Cesium carbonate → 1-(chloromethyl)-N-hydroxy-5-nitro-1,2-dihydro-3H-benzo[e]indole-7-sulfonamide

HRID 2238375Notes

Reaction equation

HRID 2238375 reaction equation
Cl.[NH2:2][OH:3].C([O-])(O)=O.[Na+].[Cl:9][CH2:10][CH:11]1[C:19]2[C:18]3[CH:20]=[CH:21][C:22]([S:24](Cl)(=[O:26])=[O:25])=[CH:23][C:17]=3[C:16]([N+:28]([O-:30])=[O:29])=[CH:15][C:14]=2[N:13](C(=O)C(F)(F)F)[CH2:12]1.C([O-])([O-])=O.[Cs+].[Cs+]>O.CO>[Cl:9][CH2:10][CH:11]1[C:19]2[C:18]3[CH:20]=[CH:21][C:22]([S:24]([NH:2][OH:3])(=[O:26])=[O:25])=[CH:23][C:17]=3[C:16]([N+:28]([O-:30])=[O:29])=[CH:15][C:14]=2[NH:13][CH2:12]1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 443297Hydroxyamine hydrochlorideHCID 516892Sodium BicarbonateHCID 866202591-(chloromethyl)-5-nitro-3-(trifluoroacetyl)-1,2-dihydro-3H-benzo[e]indole-7-sulfonyl chloride

Product 1

HCID 686929641-(chloromethyl)-N-hydroxy-5-nitro-1,2-dihydro-3H-benzo[e]indole-7-sulfonamideYield 61%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of hydroxylamine hydrochloride (55 mg, 0.8 mmol) in water (1 mL) and then a solution of NaHCO3 (132 mg, 1.6 mmol) in water (2 mL) were added to a solution of 116 (90 mg, 0.20 mmol) in DE (5 mL) at 0° C. The orange solution was stirred at 0° C. for 10 min, and then Cs2CO3 (0.12 g, 0.4 mmol) and MeOH (3 mL) were added. The cooling bath was removed and the mixture was stirred for a further 1 h. The mixture was diluted with brine and extracted with CH2Cl2 (×4). The combined extracts were dried and evaporated to give 1-(chloromethyl)-N-hydroxy-5-nitro-1,2-dihydro-3H-benzo[e]indole-7-sulfonamide (118) (43 mg, 61%) as a red-brown solid. A sample was recrystallised from EtOAc/petroleum ether as an orange solid: mp 170-175° C. (dec.); 1H NMR [(CD3)2SO] δ 9.63-9.58 (m, a H), 8.63 (d, J=1.6 Hz, 1H), 8.04 (d, J=8.9 Hz, 1H), 7.82 (dd, J=8.9, 1.7 Hz, 1H), 7.78 (s, 1H), 6.80 (s, 1H), 4.30-4.22 (m, 1H), 3.95-3.87 (m, 2H), 3.82 (dd, J=11.0, 8.2 Hz, 1H), 3.75 (dd, J=10.5, 3.1 Hz, 1H). Anal. (C13H12ClN3O5S) C, H, N.

Workup

  1. customThe cooling bath was removed
  2. stirringthe mixture was stirred for a further 1 h
  3. additionThe mixture was diluted with brine
  4. extractionextracted with CH2Cl2 (×4)
  5. customThe combined extracts were dried
  6. customevaporated

Sources & evidence

ORD record
ord-f628e0ccb68141e295803fff6e892343
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

Loading…