Trifluoroacetic acid → 6-Bromo-8-(2,4-dichlorophenyl)-2,3,4,4a,5,9b-hexahydro-1h-pyrido[4,3-b]indole

HRID 22790Notes

Reaction equation

HRID 22790 reaction equation
[Br:1][C:2]1[C:10]2[N:9](C(OC(C)(C)C)=O)[CH:8]3[CH2:18][CH2:19][N:20](C(OC(C)(C)C)=O)[CH2:21][CH:7]3[C:6]=2[CH:5]=[C:4]([C:29]2[CH:34]=[CH:33][C:32]([Cl:35])=[CH:31][C:30]=2[Cl:36])[CH:3]=1.FC(F)(F)C(O)=O>C(Cl)Cl>[Br:1][C:2]1[C:10]2[NH:9][CH:8]3[CH2:18][CH2:19][NH:20][CH2:21][CH:7]3[C:6]=2[CH:5]=[C:4]([C:29]2[CH:34]=[CH:33][C:32]([Cl:35])=[CH:31][C:30]=2[Cl:36])[CH:3]=1

Participants

4

Reactant 2

HCID 6422Trifluoroacetic acidHCID 69708076HCID 69708076, compound

Product 1

HCID 102942656-Bromo-8-(2,4-dichlorophenyl)-2,3,4,4a,5,9b-hexahydro-1h-pyrido[4,3-b]indoleYield 85%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A 100 mL round bottom flask was charged with a solution of di(tert-butyl) 6-bromo-8-(2,4-dichlorophenyl)-3,4,4a,9b-tetrahydro-1H-pyrido[4,3-b]indole-2,5-dicarboxylate (0.27 g, 0.45 mmol) in CH2Cl2 (5 mL) and cooled to 0° C. with an ice bath. Trifluoroacetic acid (5 mL) was added via pipette, the ice bath was removed, and the mixture was stirred at ambient temperature for 1.5 hours. The reaction was then concentrated in vacuo, and the residue was partitioned between 5 N NaOH and ethyl acetate (2X). The organics were combined, dried with MgSO4, filtered and concentrated to give 280 mg of a crude yellow oil. The crude was purified on a 40 g silica Biotage column using 5% methanol in CH2Cl2 as the eluent to give 151 mg (85%) of 6-bromo-8-(2,4-dichlorophenyl)-2,3,4,4a,5,9b-hexahydro-1H-pyrido[4,3-b]indole as a white foam: 1H NMR (300 MHz, CDCl3) δ 7.47 (d, J=2 Hz, 1 H), 7.26 (m, 3 H), 7.10 (s, 1 H), 4.08 (m, 2 H), 3.28 (m, 1 H), 3.14-2.86 (m, 4 H), 1.93-1.80 (m, 3 H); IR (diffuse reflectance) 2937, 2851, 1615, 1572, 1460, 1359, 1314, 1303, 1237, 1102, 1032, 869, 816, 761, 744 cm−1. OAMS supporting ions at: ESI+398.8; HRMS (FAB) calcd for C17H15BRCL2N2 +H1 396.9874, found 396.9867.

Workup

  1. customthe ice bath was removed
  2. concentrationThe reaction was then concentrated in vacuo
  3. customthe residue was partitioned between 5 N NaOH and ethyl acetate (2X)
  4. dry with materialdried with MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give 280 mg of a crude yellow oil
  8. customThe crude was purified on a 40 g silica Biotage column

Sources & evidence

ORD record
ord-51a484c73bad46608464f1f4f6972370
Source dataset
uspto-grants-2005_02
Patent number
US06849640B2

Reaction notes

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