反応 #6030

反応方程式

n-butyllithium

5-(4-cyanobenzoyl)-thiazole

ethyl acetate

→

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

溶媒

ether

hexane

ether

ether

反応条件

後処理

1. 1
   workup.ADDITIONis added at 7°
2. 2
   その他reacted with a suspension
3. 3
   workup.STIRRINGAfter stirring for 3 hours at RT
4. 4
   workup.STIRRINGthe mixture is stirred for a further 2 hours
5. 5
   温度under reflux
6. 6
   ろ過The solid material is filtered off with suction
7. 7
   濃縮the mother liquor is concentrated
8. 8
   洗浄the organic phase is washed in succession with 7 ml of 2N hydrochloric acid and with water
9. 9
   乾燥dried over sodium sulfate
10. 10
    濃縮concentrated
11. 11
    その他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)
12. 12
    その他crystallised from hexane

実験手順

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).

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