CID 406 → HCID 54032013、化合物

HRID 967737ノート

反応式

HRID 967737 の反応式
[H-].[Na+].P(=O)([O-])O[C:5]([CH2:14][CH3:15])(CC)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.P(=O)([O-])[O-].[CH3:22][C:23]1[N:24]=C(C=O)[S:26][CH:27]=1>COCCOC.C(OCC)(=O)C>[CH3:22][C:23]1[N:24]=[C:15]([CH:14]=[CH:5][C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=2)[S:26][CH:27]=1

参加物

7

反応物 4

HCID 406CID 406HCID 24758Sodium hydride2 回HCID 42634324-Methyl-1,3-thiazole-2-carbaldehydeHCID 178447633HCID 178447633、化合物

生成物 1

HCID 54032013HCID 54032013、化合物収率 16%

試薬・触媒・溶媒 2

HCID 80711,2-Dimethoxyethane溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

Sodium hydride (102 mg of a 60% suspension in mineral oil, 4.3 mmol) was slurried in dry 1,2-dimethoxyethane (DME) under argon, cooled to 0° C. in an ice bath, and diethylbenzyl phosphonate (0.89 mL, 4.3 mmol) was added dropwise to the suspension. Thirty minutes after the completion of the phosphonate addition, 4-methylthiazole-2-carboxaldehyde (120 mg, 0.94 mmol) was added as a solution in DME (5 mL). After stirring for 4 h, further NaH (40 mg of a 60% suspension in mineral oil, 1.0 mmol) was added and the reaction mixture was allowed to warm to ambient temperature and stir for 16 h. The reaction mixture was quenched by the addition of water (20 mL) and ethyl acetate (50 mL). The aqueous phase was extracted with ethyl acetate (2×30 mL), the combined organics were dried over Na2SO4, filtered, and concentrated in vacuo. The crude product was purified by column chromatography on silica gel eluting with 90:10 hexane:ethyl acetate to afford 4-methyl-2-[2-phenylethenyl]-1,3-thiazole (30 mg, 16% yield) as an oil. 1H NMR analysis showed the material to be a 10:1 mixture of E and Z isomers (spectral data are reported for the major isomer). 1H NMR (CDCl3,300 MHz) δ: 7.54-7.51 (m, 2H) 7.42-7.23 (m, 5H) 6.80 (s, 1H) 2.47 (s, 3H). MS (ESI) (minor isomer) 202.2 (M++H), (major isomer) 201.6 (M+).

後処理

  1. temperatureto warm to ambient temperature
  2. stirringstir for 16 h
  3. customThe reaction mixture was quenched by the addition of water (20 mL) and ethyl acetate (50 mL)
  4. extractionThe aqueous phase was extracted with ethyl acetate (2×30 mL)
  5. dry with materialthe combined organics were dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe crude product was purified by column chromatography on silica gel eluting with 90:10 hexane

出典と根拠

ORDレコード
ord-1bf5a34f982441ba9b8bbfa4d7d2df56
出典データセット
uspto-grants-2005_10
特許番号
US06956049B1

反応ノート

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