(1S,2R,5S)-5-methyl-2-propan-2-ylcyclohexan-1-ol

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

Procedure: d-menthol, Example 23: (R)-2-octanol, Example 24: (S)-2-octanol.

Conditions: temp:250.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 0.10 mol of 2-(benzylthio)acetaldehyde and 0.20 mol of acetamide are heated together at 100° C. with stirring, and the product solid is heated in a sublimator at 250° C. and 1 mm Hg until formation of the enamide 1-acetamido-2-benzylthioethene is complete. A 70 mL stainless steel high pressure reactor fitted with a Pyrex glass liner and magnetic stir bar is charged with THF (5 mL), D-menthol (0.5 mmol), (PPh3)2PdCl2 (36 mg, 0.05 mmol), and 1-acetamido-2-benzylthioethene (0.5 mmol). The reactor is sealed, pressurized to 1000 psig with CO, and stirred for 24 hours at 100° C. The product mixture, isolated after removal of gas from the reactor vessel, contains a mixture of two diastereomeric cysteine derivatives, N-acetyl-L-benzylcysteine D-menthyl ester and N-acetyl-D-benzylcysteine D-menthyl ester. These diastereomers are separated by column chromatography on silica gel with benzene-ethyl acetate eluent and are separately hydrolyzed by heating to 100° C. in 1N HCl for 2 hours to give pure L- and D-cysteine, benzyl alcohol, acetic acid, and D-menthol, which is thereafter recycled to a repeat of the foregoing hydrocarboxylation reaction. A 70 mL stainless steel high pressure reactor fitted with a Pyrex glass liner and magnetic stir bar The reactor is sealed stirred for 24 hours at 100° C The product mixture, isolated after removal of gas from the reactor vessel a mixture of two diastereomeric cysteine These diastereomers are separated by column chromatography on silica gel with benzene-ethyl acetate eluent by heating to 100° C. in 1N HCl for 2 hours

Conditions: temp:250.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 0.10 mol of 2-(benzylthio)acetaldehyde and 0.20 mol of acetamide are heated together at 100° C. with stirring, and the product solid is heated in a sublimator at 250° C. and 1 mm Hg until formation of the enamide 1-acetamido-2-benzylthioethene is complete. A 70 mL stainless steel high pressure reactor fitted with a Pyrex glass liner and magnetic stir bar is charged with THF (5 mL), D-menthol (0.5 mmol), (PPh3)2PdCl2 (36 mg, 0.05 mmol), and 1-acetamido-2-benzylthioethene (0.5 mmol). The reactor is sealed, pressurized to 1000 psig with CO, and stirred for 24 hours at 100° C. The product mixture, isolated after removal of gas from the reactor vessel, contains a mixture of two diastereomeric cysteine derivatives, N-acetyl-L-benzylcysteine D-menthyl ester and N-acetyl-D-benzylcysteine D-menthyl ester. These diastereomers are separated by column chromatography on silica gel with benzene-ethyl acetate eluent and are separately hydrolyzed by heating to 100° C. in 1N HCl for 2 hours to give pure L- and D-cysteine, benzyl alcohol, acetic acid, and D-menthol, which is thereafter recycled to a repeat of the foregoing hydrocarboxylation reaction. A 70 mL stainless steel high pressure reactor fitted with a Pyrex glass liner and magnetic stir bar The reactor is sealed stirred for 24 hours at 100° C The product mixture, isolated after removal of gas from the reactor vessel a mixture of two diastereomeric cysteine These diastereomers are separated by column chromatography on silica gel with benzene-ethyl acetate eluent by heating to 100° C. in 1N HCl for 2 hours

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

Procedure: d-menthol, Example 23: (R)-2-octanol, Example 24: (S)-2-octanol.

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

Procedure: A solution of 7.5 g (48 mmol) of (1S, 2R, 5S)-(+)-menthol (Aldrich) and 4.86 g (48 mmol) of triethylamine in 20 ml of toluene was dropped into 7.36 g (48 mmol) of POCl3 at 0° C. The entire solution was stirred for 23 hours at room temperature. The insoluble triethylamine hydrochloride was filtered and the solvent was evaporated. Yield 99%, 31P NMR δ 6.76 (CDCl3). (lit. T. Milobedzki, W. Janczak, Roczniki Chemji 11, 840 (1931)). The insoluble triethylamine hydrochloride was filtered the solvent was evaporated

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

Procedure: Mixtures of 50 to 70 % by weight of thymol with 50 to 30 % by weight of d-neomenthol or d-menthol were used as starting material in accordance with the general conditions described above. In Table I below, column 1 gives the composition of the starting material, column 2 the balance yield of d,l-menthol in percent of the theoretical, whilst the other columns give the contents in the reaction product of d,l-neomenthol, d,l-isomenthol, menthone and other ketones, also hydrocarbons, the OH-number, the optical rotation and the thymol content, calculated from the UV-absorption.

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

Procedure: (1S, 2R, 5S)-(+)-Menthol (7.03 g, 45 mmol), triphenylphosphine (8.65 g, 33 mmol), ethyl (Z)-2-hydroxyimino-3-oxobutyrate (4.77 g, 33 mmol) and diethyl azodicarboxylate (5.7 g, 33 mmol) were reacted by analogy with Example 4a Method 3 to give the title compound (1.37 g, 14%), νmax (CH2Cl2) 2960, 2930, 2870, 1745, 1690, 1370, 1320, 1235, 1075, and 1010cm-1 ; δH (400 MHz, CDCl3) 0.87 (3H, d, J 6.6 Hz), 0.90 (3H, d, J 6.8 Hz), 0.92 (3H, d, J 6.7 Hz), ca 0.9 (1H, m), 1.02-1.12 (2H, m), 1.1-1.3 (1H, m), 1.32 (3H, t, J 7.1 Hz), 1.50-1.65 (2H, m), 1.67-1.78 (2H, m), 2.06-2.18 (1H, m), 2.40 (1H, s), 4.34 (2H, dq, J 7.1 and 1.0 Hz), and 4.70 (1H, broad s); δ13C (100 MHz, CDCl3), 14.24 (CH3), 20.70 (CH3), 20.97 (CH3), 22.26 (CH3) 25.04 (CH2), 25.11 (CH3) 26.06 (CH), 29.10 (CH), 34.77 (CH2), 39.44 (CH2) 46.98 (CH), 61.70 (CH2), 83.43 (CH), 150.28, 161.53, 192.94 [Ammonia CI mass spectrum Found: MH+ (298); MNH+ (315)].