乙酸乙酯 → 1-(4-Cyanophenyl)-1-(5-thiazolyl)-ethylene

HRID 5934

反应方程式

HRID 5934 反应方程式
[CH2:1]([Li])CCC.[C:6]([C:8]1[CH:20]=[CH:19][C:11]([C:12]([C:14]2[S:18][CH:17]=[N:16][CH:15]=2)=O)=[CH:10][CH:9]=1)#[N:7].C(OCC)(=O)C>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CCCCCC.CCOCC>[C:6]([C:8]1[CH:20]=[CH:19][C:11]([C:12]([C:14]2[S:18][CH:17]=[N:16][CH:15]=2)=[CH2:1])=[CH:10][CH:9]=1)#[N:7]

参与物

7

反应物 3

HCID 8857乙酸乙酯HCID 189490175-(4-Cyanobenzoyl)-thiazoleHCID 178418339正丁基锂

产物 1

HCID 189253811-(4-Cyanophenyl)-1-(5-thiazolyl)-ethylene

试剂、催化剂与溶剂 3

HCID 74505甲基三苯基溴化膦催化剂HCID 3283乙醚溶剂3 次HCID 8058正己烷溶剂

实验过程

714 mg of methyltriphenylphosphonium bromide are introduced into 6.7 ml of ether, and 0.973 ml of 1.6M n-butyllithium in hexane is added at 7°. The orange suspension is stirred at the same temperature for 1.5 hours and then reacted with a suspension, cooled to 7°, of 5-(4-cyanobenzoyl)-thiazole (Example 8a) in 3 ml of ether. After stirring for 3 hours at RT, the ether is replaced by ethyl acetate and the mixture is stirred for a further 2 hours under reflux. The solid material is filtered off with suction and the mother liquor is concentrated. The residue is taken up in methylene chloride and the organic phase is washed in succession with 7 ml of 2N hydrochloric acid and with water, dried over sodium sulfate and concentrated. The crude product is purified by column chromatography (SiO2 0.04-0.06 mesh, 0.1 bar, hexane/ethyl acetate 2:1 to 1:1) and crystallised from hexane; m.p. 71°-73°; 1H-NMR (CDCl3): δ(ppm)=5.5 (s,1H), 5.73 (s,1H) 7.54 and 7.71 (m,4H), 7.69 (s,1H), 8.78 (s,1H).

后处理

  1. additionis added at 7°
  2. customreacted with a suspension
  3. stirringAfter stirring for 3 hours at RT
  4. stirringthe mixture is stirred for a further 2 hours
  5. temperatureunder reflux
  6. filtrationThe solid material is filtered off with suction
  7. concentrationthe mother liquor is concentrated
  8. washthe organic phase is washed in succession with 7 ml of 2N hydrochloric acid and with water
  9. dry with materialdried over sodium sulfate
  10. concentrationconcentrated
  11. customThe crude product is purified by column chromatography (SiO2 0.04-0.06 mesh, 0.1 bar, hexane/ethyl acetate 2:1 to 1:1)
  12. customcrystallised from hexane

来源与证据

ORD记录
ord-eedbb5551d384a5eb7e05d29c0ad602c
来源数据集
uspto-grants-1993_09
专利号
US05246952

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