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Methanol → tert-butyl 2-{[1-(chloromethyl)-5-nitro-1,2-dihydro-3H-benzo[e]indol-7-yl]sulfonyl}hydrazinecarboxylate

HRID 2238376
ノート
印刷プレビュー

反応式

HRID 2238376 の反応式
[C:1]([O:5][C:6]([CH3:9])([CH3:8])[CH3:7])(=[O:4])[NH:2][NH2:3].[Cl:10][CH2:11][CH:12]1[C:20]2[C:19]3[CH:21]=[CH:22][C:23]([S:25](Cl)(=[O:27])=[O:26])=[CH:24][C:18]=3[C:17]([N+:29]([O-:31])=[O:30])=[CH:16][C:15]=2[N:14](C(=O)C(F)(F)F)[CH2:13]1.C([O-])([O-])=O.[Cs+].[Cs+].CO>O>[Cl:10][CH2:11][CH:12]1[C:20]2[C:19]3[CH:21]=[CH:22][C:23]([S:25]([NH:3][NH:2][C:1]([O:5][C:6]([CH3:9])([CH3:8])[CH3:7])=[O:4])(=[O:26])=[O:27])=[CH:24][C:18]=3[C:17]([N+:29]([O-:31])=[O:30])=[CH:16][C:15]=2[NH:14][CH2:13]1
参加物実験手順後処理出典と根拠反応ノート

参加物

6

反応物 4

HCID 887MethanolHCID 10796Cesium carbonateHCID 70091tert-Butyl carbazateHCID 866202591-(chloromethyl)-5-nitro-3-(trifluoroacetyl)-1,2-dihydro-3H-benzo[e]indole-7-sulfonyl chloride

生成物 1

HCID 68691139tert-butyl 2-{[1-(chloromethyl)-5-nitro-1,2-dihydro-3H-benzo[e]indol-7-yl]sulfonyl}hydrazinecarboxylate収率 68.5%

試薬・触媒・溶媒

1
HCID 962Water溶媒

実験手順

t-Butyl carbazate (86 mg, 0.65 mmol) was added to a solution of 116 (107 mg, 0.23 mmol) in ThF (5 mL) and the mixture was stirred at room temperature for 16 h. Cs2CO3 (150 mg, 0.46 mmol) and MeOH (2 mL) were added and the mixture was stirred for a further 2 h. The mixture was diluted with water and extracted with CH2Cl2 (×2). The combined extracts were dried and evaporated and the residue was purified by chromatography, eluting with EtOAc/petroleum ether (1:4 then 2:3). The product was recrystallised from EtOAc/petroleum ether to give tert-butyl 2-{[1-(chloromethyl)-5-nitro-1,2-dihydro-3H-benzo[e]indol-7-yl]sulfonyl}hydrazinecarboxylate (119) (72 mg, 67%) as an orange crystalline solid: mp 179° C. (dec.); 1H NMR [(CD3)2SO] δ 9.60 (br s, 1H), 9.18 (v br s, 1H), 8.54 (d, J=1.4 Hz, 1H), 8.00 (d, J=8.9 Hz, 1H), 7.75 (s, 1H), 7.74 (dd, J=8.9, 1.8 Hz, 1H), 6.74 (s, 1H), 4.29-4.22 (m, 1H), 3.94-3.85 (m, 2H), 3.80 (dd, J=11.0, 8.0 Hz, 1H), 3.74 (dd, J=10.5, 3.0 Hz, 1H), 1.10 (br s, 9H). HRMS (FAB) calcd. for C18H2135ClN4O6S (M+) m/z 456.0870, found 456.0877.

後処理

  1. stirringthe mixture was stirred for a further 2 h
  2. extractionextracted with CH2Cl2 (×2)
  3. customThe combined extracts were dried
  4. customevaporated
  5. customthe residue was purified by chromatography
  6. washeluting with EtOAc/petroleum ether (1:4
  7. customThe product was recrystallised from EtOAc/petroleum ether

出典と根拠

ORDレコード
ord-d54a4b4a90b24e599508d15c9f414994
出典データセット
uspto-grants-2010_05
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07718688B2

反応ノート

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