2-phenylpropane-1,3-diol

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

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

Procedure: To 5.11 g of phenylmalonic acid in 50 mL of ether cooled to 0° C. was added 60 mL of a 1M solution of lithium aluminum hydride in THF. After stirring the mixture at room temperature overnight, the excess lithium aluminum hydride was quenched with ethyl acetate and dilute hydrochloric acid. The 1,3-dihydroxy-2-phenylpropane was isolated by ether extraction, and subsequent purification by flash chromatography gave 1.34 g of product characterized by NMR. This is treated with one equivalent of tosyl chloride in pyridine to afford the monotosylate. The purified monotosylate is heated in acetone with excess sodium iodide (as described in Example 23) to produce the 1-iodo-2-phenyl-3-propanol. Subsequent silylation with trimethylsilyltriflate (as in Example 16) and treatment of the iodosilylether with triphenylphosphine in toluene at 100 ° C. gives the title compound, which is characterized by its NMR and mass spectra. the excess lithium aluminum hydride was quenched with ethyl acetate and dilute hydrochloric acid

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

Procedure: Diethyl phenylmalonate is reduced with lithium aluminium hydride to give 2-phenyl-propane-1,3-diol and esterified with an equimolar amount of benzenesulphochloride in anhydrous pyridine to give 2-phenylpropane-1,3-diol monobenzenesulphonate (wax-like substance). Reaction thereof with the potassium salt of hexadecanethiol in ethanol gives the desired 3-hexadecylthio-2-phenylpropan-1-ol (wax-like substance).

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The reaction is carried out in a nitrogen atmosphere in a predried 250 ml RB flask with a side arm and a distillation apparatus leading to a nitrogen outlet. 180 mmoles of lithium aluminum hydride is added to the flask in sufficient tetrahydrofuran to dissolve the lithium aluminum hydride. The solution is cooled with rapid stirring to about 0° C. and 30 mmoles of diethyl phenylmalonic acid ester is slowly added followed by four ml of dry xylene which functions as a heat transfer material and prevents the contents of the flask from "bumping". The solution is heated to about 135° C. and maintained at such temperature for approximately two hours. The reaction mixture is cooled to about 0° C. and an extract solvent composed of equal parts tetrahydrofuran and ethyl ether is added and residual hydride is quenched with water. 90 ml of 2N hydrochloric acid is added to complete hydrolysis. The solution is then extracted twice with ether, the aqueous phase is made alkaline (pH 9-10) with a saturated potassium carbonate solution and extracted with ether. The organic phases are combined, washed with saturated potassium carbonate solution, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to yield crude 2-phenyl-1,3-propanediol. Purified 2-phenyl-1,3-propanediol (mp 51°-53° C.) was obtained by recrystallization from a mixture of hexane/toluene/ether (10:5:1) in a yield of 72%. a distillation apparatus leading to a nitrogen outlet The solution is cooled The solution is heated to about 135° C. maintained at such temperature for approximately two hours The reaction mixture is cooled to about 0° C. is added residual hydride is quenched with water 90 ml of 2N hydrochloric acid is added to complete hydrolysis The solution is then extracted twice with ether extracted with ether washed with saturated potassium carbonate solution dried over anhydrous magnesium sulfate concentrated under reduced pressure to yield crude 2-phenyl-1,3-propanediol

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

Procedure: A mixture of 20 g of diethyl phenylmalonate, 6.6 g of sodium dihydrogen phosphate monohydrate and 140 ml of absolute ethanol was cooled to 15° C. after which 7.1 g of solid sodium borohydride was added. The reaction was completed by quenching the excess of sodium borohydride with 10% HCl solution and distilling the residual ethanol. 8 ml of NaOH 50% were added in order to obtain a pH of between about 8.0 to about 9.0. The obtained 2-phenyl-1,3-propanediol was then extracted into 400 ml of ethyl acetate. The organic layer was washed with 40 ml of water and filtered through alumina. The precipitate was crystallized from toluene following solvent removal, to obtain 8.9 g of 2-phenyl-1,3-propanediol with a yield of 69%. was added by quenching the excess of sodium borohydride with 10% HCl solution distilling the residual ethanol 8 ml of NaOH 50% were added in order to obtain a pH of between about 8.0 to about 9.0 The obtained 2-phenyl-1,3-propanediol was then extracted into 400 ml of ethyl acetate The organic layer was washed with 40 ml of water filtered through alumina The precipitate was crystallized from toluene following solvent removal

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

Procedure: Sodium dihydrogen phosphate (58.3 g) was added to a solution of 50 g of diethyl phenylmalonate in 350 ml of ethanol. The mixture was cooled to 5-7° C. and a solution of 16.7 g of sodium borohydride in 38 ml of 0.2% NaOH was gradually added. The mixture was stirred for additional 2 hours and the Ethanol was distilled out. The reaction was quenched by adding 132 ml of water followed by heating to 50° C.-60° C. for 2 hours. The solution was then basified with 50% NaOH and extracted with ethyl acetate. The organic layer was washed with water and evaporated to dryness. The precipitate was crystallized from toluene. 20 g of 2-phenyl-1,3-propanediol was obtained with a yield of 63%. the Ethanol was distilled out The reaction was quenched by adding 132 ml of water by heating to 50° C.-60° C. for 2 hours extracted with ethyl acetate The organic layer was washed with water evaporated to dryness The precipitate was crystallized from toluene

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

Procedure: Sodium dihydrogen phosphate (58.3 g) was added to a solution of 50 g of diethyl phenylmalonate in 350 ml of ethanol. The mixture was cooled to 5-7° C. and a solution of 16.7 g of sodium borohydride in 38 ml of 0.2% NaOH was gradually added. The mixture was stirred for additional 2 hours and the Ethanol was distilled out. The reaction was quenched by adding 132 ml of water followed by heating to 50° C.-60° C. for 2 hours. The solution was then basified with 50% NaOH and extracted with ethyl acetate. The organic layer was washed with water and evaporated to dryness. The precipitate was crystallized from toluene. 20 g of 2-phenyl-1,3-propanediol was obtained with a yield of 63%. the Ethanol was distilled out The reaction was quenched by adding 132 ml of water by heating to 50° C.-60° C. for 2 hours extracted with ethyl acetate The organic layer was washed with water evaporated to dryness The precipitate was crystallized from toluene

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

Procedure: To 5.11 g of phenylmalonic acid in 50 mL of ether cooled to 0° C. was added 60 mL of a 1M solution of lithium aluminum hydride in THF. After stirring the mixture at room temperature overnight, the excess lithium aluminum hydride was quenched with ethyl acetate and dilute hydrochloric acid. The 1,3-dihydroxy-2-phenylpropane was isolated by ether extraction, and subsequent purification by flash chromatography gave 1.34 g of product characterized by NMR. This is treated with one equivalent of tosyl chloride in pyridine to afford the monotosylate. The purified monotosylate is heated in acetone with excess sodium iodide (as described in Example 23) to produce the 1-iodo-2-phenyl-3-propanol. Subsequent silylation with trimethylsilyltriflate (as in Example 16) and treatment of the iodosilylether with triphenylphosphine in toluene at 100 ° C. gives the title compound, which is characterized by its NMR and mass spectra. the excess lithium aluminum hydride was quenched with ethyl acetate and dilute hydrochloric acid

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

Procedure: Diethyl phenylmalonate is reduced with lithium aluminium hydride to give 2-phenyl-propane-1,3-diol and esterified with an equimolar amount of benzenesulphochloride in anhydrous pyridine to give 2-phenylpropane-1,3-diol monobenzenesulphonate (wax-like substance). Reaction thereof with the potassium salt of hexadecanethiol in ethanol gives the desired 3-hexadecylthio-2-phenylpropan-1-ol (wax-like substance).

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

Procedure: Diethyl phenylmalonate is reduced with lithium aluminium hydride to give 2-phenyl-propane-1,3-diol and esterified with an equimolar amount of benzenesulphochloride in anhydrous pyridine to give 2-phenylpropane-1,3-diol monobenzenesulphonate (wax-like substance). Reaction thereof with the potassium salt of hexadecanethiol in ethanol gives the desired 3-hexadecylthio-2-phenylpropan-1-ol (wax-like substance).

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

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

Procedure: Sodium hydride (60% dispersion in mineral oil, 525 mg, 13 mmol) was added to a round bottom flask and washed with 3×5 mL of dry hexane. Dry THF (25 mL) was then added, followed by 2-phenyl-1,3-propanediol (2.0 g, 13 mmol). Another 25 mL of dry THF was added to facilitate stirring of the resulting thick suspension. After 45 min., tert-butyldimethylsilyl chloride was added in one portion. After stirring for 2 h, the mixture was partitioned between 100 mL of ethyl ether and 60 mL of 10% aqueous potassium carbonate. The aqueous layer was extracted with 2×30 mL of ethyl ether. The combined organic layers were washed with 40 mL of brine, dried over sodium sulfate, and evaporated. Purification by flash column chromatography, eluting with 10% ethyl acetate in hexane, gave the 3.36 g of the title compound as a colorless liquid. 1NMR (400 MHz,CD3OD): δ 7.30-7.16(m, 5H), 3.90 (dd, 1H, J=11, 7 Hz), 3.88 (dd, 1H, J=10, 6 Hz), 3.83 (dd, 1H, J=10, 6 Hz), 3.76 (dd, 1H, J=11, 7 Hz), 2.91 (quintet, 1H, J=6 Hz), 0.84 (s, 9H),-0.04 (s, 3H),-0.05 (s, 3H). Mass spectrum (NH3 /CI): m/z=267 (M+1). washed with 3×5 mL of dry hexane Dry THF (25 mL) was then added After stirring for 2 h the mixture was partitioned between 100 mL of ethyl ether and 60 mL of 10% aqueous potassium carbonate The aqueous layer was extracted with 2×30 mL of ethyl ether The combined organic layers were washed with 40 mL of brine dried over sodium sulfate evaporated Purification by flash column chromatography eluting with 10% ethyl acetate in hexane