Bromine → 5-(Benzyloxy)-7-bromobenzo[d]thiazol-2-amine

HRID 712150Notes

Reaction equation

[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([NH:16][C:17]([NH2:19])=[S:18])[CH:12]=[C:13]([Br:15])[CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.BrBr>C(#N)C>[CH2:1]([O:8][C:9]1[CH:14]=[C:13]([Br:15])[C:12]2[S:18][C:17]([NH2:19])=[N:16][C:11]=2[CH:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

Conditions

Temperature: 2.5 °C

Procedure

To an ice-cold suspension of (3-benzyloxy-5-bromo-phenyl)thiourea (372 g, 1.10 mol) in acetonitrile (6 L) was added dropwise a solution of bromine (65 mL 1.26 mol in 50 mL acetonitrile) over a period of 30 min. The reaction mixture was stirred for 30 min at 0-5° C. then slowly allowed to come to rt, whereby a solid precipitated out. The resulting mixture was stirred at rt for 1 h. After completion of reaction (by TLC), the solid was filtered off and washed extensively with hexane (2×3 L). The solid residue was taken up in ice water, basified with aq. NH3 (pH 10-12) and stirred for 30 min at 5-10° C. The resulting solid was filtered off washed with water and dried under high vacuum to obtain the desired product (216 g, 59%). 1H-NMR (DMSO-d6): δ 5.12 (s, 2H), 6.92 (d, J=2.40 Hz, 1H), 6.98 (d, J=2.0 Hz, 1H), 7.30-7.45 (m, 5H) and 7.69 (br s, 2H). LCMS: 334.79 [M+H]+.

Workup

customto come to rt
customwhereby a solid precipitated out
stirringThe resulting mixture was stirred at rt for 1 h
customAfter completion of reaction (by TLC)
filtrationthe solid was filtered off
washwashed extensively with hexane (2×3 L)
stirringstirred for 30 min at 5-10° C
filtrationThe resulting solid was filtered off
washwashed with water
customdried under high vacuum

Sources & evidence

ORD record: ord-144a1e7b32a1443388be15a859589b1d
Source dataset: uspto-grants-2015_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09181234B2

Reaction notes

Loading…