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

HRID 2238376Notes

Reaction equation

HRID 2238376 reaction equation
[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

Participants

6

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-d54a4b4a90b24e599508d15c9f414994
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

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