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

HRID 428324ノート

反応式

HRID 428324 の反応式
[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]

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
115 °C

実験手順

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).

後処理

  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%)

出典と根拠

ORDレコード
ord-e81f58af9c3341f99abd810bd350d002
出典データセット
uspto-grants-2001_11
特許番号
US06313132B1

反応ノート

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