反応 #2341

反応方程式

diethyl azodicarboxylate

Methyl-4-hydroxy-3-vinylbutyrate

4-[4-(4-pyridyl)piperazin-1-yl]phenol

triphenylphosphine

→

ammonium hydroxide

methyl 4-[4-[4-(4-pyridyl)piperazin-1-yl]-phenoxy]-3-vinylbutyrate

収率 19.6%

溶媒

dichloromethane

反応条件

後処理

1. 1
   その他was obtained
2. 2
   workup.STIRRINGthe mixture stirred for 4 hours
3. 3
   その他The solid which had precipitated during the reaction
4. 4
   ろ過was filtered off
5. 5
   その他The filtrate was evaporated
6. 6
   workup.ADDITIONthe residue treated with ethyl acetate (20 ml)
7. 7
   ろ過filtered
8. 8
   抽出The filtrate was extracted with 2N hydrochloric acid (2×10 ml)
9. 9
   その他the aqueous layer separated
10. 10
    抽出The precipitate was extracted twice into ethyl acetate
11. 11
    ろ過the combined extracts filtered through phase
12. 12
    その他separating paper
13. 13
    その他evaporated
14. 14
    その他The residue was purified by flash chromatography on silica gel
15. 15
    洗浄eluting with methanol/dichloromethane/0.89 S

実験手順

To a stirred suspension of 4-[4-(4-pyridyl)piperazin-1-yl]phenol (1.98 g) in dichloromethane (30 ml) at 15° C. was added triphenylphosphine (2.04 g) followed by dropwise addition of diethyl azodicarboxylate (1.35 g). The mixture was stirred until complete solution was obtained. Methyl-4-hydroxy-3-vinylbutyrate (1.12 g) was added dropwise and the mixture stirred for 4 hours. The solid which had precipitated during the reaction was the starting phenol and was filtered off. The filtrate was evaporated and the residue treated with ethyl acetate (20 ml) and filtered. The filtrate was extracted with 2N hydrochloric acid (2×10 ml) and the aqueous layer separated and basified with 0.89 S.G. ammonium hydroxide. The precipitate was extracted twice into ethyl acetate and the combined extracts filtered through phase separating paper and evaporated. The residue was purified by flash chromatography on silica gel, eluting with methanol/dichloromethane/0.89 S. G. ammonium hydroxide v:v:v 7.5/92.5/0.75 to give RS methyl 4-[4-[4-(4-pyridyl)piperazin-1-yl]-phenoxy]-3-vinylbutyrate (0.29 g); NMR(CDCl3) δ 8.3(2H,d), 6.88(4H,m), 6.70(2H,d), 5.85(1H,m), 5.20(2H,m), 3.90(2H,m), 3.67(3H,s), 3.48(2H,m), 3.18(2H,m), 3.06(1H,m), 2.68(1H,m), 2.47(1H,m), 1.80(1H,br); m/e 382 (M+H)+.

出典