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

HRID 266765

Reaktionsgleichung

Reaktionsgleichung von HRID 266765
[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

Komponenten

7

Edukt 4

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

Produkt 2

HCID 14923Ammonium HydroxideHCID 18918477Methyl 4-[4-[4-(4-pyridyl)piperazin-1-yl]-phenoxy]-3-vinylbutyrateAusbeute 19,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

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)+.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-f1fb46ec3e18412c93661520a3cea788
Quelldatensatz
uspto-grants-1997_07
Patentnummer
US05652242

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