DL-MANDELONITRILE

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: To a solution of L(+)-diisopropyl tartarate (235 mg) in absolute dichloromethane (10 ml), tetaraisopropyl titanate (284 mg) was dropwise added and stirred at room temperature for 30 minutes. After evaporating volatile components off in the same manner as in Example 1, dichloromethane (10 ml) was added to the residue and stirred at room temperature to obtain a homogeneous solution. To the resulting solution, trimethylsilylcyanide (436 mg) and then benzaldehyde (424 mg) were added and stirred at room temperature for 15 hours. Thereafter, the reaction mixture was treated in the same manner as in Example 1 and analyzed by HPLC to reveal that α-cyanobenzyl alcohol containing the R(+) isomer in the enantiomer excess percentage of 88% was produced in the yield of 37% based on the amount of the used benzaldehyde and 148% based on the amount of the used catalyst. After evaporating volatile components off in the same manner as in Example 1, dichloromethane (10 ml) was added to the residue stirred at room temperature to obtain a homogeneous solution stirred at room temperature for 15 hours Thereafter, the reaction mixture was treated in the same manner as in Example 1 was produced in the yield of 37%

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

実験手順: To a solution of L(+)-diethyl tartarate (412 mg) in absolute dichloromethane (20 ml), tetaraisopropyl titanate (568 mg) was dropwise added and stirred at room temperature for 30 minutes. After evaporating volatile components off in the same manner as in Example 1, to the residue, dichloromethane (20 ml) was added and stirred at room temperature to obtain a homogeneous solution. After cooling the resulting solution to 0° C., hydrogen cyanide (0.4 ml) and then benzaldehyde (212 mg) were added and stirred at room temperature for 15 hours. Thereafter, the reaction mixture was treated in the same manner as in Example 1 and analyzed by HPLC to reveal that α-cyanobenzyl alcohol was produced in the yield of 55% which contained the R(+) isomer with the enantiomer excess percentage of 77%. After evaporating volatile components off in the same manner as in Example 1 to the residue, dichloromethane (20 ml) was added stirred at room temperature to obtain a homogeneous solution After cooling the resulting solution to 0° C. stirred at room temperature for 15 hours Thereafter, the reaction mixture was treated in the same manner as in Example 1 was produced in the yield of 55% which

反応条件: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Benzaldehyde cyanohydrin (13.3 grams; 0.100 moles), 3,5-lutidine (11 grams) and methylene chloride (100 ml) were placed in a 500 ml. 3-necked glass reaction flask equipped with a mechanical stirrer, thermometer, condenser and addition funnel. This mixture was cooled to 10° C. by means of an ice bath and 2-methoxy-3,6-dichlorobenzoic acid chloride (23.9 grams; 0.10 moles) was added dropwise with the temperature of the mixture maintained at 5°-10° C. After the addition of the acid chloride was completed, the reaction mixture was stirred for an additional three hours at room temperature. After the reaction was completed, the mixture was washed three times with water, dried over anhydrous magnesium sulfate, filtered and concentrated by distillation. The residue was heated to a temperature of 150° C. under vacuum from a vacuum pump. Then the residue was dissolved in cyclohexane, treated with nuchar, filtered and stripped dry to give an oil. 3-necked glass reaction flask equipped with a mechanical stirrer thermometer, condenser and addition funnel maintained at 5°-10° C the mixture was washed three times with water dried over anhydrous magnesium sulfate filtered concentrated by distillation The residue was heated to a temperature of 150° C. under vacuum from a vacuum pump Then the residue was dissolved in cyclohexane treated with nuchar filtered stripped dry to give an oil

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

実験手順: 150 g of toluene and 7 g (0.02 mol) of Cyanex® 923 are initially introduced into a phosgenation apparatus with attached carbonic acid condenser and heated. At 99° C., 13 g of phosgene are gassed in over the course of 10 minutes. Thereafter, over the course of 2 hours, 192 g (1.44 mol) of benzaldehyde cyanohydrin and a further 149 g (total=172 g or 1.74 mol) of phosgene are added in parallel. The internal temperature is maintained between 99 and 102° C. throughout. After a post-reaction of 60 minutes at 99° C., excess phosgene is stripped out using N2 at 50° C. for 2.5 h. The discharge of 359 g is fractionally distilled on a 30 cm Vigreux column. The main fraction passes over at 0.6 mbar and a head temperature of from 68 to 73° C. 192.7 g (88.3% of theory) of α-chlorophenylacetonitrile are isolated. heated At 99° C. are gassed in over the course of 10 minutes The internal temperature is maintained between 99 and 102° C. throughout After a post-reaction of 60 minutes at 99° C. at 50° C. for 2.5 h The discharge of 359 g is fractionally distilled on a 30 cm Vigreux column of from 68 to 73° C

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

実験手順: 150 g of toluene and 7 g (0.02 mol) of Cyanex® 923 are initially introduced into a phosgenation apparatus with attached carbonic acid condenser and heated. At 99° C., 13 g of phosgene are gassed in over the course of 10 minutes. Thereafter, over the course of 2 hours, 192 g (1.44 mol) of benzaldehyde cyanohydrin and a further 149 g (total=172 g or 1.74 mol) of phosgene are added in parallel. The internal temperature is maintained between 99 and 102° C. throughout. After a post-reaction of 60 minutes at 99° C., excess phosgene is stripped out using N2 at 50° C. for 2.5 h. The discharge of 359 g is fractionally distilled on a 30 cm Vigreux column. The main fraction passes over at 0.6 mbar and a head temperature of from 68 to 73° C. 192.7 g (88.3% of theory) of α-chlorophenylacetonitrile are isolated. heated At 99° C. are gassed in over the course of 10 minutes The internal temperature is maintained between 99 and 102° C. throughout After a post-reaction of 60 minutes at 99° C. at 50° C. for 2.5 h The discharge of 359 g is fractionally distilled on a 30 cm Vigreux column of from 68 to 73° C

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

実験手順: A 500 ml four-neck round bottom flask was equipped with a magnetic stirring bar, water condenser, addition funnel and drying tube. The glassware was dried and to this was charged 21.2 grams (0.2 mole) benzaldehyde and 19.5 grams (0.3 mole) potassium cyanide dissolved in 70 ml of water. The reaction flask was cooled to 10°-15° C. using a water/ice bath. To this was added 70 ml of 40% sulfuric acid over a 60 minute period. After the addition was complete, the reaction was allowed to warm to room temperature and stir for an additional two hours. At the end of this time the reaction mixture was extracted with carbon tetrachloride (3×75 ml), washed the combined carbon tetrachloride layers with water (2×50 ml), dried the carbon tetrachloride layer with anhydrous magnesium sulfate, filtered and concentrated to yield benzaldehyde cyanohydrin. A 500 ml four-neck round bottom flask was equipped with a magnetic stirring bar, water condenser, addition funnel drying tube The glassware was dried The reaction flask was cooled to 10°-15° C. After the addition At the end of this time the reaction mixture was extracted with carbon tetrachloride (3×75 ml) washed the combined carbon tetrachloride layers with water (2×50 ml) dried the carbon tetrachloride layer with anhydrous magnesium sulfate filtered concentrated

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

実験手順: A 500 ml four-neck round bottom flask was equipped with a magnetic stirring bar, water condenser, addition funnel and drying tube. The glassware was dried and to this was charged 21.2 grams (0.2 mole) benzaldehyde and 19.5 grams (0.3 mole) potassium cyanide dissolved in 70 ml of water. The reaction flask was cooled to 10°-15° C. using a water/ice bath. To this was added 70 ml of 40% sulfuric acid over a 60 minute period. After the addition was complete, the reaction was allowed to warm to room temperature and stir for an additional two hours. At the end of this time the reaction mixture was extracted with carbon tetrachloride (3×75 ml), washed the combined carbon tetrachloride layers with water (2×50 ml), dried the carbon tetrachloride layer with anhydrous magnesium sulfate, filtered and concentrated to yield benzaldehyde cyanohydrin. A 500 ml four-neck round bottom flask was equipped with a magnetic stirring bar, water condenser, addition funnel drying tube The glassware was dried The reaction flask was cooled to 10°-15° C. After the addition At the end of this time the reaction mixture was extracted with carbon tetrachloride (3×75 ml) washed the combined carbon tetrachloride layers with water (2×50 ml) dried the carbon tetrachloride layer with anhydrous magnesium sulfate filtered concentrated

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

実験手順: 4-[(6,7-Dimethoxy-4-quinolyl)oxy]-2,3-dimethylaniline (50 mg) was added to toluene (5 ml), and triethylamine (0.5 ml), and the mixture was heated under reflux to prepare a solution. A solution of triphosgene (68 mg) in methylene chloride was then added thereto, and the mixture was heated under reflux for 10 min. Next, 2-hydroxy-2-phenylacetonitrile (31 mg) was added thereto, and the mixture was further stirred with heating under reflux for 3 hr. A saturated aqueous sodium bicarbonate solution was added to stop the reaction, and the reaction solution was then extracted with chloroform, followed by washing with a 1 N aqueous hydrochloric acid solution, water, and saturated brine in that order. The extract was dried over sodium sulfate and was then concentrated. The residue was purified on a column using chloroform/methanol to give the title compound (30 mg, yield 39%). the mixture was heated under reflux to prepare a solution the mixture was heated under reflux for 10 min with heating under reflux for 3 hr the reaction the reaction solution was then extracted with chloroform by washing with a 1 N aqueous hydrochloric acid solution, water, and saturated brine in that order The extract was dried over sodium sulfate was then concentrated The residue was purified on a column

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

実験手順: 4-[(6,7-Dimethoxy-4-quinolyl)oxy]-2,5-dimethylaniline (50 mg) was added to toluene (5 ml), and triethylamine (0.5 ml), and the mixture was heated under reflux to prepare a solution. A solution of triphosgene (68 mg) in methylene chloride was then added thereto, and the mixture was heated under reflux for 10 min. Next, 2-hydroxy-2-phenylacetonitrile (31 mg) was added thereto, and the mixture was further stirred with heating under reflux for 3 hr. A saturated aqueous sodium bicarbonate solution was added to stop the reaction, and the reaction solution was then extracted with chloroform, followed by washing with a 1 N aqueous hydrochloric acid solution, water, and saturated brine in that order. The extract was dried over sodium sulfate and was then concentrated. The residue was purified on a column using chloroform/methanol to give the title compound (30 mg, yield 39%). the mixture was heated under reflux to prepare a solution the mixture was heated under reflux for 10 min with heating under reflux for 3 hr the reaction the reaction solution was then extracted with chloroform by washing with a 1 N aqueous hydrochloric acid solution, water, and saturated brine in that order The extract was dried over sodium sulfate was then concentrated The residue was purified on a column

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

実験手順: 4-[(6,7-Dimethoxy-4-quinolyl)oxy]aniline (50 mg) was added to toluene (5 ml), and triethylamine (0.5 ml), and the mixture was heated under reflux to prepare a solution. A solution of triphosgene (77 mg) in methylene chloride was then added thereto, and the mixture was heated under reflux for 10 min. Next, 2-hydroxy-2-phenylacetonitrile (35 mg) was added thereto, and the mixture was further stirred with heating under reflux for 3 hr. A saturated aqueous sodium bicarbonate solution was added to stop the reaction, and the reaction solution was then extracted with chloroform, followed by washing with a 1 N aqueous hydrochloric acid solution, water, and saturated brine in that order. The extract was dried over sodium sulfate and was then concentrated. The residue was purified on a column using chloroform/methanol to give the title compound (20 mg, yield 24%). the mixture was heated under reflux to prepare a solution the mixture was heated under reflux for 10 min with heating under reflux for 3 hr the reaction the reaction solution was then extracted with chloroform by washing with a 1 N aqueous hydrochloric acid solution, water, and saturated brine in that order The extract was dried over sodium sulfate was then concentrated The residue was purified on a column

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

実験手順: To a solution of L(+)-diisopropyl tartarate (235 mg) in absolute dichloromethane (10 ml), tetaraisopropyl titanate (284 mg) was dropwise added and stirred at room temperature for 30 minutes. After evaporating volatile components off in the same manner as in Example 1, dichloromethane (10 ml) was added to the residue and stirred at room temperature to obtain a homogeneous solution. To the resulting solution, trimethylsilylcyanide (436 mg) and then benzaldehyde (424 mg) were added and stirred at room temperature for 15 hours. Thereafter, the reaction mixture was treated in the same manner as in Example 1 and analyzed by HPLC to reveal that α-cyanobenzyl alcohol containing the R(+) isomer in the enantiomer excess percentage of 88% was produced in the yield of 37% based on the amount of the used benzaldehyde and 148% based on the amount of the used catalyst. After evaporating volatile components off in the same manner as in Example 1, dichloromethane (10 ml) was added to the residue stirred at room temperature to obtain a homogeneous solution stirred at room temperature for 15 hours Thereafter, the reaction mixture was treated in the same manner as in Example 1 was produced in the yield of 37%