition of N-nitrosomethylurea to an ice cold, equivolume mixture of ether and 40% aqueous potassium hydroxide. The diazomethane solution was added without purification to the stirred solution of the amino acid derivative. The reaction was complete when N2 was no longer evolved upon addition of diazomethane. Excess diazomethane was consumed by the addition of acetic acid. The solution was extracted successively with saturated saline, 1M sodium bicarbonate, 0.1M HCl, and again with saline and dried (MgSO4). Evaporation left 3.56 g (88.4%) of a solid melting at 110°-112° C. which was pure by TLC (chloroform/methanol acid: 85/10/5). [α]D25 =-13.8 (c=2.1, ethanol) cooled in an ice bath Excess diazomethane was consumed by the addition of acetic acid The solution was extracted successively with saturated saline, 1M sodium bicarbonate, 0.1M HCl again with saline and dried (MgSO4) Evaporation left 3.56 g (88.4%) of a solid melting at 110°-112° C. which

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

Procedure: With cooling and stirring, an ethereal diazomethane solution prepared by reaction of 5.34 g of N-nitrosomethylurea with aqueous sodium hydroxide solution in ether is added dropwise to a solution of 5 g of 4,4'-dichlorobenzil in 50 ml of dioxane. When the dropwise addition is complete, stirring is continued for 16 hours at room temperature, and the reaction solution is then concentrated by evaporation. The residual oil is crude 2-(4-chlorobenzoyl)-2-(4-chlorophenyl)oxirane which is purified by high vacuum distillation. With cooling When the dropwise addition stirring the reaction solution is then concentrated by evaporation is purified by high vacuum distillation

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

Procedure: With cooling and stirring, an ethereal diazomethane solution prepared from 3.1 g of nitrosomethylurea and aqueous sodium hydroxide solution in ether is added dropwise to a solution of 3.4 g of 2,2',4,4'-tetrachlorobenzil in 50 ml of dioxane. When the dropwise addition is complete, stirring is continued for 16 hours at room temperature, and the reaction mixture is then concentrated to dryness. The residual oil is crude 2-(2,4-dichlorobenzoyl)-2-(2,4-dichlorophenyl)oxirane which is purified by high vacuum distillation. With cooling When the dropwise addition stirring the reaction mixture is then concentrated to dryness is purified by high vacuum distillation

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

Procedure: to a solution of 8 parts of (5Z,13E,15S)-15-acetyloxy-11ξ-hydroxyprosta-5,9,13-trien-1-oic acid in 175 parts of diethyl ether is added an ethereal solution of diazomethane prepared from 30 parts of N-nitrosomethylurea, 90 parts of aqueous 40% potassium hydroxide, and 210 parts of diethyl ether as described in Org. Syn., 15, 4 (1935). The resultant mixture is allowed to stand at 5° for 30 minutes, whereupon 2 parts of acetic acid is introduced and the mixture thus obtained extracted with diethyl ether. The extract is washed with water, dried over anhydrous sodium sulfate, and stripped of solvent by vacuum distillation. The residual red oil is taken up in benzene; and the benzene solution is chromatographed on silica gel, using benzene and mixtures thereof with increasing amounts of ethyl acetate as developing solvents. From an eluate comprising 30% ethyl acetate in benzene, on evaporation of solvent, methyl (5Z,13E,15S)-15-acetyloxy-11ξ-hydroxyprosta-5,9,13-trien-1-oate is obtained as a pale yellow oil. is introduced the mixture thus obtained extracted with diethyl ether The extract is washed with water dried over anhydrous sodium sulfate stripped of solvent by vacuum distillation and the benzene solution is chromatographed on silica gel From an eluate comprising 30% ethyl acetate in benzene, on evaporation of solvent

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

Procedure: Nitrosomethylurea (99.5 mmol) is added in portions to a cold (0° C.) mixture of aqueous 50% KOH (50 ml) and diethylether (150 ml) at 0° C. The yellow ether solution of diazomethane (Note: explosive) is separated, is washed with water, and is added in portions to a solution of 5-fluoro-2-methylindene-3-acetic acid (90 mmol) in dichloromethane (200 ml). When the evolution of N2 ceases, the reaction is complete. After evaporation of the solvents, the residue is recrystallized from hexane to give methyl 5-fluoro-2-methyl-3-indenylacetate (yield 93%; m.p. 53° C.). The yellow ether solution of diazomethane (Note: explosive) is separated is washed with water After evaporation of the solvents the residue is recrystallized from hexane