methyl 2,2-dichloroacetate

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 3000 liter reactor, methyl dichloroacetate and acrylic acid methyl ester are added. The stirring is controlled to start and a first controlled temperature is adjusted to 0-60° C. Then, sodium methoxide is added slowly to form a first reaction mixture. After the sodium methoxide is added, the first reaction mixture is stirred at the first controlled temperature for 1-4 hours. Subsequently, 100-300 liter of water is added to wash the first reaction mixture. The first reaction mixture is washed with water twice. The organic phase is then separated and distillation under reduced pressure is set to obtain dimethyl 2, 2-dichloroglutarate. is adjusted to 0-60° C to form a first reaction mixture to wash the first reaction mixture The first reaction mixture is washed with water twice The organic phase is then separated distillation under reduced pressure

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

実験手順: reacting methyl dichloroacetate and acrylic acid methyl ester with sodium methoxide to obtain Dimethyl 2,2-dichloroglutarate;

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

実験手順: reacting methyl dichloroacetate and acrylic acid methyl ester with sodium methoxide to obtain Dimethyl 2,2-dichloroglutarate;

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

実験手順: reacting methyl dichloroacetate and acrylic acid methyl ester with sodium methoxide to obtain dimethyl 2,2-dichloroglutarate;

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

実験手順: reacting methyl dichloroacetate and acrylic acid methyl ester with sodium methoxide to obtain dimethyl 2,2-dichloroglutarate;

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

実験手順: reacting methyl dichloroacetate and acrylic acid methyl ester with sodium methoxide to obtain dimethyl 2,2-dichloroglutarate;

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

実験手順: A solution of sodium methoxide (made from 1.43 g of sodium in dry methanol (20 ml) was added dropwise to a stirred solution of 2-(3-chlorophenyl)propanal (10.4 g) and methyl dichloroacetate (6.4 ml) in diethyl ether (30 ml) at 0° C. under nitrogen. After 1 h the mixture was quenched with brine and the product extracted into diethyl ether. The organic phase was collected, dried (MgSO4) and evaporated under reduced pressure to leave a yellow oil. The oil and thiourea (4.72 g) were dissolved in methanol (40 ml) and the mixture set at reflux for 4 h. The solvent was removed under reduced pressure and the residue partitioned between ethyl acetate and saturated sodium bicarbonate solution. The organic phase was separated, washed with water, collected, dried (MgSO4) and solvent evaporated under reduced pressure to leave a brown solid. The solid was triturated with isohexane and ethyl acetate mixtures and filtered to leave the subtitle product. After 1 h the mixture was quenched with brine the product extracted into diethyl ether The organic phase was collected dried (MgSO4) evaporated under reduced pressure to leave a yellow oil at reflux for 4 h The solvent was removed under reduced pressure the residue partitioned between ethyl acetate and saturated sodium bicarbonate solution The organic phase was separated washed with water collected dried (MgSO4) and solvent evaporated under reduced pressure to leave a brown solid The solid was triturated with isohexane and ethyl acetate mixtures filtered

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: A suspension of potassium t-butoxide (1.44 kg) in dimethylformamide(6.61), cooled to −5° C. to −10° C., was treated with a mixture of 2-nitroanisole (690 g) and methyl dichloroacetate (915 g) over 4 hours, whilst maintaining the temperature below −5° C. The reaction mixture was then treated with acetic acid (770 ml), then with water (6.6 l) and then extracted three times with tert-butyl methyl ether (5.5 l). The combined extracts were washed with water (5.5 l), then with saturated sodium bicarbonate solution (5.5 l), then with saturated brine (5.5 l) and then dried over magnesium sulphate to give a solution of methyl α-chloro-3-methoxy-4-nitrophenylacetate. This solution was concentrated to half volume under reduced pressure and then treated with tetrahydrofuran (2l), followed by triethylamine (751 ml), followed by 10 % palladium on chareoal (58.4 g) and the mixture was hydrogenated under a pressure of 50 psi hydrogen at 50° C. for 8 hours. The mixture was cooled to room temperature and filtered. The filtrate was dried over magnesium sulphate to give a solution of methyl 4-amino-3-methoxyphenylacetate which was heated to reflux and then treated with o-tolyl isocyanate (598.5 g) over 30 minutes. After heating at reflux temperature for a further 3 hours, during which time a solid was deposited, the mixture was cooled to room temperature. The solid was collected, washed twice with tert-butyl methyl ether (4 l), then dried in a vacuum oven at 60° C. to give the title compound (764.8 g) as a white solid, m.p. 167-168° C. cooled to −5° C. to −10° C. whilst maintaining the temperature below −5° C with water (6.6 l) and then extracted three times with tert-butyl methyl ether (5.5 l) The combined extracts were washed with water (5.5 l) with saturated sodium bicarbonate solution (5.5 l), then with saturated brine (5.5 l) and then dried over magnesium sulphate