Ethyl Acetate → HCID 66869304, compound

HRID 84587Notes

Reaction equation

[H-].C([Al+]CC(C)C)C(C)C.[CH3:11][C:12]1[C:22](C(O)=O)=[N:21][C:20]2[C:19]3[S:26][CH:27]=[CH:28][C:18]=3[CH2:17][CH2:16][O:15][C:14]=2[CH:13]=1.CC[O:31]C(C)=O>C1(C)C=CC=CC=1>[OH:31][CH2:11][C:12]1[CH:22]=[N:21][C:20]2[C:19]3[S:26][CH:27]=[CH:28][C:18]=3[CH2:17][CH2:16][O:15][C:14]=2[CH:13]=1

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of 1.00 M of diisobutylaluminum hydride in toluene (4.02 mL) at 0° C. was added 3-methylcarboxy-6,7-dihydropyrido[3,2-b]thieno[2,3-d]oxepine (0.420 g, 1.61 mmol) in toluene (17.8 mL, 167 mmol). The reaction mixture was stirred at 0° C. 2 h. The reaction is diluted with EtOAc then quenched with 1M HCl. The organic layer was dried Na2SO4, concentrated to give 3-hydroxymethyl-6,7-dihydropyrido[3,2-b]thieno[2,3-d]oxepine which was dissolved in triethylamine (0.336 mL, 2.41 mmol) and N,N-dimethylformamide (10.5 mL, 136 mmol). Tert-butyldimethylsilyl chloride (0.291 g, 1.93 mmol) was added. The reaction was stirred at room temperature 20 min. The reaction was diluted with EtOAc then wash with water and brine, dried and concentrated to give 3-tert-butyldimethylsilyloxymethyl-6,7-dihydropyrido[3,2-b]thieno[2,3-d]oxepine which was dissolved in DCM/Acetic acid at 0° C. N-Bromosuccinimide (315 mg, 1.77 mmol) was added. The reaction was stirred overnight at room temperature. The reaction was concentrated and purified by flash chromatography (EtOAc/Hex) (eluted 10%) to give 3-tert-butyldimethylsilyloxymethyl-9-bromo-6,7-dihydropyrido[3,2-b]thieno[2,3-d]oxepine (61.3% yield). MS: (ESI+) 426.1

Workup

custom2 h
customthen quenched with 1M HCl
concentrationconcentrated

Sources & evidence

ORD record: ord-3e7bb05657254c1aa2f257bb6428e5e0
Source dataset: uspto-grants-2014_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08846762B2

Reaction notes

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