4-methylideneoxetan-2-one

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:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 84 g of diketene were added over 10 minutes at 10° C. to a mixture of 85 g of cyclopentylamine and 500 ml of tetrahydrofuran and after stirring the mixture for 6 hours at 20° C., the mixture was evaporated to dryness under reduced pressure. The residue was added to isopropyl ether and was cooled and vacuum filtered to obtain 107 g of N-cyclopentyl-acetylacetamide melting at 52° C. 56 g of the latter product and 1.6 g of p-toluene sulfonic acid were added to a mixture of 40 g of methyl orthoformate and 80 ml of methanol and the mixture was held at 50° C. for 8 hours and 72 hours at 25° C. 4 ml of quinoline were added and the mixture was evaporated to dryness under reduced pressure. The residue was added to toluene and the mixture was heated at 145° C. for 4 hours while distilling a toluene-methanol azeotrope. The mixture was evaporated to dryness under reduced pressure and the residue was chromatographed over silica gel. The product was eluted with an 8-2 methylene chloride-acetone mixture and was crystallized from isopropyl ether to obtain 40 g of N-cyclopentyl-3-methoxy-crotonamide melting at 94° C. The RMN spectra showed the product to be the E isomer. the mixture was evaporated to dryness under reduced pressure The residue was added to isopropyl ether was cooled vacuum filtered

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4.8 g of diketene were added to a mixture of 9 g of 1-amino-2-carbethoxy-cyclopentane and 90 ml of benzene and after stirring for 72 hours at 20° C., the mixture was evaporated to dryness under reduced pressure. The residue was chromatographed over silica gel and was eluted with an 8-2 methylene chloride-acetone mixture to obtain 7.7 g of N-(2-carbethoxycyclopentyl)-acetylacetamide with a refractive index of ND22 =1.487. 6.3 g of the latter product and 0.25 g of p-toluene sulfonic acid were added to a mixture of 4.2 g of methyl orthoformate and 60 ml of methanol and after stirring the mixture at 20° C. for 16 hours, the mixture was evaporated to dryness under reduced pressure. The residue was added to toluene and 0.5 ml of quinoline and the mixture was heated at 145° C. for 1 hour while distilling a toluene-methanol azeotrope. The mixture was evaporated to dryness under reduced pressure and the residue was chromatographed over silica gel. Elution with a 9-1 methylene chloride-acetone mixture gave 1.8 g of N-(2'-carbethoxycyclopentyl)-3-methoxy-crotonamide melting at 74° C. The RMN spectra showed it to be the E isomer. the mixture was evaporated to dryness under reduced pressure The residue was chromatographed over silica gel was eluted with an 8-2 methylene chloride-acetone mixture

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 16.8 g of diketene were added with stirring to a mixture of 30 g of 2-bornylamine and 200 ml of isopropyl ether and after stirring for 4 hours at 20° C., the mixture was evaporated to dryness under reduced pressure. The residue was chromatographed over silica gel and elution with a 9-1 methylene chloride-acetone mixture gave 39 g of N-(2-bornyl)-acetylacetamide. 30 g of the latter product and 1 g of p-toluene sulfonic acid were added to a mixture of 20 g of methyl orthoformate and 30 ml of methanol and the mixture stood at 20° C. for 16 hours. 2 ml of quinoline were added thereto and the mixture was evaporated to dryness under reduced pressure. The residue was added to toluene and the mixture was heated at 145° C. for 3 hours while distilling a toluene-methanol azeotrope. The mixture was evaporated to dryness under reduced pressure and the residue was chromatographed over silica gel. The product was eluted with an 8-2 methylene chloride-acetone mixture and was crystallized from isopropyl ether to obtain 19 g of N-(2'-bornyl)-3-methoxy-crotonamide melting at 149° C. The RMN spectra showed it was the E somer. the mixture was evaporated to dryness under reduced pressure The residue was chromatographed over silica gel and elution with a 9-1 methylene chloride-acetone mixture

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 7.5 g of diketene in 30 ml of tetrahydrofuran was added to a mixture of 10 g of 3-methylcyclohexylamine and 60 ml of tetrahydrofuran and the mixture was stirred at 20° C. for 4 hours and evaporated to dryness under reduced pressure. The residue was chromatographed over silica gel and was eluted with an 8-2 methylene chloride-acetone mixture to obtain 12 g of N-(3-methylcyclohexyl)-acetylacetamide. 12 g of the latter product and 0.3 g of p-toluene sulfonic acid were added to a mixture of 10.6 g of methyl orthoformate and 20 ml of methanol and the mixture was stirred at 20° C. for 1 hour and stood still for 16 hours at 20° C. 0.6 g of quinoline were added thereto and the mixture was evaporated to dryness under reduced pressure. The residue was added to 50 ml of toluene and the mixture was heated at 145° C. for 3 hours while distilling a toluene-methanol azeotrope and was then evaporated to dryness under reduced pressure. The residue was chromatographed over silica gel and elution with an 8-2 methylene chloride-acetone mixture gave 9.2 g of N-(3'-methylcyclohexyl)-3-methoxy-crotonamide whose RMN spectra showed it to be the E isomer. evaporated to dryness under reduced pressure The residue was chromatographed over silica gel was eluted with an 8-2 methylene chloride-acetone mixture

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 29 g of diketene were added over 20 minutes to a stirred mixture of 39 g of 4-methylcyclohexylamine in 100 ml of tetrahydrofuran and the mixture was stirred at 20° C. for 3 hours. Isopropyl ether was added thereto and the precipitate formed was recovered by vacuum filtration, was washed and dried to obtain 46 g of N-(4-methylcyclohexyl)-acetylacetamide melting at 111° C. A mixture of 46 g of the latter product, 37 g of methyl orthoformate, 1.5 g of p-toluene sulfonic acid and 100 ml of methanol was stirred for 2 hours at 20° C. and after standing for 16 hours, 3 ml of quinoline were added thereto. The mixture was distilled to dryness under reduced pressure and the residue was added to toluene. The stirred mixture was heated at 145° C. for 3 hours while distilling a toluene-methanol azeotrope and was then cooled and evaporated to dryness under reduced pressure. The residue was chromatographed over silica gel and elution with an 8-2 methylene chloride-acetone mixture gave 24 g of N-(4'-methylcyclohexyl)-3-methoxy-crotonamide melting at 125° C. The RMN spectra showed the product to be the E isomer. the precipitate formed was recovered by vacuum filtration was washed dried

Conditions: temp:6.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 37.1 g of diketene were added with stirring over 15 minutes to a mixture of 50 g of cycloheptylamine and 600 ml of tetrahydrofuran cooled to 6° C. and the mixture was stirred for 4 hours at room temperature. The mixture was distilled to dryness under reduced pressure and the residue was chromatographed over silica gel with elution with an 8-2 methylene chloride-acetone mixture to obtain 60 g of N-cycloheptyl-acetylacetamide melting at 52° C. 40 g of the said product and 1 g of p-toluene sulfonic acid were added to a mixture of 32 g of methyl orthoformate and 100 ml of methanol and after stirring the mixture for 8 hours at room temperature, 2 ml of quinoline were added thereto. The mixture was distilled to dryness under reduced pressure and the residue was added to toluene. The mixture was heated at 145° C. for 4 hours while distilling a toluene-methanol azeotrope. The toluene was evaporated by distillation under reduced pressure and the residue was chromatographed over silica gel. An 8-2 methylene chloride-methanol mixture was the eluant and the product was empasted with isopropyl ether to obtain 22 g of N-cycloheptyl-3-methoxy-crotonamide melting at 120° C. The RMN spectra showed the product to be the E isomer. The mixture was distilled to dryness under reduced pressure the residue was chromatographed over silica gel with elution with an 8-2 methylene chloride-acetone mixture

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

Procedure: 19 g of 1-amino-adamantane were added to 200 ml of benzene and then 9.5 ml of diketene were added thereto over 10 minutes. The mixture was stirred for 21/2 hours at room temperature and after the addition of activated charcoal, the mixture was stirred and filtered. The filtrate was distilled to dryness under reduced pressure and the residue was added to isopropyl ether. The mixture was vacuum filtered to obtain 23.6 g of N-(1-adamantyl)-acetylacetamide melting at 80° C. 23.5 g of the said product and 1 g of p-toluene sulfonic acid were added to a mixture of 50 ml of methanol and 15 ml of methyl orthoformate and the mixture was stirred at room temperature for 24 hours and was then cooled. 2 ml of quinoline were added and the mixture was vacuum filtered. The precipitate was dried to obtain 25.1 g of N-(1-adamantyl)-3,3-dimethoxy-butyramide melting at 140° C. the mixture was stirred filtered The filtrate was distilled to dryness under reduced pressure the residue was added to isopropyl ether filtered

Conditions: temp:-5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 84 g of diketene were added over 30 minutes to a stirred mixture of 127 g of cyclooctylamine and 800 ml of tetrahydrofuran cooled to -5° C. and the mixture was stirred for 4 hours at 20° C. and then evaporated to dryness under reduced pressure to obtain 210 g of N-cyclooctyl-acetylacetamide melting at 44° C. 63 g of the said product and 1 g of p-toluene sulfonic acid were added to a mixture of 150 ml of methanol and 40 g of methyl orthoformate and after stirring the mixture for 16 hours, 1.5 ml of quinoline were added thereto. The mixture was distilled to dryness under reduced pressure and the residual oil was dissolved in toluene. The solution was heated at 145° C. for 4 hours while distilling off a methanol-toluene azeotrope. The mixture was distilled to dryness under reduced pressure and the oil residue was chromatographed over silica gel. An 8-2 methylene chloride-acetone mixture was used as the eluant and the product was empasted with isopropyl ether to obtain 45 g of N-cyclooctyl-3-methoxy-crotonamide melting at 116° C. evaporated to dryness under reduced pressure

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 500 ml of benzene and 99 g of cyclohexyl amine were introduced over 30 minutes to 84 g of diketene and after stirring for 4 hours at 20° C., the mixture was evaporated to dryness by distillation under reduced pressure. The residue was taken up in isopropyl ether and the solution was cooled and vacuum filtered. The recovered precipitate was dried and crystallized from isopropyl ether to obtain 137 g of N-cyclohexyl-acetylacetamide melting at 74° C. the mixture was evaporated to dryness by distillation under reduced pressure the solution was cooled vacuum filtered The recovered precipitate was dried crystallized from isopropyl ether