4-bromo-2-methylbenzoyl chloride

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: To a solution of 6,11-dihydro-5H-pyrido[2,3-b][1,5]benzodiazepine (3 g, 15.2 mmol) in N,N-dimethylformamide under nitrogen was added solid potassium carbonate (6.3 g, 45.6 mmol). A solution of the crude 4-bromo-2-methylbenzoyl chloride (22.8 mmol) in N,N-diethylformamide was added dropwise, and the mixture stirred at room temperature for 15 minutes. Excess potassium carbonate was filtered off, the filtrate was washed with water and the aqueous layer was extracted with chloroform. The extracts were dried over anhydrous sodium sulfate, evaporated to dryness and the residue dissolved in dichloromethane and absorbed onto a silica Merck-60 flash column. Elution with 20% ethyl acetate in hexane provided the title compound (3.2 g) as a foam which crystallized upon sonication from ethanol hexane. Excess potassium carbonate was filtered off the filtrate was washed with water the aqueous layer was extracted with chloroform The extracts were dried over anhydrous sodium sulfate evaporated to dryness the residue dissolved in dichloromethane absorbed onto a silica Merck-60 flash column Elution with 20% ethyl acetate in hexane

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

実験手順: A suspension of 4bromo-2-methylbenzoic acid (4.9 g, 22.8 mmol) in dichioromethane containing a few drops of N,N-dimethylformamde was treated dropwise under nitrogen with oxalyl chloride (2.4 mL, 27.5 mol). After gas evolution subsided, the reaction mixture was refluxed for an additional 15 minutes and then evaporated to dryness in vacuo to provide the crude 4-bromo-2-methylbenzoyl chloride. the reaction mixture was refluxed for an additional 15 minutes evaporated to dryness in vacuo

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2.0 g (13 mmol) of 2-trimethylsilylthiazole and 6.1 g (26 mmol) of 4-bromo-2-methyl-benzoic acid chloride are combined while cooling with an ice bath and then are heated to 80° C. for 3 hours. The crude product is taken up in 30 ml of ethyl acetate, washed with H2O, saturated NaHCO3 solution and H2O, dried and purified by flash chromatography (silica gel; methylene chloride). while cooling with an ice bath washed with H2O, saturated NaHCO3 solution and H2O dried purified by flash chromatography (silica gel; methylene chloride)

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

実験手順: 2-Methyl-4-bromobenzoyl chloride (29.1 g, 0.13 mol) was treated with the dilithium salt of ethyl hydrogen malonate (28.0 g, 0.21 mol) and the product was isolated by the procedure described in Example 1 (ii). The crude product was purified on flash silica, eluting with dichloromethane-hexane (1:1 then 3:2) to give ethyl 2-methyl-4-bromobenzoylacetate as an oil. the product was isolated by the procedure The crude product was purified on flash silica eluting with dichloromethane-hexane (1:1

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

実験手順: 2-Methyl-4-bromobenzoic acid (26.8 g) was treated with oxalyl chloride (16.3 ml) in dry dichloromethane (250 ml) and the product was isolated by the method described in Example 1 (i) to give 2-methyl-4-bromobenzoyl chloride as an oil. the product was isolated by the method

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

実験手順: To a solution of 6,11-dihydro-5H-pyrido[2,3-b][1,5]benzodiazepine (3 g, 15.2 mmol) in N,N-dimethylformamide under nitrogen was added solid potassium carbonate (6.3 g, 45.6 mmol). A solution of the crude 4-bromo-2-methylbenzoyl chloride (22.8 mmol) in N,N-diethylformamide was added dropwise, and the mixture stirred at room temperature for 15 minutes. Excess potassium carbonate was filtered off, the filtrate was washed with water and the aqueous layer was extracted with chloroform. The extracts were dried over anhydrous sodium sulfate, evaporated to dryness and the residue dissolved in dichloromethane and absorbed onto a silica Merck-60 flash column. Elution with 20% ethyl acetate in hexane provided the title compound (3.2 g) as a foam which crystallized upon sonication from ethanol hexane. Excess potassium carbonate was filtered off the filtrate was washed with water the aqueous layer was extracted with chloroform The extracts were dried over anhydrous sodium sulfate evaporated to dryness the residue dissolved in dichloromethane absorbed onto a silica Merck-60 flash column Elution with 20% ethyl acetate in hexane

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

実験手順: A suspension of 4bromo-2-methylbenzoic acid (4.9 g, 22.8 mmol) in dichioromethane containing a few drops of N,N-dimethylformamde was treated dropwise under nitrogen with oxalyl chloride (2.4 mL, 27.5 mol). After gas evolution subsided, the reaction mixture was refluxed for an additional 15 minutes and then evaporated to dryness in vacuo to provide the crude 4-bromo-2-methylbenzoyl chloride. the reaction mixture was refluxed for an additional 15 minutes evaporated to dryness in vacuo