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

HRID 366832Notes

Reaction equation

HRID 366832 reaction equation
[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][OH:25])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:26][S:27](Cl)(=[O:29])=[O:28]>N1C=CC=CC=1.O>[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:25][S:27]([CH3:26])(=[O:29])=[O:28])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

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

Product 1

HCID 52493493-(tert-butyloxycarbonyl)-1-[(methanesulfonyloxy)methyl]-5-nitro-1,2-dihydro-3H-benz[e]indoleYield 89.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1049PyridineSolvent

Conditions

Temperature
20 °C

Procedure

A stirred solution of 3-(tert-butyloxycarbonyl)-1-(hydroxymethyl)-5-nitro-1,2-dihydro-3H-benz[e]indole (12) (450 mg, 1.31 mmol) in pyridine (1.3 mL) was treated dropwise at -5° C. with methanesulfonyl chloride (0.121 mL, 1.57 mmol) and then stirred at 20° C. for 2 h. The mixture was diluted with water then cooled and the resulting solid collected, washed with water and dried. This product was dissolved in CH2Cl2 and the solution was filtered through a short column of silica gel, eluting with further CH2Cl2. The resulting product was triturated with iPr2O/petroleum ether to give 3-(tert-butyloxycarbonyl)-1-[(methanesulfonyloxy)methyl]-5-nitro-1,2-dihydro-3H-benz[e]indole (494 mg, 89%), mp 147° C. (dec.). 1H NMR [(CD3)2SO] δ 8.75 (br s, 1 H, H-4), 8.32 (d, J=8.5 Hz, 1 H, H-6), 8.12 (d, J=8.2 Hz, 1 H, H-9), 7.77-7.63 (m, 2 H, H-7, 8), 4.54 (dd, J=10.0, 3.7 Hz, 1 H, H-2), 4.43 (dd, J=10.0, 6.4 Hz, 1 H, H-2), 4.42-4.33 (m, 1 H, H-1), 4.25 (t, J=10.3 Hz, 1 H, CHHO), 4.14 (dd, J=11.4, 2.5 Hz, 1 H, CHHO), 3.11 (s, 3 H, SO2CH3), 1.56 (s, 9 H, C(CH3)3). Anal. Calculated for C19H22N2O7S: C, 54.0; H, 5.3; N, 6.6; S, 7.6. Found: C, 54.3; H, 5.4; N, 6.9; S, 7.4%.

Workup

  1. temperaturethen cooled
  2. customthe resulting solid collected
  3. washwashed with water
  4. customdried
  5. dissolutionThis product was dissolved in CH2Cl2
  6. filtrationthe solution was filtered through a short column of silica gel
  7. washeluting with further CH2Cl2
  8. customThe resulting product was triturated with iPr2O/petroleum ether

Sources & evidence

ORD record
ord-717cf4e729a440a980bf258ebf004589
Source dataset
uspto-grants-2000_10
Patent number
US06130237

Reaction notes

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