4-bromo-2-chloro-1-phenylbenzene

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: 2-Chloro-4-biphenylmagnesium bromide was prepared by known methods from 53.4 g of 2-chloro-4-bromobiphenyl and 5.0 g of magnesium turnings in tetrahydrofuran. A solution of 9.2 g of acetaldehyde in 100 ml of tetrahydrofuran was added dropwise to the cooled Grignard reagent solution. The reaction mixture was stirred at room temperature overnight. The reaction mixture then was cooled, treated successively with 165 ml of saturated aqueous ammonium chloride and 100 ml of water, and poured onto ice. The reaction mixture was extracted with diethyl ether. The diethyl ether extracts were combined, washed three times with water, and dried over anhydrous sodium sulfate. The diethyl ether was evaporated under reduced pressure and the liquid residue was vacuum distilled to give 28.6 g of α-methyl-3-chloro-4-phenylbenzyl alcohol, bp 145°-157°C/0.09 mm. The following elemental analysis was obtained: The reaction mixture then was cooled poured onto ice The reaction mixture was extracted with diethyl ether washed three times with water dried over anhydrous sodium sulfate The diethyl ether was evaporated under reduced pressure distilled

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

実験手順: 2-Chloro-4-biphenylmagnesium bromide was prepared by known methods from 53.4 g of 2-chloro-4-bromobiphenyl and 5.0 g of magnesium turnings in tetrahydrofuran. A solution of 9.2 g of acetaldehyde in 100 ml of tetrahydrofuran was added dropwise to the cooled Grignard reagent solution. The reaction mixture was stirred at room temperature overnight. The reaction mixture then was cooled, treated successively with 165 ml of saturated aqueous ammonium chloride and 100 ml of water, and poured onto ice. The reaction mixture was extracted with diethyl ether. The diethyl ether extracts were combined, washed three times with water, and dried over anhydrous sodium sulfate. The diethyl ether was evaporated under reduced pressure and the liquid residue was vacuum distilled to give 28.6 g of α-methyl-3-chloro-4-phenylbenzyl alcohol, bp 145°-157°C/0.09 mm. The following elemental analysis was obtained: The reaction mixture then was cooled poured onto ice The reaction mixture was extracted with diethyl ether washed three times with water dried over anhydrous sodium sulfate The diethyl ether was evaporated under reduced pressure distilled

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Few crystals of iodine are added to tetrahydrofuran (200 mL) containing magnesium turnings (2.8 g, 0.117 mol). The mixture is heated at 60-70° C. A solution of 4-bromo-2-chlorobiphenyl (26 g, 0.097 mol) in tetrahydrofuran (50 mL) is added dropwise to the reaction mixture and refluxed for 1 hr. Reaction mixture is brought to room temperature and then cooled to −20° C. Carbon dioxide gas is passed through the reaction mixture for 45 minutes. The reaction mixture is treated with 3N HCl (125 mL) and extracted with ethyl acetate (2×200 mL). Combined organic layer is dried over sodium sulphate. Removal of solvent under reduced pressure gives a solid which is washed with diethyl ether (2×100 mL) and then dried to furnish 2-chlorobiphenyl-4-carboxylic acid. refluxed for 1 hr Reaction mixture is brought to room temperature cooled to −20° C extracted with ethyl acetate (2×200 mL) Combined organic layer is dried over sodium sulphate Removal of solvent under reduced pressure gives a solid which is washed with diethyl ether (2×100 mL) dried

反応条件: temp:52.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Isobutyl nitrite (121 g, 1.17 mol) and cupric chloride (21.2 g, 0.16 mol) are added to a solution of 4-bromo-2-chloroaniline (200 g, 0.97 mol) in benzene (500 mL) at 60-65° C. temperature. The reaction mixture is refluxed for 2 hrs. The reaction mixture is cooled to 50-55° C. temperature and to it a solution of aqueous sulfuric acid (92 mL conc. Sulfuric acid in 453 mL demineralized water). After refluxing for 1 hr the reaction mixture is cooled to room temperature and organic layer is separated. It is treated with an aqueous solution of urea (41 g in 127 mL water) and refluxed for 1 hr. Organic layer is separated, washed with demineralized water (2×200 mL) and dried over sodium sulfate. After removing the solvent under reduced pressure the residue is fractionally distilled to get 4-bromo-2-chlorobiphenyl. The reaction mixture is refluxed for 2 hrs After refluxing for 1 hr the reaction mixture is cooled to room temperature organic layer is separated It is treated with an aqueous solution of urea (41 g in 127 mL water) refluxed for 1 hr Organic layer is separated washed with demineralized water (2×200 mL) dried over sodium sulfate After removing the solvent under reduced pressure the residue is fractionally distilled

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

実験手順: 2-Chloro-4-biphenylmagnesium bromide was prepared by known methods from 53.4 g of 2-chloro-4-bromobiphenyl and 5.0 g of magnesium turnings in tetrahydrofuran. A solution of 9.2 g of acetaldehyde in 100 ml of tetrahydrofuran was added dropwise to the cooled Grignard reagent solution. The reaction mixture was stirred at room temperature overnight. The reaction mixture then was cooled, treated successively with 165 ml of saturated aqueous ammonium chloride and 100 ml of water, and poured onto ice. The reaction mixture was extracted with diethyl ether. The diethyl ether extracts were combined, washed three times with water, and dried over anhydrous sodium sulfate. The diethyl ether was evaporated under reduced pressure and the liquid residue was vacuum distilled to give 28.6 g of α-methyl-3-chloro- 4-phenylbenzyl alcohol, bp 145°-157°C/0.09 mm. The following elemental analysis was obtained: The reaction mixture then was cooled poured onto ice The reaction mixture was extracted with diethyl ether washed three times with water dried over anhydrous sodium sulfate The diethyl ether was evaporated under reduced pressure distilled

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

実験手順: 2-Chloro-4-biphenylmagnesium bromide was prepared by known methods from 53.4 g of 2-chloro-4-bromobiphenyl and 5.0 g of magnesium turnings in tetrahydrofuran. A solution of 9.2 g of acetaldehyde in 100 ml of tetrahydrofuran was added dropwise to the cooled Grignard reagent solution. The reaction mixture was stirred at room temperature overnight. The reaction mixture then was cooled, treated successively with 165 ml of saturated aqueous ammonium chloride and 100 ml of water, and poured onto ice. The reaction mixture was extracted with diethyl ether. The diethyl ether extracts were combined, washed three times with water, and dried over anhydrous sodium sulfate. The diethyl ether was evaporated under reduced pressure and the liquid residue was vacuum distilled to give 28.6 g of α-methyl-3-chloro-4-phenylbenzyl alcohol, bp 145°-157°C/0.09 mm. The following elemental analysis was obtained: The reaction mixture then was cooled poured onto ice The reaction mixture was extracted with diethyl ether washed three times with water dried over anhydrous sodium sulfate The diethyl ether was evaporated under reduced pressure distilled