Hydrochloric Acid → tert-butyl 7-acetyl-2,3,4,5-tetrahydro-1H-3-benzazepine-3-carboxylate

HRID 33219Notes

Reaction equation

HRID 33219 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:14][CH2:13][C:12]2[CH:15]=[CH:16][C:17](OS(C(F)(F)F)(=O)=O)=[CH:18][C:11]=2[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(N(CC)CC)C.[CH:34]([O:36]CCCC)=[CH2:35].Cl>CN(C)C=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:34]([C:17]1[CH:16]=[CH:15][C:12]2[CH2:13][CH2:14][N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[CH2:9][CH2:10][C:11]=2[CH:18]=1)(=[O:36])[CH3:35]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 8108Butyl vinyl etherHCID 8471TriethylamineHCID 181732813-(tert-butoxycarbonyl)-7-trifluoromethylsulfonyloxy-2,3,4,5-tetrahydro-1H-3-benzazepine

Product 1

HCID 18173273tert-butyl 7-acetyl-2,3,4,5-tetrahydro-1H-3-benzazepine-3-carboxylateYield 79.2%

Reagents, catalysts & solvents 3

HCID 812191,3-Bis(diphenylphosphino)propaneCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Procedure

To a stirred solution of 3-(tert-butyloxycarbonyl)-7-trifluoromethylsulfonyloxy-2,3,4,5-tetrahydro-1H-3-benzazepine (10 g, 25.3 mmol) in anhydrous dimethylformamide (100 ml) under argon at room temperature, was added triethylamine (7.05 ml, 50.6 mmol), butyl vinyl ether (16.4 ml, 126.6 mmol), 1,3-bis(diphenylphosphino)propane (0.412 g, 1 mmol) and palladium acetate (0.202 g, 0.9 mmol) sequentially. The resultant mixture was heated at 85° C. for 1.5 h and cooled to room temperature. 4% Aqueous hydrochloric acid (150 ml) was added and stirring continued for 0.5 h. The reaction mixture was extracted with dichloromethane (3×300 ml) and the combined organics washed with water (4×500 ml), dried (Na2SO4) and evaporated in vacuo to afford a brown gum. Chromatography on silica gel with 0-30% ethyl acetate—hexane gradient elution gave the title compound (5.8 g, 79%) as a colourless solid.

Workup

  1. extractionThe reaction mixture was extracted with dichloromethane (3×300 ml)
  2. washthe combined organics washed with water (4×500 ml)
  3. dry with materialdried (Na2SO4)
  4. customevaporated in vacuo
  5. customto afford a brown gum
  6. washChromatography on silica gel with 0-30% ethyl acetate—hexane gradient elution

Sources & evidence

ORD record
ord-01d8f7ed59ec4dc3b771a2c775006dd7
Source dataset
uspto-grants-2008_09
Patent number
US07429579B2

Reaction notes

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