Thioglycolic Acid → 4-(4-Bromo-2-methyl-phenyl)-1-methyl-3-(2-pyridyl)-4,8-dihydropyrazolo[3,4-e][1,4]thiazepin-7-one

HRID 1748795Notes

Reaction equation

[CH3:1][N:2]1[C:6]([NH2:7])=[CH:5][C:4]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][N:9]=2)=[N:3]1.[Br:14][C:15]1[CH:22]=[CH:21][C:18]([CH:19]=O)=[C:17]([CH3:23])[CH:16]=1.[C:24](O)(=[O:27])[CH2:25][SH:26]>C(#N)C>[Br:14][C:15]1[CH:22]=[CH:21][C:18]([CH:19]2[S:26][CH2:25][C:24](=[O:27])[NH:7][C:6]3[N:2]([CH3:1])[N:3]=[C:4]([C:8]4[CH:13]=[CH:12][CH:11]=[CH:10][N:9]=4)[C:5]2=3)=[C:17]([CH3:23])[CH:16]=1

Participants

Conditions

Temperature: 150 °C

Procedure

A mixture of 1-methyl-3-(2-pyridyl)pyrazol-5-amine (1.74 g, 10 mmol), 4-bromo-2-methylbenzaldehyde (2.0 g, 10 mmol, Ark Pharm Inc.), and thioglycolic acid (3.90 g, 32 mmol) in acetonitrile (15 mL) was heated, in a sealed microwave vessel, for about 25 min, at about 150° C., in a microwave. After cooling to rt the precipitated solid was collected by filtration and washed with acetonitrile and diethyl ether to afford 4-(4-bromo-2-methyl-phenyl)-1-methyl-3-(2-pyridyl)-4,8-dihydropyrazolo[3,4-e][1,4]thiazepin-7-one (2.92 g, 6.8 mmol, 68%), which was used as such. 1H-NMR (CDCl3, Bruker 400 MHz) δ 2.56 (3H, s), 3.29 (1H, d, J=15 Hz); 3.37 (1H, d, J=15 Hz); 3.95 (3H, s); 6.58 (1H, s); 6.66 (1H, d, J=8 Hz); 7.03 (2H, m); 7.24 (1H, d, J=11 Hz); 7.56 (1H, dt, J=8 Hz, 2 Hz); 7.75 (1H, m), 8.30 (1H, d, J=4 Hz).

Workup

temperatureAfter cooling to rt the precipitated solid
filtrationwas collected by filtration
washwashed with acetonitrile and diethyl ether

Sources & evidence

ORD record: ord-b91e0412d7b041168f38b5a8eb0c9e4d
Source dataset: uspto-grants-2015_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09150592B2

Reaction notes

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