Triethylamine → Ethyl 9-bromo-4,5-dihydrobenzo[b]pyrazolo[1,5-d][1,4]oxazepine-2-carboxylate

HRID 886072Notes

Reaction equation

[CH2:1]([O:3][C:4](=[O:21])[C:5](Cl)=[N:6][NH:7][C:8]1[CH:13]=[C:12]([Br:14])[CH:11]=[CH:10][C:9]=1[O:15][CH2:16][CH2:17][C:18]#[CH:19])[CH3:2].C(N(CC)CC)C>C1(C)C=CC=CC=1>[CH2:1]([O:3][C:4]([C:5]1[CH:19]=[C:18]2[N:7]([N:6]=1)[C:8]1[CH:13]=[C:12]([Br:14])[CH:11]=[CH:10][C:9]=1[O:15][CH2:16][CH2:17]2)=[O:21])[CH3:2]

Participants

Conditions

Temperature: 120 °C

Procedure

A mixture of chloro-(5-bromo-2-but-3-ynyloxyphenylhydrazono)acetic acid ethyl ester (3.28 g, 8.78 mmol) and triethylamine (12.2 mL, 88 mmol) in dry toluene (900 mL) was heated at gentle reflux (120° C.) for 54 h. The cooled mixture was filtered, the residue washed with ethyl acetate and the filtrate concentrated in vacuo. The resultant residue was subjected to flash chromatography (SiO2, gradient 10 to 15% ethyl acetate in cyclohexane) to give 9-Bromo-4,5-dihydro-6-oxa-1,10b-diaza-benzo[e]azulene-2-carboxylic acid ethyl ester as a yellow solid (2.52 g, 85%). LCMS: RT=4.52 min, M+H+=337/339, [M+Na]+=359/361.

Workup

temperaturewas heated
filtrationThe cooled mixture was filtered
washthe residue washed with ethyl acetate
concentrationthe filtrate concentrated in vacuo

Sources & evidence

ORD record: ord-237566114a4b48e999c012062b46218a
Source dataset: uspto-grants-2012_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08242104B2

Reaction notes

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