6-methylheptan-1-ol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:175.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Methyl 3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate (353 g, 1 mol), isooctanol (260 g, 2 mol, from Exxon) and dibutyltin oxide (0.5 g, 0.002 mol) are charged to a reaction flask and heated to 175° C. While heating to 175° C., a 300 mm Hg vacuum is applied. After holding at 175° C. for 30 minutes, the excess isooctanol is distilled by slowly reducing the pressure to <5 mm Hg. The desired product is cooled and discharged. The title compound is obtained in a yield of 451 g (100%) as a light yellow oil whose structure is verified by 1Hnmr and mass spectroscopy. The non-distilled product is analyzed by ICP (Inductively Coupled Plasma) for tin and is found to contain 170 ppm of tin. While heating to 175° C. the excess isooctanol is distilled The desired product is cooled

反応条件: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A reactor of the kind described in Example 8 is charged with 130.23 g (1.0 mol) of isooctanol (mixture of isomers), 5.57 g (0.02 mol) of powdered tin dibromide and 5.28 g (0.02 mol) of 18-crown-6 (crown ether) and the charge is heated to 130° C. Then, with efficient stirring, 86.26 ml (1.1 mol) of epichlorohydrin are added over 30 minutes. The reaction is allowed to continue for 12 hours, during which time the temperature rises to about 135° C. The reaction mixture is cooled to 55° C. and then, at this temperature, 88 g (1.1 mol) of a 50% solution of sodium hydroxide are added dropwise with efficient stirring over 30 minutes. After stirring for 2.5 hours at 55°-60° C. and cooling to room temperature, the suspension is filtered and the filtrate is washed with ethyl acetate. The phases are separated, and the aqueous phase is extracted once with 100 ml of ethyl acetate. The combined organic phases are washed with as small an amount of 10% KH2PO4 solution as possible and then with water until neutral, dried over magnesium sulfate and filtered. The filtrate is freed from solvent on a rotary evaporator under vacuum (bath temperature 50° C.). Yield: 181.8 g (98% of theory) of yellowish isooctanol glycidyl ether (mixture of isomers) for which the following analytical values are obtained: epoxy value: 3.69 eq/kg (69% of theory); total chlorine content: 3.31%; hydrolysable chlorine content: 750 ppm. A reactor of the kind described in Example 8 rises to about 135° C The reaction mixture is cooled to 55° C. After stirring for 2.5 hours at 55°-60° C. cooling to room temperature the suspension is filtered the filtrate is washed with ethyl acetate The phases are separated the aqueous phase is extracted once with 100 ml of ethyl acetate The combined organic phases are washed with as small an amount of 10% KH2PO4 solution as possible and then with water until neutral, dried over magnesium sulfate filtered The filtrate is freed from solvent on a rotary evaporator under vacuum (bath temperature 50° C.)

反応条件: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A reactor equipped with stirrer, reflux condenser, dropping funnel and thermometer is charged with 130.23 g (1.0 mol) of isooctanol (mixture of isomers), 4.51 g (0.02 mol) of SnCl2.2H2O and 5.28 g (0.02 mol) of 18-crown-6 (crown ether) and the charge is heated to 130° C. Then, with efficient stirring, 86.26 ml (1.1 mol) of epichlorohydrin are added over 30 minutes. The reaction is allowed to continue for 20 hours, during which time the temperature rises to about 135° C. The reaction mixture is cooled to 55° C. and then, at this temperature, 88 g (1.1 mol) of a 50% solution of sodium hydroxide are added dropwise with efficient stirring over 30 minutes. After stirring for 5 hours at 55°-60° C. and cooling to room temperature, the suspension is filtered and the filtrate is washed with ethyl acetate. The phases are separated, and the aqueous phase is extracted with 2×100 ml of ethyl acetate. The combined organic phases are washed with as small an amount of 10% KH2PO4 solution as possible and then with water until neutral, dried over magnesium sulfate and filtered. The filtrate is freed from solvent on a rotary evaporator under vacuum (bath temperature 50° C.). Yield: 167.4 g (90% of theory) of yellowish isooctanol glycidyl ether (mixture of isomers) for which the following analytical values are obtained: epoxy value: 3.93 eq/kg (73% of theory); total chlorine content: 2.44%; hydrolysable chlorine content: 232 ppm. A reactor equipped with stirrer reflux condenser rises to about 135° C The reaction mixture is cooled to 55° C. After stirring for 5 hours at 55°-60° C. cooling to room temperature the suspension is filtered the filtrate is washed with ethyl acetate The phases are separated the aqueous phase is extracted with 2×100 ml of ethyl acetate The combined organic phases are washed with as small an amount of 10% KH2PO4 solution as possible and then with water until neutral, dried over magnesium sulfate filtered The filtrate is freed from solvent on a rotary evaporator under vacuum (bath temperature 50° C.)

反応条件: temp:125.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A reactor equipped with stirrer, reflux condenser, dropping funnel and thermometer is charged with 130.23 g (1.0 mol) of isooctanol (mixture of isomers), 3.14 g (0.02 mol) of powdered tin difluoride and 5.28 g (0.02 mol) of 18-crown-6 (crown ether) and the charge is heated to 125° C. The, with efficient stirring, 86.26 ml (1.1 mol) of epichlorohydrin are added over 30 minutes. The reaction is allowed to continue for 20 hours, during which time the temperature rises to about 130° C. The reaction mixture is cooled to 55° C. and then, at this temperature, 88 g (1.1 mol) of a 50% aqueous solution of sodium hydroxide are added dropwise with efficient stirring over 30 minutes. After stirring for 6 hours at 55°-60° C. and cooling to room temperature, the suspension is filtered and the filtrate is washed with ethyl acetate. The phases are separated, and the aqueous phase is extracted with 2×100 ml of ethyl acetate. The combined organic phases are washed with as small an amount of 10% KH2PO4 solution as possible and then with water until neutral, dried over magnesium sulfate and filtered. The filtrate is freed from solvent on a rotary evaporator under vacuum (bath temperature 50° C.). Yield: 180.7 g (97% of theory) of colourless isooctanol glycidyl ether (mixture of isomers) for which the following analytical values are obtained: epoxy value: 4.71 eq/kg (88% of theory); total chlorine content: 2.7%; hydrolysable chlorine content: 122 ppm. A reactor equipped with stirrer reflux condenser rises to about 130° C The reaction mixture is cooled to 55° C. After stirring for 6 hours at 55°-60° C. cooling to room temperature the suspension is filtered the filtrate is washed with ethyl acetate The phases are separated the aqueous phase is extracted with 2×100 ml of ethyl acetate The combined organic phases are washed with as small an amount of 10% KH2PO4 solution as possible and then with water until neutral, dried over magnesium sulfate filtered The filtrate is freed from solvent on a rotary evaporator under vacuum (bath temperature 50° C.)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 77.1 g (0.5 mol) of thiosalicylic acid are dissolved, with stirring, in 250 ml of hot isooctanol. After the addition of 100 ml of toluene and a catalytic amount of paratoluenesulfonic acid, the reaction mixture is heated under reflux. Under azeotropic conditions, 8.5 ml of water (calculated: 9 ml) separate off after 25 hours. The residue is extracted by shaking with a bicarbonate solution, then washed with water and dried. The volatile constituents are removed in vacuo. The product is obtained after rectification with a mercury diffusion pump. a catalytic amount of paratoluenesulfonic acid, the reaction mixture is heated under reflux Under azeotropic conditions, 8.5 ml of water (calculated: 9 ml) separate off after 25 hours The residue is extracted washed with water dried The volatile constituents are removed in vacuo

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 77.1 g (0.5 mol) of thiosalicylic acid are dissolved, with stirring, in 250 ml of hot isooctanol. After the addition of 100 ml of toluene and a catalytic amount of paratoluenesulfonic acid, the reaction mixture is heated under reflux. Under azeotropic conditions, 8.5 ml of water (calculated: 9 ml) separate off after 25 hours. The residue is extracted by shaking with a bicarbonate solution, then washed with water and dried. The volatile constituents are removed in vacuo. The product is obtained after rectification with a mercury diffusion pump. a catalytic amount of paratoluenesulfonic acid, the reaction mixture is heated under reflux Under azeotropic conditions, 8.5 ml of water (calculated: 9 ml) separate off after 25 hours The residue is extracted washed with water dried The volatile constituents are removed in vacuo

反応条件: temp:270.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 30.94 g of isooctyl carbamate, 48.90 g of isooctanol, 0.40 g of triphenylphosphine and 2.0 ml of a 20% strength solution of diisobutyl-aluminium hydride in toluene were warmed together, whilst stirring. The mixture started to boil at about 165° C. The mixture was now heated in such a way that a continuous reflux of isooctanol was set up in a Vigreux column (jacket length 30 cm) fitted on the reaction vessel. The temperature was raised continuously to 270° C. over a period of 7 hours; after that time 2.78 g (91.3% of theory) of NH3 had been separated off and 24.95 g of liquid and a little solid had been distilled off (isooctanol, urethane and urea). The mixture was then subjected to fractional distillation. A fraction of 4.35 g with a boiling point14 of 81.5 (isooctanol) and a fraction of 46.96 g with a boiling point~ 0.05 of 98-102 (diisooctyl carbonate) resulted. Yield 92.33%, based on urethane employed. to boil at about 165° C The mixture was now heated in such a way that fitted on the reaction vessel after that time 2.78 g (91.3% of theory) of NH3 had been separated off 24.95 g of liquid and a little solid had been distilled off (isooctanol, urethane and urea) The mixture was then subjected to fractional distillation

反応条件: temp:270.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 30.94 g of isooctyl carbamate, 48.90 g of isooctanol, 0.40 g of triphenylphosphine and 2.0 ml of a 20% strength solution of diisobutyl-aluminium hydride in toluene were warmed together, whilst stirring. The mixture started to boil at about 165° C. The mixture was now heated in such a way that a continuous reflux of isooctanol was set up in a Vigreux column (jacket length 30 cm) fitted on the reaction vessel. The temperature was raised continuously to 270° C. over a period of 7 hours; after that time 2.78 g (91.3% of theory) of NH3 had been separated off and 24.95 g of liquid and a little solid had been distilled off (isooctanol, urethane and urea). The mixture was then subjected to fractional distillation. A fraction of 4.35 g with a boiling point14 of 81.5 (isooctanol) and a fraction of 46.96 g with a boiling point~ 0.05 of 98-102 (diisooctyl carbonate) resulted. Yield 92.33%, based on urethane employed. to boil at about 165° C The mixture was now heated in such a way that fitted on the reaction vessel after that time 2.78 g (91.3% of theory) of NH3 had been separated off 24.95 g of liquid and a little solid had been distilled off (isooctanol, urethane and urea) The mixture was then subjected to fractional distillation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The acid prepared in Example 39 (8 g, 0.02 mol), EXXAL® 8 (isooctanol isomers, Exxon, 5 g, 0.038 mol), p-toluenesulfonic acid hydrate (0.5 g, 0.0026 mol) and xylenes (100 mL) are charged to a reactor and refluxed for six hours. TLC shows when the reaction is complete. The solvent is removed and the resulting oil is chromatographed on silical gel. The title compound is obtained in 99.5% yield as a light yellow oil. refluxed for six hours The solvent is removed the resulting oil is chromatographed on silical gel

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The acid prepared in Example 39 (8 g, 0.02 mol), EXXAL® 8 (isooctanol isomers, Exxon, 5 g, 0.038 mol), p-toluenesulfonic acid hydrate (0.5 g, 0.0026 mol) and xylenes (100 mL) are charged to a reactor and refluxed for six hours. TLC shows when the reaction is complete. The solvent is removed and the resulting oil is chromatographed on silical gel. The title compound is obtained in 99.5% yield as a light yellow oil. refluxed for six hours The solvent is removed the resulting oil is chromatographed on silical gel