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

HRID 428324노트

반응식

HRID 428324 반응식
[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]

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 167845palladium(II) acetate촉매HCID 6228Dimethylformamide용매

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온도
115 °C

실험 절차

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).

후처리

  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%)

출처 및 근거

ORD 기록
ord-e81f58af9c3341f99abd810bd350d002
출처 데이터셋
uspto-grants-2001_11
특허 번호
US06313132B1

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