Tributylstannane → tert-butyl 1-(chloromethyl)-7-cyano-1,2-dihydro-3H-benzo[e]indole-3-carboxylate

HRID 2238395ノート

反応式

HRID 2238395 の反応式
Br[C:2]1[C:11]2[C:6](=[CH:7][C:8]([C:12]#[N:13])=[CH:9][CH:10]=2)[CH:5]=[CH:4][C:3]=1[N:14]([CH2:22][CH:23]=[CH:24][Cl:25])[C:15](=[O:21])[O:16][C:17]([CH3:20])([CH3:19])[CH3:18].CCCC[SnH](CCCC)CCCC.CC(N=NC(C#N)(C)C)(C#N)C>C1C=CC=CC=1>[Cl:25][CH2:24][CH:23]1[C:2]2[C:11]3[CH:10]=[CH:9][C:8]([C:12]#[N:13])=[CH:7][C:6]=3[CH:5]=[CH:4][C:3]=2[N:14]([C:15]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:21])[CH2:22]1

参加物

5

反応物 3

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 75066177Tert-butyl 1-bromo-6-cyano-2-naphthyl(3-chloro-2-propenyl)carbamate

生成物 1

HCID 44550490tert-butyl 1-(chloromethyl)-7-cyano-1,2-dihydro-3H-benzo[e]indole-3-carboxylate

試薬・触媒・溶媒 1

HCID 241Benzene溶媒

実験手順

A solution of 142 (6.78 g, 16.1 mmol) in dry benzene (80 mL) was treated with Bu3SnH (4.33 mL, 16.1 mmol), followed by AIBN (0.3 g, 1.8 mmol). The mixture was stirred at reflux under N2 for 2 h, then concentrated under reduced pressure, and the residue was chromatographed on silica gel. Elution with CH2Cl2 gave an oil that was triturated with iPr2O, to provide 143 contaminated with tert-butyl 7-cyano-1-methyl-1,2-dihydro-3H-benzo[e]indole-3-carboxylate. Two recrystallizations from CH2ClrPr2O gave pure tert-butyl 1-(chloromethyl)-7-cyano-1,2-dihydro-3H-benzo[e]indole-3-carboxylate (143) (4.49 g, 81%): mp 171-172° C.; 1H MR [(CD3)2SO] δ 8.55 (d, J=1.4 Hz, 1H), 8.18 (v br, 1H), 8.07 (d, J=8.7 Hz, 1H), 8.01 (d, J=8.9 Hz, 1H), 7.75 (dd, J=8.7, 1.7 Hz, 1 H), 4.34-4.25 (m, 1H), 4.21 (t, J=10.5 Hz, 1H), 4.09 (dd, J=11.3, 2.8 Hz, 1H), 4.03 (dd, J=11.1, 3.1 Hz, 1H), 3.93 (dd, J=11.1, 6.7 Hz, 1H), 1.55 (s, 9H). Anal. (C19H19ClN2O2.¼H2O) C, H, N.

後処理

  1. temperatureat reflux under N2 for 2 h
  2. concentrationconcentrated under reduced pressure
  3. customthe residue was chromatographed on silica gel
  4. washElution with CH2Cl2
  5. customgave an oil that
  6. customwas triturated with iPr2O

出典と根拠

ORDレコード
ord-3febfa2b80324bdf8bb9dbb325385fc4
出典データセット
uspto-grants-2010_05
特許番号
US07718688B2

反応ノート

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