1-bromo-3-(trifluoromethyl)benzene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:100.01; pressure:0.00; stir:

Procedure: The general procedure A was followed using 1-bromo-3-(trifluoromethyl)benzene (67.5 uL, 0.5 mmol) and B2pin2 (126.9 mg, 0.5 mmol, 1.0 eq.) as starting material. The resulting mixture was allowed to stir 16 hours at 100 oC. 5h was obtained as colorless oil (173.1 mg, 99%) after purification by silica gel flash chromatography (EtOAc/PE=1:30 v/v).

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: 4-Methyl-3-(n-propylthio)phenol (8.4 g, 0.05 mole) and 85.5 % potassium hydroxide (3.3 g, 0.05 mole) were dissolved in N,N-dimethylacetamide (50 ml) above 90° C. 3-Bromotrifluoromethylbenzene (11.2 g, 0.05 mole) and Cu powder (0.5 g, 0.008 mole) were added to this solution below 90° C and the mixture was stirred at 110°-160° C for 14 hr. After cooling, the reaction mixture was poured into water (150 ml) and extracted twice benzene. The combined organic layers were washed with 5 % sodium hydroxide solution, 5 % hydrochloric acid solution, and water, then dried over sodium fulfate. The solvent was removed, and the residue was purified by column chromatography on silica gel using n-hexane benzene (2 : 1). The yield of 4-methyl-3-n-propylthiophenyl 3-trifluoromethylphenyl ether was 8.9 g (54.8 %), colorless oil, nD25 1.5319. Anal. Found: C, 62.61; H, 5.33. Calcd. for C17H17F3OS : C, 62.56; H, 5.25 %. After cooling extracted twice benzene The combined organic layers were washed with 5 % sodium hydroxide solution, 5 % hydrochloric acid solution, and water dried over sodium fulfate The solvent was removed the residue was purified by column chromatography on silica gel

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

Procedure: To a Grignard reactant prepared from 1.46 g. of magnesium turnings and 13.5 g. of 3-trifluoromethyl-bromobenzene in 34 ml. of dry tetrahydrofurane a solution of 9.61 g. of 4-benzyloxy-propiophenone in 50 ml. of dry tetrahydrofurane is added dropwise, under moderate reflux. The reaction mixture is slightly boiled for a further hour. The progress of the reaction can be monitored by thin layer chromatography. After termination of the reaction the reaction mixture is cooled and poured onto a mixture of glacial acetic acid and ice. The solvent phase is washed with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent is distilled off in vacuo. 15 g. of the named compound are obtained, which can be recrystallized from n-heptane. Melting point: 50°-51° C. The reaction mixture is slightly boiled for a further hour The progress of the reaction After termination of the reaction the reaction mixture is cooled The solvent phase is washed with a saturated aqueous sodium chloride solution dried over anhydrous magnesium sulfate The solvent is distilled off in vacuo of the named compound are obtained which can be recrystallized from n-heptane

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

Procedure: Under anhydrous conditions, to a mixture of 11 g. of magnesium in 15 ml. of ethyl ether an iodine crystal is added followed by the addition of a solution of 100 g. of m-bromotrifluoromethylbenzene in 300 ml. of ether over a two hour period. The resulting mixture is stirred for two hours at ambient temperature then cooled to 5° C. A solution of 70 g. of N-benzyl-3-piperidone in 300 ml. of ether is added at this temperature over one hour. After stirring for 15 minutes at 5° C. and one hour at 20°-25° C., the reaction mixture was poured onto 800 ml. of ice-water with stirring. The mixture is filtered, the organic layer extracted with 4×100 ml. of 1 N hydrochloric acid and once with brine. The aqueous phase is made alkaline by addition of triethylamine in the cold and the resulting mixture extracted with ethyl acetate. The combined extracts are washed with brine, dried (MgSO4) and evaporated to dryness. The crude product is purified by silica gel chromatography, eluting with cyclohexane/chloroform/triethylamine (85:10:5 by volume) to obtain the desired product as an orange colored solid. Under anhydrous conditions, to a mixture of 11 g followed by the addition of a solution of 100 g then cooled to 5° C After stirring for 15 minutes at 5° C. and one hour at 20°-25° C. the reaction mixture was poured onto 800 ml The mixture is filtered the organic layer extracted with 4×100 ml by addition of triethylamine in the cold and the resulting mixture extracted with ethyl acetate The combined extracts are washed with brine dried (MgSO4) evaporated to dryness The crude product is purified by silica gel chromatography eluting with cyclohexane/chloroform/triethylamine (85:10:5 by volume)

Conditions: temp:0.00; pressure:0.00; stir: