2-methyldecanoic acid

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

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

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

Procedure: To thionyl chloride (93 g, 782 mmol), cooled to 15° C. in a water bath was added during 1 hour 2-methyl decanoic acid (64 g, 344 mmol). The cold water bath was removed and the mixture was heated at 50° C. with stirring for 45 minutes. The excess thionyl chloride was removed by distillation and the crude acid chloride was then fractionally distilled (b.p. 143°-45° C./5.8 mm) to give 69 g of product (99% yield) that showed an assay of >98% by GC. The cold water bath was removed The excess thionyl chloride was removed by distillation the crude acid chloride was then fractionally distilled (b.p. 143°-45° C./5.8 mm)

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

Procedure: Sodium (12.5 g, 0.54 g-atoms) was gradually added in small pieces to absolute ethanol (375 ml) while stirring under an inert (N2) atmosphere until complete solution of the sodium has taken place. Diethyl methylmalonate (95.5 g, 570 mmol) was then added dropwise to the sodium ethoxide solution over 20 minutes and the mixture was heated at reflux for about 15 minutes. After cooling to room temperature, 1-bromooctane (99 g, 512 mmol) was added dropwise over 15 minutes; the mixture was heated at reflux for 2 hours, cooled and neutralized by adding a few drops of glacial acetic acid. About two-thirds of the alcohol was removed by distillation and the residue was washed with 500 ml of water. The organic phase was separated and the aqueous phase extracted with three 50 ml portions of benzene. The organic phase and extracts were combined, washed with water, and dried over anhydrous magnesium sulfate. The residue obtained upon evaporation of the solvent was treated with a solution of 115 g of 86% potassium hydroxide Pellets in 900 ml of reagent ethanol and the mixture heated at reflux, with stirring, for 4 hours. About two-thirds of the solvent was removed by distillation, 750 ml water was added, followed by sufficient (520 ml) 6N sulfuric acid to bring the pH of the solution to 1-2. The organic phase was separated and the aqueous phase was extracted with two portions of ether. The organic phase and extracts were combined, washed with water, then with saturated sodium chloride solution, and finally dried over magnesium sulfate. The residue obtained upon evaporation of the solvent was heated to 180°-190° C. at which temperature decarboxylation occurred smoothly over a period of several minutes. The crude acid was then distilled through a short Vigreux column to give 64 g of product (73% yield), b.p. 143°/5.8 mm (lit. b.p. 137°/4.4 mm), which showed a purity of >99% by GC. the mixture was heated at reflux for about 15 minutes the mixture was heated at reflux for 2 hours cooled About two-thirds of the alcohol was removed by distillation the residue was washed with 500 ml of water The organic phase was separated the aqueous phase extracted with three 50 ml portions of benzene washed with water dried over anhydrous magnesium sulfate The residue obtained upon evaporation of the solvent the mixture heated at reflux About two-thirds of the solvent was removed by distillation, 750 ml water was added The organic phase was separated the aqueous phase was extracted with two portions of ether washed with water with saturated sodium chloride solution, and finally dried over magnesium sulfate The residue obtained upon evaporation of the solvent was heated to 180°-190° C. at which temperature decarboxylation occurred smoothly over a period of several minutes The crude acid was then distilled through a short Vigreux column

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

Procedure: Sodium (12.5 g, 0.54 g-atoms) was gradually added in small pieces to absolute ethanol (375 ml) while stirring under an inert (N2) atmosphere until complete solution of the sodium has taken place. Diethyl methylmalonate (95.5 g, 570 mmol) was then added dropwise to the sodium ethoxide solution over 20 minutes and the mixture was heated at reflux for about 15 minutes. After cooling to room temperature, 1-bromooctane (99 g, 512 mmol) was added dropwise over 15 minutes; the mixture was heated at reflux for 2 hours, cooled and neutralized by adding a few drops of glacial acetic acid. About two-thirds of the alcohol was removed by distillation and the residue was washed with 500 ml of water. The organic phase was separated and the aqueous phase extracted with three 50 ml portions of benzene. The organic phase and extracts were combined, washed with water, and dried over anhydrous magnesium sulfate. The residue obtained upon evaporation of the solvent was treated with a solution of 115 g of 86% potassium hydroxide Pellets in 900 ml of reagent ethanol and the mixture heated at reflux, with stirring, for 4 hours. About two-thirds of the solvent was removed by distillation, 750 ml water was added, followed by sufficient (520 ml) 6N sulfuric acid to bring the pH of the solution to 1-2. The organic phase was separated and the aqueous phase was extracted with two portions of ether. The organic phase and extracts were combined, washed with water, then with saturated sodium chloride solution, and finally dried over magnesium sulfate. The residue obtained upon evaporation of the solvent was heated to 180°-190° C. at which temperature decarboxylation occurred smoothly over a period of several minutes. The crude acid was then distilled through a short Vigreux column to give 64 g of product (73% yield), b.p. 143°/5.8 mm (lit. b.p. 137°/4.4 mm), which showed a purity of >99% by GC. the mixture was heated at reflux for about 15 minutes the mixture was heated at reflux for 2 hours cooled About two-thirds of the alcohol was removed by distillation the residue was washed with 500 ml of water The organic phase was separated the aqueous phase extracted with three 50 ml portions of benzene washed with water dried over anhydrous magnesium sulfate The residue obtained upon evaporation of the solvent the mixture heated at reflux About two-thirds of the solvent was removed by distillation, 750 ml water was added The organic phase was separated the aqueous phase was extracted with two portions of ether washed with water with saturated sodium chloride solution, and finally dried over magnesium sulfate The residue obtained upon evaporation of the solvent was heated to 180°-190° C. at which temperature decarboxylation occurred smoothly over a period of several minutes The crude acid was then distilled through a short Vigreux column

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

Procedure: Then, the same procedure as in Example 1 was repeated except that the above (+)-2-methyl decanoic acid was used instead of (+)-2-methyl butanoic acid to convert this compound into an acid chloride, which was reacted with phenol through aluminum chloride in methylene chloride to obtain (+)-4-(2-methyldecanoyl) phenol having the aforementioned physical and chemical properties at a yield of 40%.

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

Procedure: After 14.6 g of concentrated sulfuric acid and 8.6 g (50 mmol) of (-)-2-methyldecanol were added to 96 ml of water, 16.4 g (10.4 mmol) of potassium permanganate was added dropwise over 4 hours while the reaction temperature was held below 25° C. The thus obtained reaction mixture was poured into 300 ml of ice water, added with 30 g of sodium hydrogen sulfite, adjusted to pH of not more than 1 with hydrochloric acid, extracted with ether and then extracted with a 10% aqueous solution of sodium hydroxide. This extract was added with hydrochloric acid to adjust pH to not more than 1 and again extracted with chloroform. The thus obtained extract was washed with water, dried, concentrated, and distilled under a reduced pressure (0.4 mmHg, 116°~120° C.) to obtain 5.2 g (yield 63%) of (+)-2-metyl decanoic acid. was added dropwise over 4 hours while the reaction temperature was held below 25° C The thus obtained reaction mixture extracted with ether extracted with a 10% aqueous solution of sodium hydroxide This extract was added with hydrochloric acid again extracted with chloroform The thus obtained extract was washed with water dried concentrated distilled under a reduced pressure (0.4 mmHg, 116°~120° C.)

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

Procedure: After 14.6 g of concentrated sulfuric acid and 8.6 g (50 mmol) of (-)-2-methyldecanol were added to 96 ml of water, 16.4 g (10.4 mmol) of potassium permanganate was added dropwise over 4 hours while the reaction temperature was held below 25° C. The thus obtained reaction mixture was poured into 300 ml of ice water, added with 30 g of sodium hydrogen sulfite, adjusted to pH of not more than 1 with hydrochloric acid, extracted with ether and then extracted with a 10% aqueous solution of sodium hydroxide. This extract was added with hydrochloric acid to adjust pH to not more than 1 and again extracted with chloroform. The thus obtained extract was washed with water, dried, concentrated, and distilled under a reduced pressure (0.4 mmHg, 116°~120° C.) to obtain 5.2 g (yield 63%) of (+)-2-metyl decanoic acid. was added dropwise over 4 hours while the reaction temperature was held below 25° C The thus obtained reaction mixture extracted with ether extracted with a 10% aqueous solution of sodium hydroxide This extract was added with hydrochloric acid again extracted with chloroform The thus obtained extract was washed with water dried concentrated distilled under a reduced pressure (0.4 mmHg, 116°~120° C.)

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

Procedure: The 2-benzylalkanoic and 2-butylalkanoic acids were prepared by the malonic ester method starting from diethyl benzylmalonate or diethyl butylmalonate and the appropriate alkyl bromide. The procedure used was analogous to that for the preparation of 2-methyldecanoic acid. Preparation of 2,2-dibutyldodecanoic acid was accomplished by alkylation of 2-butyldodecanoic acid using the method of Pfeffer, Silbert, and Chirinko. Hydrogenation of phytol followed by oxidation of the resulting saturated alcohol with a solution of chromium trioxide in acetic acid gave 3,7,11,15-tetramethylhexadecanoic acid.

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

Procedure: The 2-benzylalkanoic and 2-butylalkanoic acids were prepared by the malonic ester method starting from diethyl benzylmalonate or diethyl butylmalonate and the appropriate alkyl bromide. The procedure used was analogous to that for the preparation of 2-methyldecanoic acid. Preparation of 2,2-dibutyldodecanoic acid was accomplished by alkylation of 2-butyldodecanoic acid using the method of Pfeffer, Silbert, and Chirinko. Hydrogenation of phytol followed by oxidation of the resulting saturated alcohol with a solution of chromium trioxide in acetic acid gave 3,7,11,15-tetramethylhexadecanoic acid.

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

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