Allyl bromide → (+/-)-Chloro-APB hydrobromide

HRID 1701330Notes

Reaction equation

HRID 1701330 reaction equation
[Cl:1][C:2]1[C:12]2[CH2:11][CH2:10][NH:9][CH2:8][CH:7]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[C:6]=2[CH:5]=[C:4]([O:19]C)[C:3]=1[O:21]C.C(=O)([O-])[O-].[K+].[K+].[CH2:29]([Br:32])[CH:30]=[CH2:31].B(Br)(Br)Br>CN(C)C=O.C(Cl)Cl.CO>[BrH:32].[CH2:31]([N:9]1[CH2:8][CH:7]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C:6]2[CH:5]=[C:4]([OH:19])[C:3]([OH:21])=[C:2]([Cl:1])[C:12]=2[CH2:11][CH2:10]1)[CH:30]=[CH2:29]

Participants

8

Reactant 4

HCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 25134Boron tribromideHCID 12668015HCID 12668015, compound

Product 1

HCID 9909521(+/-)-Chloro-APB hydrobromideYield 52%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of 3.0 g (0.0095 mole) of 6-chloro-7,8-dimethoxy-1-phenyl-2,3,4,5-tetrahydro-1H-3-benzazepine, 5.5 g (0.04 mole) of potassium carbonate and 1.15 g (0.0095 mole) of allyl bromide in 80 ml of dry dimethylformamide was refluxed for 45 minutes, filtered and the filtrate evaporated to dryness. The residue was dissolved in ethyl acetate, washed with water and dried and concentrated to the light yellow oil (2.46 g, 78%). T.l.c. (10% methanol in chloroform) showed no starting material. The crude benzazepine was dissolved in 50 ml of dry methylene chloride and treated dropwise at -15° to -10° with 4.5 g (0.018 mole) of boron tribromide in 25 ml of dry methylene chloride. After being stirred at 0° for 2 hours, then at room temperature for one hour, the reaction was recooled, treated with excess methanol and evaporated to a tan solid. The crude product was dissolved in a little 2-propanol, diluted with ether and chilled to give 1.25 g (52%) of white 3-allyl-6-chloro-7,8-dihydroxy-1-phenyl-2,3,4,5-tetrahydro-1H-3-benzazepine hydrobromide; m.p. 200°-201°.

Workup

  1. temperaturewas refluxed for 45 minutes
  2. filtrationfiltered
  3. customthe filtrate evaporated to dryness
  4. dissolutionThe residue was dissolved in ethyl acetate
  5. washwashed with water
  6. customdried
  7. concentrationconcentrated to the light yellow oil (2.46 g, 78%)
  8. dissolutionThe crude benzazepine was dissolved in 50 ml of dry methylene chloride
  9. waitat room temperature for one hour
  10. customevaporated to a tan solid
  11. dissolutionThe crude product was dissolved in a little 2-propanol
  12. additiondiluted with ether
  13. temperaturechilled

Sources & evidence

ORD record
ord-a8b42378f878448cb712b310c7439ca9
Source dataset
uspto-grants-1980_03
Patent number
US04192872

Reaction notes

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