Aluminum(III) Chloride → 4,5,7,8-Tetrahydro-thieno[2,3-d]azepine-6-carboxylic acid ethyl ester

HRID 2237428Notes

Reaction equation

HRID 2237428 reaction equation
[Al+3].[Cl-].[Cl-].[Cl-].[CH2:5]([O:7][C:8]([N:10]1[CH2:16][C:15](=O)[C:14]2[CH:18]=[CH:19][S:20][C:13]=2[CH2:12][CH2:11]1)=[O:9])[CH3:6]>C(Cl)Cl>[CH2:5]([O:7][C:8]([N:10]1[CH2:16][CH2:15][C:14]2[CH:18]=[CH:19][S:20][C:13]=2[CH2:12][CH2:11]1)=[O:9])[CH3:6]

Participants

4

Reactant 2

HCID 6451240Aluminum(III) Chloride2×HCID 574239834-Oxo-4,5,7,8-tetrahydro-thieno[2,3-d]azepine-6-carboxylic acid ethyl ester

Product 1

HCID 593025414,5,7,8-Tetrahydro-thieno[2,3-d]azepine-6-carboxylic acid ethyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

AlCl3 (3.95 g, 29.7 mmol) was added to 50 mL DCM at 0° C. Borane-t-butyl amine complex (5.2 g, 59.5 mmol) was added followed by the product of step c) (2.37 g, 9.9 mmol) dissolved in DCM (50 mL). The reaction was stirred for 2 hours at room temperature after which time another 3.95 g (29.7 mmol) of AlCl3 was added. After stirring 10 minutes, the reaction was quenched carefully with 0.1 M HCl (˜50 mL). After concentration of the organic solvent, the crude reaction mixture was partitioned between 1M HCl and EtOAc (70 mL each). The aqueous layer was back extracted 1× EtOAc. The combined organic layers were dried over MgSO4 and concentrated. The subtitle product (1.45 g) was obtained after purification by silica gel chromatography (EtOAc/Hexanes-gradient). 1H NMR (300 MHz, CDCl3) 6.96 (d, J=5 Hz, 1H), 6.76 (d, J=5 Hz, 1H), 4.18 (q, J=7 Hz, 2H), 3.52-3.78 (m, 4H), 2.78-3.08 (m, 4H), 1.28 (t, J=7 Hz, 3H). MS: ESI (positive): 226 (M+H).

Workup

  1. additionBorane-t-butyl amine complex (5.2 g, 59.5 mmol) was added
  2. additionwas added
  3. customthe reaction was quenched carefully with 0.1 M HCl (˜50 mL)
  4. customAfter concentration of the organic solvent, the crude reaction mixture
  5. customwas partitioned between 1M HCl and EtOAc (70 mL each)
  6. extractionThe aqueous layer was back extracted 1× EtOAc
  7. dry with materialThe combined organic layers were dried over MgSO4
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-4fabccf8ba054c04b6605305370e6b59
Source dataset
uspto-grants-2010_05
Patent number
US07718647B2

Reaction notes

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