Chlorosulfonic acid → 1-(chloromethyl)-3-(trifluoroacetyl)-1,2-dihydro-3H-benzo[e]indole-7-sulfonyl chloride

HRID 2238370Notes

Reaction equation

HRID 2238370 reaction equation
[Cl:1][CH2:2][CH:3]1[C:11]2[C:10]3[CH:12]=[CH:13][CH:14]=[CH:15][C:9]=3[CH:8]=[CH:7][C:6]=2[N:5]([C:16](=[O:21])[C:17]([F:20])([F:19])[F:18])[CH2:4]1.[Cl:22][S:23](O)(=[O:25])=[O:24]>>[Cl:1][CH2:2][CH:3]1[C:11]2[C:10]3[CH:12]=[CH:13][C:14]([S:23]([Cl:22])(=[O:25])=[O:24])=[CH:15][C:9]=3[CH:8]=[CH:7][C:6]=2[N:5]([C:16](=[O:21])[C:17]([F:20])([F:18])[F:19])[CH2:4]1

Participants

3

Reactant 2

HCID 24638Chlorosulfonic acidHCID 445491451-(chloromethyl)-3-(trifluoroacetyl)-1,2-dihydro-3H-benz[e]indole

Product 1

HCID 445492671-(chloromethyl)-3-(trifluoroacetyl)-1,2-dihydro-3H-benzo[e]indole-7-sulfonyl chlorideYield 25.2%

Conditions

Temperature
60 °C

Procedure

Solid 108 (1.6 g, 5.1 mmol) was gradually added to chlorosulfonic acid (6.0 mL, 90 mmol) with ice bath cooling. The mixture was then heated to 60° C. for 2 h, and the reaction was quenched by pouring slowly, with stirring, into ice-water. The precipitated solid was collected, washed with water, dried and chromatographed on silica gel. Elution with EtOAc/petroleum ether (from 1:4 to 1:1) gave 1-(chloromethyl)-3-(trifluoroacetyl)-1,2-dihydro-3H-benzo[e]indole-7-sulfonyl chloride (113) (0.53 g, 25%) as a pale yellow solid: mp (EtOAc/petroleum ether) 189-192° C.; 1H NMR (CDCl3) δ 8.70-8.64 (m, 2H), 8.13-8.08 (m, 2H), 8.00 (d, J=9.0 Hz, 1H), 4.72-4.68 (m, 1H), 4.55-4.48 (m, 1H), 4.33-4.25 (m, 1H), 3.98-3.93 (m, 1H), 3.68-3.61 (m, 1H), 13C NMR δ 154.9 (q, JC-F 38.4 Hz), 143.9, 140.7, 132.7, 131.8, 130.1, 130.0, 125.8, 124.8, 123.2, 119.6, 115.9 (q, JC-F 288 Hz), 52.8, 45.4, 42.4. Anal. (C15H10Cl2F3NO3S) C, H, N, Cl.

Workup

  1. temperaturecooling
  2. customthe reaction was quenched
  3. additionby pouring slowly
  4. customThe precipitated solid was collected
  5. washwashed with water
  6. customdried
  7. customchromatographed on silica gel
  8. washElution with EtOAc/petroleum ether (from 1:4 to 1:1)

Sources & evidence

ORD record
ord-add5d309773e4d9d9d19bb6bd140fc51
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

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