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

HRID 1848205Notes

Reaction equation

HRID 1848205 reaction equation
[Br:1][C:2]1[CH:20]=[CH:19][C:5]([NH:6][CH2:7][C:8]2[CH:18]=[CH:17][C:11]3[N:12]=[C:13]([S:15][CH3:16])[O:14][C:10]=3[CH:9]=2)=[C:4]([N+:21]([O-])=O)[CH:3]=1.CC(O)=O.CO>C(Cl)Cl.[Zn]>[Br:1][C:2]1[CH:3]=[C:4]([NH2:21])[C:5]([NH:6][CH2:7][C:8]2[CH:18]=[CH:17][C:11]3[N:12]=[C:13]([S:15][CH3:16])[O:14][C:10]=3[CH:9]=2)=[CH:19][CH:20]=1

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 887MethanolHCID 866811794-bromo-N-((2-(methylthio)benzo[d]oxazol-6-yl)methyl)-2-nitroaniline

Product 1

HCID 866811804-bromo-N1-((2-(methylthio)benzo[d]oxazol-6-yl)methyl)benzene-1,2-diamineYield 71.9%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 4-bromo-N-((2-(methylthio)benzo[d]oxazol-6-yl)methyl)-2-nitroaniline (704 mg, 1.79 mmol), HOAc (2.1 mL) and methanol (2.1 mL) in DCM (18 mL) at 0° C. was added zinc dust (1.16 g, 17.9 mmol) portionwise. After stirring for 2 h, the mixture was filtered. The filtrate was washed with aq NaHCO3 and brine. The organic layer was dried over NaSO4, filtered and concentrated under reduced pressure to give 4-bromo-N1-((2-(methylthio)benzo[d]oxazol-6-yl)methyl)benzene-1,2-diamine (469 mg, 71.9%) as a yellow solid. 1H NMR (300 MHz, DMSO-d6) δ 7.72-7.60 (m, 2H), 7.53 (d, J=5.4 Hz, 1H), 6.68 (s, 1H), 6.49 (d, J=1.8 Hz, 1H), 6.23 (d, J=8.1 Hz, 1H), 5.36 (t, 1H), 4.90 (s, 2H), 4.38 (d, J=6.0 Hz, 2H), 2.74 (s, 3H). LCMS (ESI) m/z 365 (M+H)+.

Workup

  1. filtrationthe mixture was filtered
  2. washThe filtrate was washed with aq NaHCO3 and brine
  3. dry with materialThe organic layer was dried over NaSO4
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-5c08b2e064074c11b307a7f5c5da5eff
Source dataset
uspto-grants-2015_02
Patent number
US08952058B2

Reaction notes

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