2-chloro-1-(4-chlorophenyl)ethanone

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5.0 g (0.031 mol) of 2-chlorobenzyl chloride are added within 5 minutes at from 24° to 36° C. to 9.7 g (0.404 mol) of magnesium turnings in 20 ml of absolute ether. After the reaction has commenced, a solution of 200 ml of absolute ether and 50.2 g (0.31 mol) of 2-chlorobenzyl chloride is added dropwise. The mixture is subsequently refluxed for about a further 10 minutes, the excess magnesium is decanted off under nitrogen, and the Grignard solution is cooled to 0° C. 55.7 g (0.3 mol) of para-chloro-ω-chloroacetophenone dissolved in 350 ml of toluene are then added dropwise, and the reaction mixture is stirred at 0° C. for 1.5 hours and added dropwise at from about 2° to 6° C. to 1.5 l of concentrated ammonium chloride solution. Extraction with methyl tert.-butyl ether and subsequent conventional work-up gives 92.9 g (yield 99%, purity according to HPLC: 68.2%) of 1-chloro-2-(4-chlorophenyl)-3-(2-chlorophenyl)propan-2-ol as a crude oil, which can be further reacted directly. For characterization, the product was recrystallized from n-hexane. The mixture is subsequently refluxed for about a further 10 minutes the excess magnesium is decanted off under nitrogen are then added dropwise Extraction with methyl tert.-butyl ether and subsequent conventional work-up

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: Bio-reaction and analysis were carried out in the same way as described in Example 2 except that as substrate was used 3.25 g each of 2-bromo-1-(2'-chlorophenyl) ethanone, 2-chloro-1-(3'-chlorophenyl) ethanone and 2-chloro-1-(4'-chlorophenyl) ethanone instead of 2-bromo-1-(3'-chlorophenyl) ethanone and as the reaction products (-)-2-chloro-1-(2'-chlorophenyl) ethanol, (-)-2-chloro-1-(3'-chlorophenyl) ethanol and (-)-2-chloro-1-(4'-chlorophenyl) ethanol were obtained respectively. The yields and physical properties of the respective reaction products were as shown in Table 4.

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

実験手順: Bio-reaction and analysis were carried out in the same way as described in Example 2 except that as substrate was used 3.25 g each of 2-bromo-1-(2'-chlorophenyl) ethanone, 2-chloro-1-(3'-chlorophenyl) ethanone and 2-chloro-1-(4'-chlorophenyl) ethanone instead of 2-bromo-1-(3'-chlorophenyl) ethanone and as the reaction products (-)-2-chloro-1-(2'-chlorophenyl) ethanol, (-)-2-chloro-1-(3'-chlorophenyl) ethanol and (-)-2-chloro-1-(4'-chlorophenyl) ethanol were obtained respectively. The yields and physical properties of the respective reaction products were as shown in Table 4.

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

実験手順: A solution of 945 mg (5 mmol) 2,4′-dichloroacetophenone and 583 mg (6 mmol) potassium rhodanide was heated to reflux for 30 minutes. After a few minutes a precipitation was formed. The solvent was evaporated under reduced pressure and the residue was suspended in tetrahydrofurane, stirred for 1 hour at room temperature, filtered and the filtrate was concentrated in vacuo. The residue was stirred with heptane and little ethanol for 15 minutes. The product was filtered off and dried to yield 953 mg (90%) 1-(4-chloro-phenyl)-2-thiocyanato-ethanone as a light yellow solid. 1H NMR (CDCl3, 250 MHz): δ (ppm)=7.89 (d, 2H), 7.51 (d, 2H), 4.692 (s, 2H). to reflux for 30 minutes After a few minutes a precipitation was formed The solvent was evaporated under reduced pressure filtered the filtrate was concentrated in vacuo The residue was stirred with heptane and little ethanol for 15 minutes The product was filtered off dried

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

実験手順: A solution of 945 mg (5 mmol) 2,4′-dichloroacetophenone and 583 mg (6 mmol) potassium rhodanide was heated to reflux for 30 minutes. After a few minutes a precipitation was formed. The solvent was evaporated under reduced pressure and the residue was suspended in tetrahydrofurane, stirred for 1 hour at room temperature, filtered and the filtrate was concentrated in vacuo. The residue was stirred with heptane and little ethanol for 15 minutes. The product was filtered off and dried to yield 953 mg (90%) 1-(4-chloro-phenyl)-2-thiocyanato-ethanone as a light yellow solid. 1H NMR (CDCl3, 250 MHz): δ (ppm)=7.89 (d, 2H), 7.51 (d, 2H), 4.692 (s, 2H). to reflux for 30 minutes After a few minutes a precipitation was formed The solvent was evaporated under reduced pressure filtered the filtrate was concentrated in vacuo The residue was stirred with heptane and little ethanol for 15 minutes The product was filtered off dried

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

実験手順: Employing the procedure of Example I but replacing pyridine with a substantially equimolecular amount of pyridazine and replacing 4-methoxyphenacyl bromide with a substantially equimolecular amount of 4-chlorophenacyl chloride there is obtained N-(4-chlorophenacyl) pyridazinium chloride, a solid soluble in water.

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5.0 g (0.031 mol) of 2-chlorobenzyl chloride are added within 5 minutes at from 24° to 36° C. to 9.7 g (0.404 mol) of magnesium turnings in 20 ml of absolute ether. After the reaction has commenced, a solution of 200 ml of absolute ether and 50.2 g (0.31 mol) of 2-chlorobenzyl chloride is added dropwise. The mixture is subsequently refluxed for about a further 10 minutes, the excess magnesium is decanted off under nitrogen, and the Grignard solution is cooled to 0° C. 55.7 g (0.3 mol) of para-chloro-ω-chloroacetophenone dissolved in 350 ml of toluene are then added dropwise, and the reaction mixture is stirred at 0° C. for 1.5 hours and added dropwise at from about 2° to 6° C. to 1.5 l of concentrated ammonium chloride solution. Extraction with methyl tert.-butyl ether and subsequent conventional work-up gives 92.9 g (yield 99%, purity according to HPLC: 68.2%) of 1-chloro-2-(4-chlorophenyl)-3-(2-chlorophenyl)propan-2-ol as a crude oil, which can be further reacted directly. For characterization, the product was recrystallized from n-hexane. The mixture is subsequently refluxed for about a further 10 minutes the excess magnesium is decanted off under nitrogen are then added dropwise Extraction with methyl tert.-butyl ether and subsequent conventional work-up

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 5.0 g (0.031 mol) of 2-chlorobenzyl chloride are added within 5 minutes at from 24° to 36° C. to 9.7 g (0.404 mol) of magnesium turnings in 20 ml of absolute ether. After the reaction has commenced, a solution of 200 ml of absolute ether and 50.2 g (0.31 mol) of 2-chlorobenzyl chloride is added dropwise. The mixture is subsequently refluxed for about a further 10 minutes, the excess magnesium is decanted off under nitrogen, and the Grignard solution is cooled to 0° C. 55.7 g (0.3 mol) of para-chloro-ω-chloroacetophenone dissolved in 350 ml of toluene are then added dropwise, and the reaction mixture is stirred at 0° C. for 1.5 hours and added dropwise at from about 2° to 6° C. to 1.5 l of concentrated ammonium chloride solution. Extraction with methyl tert.-butyl ether and subsequent conventional work-up gives 92.9 g (yield 99%, purity according to HPLC: 68.2%) of 1-chloro-2-(4-chlorophenyl)-3-(2-chlorophenyl)propan-2-ol as a crude oil, which can be further reacted directly. For characterization, the product was recrystallized from n-hexane. The mixture is subsequently refluxed for about a further 10 minutes the excess magnesium is decanted off under nitrogen are then added dropwise Extraction with methyl tert.-butyl ether and subsequent conventional work-up

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

実験手順: Bio-reaction and analysis were carried out in the same way as described in Example 2 except that as substrate was used 3.25 g each of 2-bromo-1-(2'-chlorophenyl) ethanone, 2-chloro-1-(3'-chlorophenyl) ethanone and 2-chloro-1-(4'-chlorophenyl) ethanone instead of 2-bromo-1-(3'-chlorophenyl) ethanone and as the reaction products (-)-2-chloro-1-(2'-chlorophenyl) ethanol, (-)-2-chloro-1-(3'-chlorophenyl) ethanol and (-)-2-chloro-1-(4'-chlorophenyl) ethanol were obtained respectively. The yields and physical properties of the respective reaction products were as shown in Table 4.

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

実験手順: 2,4'-Dichloroacetophenone (0.03 mol) and 1,2,4-triazole (0.03 mol) were suspended in acetonitrile (50 ml) and cooled to -20°. Triethylamine (0.03 mol) was added dropwise with stirring. After stirring at -20° for 2 hours, the mixture was poured into water, and the product filtered off, washed with water, dried and crystallised from toluene to give pale yellow needles of 2-(1,2,4-triazol-1-yl)-4'-chloroacetophenone, m.p. 151°-3°. cooled to -20° After stirring at -20° for 2 hours the product filtered off washed with water dried crystallised from toluene