Methanamine, N-methoxy-, hydrochloride (1:1) → 4-Methoxymethyl-2-phenyl-thiazole-5-carboxylic Acid Methoxy-methyl Amide

HRID 396387

反応式

HRID 396387 の反応式
Cl.[CH3:2][NH:3][O:4][CH3:5].[Cl-].C[Al+]C.CO[C:12]([C:14]1[S:18][C:17]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[N:16][C:15]=1[CH2:25][O:26][CH3:27])=[O:13]>C(Cl)Cl>[CH3:5][O:4][N:3]([CH3:2])[C:12]([C:14]1[S:18][C:17]([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)=[N:16][C:15]=1[CH2:25][O:26][CH3:27])=[O:13]

参加物

5

反応物 3

HCID 81138Methanamine, N-methoxy-, hydrochloride (1:1)HCID 99651204-Methoxymethyl-2-phenyl-thiazole-5-carboxylic acid methyl esterHCID 16686359Dimethylalumanylium chloride

生成物 1

HCID 213547804-Methoxymethyl-2-phenyl-thiazole-5-carboxylic Acid Methoxy-methyl Amide収率 97.9%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

反応条件

温度
0 °C

実験手順

A solution of N,O-dimethylhydroxylamine hydrochloride(13.3 g, 136.3 mmole, 6.0 eq) in dry CH2Cl2(250 ml) at 0° C. was treated dropwise with neat dimethylaluminum chloride (12.7 ml, 136.3 mmole, 6.0 eq) and the resulting mixture stirred at 0° C. for 2 hours then allowed to warm to RT. To this mixture was added dropwise a solution of the above-prepared 4-methoxymethyl-2-phenyl-thiazole-5-carboxylic acid methyl ester (5.98 g, 22.71 mmole, 1.0 eq) in CH2Cl2 (20 ml). The yellow mixture was then stirred at room temperature under nitrogen for one hour and re-cooled to 0° C. The mixture was quenched slowly by adding 2.0N NaOH dropwise, warmed to room temperature, and extracted with two portions of CH2Cl2. The organic phase was washed successively with 1.0N NaOH and brine, dried over MgSO4, and concentrated in vacuo to give a yellow oil. Silica gel chromatography eluting with (4:1) hexanes-ethyl acetate to give 6.5 g (97%) of the title compound as a yellow waxy crystalline solid. 1H NMR (CDCl3): δ 3.35 (s, 3H), 3.5 (s, 3H), 3.7 (s, 3H), 4.95 (s, 2H), 7.4-7.5 (m, 3H), 8.0 (m, 2H).

後処理

  1. temperatureto warm to RT
  2. stirringThe yellow mixture was then stirred at room temperature under nitrogen for one hour
  3. temperaturere-cooled to 0° C
  4. customThe mixture was quenched slowly
  5. additionby adding 2.0N NaOH dropwise
  6. temperaturewarmed to room temperature
  7. extractionextracted with two portions of CH2Cl2
  8. washThe organic phase was washed successively with 1.0N NaOH and brine
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated in vacuo
  11. customto give a yellow oil
  12. washSilica gel chromatography eluting with (4:1) hexanes-ethyl acetate

出典と根拠

ORDレコード
ord-9bdddc230afe46a8850f446dda0b68e1
出典データセット
uspto-grants-2003_08
特許番号
US06608087B1

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