1,2-Dichloroethane → N-(3-Phenylpropyl)-6-amino-4a-(3-methoxyphenyl)-8a-methyloctahydro-isoquinoline Phthalimide

HRID 1453974ノート

反応式

HRID 1453974 の反応式
[CH:1](=O)[CH2:2][CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[C:11]1(=[O:21])[NH:15][C:14](=[O:16])[C:13]2=[CH:17][CH:18]=[CH:19][CH:20]=[C:12]12.N[CH:23]1C2(C)[C:27]([C:34]3[CH:39]=[CH:38][CH:37]=[C:36]([O:40][CH3:41])[CH:35]=3)([CH2:28][CH2:29][CH2:30][CH2:31]2)[CH2:26][CH2:25][NH:24]1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].Cl[CH2:57][CH2:58]Cl>>[C:11]1(=[O:21])[NH:15][C:14](=[O:16])[C:13]2=[CH:17][CH:18]=[CH:19][CH:20]=[C:12]12.[C:4]1([CH2:3][CH2:2][CH2:1][N:24]2[CH2:25][CH2:26][C:27]3([C:34]4[CH:39]=[CH:38][CH:37]=[C:36]([O:40][CH3:41])[CH:35]=4)[C:57]([CH3:58])([CH2:31][CH2:30][CH:29]([NH2:15])[CH2:28]3)[CH2:23]2)[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

参加物

5

反応物 4

HCID 111,2-DichloroethaneHCID 7707BenzenepropanalHCID 5049666Sodium triacetoxyborohydrideHCID 68828071Amino-4a-(3-methoxyphenyl)-8a-methyloctahydroisoquinoline Phthalimide

生成物 1

HCID 68827564N-(3-Phenylpropyl)-6-amino-4a-(3-methoxyphenyl)-8a-methyloctahydro-isoquinoline Phthalimide収率 87%

実験手順

Hydrocinnamaldehyde (0.65 mL, 0.0049 mol) and compound 22 (2.00 g, 0.0049 mol) were mixed in anhydrous 1,2-dichloroethane (50 mL) and then treated with sodium triacetoxyborohydride (1.57 g, 0.0074 mol). The reaction mixture remains cloudy throughout the reaction. The mixture was stirred at room temperature under N2 atmosphere for 3 h. Reaction was monitored by TLC (20% EtOAc/hexanes; neutral Al2O3 Brockman activity II-III). After completion, the reaction mixture was quenched by adding saturated aqueous NaHCO3, and the product was extracted with EtOAc (3×50 mL). The combined EtOAc extract were dried (MgSO4), and the solvent was removed under reduced pressure to give crude product. The crude product was purified by flash chromatography (10% EtOAc/hexanes on neutral Al2O3 Brockman activity II-III) to afford 2.25 g (87%) of 23 as a white shiny solid. The sample used for X-ray analysis was recrystallized from a hexane and methylene chloride mixture: mp 136-138° C.; LCMS (ESI): m/z 523.7 (M+H)+; 1H NMR (CDCl3, 300 MHz) δ 7.79-7.82 [m, 2H], 7.68-7.71 [m, 2H], 7.18-7.32 [m, 8H], 6.76-6.81 [m, 1H], 4.81 [m, 1H], 3.85 [s, 3H], 3.31 [t, J=12 Hz, 1H], 2.94 [d, J=12 Hz, 1H], 2.80 [d, J=9 Hz, 1H], 2.67-2.73 [m, 3H], 2.34-2.53 [m, 4H], 2.25 [d, J=12 Hz, 1H], 1.78-1.94 [m, 3H], 1.51-1.62 [m, 2H], 1.49 [d, J=12 Hz, 1H], 1.31-1.37 [m, 1H], 1.26 [s, 3H]; 13C NMR (CDCl3, 300 MHz) δ 170.4, 160.9, 150.3, 144.5, 135.7, 134.0, 130.4, 130.3, 130.2, 127.6, 124.9, 123.5, 117.6, 112.6, 90.0, 63.6, 59.9, 57.2, 52.9, 49.5, 46.2, 38.6, 38.5, 37.3, 35.7, 35.6, 31.0, 28.3, 25.9. Anal. (C34H38N2O3) C, H, N.

後処理

  1. customThe reaction mixture remains cloudy throughout the reaction
  2. customReaction
  3. customAfter completion, the reaction mixture was quenched
  4. additionby adding saturated aqueous NaHCO3
  5. extractionthe product was extracted with EtOAc (3×50 mL)
  6. extractionThe combined EtOAc extract
  7. dry with materialwere dried (MgSO4)
  8. customthe solvent was removed under reduced pressure
  9. customto give crude product
  10. customThe crude product was purified by flash chromatography (10% EtOAc/hexanes on neutral Al2O3 Brockman activity II-III)

出典と根拠

ORDレコード
ord-e0aa1dd06b784f1aa83ae85d4a004541
出典データセット
uspto-grants-2009_01
特許番号
US07476679B2

反応ノート

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