Aniline → HCID 22396897, compound

HRID 1356362Notes

Reaction equation

HRID 1356362 reaction equation
Br[C:2]1[C:3]2[C:4]3[CH2:15][CH2:14][N:13](C(OC(C)(C)C)=O)[CH2:12][CH2:11][C:5]=3[NH:6][C:7]=2[CH:8]=[CH:9][CH:10]=1.CC(C)([O-])C.[Na+].[NH2:29][C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1.C(P(C(C)(C)C)C1C=CC=CC=1C1C=CC=CC=1)(C)(C)C>[Cl-].[Na+].O.[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1>[C:30]1([NH:29][C:2]2[C:3]3[C:4]4[CH2:15][CH2:14][NH:13][CH2:12][CH2:11][C:5]=4[NH:6][C:7]=3[CH:8]=[CH:9][CH:10]=2)[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1

Participants

7

Reactant 4

HCID 6115AnilineHCID 27342152-(Di-tert-butylphosphino)biphenylHCID 22396611HCID 22396611, compoundHCID 23676156Sodium t-butoxide

Product 1

HCID 22396897HCID 22396897, compound

Reagents, catalysts & solvents 2

HCID 9832798Tris(dibenzylideneacetone) dipalladiumCatalystHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of tert-butyl 10-bromo-1,4,5,6-tetrahydroazepino[4,5-b]indole-3(2H)-carboxylate (600 mg), sodium t-butoxide (220 mg), tris(dibenzylideneacetone) dipalladium (23 mg), aniline (183 mg) toluene (1.64 ml) was added 2-(di-t-butylphosphino)biphenyl (30 mg) and the reaction mixture was heated at 50° C. The reaction mixture stirred 16 h, was poured into brine, extracted with CH2Cl2, dried over MgSO4, filtered and concentrated. The crude product was stirred in CH2Cl2 (8 ml) and TFA (2 ml) was added. The reaction mixture stirred 1 h, was quenched with 2N NaOH, extracted with CH2Cl2, dried over MgSO4, filtered and concentrated. Purification via flash chromatography (silica gel, CH2Cl2/MeOH, 9/1 with 0.5% NH4OH) provided the title compound: 1H NMR (DMSO-d6) δ 2.68, 2.83-2.90, 6.58-6.67, 6.89, 7.06, 7.54, 10.71.

Workup

  1. extractionextracted with CH2Cl2
  2. dry with materialdried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. stirringThe crude product was stirred in CH2Cl2 (8 ml)
  6. additionTFA (2 ml) was added
  7. stirringThe reaction mixture stirred 1 h
  8. customwas quenched with 2N NaOH
  9. extractionextracted with CH2Cl2
  10. dry with materialdried over MgSO4
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customPurification via flash chromatography (silica gel, CH2Cl2/MeOH, 9/1 with 0.5% NH4OH)

Sources & evidence

ORD record
ord-b385ddce34bc410ba8a6e9586449e7ef
Source dataset
uspto-grants-2003_07
Patent number
US06586421B2

Reaction notes

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