Acrylonitrile → (R)-N,N-Diisopropyl-3-[2-benzyloxy-5-(2-cyanoethenyl)phenyl]-3-phenylpropylamine

HRID 428324Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 428324
[CH:1]([N:4]([CH:29]([CH3:31])[CH3:30])[CH2:5][CH2:6][C@@H:7]([C:14]1[CH:19]=[C:18](Br)[CH:17]=[CH:16][C:15]=1[O:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)([CH3:3])[CH3:2].C(N(CC)CC)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[C:61](#[N:64])[CH:62]=[CH2:63]>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH:1]([N:4]([CH2:5][CH2:6][C@@H:7]([C:14]1[CH:19]=[C:18]([CH:63]=[CH:62][C:61]#[N:64])[CH:17]=[CH:16][C:15]=1[O:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[CH:29]([CH3:31])[CH3:30])([CH3:3])[CH3:2]

Komponenten

7

Edukt 4

HCID 7855AcrylonitrileHCID 8471TriethylamineHCID 80271Tri-o-tolylphosphineHCID 24885301(R)-3-(2-benzyloxy)-5-bromophenyl)-N,N-diisopropyl-3-phenylpropan-1-amine

Produkt 1

HCID 54021240(R)-N,N-Diisopropyl-3-[2-benzyloxy-5-(2-cyanoethenyl)phenyl]-3-phenylpropylamine

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
115 °C

Versuchsvorschrift

To a solution of (R)-N,N-diisopropyl-3-(2-benzyloxy-5-bromophenyl)-3-phenylpropanamine (13.87 g, 28.87 mmol) (prepared as described in WO 94/11337, Example 1) in DMF (140 mL) was added triethylamin (5.00 mL, 36.10 mmol), Pd(OAc)2 (0.32 g, 1.44 mmol), tri(o-tolyl)phosphine (1.76 g, 5.77 mmol) and acrylonitrile (2.39 mL, 36.10 mmol). The reaction mixture was stirred overnight at 115° C. in a sealed flask equipped with a reflux condenser under nitrogen atmosphere. The resulting mixture was concentrated, and the residue was dissolved in diethyl ether, washed with aqueous 2 M sodium hydroxide and water. The organic phase was dried (MgSO4) where after petroleum ether was added to the organic phase and a precipitate was formed. Recrystallisation from ethanol yielded 5.50 g (42%). 1H NMR (CDCl3) δ0.90 (s, 6H), 0.95 (s, 6H), 2.15 (q, 2H), 2.35 (q, 2H), 2.95 (m, 2H), 4.40 (t, 1H), 5.05 (s, 2H), 5.70 (d, 1H), 6.85 (d, 1H), 7.10-7.50 (m, 13H).

Aufarbeitung

  1. customequipped with a reflux condenser under nitrogen atmosphere
  2. concentrationThe resulting mixture was concentrated
  3. dissolutionthe residue was dissolved in diethyl ether
  4. washwashed with aqueous 2 M sodium hydroxide and water
  5. dry with materialThe organic phase was dried (MgSO4) where after petroleum ether
  6. additionwas added to the organic phase
  7. customa precipitate was formed
  8. customRecrystallisation from ethanol
  9. customyielded 5.50 g (42%)

Quellen und Nachweise

ORD-Eintrag
ord-e81f58af9c3341f99abd810bd350d002
Quelldatensatz
uspto-grants-2001_11
Patentnummer
US06313132B1

Notizen zur Reaktion

Wird geladen…