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4-Toluenesulfonyl chloride → tert-butyl 7-bromo-9-tosyl-3,4-dihydro-1H-pyrido[3,4-b]indole-2(9H)-carboxylate

HRID 930722
Notes
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Reaction equation

HRID 930722 reaction equation
[OH-].[Na+].[S:3](Cl)([C:6]1[CH:12]=[CH:11][C:9]([CH3:10])=[CH:8][CH:7]=1)(=[O:5])=[O:4].[Br:14][C:15]1[CH:23]=[C:22]2[C:18]([C:19]3[CH2:27][CH2:26][N:25]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[CH2:24][C:20]=3[NH:21]2)=[CH:17][CH:16]=1.CCOC(C)=O>O.C1(C)C=CC=CC=1>[Br:14][C:15]1[CH:23]=[C:22]2[C:18]([C:19]3[CH2:27][CH2:26][N:25]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[CH2:24][C:20]=3[N:21]2[S:3]([C:6]2[CH:12]=[CH:11][C:9]([CH3:10])=[CH:8][CH:7]=2)(=[O:5])=[O:4])=[CH:17][CH:16]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 8857Ethyl AcetateHCID 14798Sodium HydroxideHCID 19605584tert-Butyl 7-bromo-3,4-dihydro-1H-pyrido[3,4-b]indole-2(9H)-carboxylate

Product 1

HCID 57950467tert-butyl 7-bromo-9-tosyl-3,4-dihydro-1H-pyrido[3,4-b]indole-2(9H)-carboxylateYield 90.2%

Reagents, catalysts & solvents

2
HCID 962WaterSolvent2×HCID 1140TolueneSolvent

Conditions

Temperature
25 °C

Procedure

6 N NaOH solution (6 mL), (Bu4N)2SO4 (50% wt. solution in H2O, 0.20 mL), and TsCl (646 mg, 3.39 mmol) were added to a suspension of tert-butyl 7-bromo-3,4-dihydro-1H-pyrido[3,4-b]indole-2(9H)-carboxylate (991 mg, 2.82 mmol) in toluene (20 mL) and the resulting suspension was stirred at 25° C. for 1.5 h. H2O and EtOAc were added to the suspension and the phases were separated. The organic phase was washed with H2O, dried over Na2SO4 and concentrated under reduced pressure to afford the title compound (1.285 g, 90%) as a white foam: 1H NMR (300 MHz, CDCl3) δ 8.32 (d, J=1.5 Hz, 1H), 7.78-7.66 (m, 2H), 7.36 (dd, J=8.4, 1.5 Hz, 1H), 7.25-7.21 (m, 2H), 7.21-7.13 (m, 1H), 4.92-4.81 (m, 2H), 3.74-3.63 (m, 2H), 2.70-2.61 (m, 2H), 2.37 (s, 3H), 1.50 (s, 9H).

Workup

  1. customthe phases were separated
  2. washThe organic phase was washed with H2O
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-12ec0394e1c54720ac4e116347783f1a
Source dataset
uspto-grants-2016_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09296743B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes