Triphenylphosphine → Methyl 4-[4-[4-(4-pyridyl)piperazin-1-yl]-phenoxy]-3-vinylbutyrate

HRID 1290540

Reaction equation

HRID 1290540 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([N:7]2[CH2:12][CH2:11][N:10]([C:13]3[CH:18]=[CH:17][C:16]([OH:19])=[CH:15][CH:14]=3)[CH2:9][CH2:8]2)=[CH:3][CH:2]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.[CH3:51][O:52][C:53](=[O:60])[CH2:54][CH:55]([CH:58]=[CH2:59])[CH2:56][OH:57]>ClCCl>[OH-:19].[NH4+:1].[N:1]1[CH:2]=[CH:3][C:4]([N:7]2[CH2:12][CH2:11][N:10]([C:13]3[CH:18]=[CH:17][C:16]([O:57][CH2:56][CH:55]([CH:58]=[CH2:59])[CH2:54][C:53]([O:52][CH3:51])=[O:60])=[CH:15][CH:14]=3)[CH2:9][CH2:8]2)=[CH:5][CH:6]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 149869034-(4-(4-Pyridyl)piperazin-1-yl)phenolHCID 18918398Methyl-4-hydroxy-3-vinylbutyrate

Product 2

HCID 14923Ammonium HydroxideHCID 18918477Methyl 4-[4-[4-(4-pyridyl)piperazin-1-yl]-phenoxy]-3-vinylbutyrateYield 19.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To stirred suspension of 4-[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 azodicaboxylate (1.35 g). The mixture was stirred until complete solution was obtained. Methyl-4-hydroxy-3-vinylbutyrate (1.2 g) was added drowise 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. ammoniium 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)+.

Workup

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

Sources & evidence

ORD record
ord-c3c0c231ba9f43b9a88ed382e9fafad6
Source dataset
uspto-grants-1998_05
Patent number
US05750754

Linked notes

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