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

HRID 1848168Notes

Reaction equation

HRID 1848168 reaction equation
[CH3:1][O:2][C:3]1[CH:21]=[CH:20][C:6]([NH:7][CH2:8][C:9]2[CH:19]=[CH:18][C:12]3[N:13]=[C:14]([S:16][CH3:17])[O:15][C:11]=3[CH:10]=2)=[C:5]([N+:22]([O-])=O)[CH:4]=1.CC(O)=O.CO>C(Cl)Cl.[Zn]>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([NH2:22])[C:6]([NH:7][CH2:8][C:9]2[CH:19]=[CH:18][C:12]3[N:13]=[C:14]([S:16][CH3:17])[O:15][C:11]=3[CH:10]=2)=[CH:20][CH:21]=1

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 887MethanolHCID 866811364-methoxy-N-((2-(methylthio)benzo[d]oxazol-6-yl)methyl)-2-nitroaniline

Product 1

HCID 866811384-methoxy-N1-((2-(methylthio)benzo[d]oxazol-6-yl)methyl)benzene-1,2-diamineYield 79.1%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 4-methoxy-N-((2-(methylthio)benzo[d]oxazol-6-yl)methyl)-2-nitroaniline (1.07 g, 3.11 mmol), HOAc (3.7 mL) and MeOH (3.7 mL) in DCM (40 mL) at 0° C. was added zinc dust (2.02 g, 31.1 mmol) portionwise. After stirring for 2 h, the mixture was filtered. The filtrate was washed with aq NaHCO3 and brine, dried over Na2SO4 and concentrated under reduced pressure to give 4-methoxy-N1-((2-(methylthio)benzo[d]oxazol-6-yl)methyl)benzene-1,2-diamine (775 mg, 79.1%). 1H NMR (300 MHz, DMSO-d6) δ 7.60 (s, 1H), 7.55 (d, J=8.4 Hz, 1H), 7.35 (d, J=9.6 Hz, 1H), 6.26 (d, J=8.1 Hz, 1H), 6.21 (s, 1H), 5.97 (d, J=9.0 Hz, 2H), 4.74 (t, 1H), 4.68 (s, 1H), 4.31 (d, J=5.7 Hz, 1H), 3.55 (s, 3H), 2.74 (s, 3H). LCMS (ESI) m/z 316 (M+H)+.

Workup

  1. filtrationthe mixture was filtered
  2. washThe filtrate was washed with aq NaHCO3 and brine
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-0859264febf940629309cb4a760a8b62
Source dataset
uspto-grants-2015_02
Patent number
US08952058B2

Reaction notes

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