Acetic Acid → 4-(benzyloxy)-N1-((2-(methylthio)benzo[d]thiazol-6-yl)methyl)benzene-1,2-diamine

HRID 1848160Notes

Reaction equation

[CH2:1]([O:8][C:9]1[CH:27]=[CH:26][C:12]([NH:13][CH2:14][C:15]2[CH:25]=[CH:24][C:18]3[N:19]=[C:20]([S:22][CH3:23])[S:21][C:17]=3[CH:16]=2)=[C:11]([N+:28]([O-])=O)[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC(O)=O.CO>[Zn].C(Cl)Cl>[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([NH2:28])[C:12]([NH:13][CH2:14][C:15]2[CH:25]=[CH:24][C:18]3[N:19]=[C:20]([S:22][CH3:23])[S:21][C:17]=3[CH:16]=2)=[CH:26][CH:27]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

Conditions

Temperature: 5 °C

Procedure

To a mixture of 4-(benzyloxy)-N-((2-(methylthio)benzo[d]thiazol-6-yl)methyl)-2-nitroaniline (2.8 g, 6.42 mmol) from the previous step, HOAc (7.5 mL), MeOH (7.5 mL) and DCM (50 mL) at 0° C. was added portionwise zinc dust (4.25 g, 65.4 mmol). The reaction mixture was stirred at 5° C. for 1 h. The mixture was filtered and the filtrate was diluted with DCM and washed sequentially with water and saturated aq NaHCO3. The organic layer was separated, dried over Na2SO4, filtered, and concentrated under reduced pressure to afford 4-(benzyloxy)-N1-((2-(methylthio)benzo[d]thiazol-6-yl)methyl)benzene-1,2-diamine (2.49 g, 95%) as a light orange solid which was not purified further. 1H NMR (300 MHz, CDCl3) δ 7.83 (d, J=8.4 Hz, 1H), 7.77 (s, 1H), 7.26-7.44 (m, 7H), 6.59 (d, J=8.4 Hz, 1H), 6.46 (s, 1H), 6.38 (m, 1H), 4.97 (s, 2H), 4.34 (s, 2H), 3.54 (br s, 2H), 2.80 (s, 3H). LCMS (ESI) m/z 408 (M+H)+.

Workup

filtrationThe mixture was filtered
additionthe filtrate was diluted with DCM
washwashed sequentially with water and saturated aq NaHCO3
customThe organic layer was separated
dry with materialdried over Na2SO4
filtrationfiltered
concentrationconcentrated under reduced pressure

Sources & evidence

ORD record: ord-bc56a2b0d79642a9b233c26d45bd664b
Source dataset: uspto-grants-2015_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08952058B2

Reaction notes

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