Methanesulfonyl chloride → 3-(tert-butyloxycarbonyl)-1-chloromethyl-5-nitro-1,2-dihydro-3H-benz[e]indole

HRID 366804

反応式

HRID 366804 の反応式
[C:1]([O:5][C:6]([N:8]1[C:16]2[CH:15]=[C:14]([N+:17]([O-:19])=[O:18])[C:13]3[CH:20]=[CH:21][CH:22]=[CH:23][C:12]=3[C:11]=2[CH:10]([CH2:24]O)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].S([Cl:30])(C)(=O)=O.S([O-])(=O)(=O)C.[Li+].[Cl-]>N1C=CC=CC=1.O.CN(C=O)C.C(Cl)Cl>[C:1]([O:5][C:6]([N:8]1[C:16]2[CH:15]=[C:14]([N+:17]([O-:19])=[O:18])[C:13]3[CH:20]=[CH:21][CH:22]=[CH:23][C:12]=3[C:11]=2[CH:10]([CH2:24][Cl:30])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

参加物

9

反応物 4

HCID 31297Methanesulfonyl chlorideHCID 85257MethanesulfonateHCID 433294Lithium ChlorideHCID 107124643-(tert-butyloxycarbonyl)-1-hydroxymethyl-5-nitro,1,2-dihydro-3H-benz[e]indole

生成物 1

HCID 153804133-(tert-butyloxycarbonyl)-1-chloromethyl-5-nitro-1,2-dihydro-3H-benz[e]indole収率 77%

試薬・触媒・溶媒 4

HCID 962Water溶媒2 回HCID 1049Pyridine溶媒HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
20 °C

実験手順

A stirred solution of 12 (0.42 g, 1.22 mmol) in pyridine (1.8 mL) was treated dropwise at 0° C. with mesyl chloride (1.13 mL, 1.46 mmol) and then stirred at 20° C. for a further 2 h. The mixture was diluted with water and the resulting solid was collected, dissolved in CH2Cl2, and the solution was washed twice with water, dried (Na2SO4) and evaporated under reduced pressure below 30° C. A mixture of the resulting crude mesylate and LiCl (0.21 g, 5 mmol) in DMF (4 mL) was stirred at 80° C. for 30 min, then cooled and diluted with water. The precipitated solid was dissolved in CH2Cl2 and filtered through a column of silica gel to give a crude product which was triturated with iPr2O/petroleum ether, yielding 3-(tert-butyloxycarbonyl)-1-chloromethyl-5-nitro-1,2-dihydro-3H-benz[e]indole (13) (0.34 g, 77%). A sample recrystallised from iPr2 o/petroleum ether had mp 168-169° C. 1H NMR (CDCl3) δ8.88 (br s, 1 H, H-9), 8.42 (br s, 1 H, H-7), 7.80 (d, J=8.1 Hz, 1 H, H-4), 7.67-7.51 (m, 2 H, H-5,6), 4.34 (br s, 1 H, H-2), 4.20 (t, J=10.2 Hz, 1 H, H-2), 4.17-4.08 (m, 1 H, H-3), 3.92 (dd, J=11.2, 2.5 Hz, 1 H, CHHCl), 3.54 (t, J=10.3 Hz, CHHCl), 1.62 (s, 9 H, C(CH3)3).

後処理

  1. customthe resulting solid was collected
  2. dissolutiondissolved in CH2Cl2
  3. washthe solution was washed twice with water
  4. dry with materialdried (Na2SO4)
  5. customevaporated under reduced pressure below 30° C
  6. stirringwas stirred at 80° C. for 30 min
  7. temperaturecooled
  8. filtrationfiltered through a column of silica gel
  9. customto give a crude product which
  10. customwas triturated with iPr2O/petroleum ether

出典と根拠

ORDレコード
ord-69555dce7a7144239adb6449ae8606cb
出典データセット
uspto-grants-2000_10
特許番号
US06130237

関連ノート

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