1,4-Dibromobutane → HCID 67155880, compound

HRID 1972105Notes

Reaction equation

HRID 1972105 reaction equation
[H-].[Na+].[Br:3][C:4]1[CH:5]=[CH:6][C:7]2[NH:8][C:9]3[C:14]([C:15]=2[CH:16]=1)=[CH:13][C:12]([Br:17])=[CH:11][CH:10]=3.[Br:18][CH2:19][CH2:20][CH2:21][CH2:22]Br>CN(C=O)C>[Br:17][C:12]1[CH:11]=[CH:10][C:9]2[N:8]([CH:19]([Br:18])[CH2:20][CH2:21][CH3:22])[C:7]3[C:15]([C:14]=2[CH:13]=1)=[CH:16][C:4]([Br:3])=[CH:5][CH:6]=3

Participants

5

Reactant 3

HCID 80561,4-DibromobutaneHCID 24758Sodium hydrideHCID 2748743,6-Dibromocarbazole

Product 1

HCID 67155880HCID 67155880, compoundYield 65%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Under a nitrogen atmosphere, sodium hydride (0.3 g, 12.5 mmol, Aldrich) was added to a solution of 3,6-dibromo-9H-carbazole (2 g, 6.1 mmol, Aldrich) in DMF (10 ml). The mixture was stirred for 5 min, 1,4-dibromobutane (3.9 g, 18 mmol, Aldrich) was added, and the mixture was refluxed for 12 h. Flash chromatography (N-hexane/ethyl acetate 2:1) gave 3,6-dibromo-9-(1-bromobutyl)carbazole (yield: 65%). A solution of the obtained compound (1.84 g, 4 mmol) and piperidine (0.68 g, 8 mmol, Aldrich) in ethanol (30 ml) was refluxed in the presence of a trace of NaI for 24 h. The product of the reaction was purified by column chromatography (n-Hexane/ethyl acetate 1:2) and added into a high pressure flask containing a mixture of palladium(II) acetate (0.005 g, 0.02 mmol, Aldrich) and tri-o-tolylphosphine (0.04 g, 0.13 mmol, Aldrich). After addition of triethylamine (5 ml), acetonitrile (10 ml), and 4-vinylpyridine (0.53 g, 5 mmol, Aldrich), the flask was sealed, nitrogen was bubbled for 5 min, and the reaction was kept at ˜105° C. for 48 h. The precipitate was collected, extracted twice with H2O and CH2Cl2, dried over anhydrous MgSO4, dissolved in THF, filtered, and the product was recrystallized from acetone. A solution of this product (0.5 g, 1 mmol) in DMF (10 ml) was refluxed with an excess of CH3I for 6 h, and the resulting product was recrystallized twice from methanol (35% overall yield, 300° C.). 1H NMR (400 MHz, DMSO-d6) δ: 8.83 (d, J=6 Hz, 4H), 8.62 (s, 2H), 8.23 (d, J=12.4 Hz, 2H), 8.20 (d, J=4.4 Hz, 4H), 7.96 (d, J=8.4 Hz, 2H), 7.82 (d, J=8.4 Hz, 2H), 7.57 (d, J=15.6 Hz, 2H), 4.52 (t, 2H), 4.25 (s, 6H), 2.94 (s, 3H), 2.25 (t, 4H), 2.21 (t, 2H), 1.84 (m, 4H), 1.53 (m, 4H), 1.48 (m, 2H). EA (C38H45I3N4.0.5H2O): calc (obs %) C, 48.17 (48.03); H, 4.89 (4.91); N, 5.91 (5.86).

Workup

  1. temperaturethe mixture was refluxed for 12 h

Sources & evidence

ORD record
ord-0c6d5e5570124026a2584a1def65ab1b
Source dataset
uspto-grants-2013_04
Patent number
US08431708B2

Reaction notes

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