Pivaloyl chloride → 2-(2,2-Dimethyl-propionyl)-4,5,7,8-tetrahydro-thieno[2,3-d]azepine-6-carboxylic acid ethyl ester

HRID 1019613Notes

Reaction equation

[CH2:1]([O:3][C:4]([N:6]1[CH2:12][CH2:11][C:10]2[CH:13]=[CH:14][S:15][C:9]=2[CH2:8][CH2:7]1)=[O:5])[CH3:2].[CH3:16][C:17]([CH3:22])([CH3:21])[C:18](Cl)=[O:19].[Al+3].[Cl-].[Cl-].[Cl-]>ClC(Cl)C>[CH2:1]([O:3][C:4]([N:6]1[CH2:12][CH2:11][C:10]2[CH:13]=[C:14]([C:18](=[O:19])[C:17]([CH3:22])([CH3:21])[CH3:16])[S:15][C:9]=2[CH2:8][CH2:7]1)=[O:5])[CH3:2]

Participants

Conditions

Temperature: 0 °C

Procedure

A solution of the product from Example 1, step (d) (160 mg, 0.71 mmol) in dichloroethane (5 ml) at 0° C. was treated with trimethyl acetyl chloride (0.17 ml, 1.42 mmol) and AlCl3 (190 mg, 1.42 mmol). The reaction mixture was allowed to stir at 0° C. for 30 minutes and then allowed to warm to room temperature. The reaction mixture was quenched by the addition of saturated solution of NaHCO3 (30 ml) and extracted with dichloromethane (3×30 ml). The combined organic extracts were washed with brine (50 ml), dried (MgSO4), and solvent evaporated in vacuo to give a tan oil. The crude oil was purified by silica gel chromatography (0% to 50% EtOAc in Hex) to give the subtitle compound as a clear oil (60 mg, 27%). MS: ESI (positive): 310 (M+H).

Workup

temperatureto warm to room temperature
customThe reaction mixture was quenched by the addition of saturated solution of NaHCO3 (30 ml)
extractionextracted with dichloromethane (3×30 ml)
washThe combined organic extracts were washed with brine (50 ml)
dry with materialdried (MgSO4), and solvent
customevaporated in vacuo
customto give a tan oil
customThe crude oil was purified by silica gel chromatography (0% to 50% EtOAc in Hex)

Sources & evidence

ORD record: ord-b82514e60dc14b628e9f70ebc7e974af
Source dataset: uspto-grants-2014_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08716276B2

Reaction notes

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