3,3,5-trimethylcyclohexan-1-ol

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

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

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

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(2H-Benzotriazol-2-yl)-6-chloromethyl-4-methyl-phenol (0.8 g, 2.9 mmol) is partly solved in dioxane (23 mL) at 80° C. 3,3,5-Trimethyl-cyclohexanol (12.3 g, 86 mmol) and sodium hydride (200 mg, 5 mmol, 60% in mineral oil) are added subsequently. The orange reaction mixture is stirred at 70° C. for one hour and evaporated to dryness. The residue is dissolved in ethyl acetate and extracted with water. The organic layer is dried over sodium sulphate, filtered and evaporated to dryness. The crude product is purified by column chromatography (ethyl acetate/heptane 1:4) to yield 0.8 g of 2-(2H-Benzotriazol-2-yl)-6-(3,3,5-trimethyl-cyclohexyloxymethyl)-4-methyl-phenol. evaporated to dryness The residue is dissolved in ethyl acetate extracted with water The organic layer is dried over sodium sulphate filtered evaporated to dryness The crude product is purified by column chromatography (ethyl acetate/heptane 1:4)

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

Procedure: 71 g of 3,3,5-trimethylcyclohexanol having a cis content of 90% are placed in a 1-l reaction flask together with 60 g of pyridine in 300 ml of methyl tert-butyl ether and 63 g of crotonic acid chloride are added at 0 to 5° C. over 30 minutes. The reaction mixture is left to continue reacting for a further one hour at this temperature; it is then allowed to heat up to room temperature. After one hour it is heated for a further 30 min to 50° C. After cooling, it is fractionated with water, the organic phase is separated off and first washed with dilute hydrochloric acid and then stirred for a further 30 min with 5-percent sodium hydroxide solution. After washing until it is neutral, the solvent is drawn off and the residue distilled using a short column. 63 g of pure 3,3,5-trimethylcyclohexyl crotonate having a cis content of 90% are obtained at a boiling point of 121° C. under 20 mbar. MS: 210 (M*, 0,3), 195 (0,5), 141 (3), 124 (75), 109 (100), 95 (24), 87 (24), 82 (25), 69 (75), 55 (11), 41 (33). The cis-3,3,5-trimethylcyclohexyl esters of propionic acid, isobutyric acid and butyric acid can be prepared in an analogous manner. are added at 0 to 5° C. over 30 minutes The reaction mixture is left After one hour it is heated for a further 30 min to 50° C After cooling the organic phase is separated off first washed with dilute hydrochloric acid After washing until it the residue distilled

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

Procedure: 12.5 g (0.034 mol) of 2-(4-(2-parachlorobenzamidoethyl)phenoxy)-2-methylpropionic acid are dissolved in 100 ml of anhydrous dimethylformamide, and 4.8 g of 3,3,5-trimethylcyclohexanol (transform) (0.034 mol) and 0.5 g of dimethylaminopyridine are added. After solubilization, a solution of 7 g of dicyclohexylcarbodiimide (0.034 mol) in 20 ml of dimethylformamide is added slowly at a temperature of around 0° C. The reaction is allowed to continue for 24 hours at ordinary temperature and the precipitate of dicyclohexylurea is filtered off; after evaporation of the filtrate under reduced pressure, the residue is chromatographed on a silica column in a mixture of petroleum ether and ethyl acetate. After evaporation of the solvent, the title derivative is obtained in the form of white crystals melting at 100° C.; the yield is 45%. This product, chromatographed under the conditions of Example 1, shows a single spot of Rf 0.2. The IR spectrum run in KBr has the following characteristic bands: one broad band at 3250 cm-1, a group of fine bands at 3000-2840 cm-1 an strong bands at 1750 cm-1 and 1640 cm-1. the precipitate of dicyclohexylurea is filtered off after evaporation of the filtrate under reduced pressure the residue is chromatographed on a silica column in a mixture of petroleum ether and ethyl acetate After evaporation of the solvent

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

Procedure: 5 g of 3,3,5-trimethylcyclohexanol, CIS form, and then 3.5 g of triethylamine dissolved in 10 ml of chloroform are added to 50 ml of pure chloroform. 12 g of 2-(4-(4-chlorobenzoyl)phenoxy)-2-methylpropionyl chloride diluted in a few ml of chloroform are then added slowly to the solution at low temperature. The mixture is refluxed for three hours and then, after cooling, the organic layer is washed successively with a normal solution of hydrochloric acid, sodium hydroxide and then distilled water. It is evaporated under reduced pressure and the residue is then chromatographed on a silica column with a mixture of petroleum ether and ethyl acetate and finally recrystallized from ethanol to give the title derivative in the form of attractive white crystals melting at 65° C., which in thin layer chromatography give a single spot of Rf 0.45 in the solvent system described in Example 1. are then added slowly to the solution at low temperature The mixture is refluxed for three hours after cooling the organic layer is washed successively with a normal solution of hydrochloric acid, sodium hydroxide It is evaporated under reduced pressure the residue is then chromatographed on a silica column with a mixture of petroleum ether and ethyl acetate finally recrystallized from ethanol

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

Procedure: 5 g of 3,3,5-trimethylcyclohexanol, CIS form, and then 3.5 g of triethylamine dissolved in 10 ml of chloroform are added to 50 ml of pure chloroform. 12 g of 2-(4-(4-chlorobenzoyl)phenoxy)-2-methylpropionyl chloride diluted in a few ml of chloroform are then added slowly to the solution at low temperature. The mixture is refluxed for three hours and then, after cooling, the organic layer is washed successively with a normal solution of hydrochloric acid, sodium hydroxide and then distilled water. It is evaporated under reduced pressure and the residue is then chromatographed on a silica column with a mixture of petroleum ether and ethyl acetate and finally recrystallized from ethanol to give the title derivative in the form of attractive white crystals melting at 65° C., which in thin layer chromatography give a single spot of Rf 0.45 in the solvent system described in Example 1. are then added slowly to the solution at low temperature The mixture is refluxed for three hours after cooling the organic layer is washed successively with a normal solution of hydrochloric acid, sodium hydroxide It is evaporated under reduced pressure the residue is then chromatographed on a silica column with a mixture of petroleum ether and ethyl acetate finally recrystallized from ethanol

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

Procedure: In a four necked flask (1 L) sufficiently dried, substituted with nitrogen, and equipped with a dropping funnel, Dimroth condenser tube, thermometer and stirring blade, resorcinol (42 g, 0.38 mol), 3,3,5-trimethylcyclohexanol (54 g, 0.57 mol) and triphenylphosphine (150 g, 0.57 mol) were dissolved in dried tetrahydrofuran (200 ml) under a nitrogen gas stream, and a mixed solution of diisopropyl azodicarboxylate (100 g, 0.5 mol) and dried tetrahydrofuran (150 ml) was dropped for 1 hour while cooling with an iced saline solution. Next, it was stirred at room temperature for 12 hours. After the reaction terminated, 30% hydrogen peroxide (75 ml) was dropped through the dropping funnel for 10 minutes, then the reaction solution was dissolved in 1 L toluene, and washed three times with 500 ml water. Toluene was distilled away by evaporation, and the residue was purified by column chromatography using hexane and ethyl acetate as developing solvents, to obtain a red brown objective product (hereinafter, referred to as R-4A) (19.5 g, 22% yield, 99% GC purity). In a four necked flask (1 L) sufficiently dried equipped with a dropping funnel, Dimroth condenser tube while cooling with an iced saline solution After the reaction terminated 30% hydrogen peroxide (75 ml) was dropped through the dropping funnel for 10 minutes the reaction solution was dissolved in 1 L toluene washed three times with 500 ml water Toluene was distilled away by evaporation the residue was purified by column chromatography to obtain a red brown objective product (hereinafter,

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

Procedure: 34.2 g (0.13 mol) of N-benzyloxycarbonyl-L-pyroglutamic acid (prepared according to Berichte 97, 2434 [1964] or Annalen 649, 183 [1961] ) are added to 150 ml of dimethylformamide, followed by 2 g of dimethylaminopyridine and then 18.48 g (0.13 mol) of 3,3,5-trimethylcyclohexanol (mixture of 90% trans isomer and 10% cis isomer) diluted in 50 ml of dimethylformamide. 26.8 g (0.13 mol) of dicyclohexylcarbodiimide are then run in over a period of about 15 minutes, the reaction medium being kept at +5° C. The mixture is then stirred at room temperature for 24 hours, after which the solvent is evaporated off, the residue is taken up with dilute hydrochloric acid and extraction is carried out with chloroform. are then run in over a period of about 15 minutes being kept at +5° C after which the solvent is evaporated off the residue is taken up with dilute hydrochloric acid and extraction

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

Procedure: 34.2 g (0.13 mol) of N-benzyloxycarbonyl-L-pyroglutamic acid (prepared according to Berichte 97, 2434 [1964] or Annalen 649, 183 [1961] ) are added to 150 ml of dimethylformamide, followed by 2 g of dimethylaminopyridine and then 18.48 g (0.13 mol) of 3,3,5-trimethylcyclohexanol (mixture of 90% trans isomer and 10% cis isomer) diluted in 50 ml of dimethylformamide. 26.8 g (0.13 mol) of dicyclohexylcarbodiimide are then run in over a period of about 15 minutes, the reaction medium being kept at +5° C. The mixture is then stirred at room temperature for 24 hours, after which the solvent is evaporated off, the residue is taken up with dilute hydrochloric acid and extraction is carried out with chloroform. are then run in over a period of about 15 minutes being kept at +5° C after which the solvent is evaporated off the residue is taken up with dilute hydrochloric acid and extraction

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(2H-Benzotriazol-2-yl)-6-chloromethyl-4-methyl-phenol (0.8 g, 2.9 mmol) is partly solved in dioxane (23 mL) at 80° C. 3,3,5-Trimethyl-cyclohexanol (12.3 g, 86 mmol) and sodium hydride (200 mg, 5 mmol, 60% in mineral oil) are added subsequently. The orange reaction mixture is stirred at 70° C. for one hour and evaporated to dryness. The residue is dissolved in ethyl acetate and extracted with water. The organic layer is dried over sodium sulphate, filtered and evaporated to dryness. The crude product is purified by column chromatography (ethyl acetate/heptane 1:4) to yield 0.8 g of 2-(2H-Benzotriazol-2-yl)-6-(3,3,5-trimethyl-cyclohexyloxymethyl)-4-methyl-phenol. evaporated to dryness The residue is dissolved in ethyl acetate extracted with water The organic layer is dried over sodium sulphate filtered evaporated to dryness The crude product is purified by column chromatography (ethyl acetate/heptane 1:4)