Methanol → 8-Bromo-2,3,4,5-tetrahydro-1H-benzo[b]azepine

HRID 2235169Notes

Reaction equation

HRID 2235169 reaction equation
O1CCCC1.B.[Br:7][C:8]1[CH:9]=[CH:10][C:11]2[CH2:17][CH2:16][CH2:15][C:14](=O)[NH:13][C:12]=2[CH:19]=1.BrC1C=C2C(CCCC2=O)=CC=1.CO>O1CCCC1>[Br:7][C:8]1[CH:9]=[CH:10][C:11]2[CH2:17][CH2:16][CH2:15][CH2:14][NH:13][C:12]=2[CH:19]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 2527317-Bromo-1,2,3,4-tetrahydronaphthalen-1-oneHCID 2723981Borane;tetrahydrofuranHCID 50926208-bromo-2,3,4,5-tetrahydro-1H-1-benzazepin-2-one

Product 1

HCID 162444748-Bromo-2,3,4,5-tetrahydro-1H-benzo[b]azepineYield 92%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Borane tetrahydrofuran complex (1 M solution in tetrahydrofuran, 21 mL, 21 mmol) was added to a solution of 8-bromo-1,3,4,5-tetrahydro-benzo[b]azepin-2-one (prepared from 7-bromo-3,4-dihydro-2H-naphthalen-1-one in analogy with the general procedure described in J Chem. Soc. (C) 1969, 183; 1.00 g, 4.17 mmol) in tetrahydrofuran, and the solution was heated at reflux for 2 h. After cooling, methanol (21 mL) was added, and volatile material was removed by distillation. The residue was taken up in 5% ethanolic sulfuric acid solution (12 mL) and heated at reflux for 2 h, then basified to pH 10 by addition of 2 M aq. sodium hydroxide solution and partitioned between water and ethyl acetate. The organic layer was dried (MgSO4) and evaporated. Chromatography (SiO2, heptane-ethyl acetate 2:1) yielded 8-bromo-2,3,4,5-tetrahydro-1H-benzo[b]azepine (865 mg, 92%). White solid, MS (ISP) m/e 226.1 (M+H).

Workup

  1. temperatureat reflux for 2 h
  2. temperatureAfter cooling
  3. customvolatile material was removed by distillation
  4. temperatureheated
  5. temperatureat reflux for 2 h
  6. additionbasified to pH 10 by addition of 2 M aq. sodium hydroxide solution
  7. custompartitioned between water and ethyl acetate
  8. dry with materialThe organic layer was dried (MgSO4)
  9. customevaporated

Sources & evidence

ORD record
ord-d7aa74c309c543318abeb17a23688049
Source dataset
uspto-grants-2010_05
Patent number
US07713996B2

Reaction notes

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