Borane;2-methylpropan-2-amine → ethyl 5,6-dihydro-4H-thieno[2,3-c]azepine-7(8H)-carboxylate

HRID 446724Notes

Reaction equation

HRID 446724 reaction equation
B.C(N)(C)(C)C.[Cl-].[Cl-].[Cl-].[Al+3].O=[C:12]1[CH2:18][CH2:17][N:16]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH2:15][C:14]2[S:24][CH:25]=[CH:26][C:13]1=2>C(Cl)Cl>[S:24]1[C:14]2[CH2:15][N:16]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH2:17][CH2:18][CH2:12][C:13]=2[CH:26]=[CH:25]1

Participants

5

Reactant 3

HCID 517393Borane;2-methylpropan-2-amineHCID 6451240Aluminum(III) ChlorideHCID 13600418ethyl 4-oxo-5,6-dihydro-4H-thieno[2,3-c]azepine-7(8H)-carboxylate

Product 1

HCID 58293757ethyl 5,6-dihydro-4H-thieno[2,3-c]azepine-7(8H)-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Solid borane-t-butylamine pellets (2.77 g, 31.84 mmol) were crushed and suspended in methylene chloride (300 mL) at 0° C. Solid aluminum trichloride (2.12 g, 15.92 mmol) was added and the mixture was stirred for 1 hour. Compound 1043 (1.27 g, 5.31 mmol) was added slowly and the reaction mixture allowed to warm to room temperature overnight. The reaction was quenched by addition of ethanol (50 mL) then saturated ammonium chloride (100 mL). The mixture was brought to a neutral pH with saturated sodium bicarbonate, extracted with ethyl acetate (3×100 mL), and concentrated to give ethyl 5,6-dihydro-4H-thieno[2,3-c]azepine-7(8H)-carboxylate (Compound 1044) as a tan oil; 1H NMR (300 MHz, CDCl3): δ 6.95-6.85 (m, 1H), 6.70 (d, J=4.7 Hz, 1H), 4.49 (s, 2H), 4.18-4.00 (m, 2H), 3.66-3.58 (m, 2H), 2.77 (t, J=5.7 Hz, 2H), 1.62 (qn, J=6.0 Hz, 2H) and 1.24-1.08 (m, 3H).

Workup

  1. customThe reaction was quenched by addition of ethanol (50 mL)
  2. extractionextracted with ethyl acetate (3×100 mL)
  3. concentrationconcentrated

Sources & evidence

ORD record
ord-00400f90ba3a4eb499348ac46ba752ee
Source dataset
uspto-grants-2013_07
Patent number
US08481524B2

Reaction notes

Loading…