cyclotridecanone

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

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

Procedure: To a stirred mixture of 3 g of zinc dust, 50 ml of anhydrous tetrahydrofuran and 2.66 g of dibromomethane, was added dropwise a solution of 2.13 g of anhydrous titanium tetrachloride in 5 ml of dichloromethane. After 15 minutes, to the resulting solution was added dropwise a solution of 2 g of cyclotridecanone in 8 ml of anhydrous tetrahydrofuran. The mixture was allowed to react at room temperature for 12 hours. The reaction mixture was diluted with 50 ml of pentane, admixed with 100 ml of 1-M hydrochloric acid, and intermixed by shaking. The organic layer was washed successively with water, dilute aqueous sodium hydrogencarbonate solution, and saturated aqueous sodium chloride solution, then dried, and concentrated to yield methylenecyclotridecane. To a solution of this substance in 40 ml of anhydrous dichloromethane, after having been cooled to -15° C., was added dropwise with stirring a solution of 2.64 g of m-chloroperbenzoic acid in 40 ml of anhydrous dichloromethane. After 3 hours of reaction, the organic layer was washed successively with 10-% sodium sulfite solution, 7-% sodium hydrogencarbonate solution, and saturated sodium chloride solution, then dried and concentrated under reduced pressure. The residue was purified by the silica gel chromatography [developed with a petroleum ether-ethyl acetate (20:1) mixture] to yield 2.04 g (95% yield based on the ketone compound) of an epoxide. To a solution of the epoxide in anhydrous dichloromethane, after having been cooled to -18° C., was added dropwise a borontrifluoride-ether complex. After completion of the addition, water was added to the reaction mixture. The organic layer was separated, then concentrated, and purified by the silica gel chromatography to yield only cyclotridecanecarbaldehyde in a yield of 60-70%. to react at room temperature for 12 hours The organic layer was washed successively with water, dilute aqueous sodium hydrogencarbonate solution, and saturated aqueous sodium chloride solution dried concentrated

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

Procedure: To a stirred mixture of 3 g of zinc dust, 50 ml of anhydrous tetrahydrofuran and 2.66 g of dibromomethane, was added dropwise a solution of 2.13 g of anhydrous titanium tetrachloride in 5 ml of dichloromethane. After 15 minutes, to the resulting solution was added dropwise a solution of 2 g of cyclotridecanone in 8 ml of anhydrous tetrahydrofuran. The mixture was allowed to react at room temperature for 12 hours. The reaction mixture was diluted with 50 ml of pentane, admixed with 100 ml of 1-M hydrochloric acid, and intermixed by shaking. The organic layer was washed successively with water, dilute aqueous sodium hydrogencarbonate solution, and saturated aqueous sodium chloride solution, then dried, and concentrated to yield methylenecyclotridecane. To a solution of this substance in 40 ml of anhydrous dichloromethane, after having been cooled to -15° C., was added dropwise with stirring a solution of 2.64 g of m-chloroperbenzoic acid in 40 ml of anhydrous dichloromethane. After 3 hours of reaction, the organic layer was washed successively with 10-% sodium sulfite solution, 7-% sodium hydrogencarbonate solution, and saturated sodium chloride solution, then dried and concentrated under reduced pressure. The residue was purified by the silica gel chromatography [developed with a petroleum ether-ethyl acetate (20:1) mixture] to yield 2.04 g (95% yield based on the ketone compound) of an epoxide. To a solution of the epoxide in anhydrous dichloromethane, after having been cooled to -18° C., was added dropwise a borontrifluoride-ether complex. After completion of the addition, water was added to the reaction mixture. The organic layer was separated, then concentrated, and purified by the silica gel chromatography to yield only cyclotridecanecarbaldehyde in a yield of 60-70%. to react at room temperature for 12 hours The organic layer was washed successively with water, dilute aqueous sodium hydrogencarbonate solution, and saturated aqueous sodium chloride solution dried concentrated

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

Procedure: The cyclotridecanecarbaldehyde listed above is also a novel compound which is prepared in the following manner: Titanium tetrachloride is added to a mixture of zinc dust, anhydrous tetrahydrofuran and dibromomethane. To the resulting mixture is added cyclotridecanone to yield methylene cyclotridecane which is then epoxidized with m-chloroperbenzoic acid. After purification, the epoxidized product is reacted with boron trifluoride-ether complex in anhydrous dichloromethane to yield cyclotridecanecarbaldehyde. is prepared in the following manner

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

Procedure: The cyclotridecanecarbaldehyde listed above is also a novel compound which is prepared in the following manner: Titanium tetrachloride is added to a mixture of zinc dust, anhydrous tetrahydrofuran and dibromomethane. To the resulting mixture is added cyclotridecanone to yield methylene cyclotridecane which is then epoxidized with m-chloroperbenzoic acid. After purification, the epoxidized product is reacted with boron trifluoride-ether complex in anhydrous dichloromethane to yield cyclotridecanecarbaldehyde. is prepared in the following manner

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

Procedure: cyclotridecanone: 200 ml of a 50 % aqueous solution of NaOH were added dropwise under vigorous stirring to a mixture of 132 g of cyclododecene (CHEMICAL SAMPLE Co - Columbus, Ohio - USA), 600 g of bromoform and 4 g of tetramethylammonium bromide. The mixture was then left at a temperature between 40° and 50° under stirring during 2 h, whereupon it was left at room temperature overnight and diluted with water. Finally the reaction mixture was extracted with 3 fractions of 300 ml each of ether. The combined extracts, after the usual treatments of washing, drying and evaporation, gave a residue which upon fractional distillation under reduced pressure yielded 173 g (92 %) of 2,2-dibromo-bicyclo[10.1.0]tridecane. The mixture was then left at a temperature between 40° and 50° was left at room temperature overnight Finally the reaction mixture was extracted with 3 fractions of 300 ml each of ether The combined extracts, after the usual treatments of washing drying evaporation gave a residue which upon fractional distillation under reduced pressure

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

Procedure: cyclotridecanone: 200 ml of a 50 % aqueous solution of NaOH were added dropwise under vigorous stirring to a mixture of 132 g of cyclododecene (CHEMICAL SAMPLE Co - Columbus, Ohio - USA), 600 g of bromoform and 4 g of tetramethylammonium bromide. The mixture was then left at a temperature between 40° and 50° under stirring during 2 h, whereupon it was left at room temperature overnight and diluted with water. Finally the reaction mixture was extracted with 3 fractions of 300 ml each of ether. The combined extracts, after the usual treatments of washing, drying and evaporation, gave a residue which upon fractional distillation under reduced pressure yielded 173 g (92 %) of 2,2-dibromo-bicyclo[10.1.0]tridecane. The mixture was then left at a temperature between 40° and 50° was left at room temperature overnight Finally the reaction mixture was extracted with 3 fractions of 300 ml each of ether The combined extracts, after the usual treatments of washing drying evaporation gave a residue which upon fractional distillation under reduced pressure

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

Procedure: To a stirred mixture of 3 g of zinc dust, 50 ml of anhydrous tetrahydrofuran and 2.66 g of dibromomethane, was added dropwise a solution of 2.13 g of anhydrous titanium tetrachloride in 5 ml of dichloromethane. After 15 minutes, to the resulting solution was added dropwise a solution of 2 g of cyclotridecanone in 8 ml of anhydrous tetrahydrofuran. The mixture was allowed to react at room temperature for 12 hours. The reaction mixture was diluted with 50 ml of pentane, admixed with 100 ml of 1-M hydrochloric acid, and intermixed by shaking. The organic layer was washed successively with water, dilute aqueous sodium hydrogencarbonate solution, and saturated aqueous sodium chloride solution, then dried, and concentrated to yield methylenecyclotridecane. To a solution of this substance in 40 ml of anhydrous dichloromethane, after having been cooled to -15° C., was added dropwise with stirring a solution of 2.64 g of m-chloroperbenzoic acid in 40 ml of anhydrous dichloromethane. After 3 hours of reaction, the organic layer was washed successively with 10-% sodium sulfite solution, 7-% sodium hydrogencarbonate solution, and saturated sodium chloride solution, then dried and concentrated under reduced pressure. The residue was purified by the silica gel chromatography [developed with a petroleum ether-ethyl acetate (20:1) mixture] to yield 2.04 g (95% yield based on the ketone compound) of an epoxide. To a solution of the epoxide in anhydrous dichloromethane, after having been cooled to -18° C., was added dropwise a borontrifluoride-ether complex. After completion of the addition, water was added to the reaction mixture. The organic layer was separated, then concentrated, and purified by the silica gel chromatography to yield oily cyclotridecanecarbaldehyde in a yield of 60-70%. to react at room temperature for 12 hours The organic layer was washed successively with water, dilute aqueous sodium hydrogencarbonate solution, and saturated aqueous sodium chloride solution dried concentrated

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

Procedure: The cyclotridecanecarbaldehyde listed above is also a novel compound which is prepared in the following manner: Titanium tetrachloride is added to a mixture of zinc dust, anhydrous tetrahydrofuran and dibromomethane. To the resulting mixture is added cyclotridecanone to yield methylene cyclotridecane which is then epoxidized with m-chloroperbenzoic acid. After purification, the epoxidized product is reacted with boron trifluoride-ether complex in anhydrous dichloromethane to yield cyclotridecanecarbaldehyde. is prepared in the following manner

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

Procedure: To a stirred mixture of 3 g of zinc dust, 50 ml of anhydrous tetrahydrofuran and 2.66 g of dibromomethane, was added dropwise a solution of 2.13 g of anhydrous titanium tetrachloride in 5 ml of dichloromethane. After 15 minutes, to the resulting solution was added dropwise a solution of 2 g of cyclotridecanone in 8 ml of anhydrous tetrahydrofuran. The mixture was allowed to react at room temperature for 12 hours. The reaction mixture was diluted with 50 ml of pentane, admixed with 100 ml of 1-M hydrochloric acid, and intermixed by shaking. The organic layer was washed successively with water, dilute aqueous sodium hydrogencarbonate solution, and saturated aqueous sodium chloride solution, then dried, and concentrated to yield methylenecyclotridecane. To a solution of this substance in 40 ml of anhydrous dichloromethane, after having been cooled to -15° C., was added dropwise with stirring a solution of 2.64 g of m-chloroperbenzoic acid in 40 ml of anhydrous dichloromethane. After 3 hours of reaction, the organic layer was washed successively with 10-% sodium sulfite solution, 7-% sodium hydrogencarbonate solution, and saturated sodium chloride solution, then dried and concentrated under reduced pressure. The residue was purified by the silica gel chromatography [developed with a petroleum ether-ethyl acetate (20:1) mixture] to yield 2.04 g (95% yield based on the ketone compound) of an epoxide. To a solution of the epoxide in anhydrous dichloromethane, after having been cooled to -18° C., was added dropwise a borontrifluoride-ether complex. After completion of the addition, water was added to the reaction mixture. The organic layer was separated, then concentrated, and purified by the silica gel chromatography to yield only cyclotridecanecarbaldehyde in a yield of 60-70%. to react at room temperature for 12 hours The organic layer was washed successively with water, dilute aqueous sodium hydrogencarbonate solution, and saturated aqueous sodium chloride solution dried concentrated

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

Procedure: The cyclotridecanecarbaldehyde listed above is also a novel compound which is prepared in the following manner: Titanium tetrachloride is added to a mixture of zinc dust, anhydrous tetrahydrofuran and dibromomethane. To the resulting mixture is added cyclotridecanone to yield methylene cyclotridecane which is then epoxidized with m-chloroperbenzoic acid. After purification, the epoxidized product is reacted with boron trifluoride-ether complex in anhydrous dichloromethane to yield cyclotridecanecarbaldehyde. is prepared in the following manner

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

Procedure: cyclotridecanone: 200 ml of a 50 % aqueous solution of NaOH were added dropwise under vigorous stirring to a mixture of 132 g of cyclododecene (CHEMICAL SAMPLE Co - Columbus, Ohio - USA), 600 g of bromoform and 4 g of tetramethylammonium bromide. The mixture was then left at a temperature between 40° and 50° under stirring during 2 h, whereupon it was left at room temperature overnight and diluted with water. Finally the reaction mixture was extracted with 3 fractions of 300 ml each of ether. The combined extracts, after the usual treatments of washing, drying and evaporation, gave a residue which upon fractional distillation under reduced pressure yielded 173 g (92 %) of 2,2-dibromo-bicyclo[10.1.0]tridecane. The mixture was then left at a temperature between 40° and 50° was left at room temperature overnight Finally the reaction mixture was extracted with 3 fractions of 300 ml each of ether The combined extracts, after the usual treatments of washing drying evaporation gave a residue which upon fractional distillation under reduced pressure