N-bromobutanimide → 3-bromo-2-(o-tolyl)-9H-benzo[f]imidazo[1,2-d]pyrido[2,3-b][1,4]diazepine

HRID 1046970Notes

Reaction equation

HRID 1046970 reaction equation
[C:1]1([CH3:25])[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:7]1[N:8]=[C:9]2[C:15]3[CH:16]=[CH:17][CH:18]=[CH:19][C:14]=3[NH:13][C:12]3[N:20]=[CH:21][CH:22]=[CH:23][C:11]=3[N:10]2[CH:24]=1.[Br:26]N1C(=O)CCC1=O>C1COCC1>[Br:26][C:24]1[N:10]2[C:11]3[CH:23]=[CH:22][CH:21]=[N:20][C:12]=3[NH:13][C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=3[C:9]2=[N:8][C:7]=1[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][C:1]=1[CH3:25]

Participants

4

Reactant 2

HCID 67184N-bromobutanimideHCID 1363903822-(o-tolyl)-9H-benzo[f]imidazo[1,2-d]pyrido[2,3-b][1,4]diazepine

Product 1

HCID 675042963-bromo-2-(o-tolyl)-9H-benzo[f]imidazo[1,2-d]pyrido[2,3-b][1,4]diazepineYield 77%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2-(o-tolyl)-9H-benzo[f]imidazo[1,2-d]pyrido[2,3-b][1,4]diazepine (0.2 g, 1 eq.) in THF (5 mL) was added N-bromosuccinimide (0.11 g, 1 eq.). The reaction was stirred at room temperature for 15 minutes, poured onto water (30 mL) and extracted with ethyl acetate (2×30 mL). The organic extracts were combined, washed with saturated sodium bicarbonate (1×50 mL), water (1×50 mL), brine (1×50 mL) and dried over sodium sulfate. After filtration and concentration under reduced pressure, the crude product was purified by column chromatography (20% ethyl acetate in hexanes). The 3-bromo-2-(o-tolyl)-9H-benzo[f]imidazo[1,2-d]pyrido[2,3-b][1,4]diazepine (0.19 g, 77%) was obtained as an off-white solid. M.p.: 220-222° C.; 1H NMR (DMSO-d6) 400 MHz δ 8.64 (s, 1H), 8.27 (dd, JA=3.6 Hz, JB=1.6 Hz, 1H), 8.03 (dd, JA=7.2 Hz, JB=1.6 Hz, 1H), 7.78 (dd, JA=7.6 Hz, JB=1.2 Hz, 1H), 7.44 (d, J=6.8 Hz, 1H), 7.38-7.23 (m, 6H), 7.09 (t, J=7.6 Hz, 1H), 2.37 (s, 3H); LCMS: 403 [M+H].

Workup

  1. additionpoured onto water (30 mL)
  2. extractionextracted with ethyl acetate (2×30 mL)
  3. washwashed with saturated sodium bicarbonate (1×50 mL), water (1×50 mL), brine (1×50 mL)
  4. dry with materialdried over sodium sulfate
  5. filtrationAfter filtration and concentration under reduced pressure
  6. customthe crude product was purified by column chromatography (20% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-698bad93631949b4826ac5fbd02bf50d
Source dataset
uspto-grants-2013_10
Patent number
US08569331B2

Reaction notes

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