2,2,2-trifluoroacetaldehyde

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:0.00; pressure:0.00; stir:

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

実験手順: In a mixture of propargyl bromide (3.46 g, 29 mmol), zinc powder (2.3 g, 0.035 gram-atom) in tetrahydrofuran (60 ml), trifluoroacetaldehyde (1.9 g, 19 mmol) was added under bubbling. An hour later, the reaction mixture was poured into aqueous 2% HCl solution for a similar treatment to the one used in the above Examples. Distillation gave 1,1,1-trifluoro-4-pentyne-2-ol (b.p.: 95°-96° C.) at a yield of 65%. The above product gave the following analytical data: was added under bubbling An hour later, the reaction mixture was poured into aqueous 2% HCl solution for a similar treatment to the one Distillation

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a solution of phenylacetylene (4.08 g, 40 mmol) in dry ether (30 ml), n-butyllithium (27 ml, 1.5 M in hexane) was slowly added at -78° C. Trifluoroacetaldehyde (3.7 g, 38 mmol) was introduced in the above mixture under bubbling and the mixture was then agitated 2 hours at -78° C. After the temperature of reaction mixture was elevated to room temperature, the whole solution was poured into aqueous 2% HCl solution. Extraction was made for the oily layer using diethyl ether. The extracts were dried on magnesium sulfate and solvent was removed. Distillation gave 1,1,1-trifluoro-4-phenyl-3-butyne-2-ol (b.p.: 82° C./1.8 mmHg) at a yield of 74%. The above product gave the following analytical data: under bubbling After the temperature of reaction mixture was elevated to room temperature Extraction The extracts were dried on magnesium sulfate and solvent was removed Distillation

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

実験手順: 1-hexene (6.2 g, 76 mmol) and n-butyllithium (52 ml, 1.5 M in hexane) and trifluoroacetaldehyde (7 g, 71 mmol) were reacted 3 hours under the action of ultrasonic irradiation (as generated by a commercially available ultrasonic cleaner 220H manufactured by Branson Cleaning Equipment Company). The reaction mixture was poured into aqueous 2% HCl solution and diethyl ether was used for extraction of the oily layer. The extracts were then distilled to give 1,1,1-trifluoro-3-octyne-2-ol (b.p.: 83-85° C./21 mmHg) in a yield of 72%. This hydroxyalkyne gave the following analytical data: was used for extraction of the oily layer The extracts were then distilled

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

実験手順: A solution of benzyl 3-toluenesulfonyloxy-1-azabicyclo[3.2.0]hept-2-en-7-one-2-carboxylate (41 mg) in anhydrous THF (0.5 ml) is added dropwise over 5 mins to a stirring solution of lithium diisopropylamide (from 15.5 μl of diisopropylamine and 70 μl of 1.6N BuLi) in anhydrous THF (1.5 ml) at -78°. The resulting solution is stirred under a N2 atm at -78° for 10 mins and then trifluoroacetaldehyde (50 mg) is added all at once. After 1 more min, saturated aqueous NH4Cl solution (1.5 ml) is added and the mixture is allowed to warm to room temperature. The mixture is diluted with EtOAc (20 ml), washed with water and brine, dried with MgSO4, filtered, and evaporated in vacuo. The benzyl 6-(2,2,2-trifluoro-1-hydroxyethyl)-3-toluenesulfonyloxy-1-azabicyclo[3.2.0]hept-2-en-7-one-2-carboxylate. washed with water and brine dried with MgSO4 filtered evaporated in vacuo

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

実験手順: A solution of benzyl 3-toluenesulfonyloxy-1-azabicyclo[3.2.0]hept-2-en-7-one-2-carboxylate (41 mg) in anhydrous THF (0.5 ml) is added dropwise over 5 mins to a stirring solution of lithium diisopropylamide (from 15.5 μl of diisopropylamine and 70 μl of 1.6N BuLi) in anhydrous THF (1.5 ml) at -78°. The resulting solution is stirred under a N2 atm at -78° for 10 mins and then trifluoroacetaldehyde (50 mg) is added all at once. After 1 more min, saturated aqueous NH4Cl solution (1.5 ml) is added and the mixture is allowed to warm to room temperature. The mixture is diluted with EtOAc (20 ml), washed with water and brine, dried with MgSO4, filtered, and evaporated in vacuo. The benzyl 6-(2,2,2-trifluoro-1-hydroxyethyl)-3-toluenesulfonyloxy-1-azabicyclo[3.2.0]hept-2-en-7-one-2-carboxylate. washed with water and brine dried with MgSO4 filtered evaporated in vacuo

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

実験手順: A solution of benzyl 3-toluenesulfonyloxy-1-azabicyclo[3.2.0]hept-2-en-7-one-2-carboxylate (41 mg) in anhydrous THF (0.5 ml) is added dropwise over 5 mins to a stirring solution of lithium diisopropylamide (from 15.5 μl of diisopropylamine and 70 μl of 1.6N BuLi) in anhydrous THF (1.5 ml) at -78°. The resulting solution is stirred under a N2 atm at -78° for 10 mins and then trifluoroacetaldehyde (50 mg) is added all at once. After 1 more min, saturated aqueous NH4Cl solution (1.5 ml) is added and the mixture is allowed to warm to room temperature. The mixture is diluted with EtOAc (20 ml), washed with water and brine, dried with MgSO4, filtered, and evaporated in vacuo. The benzyl 6-(2,2,2-trifluoro-1-hydroxyethyl)-3-toluenesulfonyloxy-1-azabicyclo[3.2.0]hept-2-en-7-one-2-carboxylate. washed with water and brine dried with MgSO4 filtered evaporated in vacuo

反応条件: temp:25.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: At first, 5.5 g (40 mmol) of zinc chloride were added to a toluene solution (4 liters) containing 649 g (4.2 mol) of 4-chloroacetophenone (1b) as a ketone and 484 g (4.0 mol) of (S)-1-phenylethylamine ((S)-2a) as an optically active primary amine, followed by heating under reflux for 20 hr and by removing water (formed as a by-product) with a Dean-Stark tube during the reaction, in order to conduct the reaction. Then, 564 g (4.0 mol) of fluoral.ethylhemiacetal (4a) were dropped to the reaction liquid by spending 80 minutes at a temperature of not higher than 5° C., followed by stirring at 25-26° C. for 24 hr, thereby conducting the reaction. Then, 4-liter of 1N HCl were added to the reaction liquid, followed by stirring at room temperature for 1 hr, then washing with 2-liter of water, then concentration, and then vacuum drying, thereby obtaining 999 g of (R)-4,4,4-trifluoro-3-hydroxy-1-(4-chlorophenyl)-1-butanone ((R)-5ba, purity: 72%). Its optical purity was found to be 54% ee by the chiral HPLC as that of Example 1-30 by heating under reflux for 20 hr by removing water ( formed as a by-product) with a Dean-Stark tube during the reaction the reaction higher than 5° C. the reaction by stirring at room temperature for 1 hr washing with 2-liter of water concentration vacuum drying