2-Nitroanisole → Methyl alpha-chloro-3-methoxy-4-nitrophenylacetate

HRID 275892

反応式

HRID 275892 の反応式
CC(C)([O-])C.[K+].[N+:7]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[O:16][CH3:17])([O-:9])=[O:8].[Cl:18][CH:19](Cl)[C:20]([O:22][CH3:23])=[O:21]>C(O)(=O)C>[Cl:18][CH:19]([C:13]1[CH:14]=[CH:15][C:10]([N+:7]([O-:9])=[O:8])=[C:11]([O:16][CH3:17])[CH:12]=1)[C:20]([O:22][CH3:23])=[O:21]

参加物

5

反応物 3

HCID 70482-NitroanisoleHCID 8315Methyl dichloroacetateHCID 23665647Potassium tert-butoxide

生成物 1

HCID 10061131Methyl alpha-chloro-3-methoxy-4-nitrophenylacetate

試薬・触媒・溶媒 1

HCID 176Acetic Acid溶媒

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.

後処理

  1. temperaturecooled to −5° C. to −10° C.
  2. temperaturewhilst maintaining the temperature below −5° C
  3. extractionwith water (6.6 l) and then extracted three times with tert-butyl methyl ether (5.5 l)
  4. washThe combined extracts were washed with water (5.5 l)
  5. dry with materialwith saturated sodium bicarbonate solution (5.5 l), then with saturated brine (5.5 l) and then dried over magnesium sulphate

出典と根拠

ORDレコード
ord-3a3fe73f364e416d9d447825d96fc14b
出典データセット
uspto-grants-2002_03
特許番号
US06352977B1

関連ノート

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