(2S)-2-methylbutan-1-ol

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a −25° C. cooled solution of (2S)-2-methylbutan-1-ol (8.8 g) and triethylamine (30 ml) in THF (50 ml), a solution of methanesulfonyl chloride (1.14 g) in THF (10 ml) was drop wise added. After complete addition (15 min) the reaction mixture was further stirred for 2 h at −10° C. then for 30 min at 0° C. It was then filtered over celite and evaporated to dryness to give nearly pure (2S)-2-methylbutyl methanesulfonate as yellowish oil. wise added After complete addition (15 min) the reaction mixture for 30 min at 0° C It was then filtered over celite evaporated to dryness

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

Procedure: 6.54 g of p-benzyloxybenzoic acid was heated under reflux together with 12.5 g of thionyl chloride in 40 ml of carbon tetrachloride for 3 hours. Then the unreacted thionyl chloride and carbon tetrachloride were distilled off to obtain a yellow oily residue. A solution obtained by dissolving 1.64 g of (S)-2-methylbutyl alcohol in 40.0 ml of toluene was added to the oily residue and the resulting mixture was heated under reflux for 3 hours. After completion of the reaction, 30.0 ml of ethyl acetate and 100 ml of 5 wt% hydrochloric acid were added to the reaction mixture to extract the reaction product with the ethyl acetate. Further, the ethyl acetate phase was washed with 100 ml of a 5 wt% aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of common salt and then dried over anhydrous sodium sulfate. The ethyl acetate was distilled off and the residue was subjected to silica gel column chromatography with a mixture of n-hexane and ethyl acetate (mixing ratio: 10/1 by volume) as an eluent. Thus 4.49 g of an colorless oily substance was obtained. Then the oily substance was dissolved in 15 ml of ethanol and heated under reflux in the presence of 6.75 g of cyclohexene and 0.45 g of palladium black for 1 hour. Then the palladium black was removed by filtering the reaction mixture and the ethanol and cyclohexene were distilled off. The colorless oily substance thus obtained was dissolved in 80.0 ml of toluene, washed with 20.0 ml of water and dried over anhydrous sodium sulfate. The toluene was distilled off to thereby obtain 2.99 g of (S)-2-methylbutyl 4 hydroxybenzoate (yield: 93%). Next, 0.80 g of p-benzyloxybenzoic acid was heated under reflux together with 4.17 g of thionyl chloride in 15 ml of carbon tetrachloride for 3 hours. Then the unreacted thionyl chloride and carbon tetrachloride were distilled off to obtain yellow oily substance. A solution prepared by dissolving 0.73 g of the above prepared (S)-2-methylbutyl 4-hydroxybenzoate in 7.00 ml of toluene was added to the oily substance. Further, 3.50 g of pyridine was added and the resulting mixture was stirred at 80° C. for 3 hours. After completion of the reaction, 30.0 ml of ethyl acetate and 50.0 ml of 5 wt% hydrochloric acid were added to extract the reaction product with the ethyl acetate. The ethyl acetate phase was washed with 50.0 ml of a 5 wt% aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of common salt and dried over anhydrous sodium sulfate. The ethyl acetate was distilled off and the residue was recrystallized from methanol to obtain 0.89 g of 4-((S)-2-methylbutoxycarbonyl)phenyl 4-benzyloxybenzoate. Then this product was dissolved in 10.0 ml of ethanol and heated under reflux in the presence of 1.01 g of cyclohexene and 0.18 g of palladium black for 1 hour. The palladium black was removed by filtering the reaction mixture and the ethanol and cyclohexene were distilled off. Thus 0.69 g of 4-((S)-2-methylbutoxycarbonyl)phenyl 4-hydroxybenzoate was obtained. Then the unreacted thionyl chloride and carbon tetrachloride were distilled off to obtain a yellow oily residue A solution obtained was added to the oily residue the resulting mixture was heated under reflux for 3 hours were added to the reaction mixture to extract the reaction product with the ethyl acetate Further, the ethyl acetate phase was washed with 100 ml of a 5 wt% aqueous solution of sodium hydrogencarbonate a saturated aqueous solution of common salt and then dried over anhydrous sodium sulfate The ethyl acetate was distilled off the residue was subjected to silica gel column chromatography with a mixture of n-hexane and ethyl acetate (mixing ratio: 10/1 by volume) as an eluent Thus 4.49 g of an colorless oily substance was obtained heated Then the palladium black was removed by filtering the reaction mixture the ethanol and cyclohexene were distilled off The colorless oily substance thus obtained washed with 20.0 ml of water dried over anhydrous sodium sulfate The toluene was distilled off

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

Procedure: 3.75 g of 4-hydroxybiphenyl-4'-carboxylic acid was heated under reflux together with (S)-2-methylbutyl alcohol in the presence of 0.10 g of p-toluenesulfonic acid for about 6 hours. Then the mixture was filtered to remove the unreacted 4-hydroxybiphenyl-4'-carboxylic acid. Next, the filtrate was evaporated and the unreacted (S)-2-methylbutyl alcohol was distilled off. The crystals thus obtained were recrystallized from 200 ml of n-hexane. Thus, 2.05 g of the corresponding colorless compound was obtained (Yield: 41%). Then the mixture was filtered to remove the unreacted 4-hydroxybiphenyl-4'-carboxylic acid Next, the filtrate was evaporated the unreacted (S)-2-methylbutyl alcohol was distilled off The crystals thus obtained were recrystallized from 200 ml of n-hexane

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

Procedure: 0.29 mol (40.0 g) of p-hydroxybenzoic acid and 0.35 mol (30.9 g) of (S)-(-)-2-methylbutanol were refluxed for 20 hours in 150 ml of toluene in the presence of 1 ml of concentrated sulfuric acid. The reaction solution was concentrated and then purified by column chromatography to obtain 53.2 g of 2-methylbutyl p-hydroxybenzoate [[α]D23 =+4.95° (CHCl3)]. (Yield: 88%) The reaction solution was concentrated purified by column chromatography

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

Procedure: 0.29 mol (40.0 g) of p-hydroxybenzoic acid and 0.35 mol (30.9 g) of (S)-(-)-2-methylbutanol were refluxed for 20 hours in 150 ml of toluene in the presence of 1 ml of concentrated sulfuric acid. The reaction solution was concentrated and then purified by column chromatography to obtain 53.2 g of 2-methylbutyl p-hydroxybenzoate [[α]D23 =+4.95° (CHCl3)]. (Yield: 88%) The reaction solution was concentrated purified by column chromatography

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

Procedure: 0.29 mole(40.0 g) of 4-hydroxybenzoic acid and 0.35 mole(30.9 g) of (S)-(-)-2-methylbutanol were refluxed for 20 hours in 150 ml of toluene in the presence of 1 ml of conc. sulfuric acid. The reaction solution was concentrated, and then purified by column chromatography to obtain 53.2 g of 4-hydroxybenzoic acid 2-methylbutyl ester [[α]D23 =+4.95°(CHCl3)]. (yield: 88%) The reaction solution was concentrated purified by column chromatography

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

Procedure: 0.29 mol (40.0 g) of p-hydroxybenzoic acid and 0.35 mol (30.9 g) of (S)-(-)-2-methylbutanol were refluxed for 20 hours in 150 ml of toluene in the presence of 1 ml of concentrated sulfuric acid. The reaction solution was concentrated and then purified by column chromatography to obtain 53.2 g of 2-methylbutyl p-hydroxybenzoate [[α]D23 =+4.95. (CHCl3)]. (Yield: 88%). The reaction solution was concentrated purified by column chromatography

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

Procedure: 0.29 mol (40.0 g) of p-hydroxybenzoic acid and 0.35 mol (30.9 g) of (S)-(-)-2-methylbutanol were refluxed for 20 hours in 150 ml of toluene in the presence of 1 ml of concentrated sulfuric acid. The reaction solution was concentrated and then purified by column chromatography to obtain 53.2 g of 2-methylbutyl p-hydroxybenzoate [[α]D23 =+4.95. (CHCl3)]. (Yield: 88%). The reaction solution was concentrated purified by column chromatography

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

Procedure: Quantities: (S)-(-)-2-methylbutan-1-ol (5.00 g, 0.057 mol), ethyl 4-hydroxybenzoate (7) (9.47 g, 0.057 mol), DEAD (9.93 g, 0.057 mol), triphenylphosphine (14.95 g, 0.057 mol). The experimental preocedure was as described for the preparation of compound 5. The crude product was purified by column chromatography (10% petrol/dichloromethane) to give a colourless oil. The crude product was purified by column chromatography (10% petrol/dichloromethane) to give a colourless oil

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

Procedure: 28.51 g (0.23 moles) of a commercially available (S)-2-methylbutanol was dissolved in 100 ml of pyridine. The mixture was cooled and 50 g (0.23 moles) of a commercially available 4-methylbenzoic chloride was added thereto while cooling. The mixture was then allowed to react with stirring at 50° to 60° C. for 2 hours. On completion of the reaction, 300 ml of water and 300 ml of toluene were added, and after vigorous stirring, the toluene layer was separated out and washed with 6N HCl. Washing was continued until this layer was neutral. This toluene layer was dried with anhydrous magnesium sulfate after which the toluene was distilled away. The residue was further subjected to evaporation under reduced pressure at 118° to 120° C. (5 mm Hg) and the distillate recovered, whereby 59.61 g of the objective 4-methylbenzoic((S)-2-methylbutyl) ester was obtained. The mixture was cooled while cooling to react were added after vigorous stirring, the toluene layer was separated out and washed with 6N HCl Washing This toluene layer was dried with anhydrous magnesium sulfate after which the toluene was distilled away The residue was further subjected to evaporation under reduced pressure at 118° to 120° C. (5 mm Hg) the distillate recovered

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

Procedure: 28.51 g (0.23 moles) of a commercially available (S)-2-methylbutanol was dissolved in 100 ml of pyridine. The mixture was cooled and 50 g (0.23 moles) of a commercially available 4-methylbenzoic chloride was added thereto while cooling. The mixture was then allowed to react with stirring at 50° to 60° C. for 2 hours. On completion of the reaction, 300 ml of water and 300 ml of toluene were added, and after vigorous stirring, the toluene layer was separated out and washed with 6N HCl. Washing was continued until this layer was neutral. This toluene layer was dried with anhydrous magnesium sulfate after which the toluene was distilled away. The residue was further subjected to evaporation under reduced pressure at 118° to 120° C. (5 mm Hg) and the distillate recovered, whereby 59.61 g of the objective 4-methylbenzoic((S)-2-methylbutyl) ester was obtained. The mixture was cooled while cooling to react were added after vigorous stirring, the toluene layer was separated out and washed with 6N HCl Washing This toluene layer was dried with anhydrous magnesium sulfate after which the toluene was distilled away The residue was further subjected to evaporation under reduced pressure at 118° to 120° C. (5 mm Hg) the distillate recovered

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

Procedure: In a 250-ml, round-bottomed flask equipped with a heating mantle, magnetic stirrer, condenser and Dean Stark trap, were placed 2.5 g (16.0 mmol) of 3-fluoro-4-hydroxybenzoic acid, ten g (113.4 mmol) of (S)-2-methyl-1-butanol, 0.347 g of p-toluenesulfonic acid monohydrate and 100 mls of benzene. The reaction mixture was stirred overnight under reflux. The reaction mixture was extracted using saturated aqueous sodium bicarbonate. The organic phase was dried over sodium sulfate, filtered through cotton and evaporated to an oil. The product was purified by flash chromatography on silica gel with 3% diethyl ether in dichloromethane. Fractions containing the desired product were combined and evaporated to a pale-yellow oil. Analysis by NMR showed that considerable starting alcohol remained. The oil was placed under vacuum (at 70° C.) for two days. No alcohol was shown by gas chromatography to be present. The desired product was obtained in the amount of 2.39 g (66% yield) and had the following structure. ##STR44## In a 250-ml, round-bottomed flask equipped with a heating mantle, magnetic stirrer, condenser and Dean Stark trap under reflux The reaction mixture was extracted The organic phase was dried over sodium sulfate filtered through cotton evaporated to an oil The product was purified by flash chromatography on silica gel with 3% diethyl ether in dichloromethane Fractions containing the desired product evaporated to a pale-yellow oil The oil was placed under vacuum (at 70° C.) for two days