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

HRID 2238395노트

반응식

HRID 2238395 반응식
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

참가 물질

5

반응물 3

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

생성물 1

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

시약·촉매·용매 1

HCID 241Benzene용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-3febfa2b80324bdf8bb9dbb325385fc4
출처 데이터셋
uspto-grants-2010_05
특허 번호
US07718688B2

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