Bromine → 7-Bromo-3,3-dimethyl-2,3-dihydro-1H-pyrido[2,3-e][1,4]diazepine

HRID 1879967Notes

Reaction equation

HRID 1879967 reaction equation
[CH3:1][C:2]1([CH3:13])[CH2:8][NH:7][C:6]2[N:9]=[CH:10][CH:11]=[CH:12][C:5]=2[CH2:4][NH:3]1.[Br:14]Br>CN(C=O)C>[Br:14][C:11]1[CH:10]=[N:9][C:6]2[NH:7][CH2:8][C:2]([CH3:13])([CH3:1])[N:3]=[CH:4][C:5]=2[CH:12]=1

Participants

4

Reactant 2

HCID 24408BromineHCID 593328723,3-Dimethyl-2,3,4,5-tetrahydro-1H-pyrido[2,3-e][1,4]diazepine

Product 1

HCID 593328417-Bromo-3,3-dimethyl-2,3-dihydro-1H-pyrido[2,3-e][1,4]diazepineYield 56.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 3,3-dimethyl-2,3,4,5-tetrahydro-1H-pyrido[2,3-e][1,4]diazepine (0.43 g, 1.8 mmol) in DMF (20 mL) was cooled in an ice bath and treated drop-wise with Br2 (0.19 mL, 3.7 mmol). After stirring in the ice bath for 2.5 h, the reaction was quenched with H2O (25 mL) and NaHCO3 (50 mL) and extracted with EtOAc (3×100 mL). The combined organic layers were washed with H2O (2×50 mL) and brine (50 mL), dried over Na2SO4, filtered and concentrated to an orange oil. Purification by flash column chromatography (silica gel, CH2Cl2/MeOH, 98:2 to 96:4) gave the title compound (0.26 g, 54%) as a yellow solid: 1H NMR (300 MHz, DMSO-d6) δ 8.15 (d, J=2.3 Hz, 1H), 8.03 (s, 1H), 7.73 (d, J=2.3 Hz, 1H), 5.93 (br s, 1H), 3.09 (d, J=4.9 Hz, 2H), 1.30 (s, 6H); MS (ESI) m/e 254 (M+H)+.

Workup

  1. customthe reaction was quenched with H2O (25 mL) and NaHCO3 (50 mL)
  2. extractionextracted with EtOAc (3×100 mL)
  3. washThe combined organic layers were washed with H2O (2×50 mL) and brine (50 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated to an orange oil
  7. customPurification by flash column chromatography (silica gel, CH2Cl2/MeOH, 98:2 to 96:4)

Sources & evidence

ORD record
ord-e01c556bc84e4418bef72e07dccafcf3
Source dataset
uspto-grants-2012_11
Patent number
US08318720B2

Reaction notes

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