Triphenylphosphine → 3-Vinylbutyrate

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. ammonia 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) δ8.3(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)+.

1. customwas obtained
2. stirringthe mixture stirred for 4 hours
3. customThe solid which had precipitated during the reaction
4. filtrationwas filtered off
5. customThe filtrate was evaporated
6. additionthe residue treated with ethyl acetate (20 ml)
7. filtrationfiltered
8. extractionThe filtrate was extracted with 2N hydrochloric acid (2×10 ml)
9. customthe aqueous layer separated
10. extractionThe precipitate was extracted twice into ethyl acetate
11. filtrationthe combined extracts filtered through phase
12. customseparating paper
13. customevaporated
14. customThe residue was purified by flash chromatography on silica gel
15. washeluting with methanol/dichloromethane/0.89 S

ORDレコード

ord-a6a07d17dac9457f903307a5faaaffbc

出典データセット

uspto-grants-1996_09

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US05556977