Acetic Acid → HCID 86681110, compound

HRID 1848141Notes

Reaction equation

HRID 1848141 reaction equation
[F: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])[S:14][C:10]=3[CH:9]=2)=[C:4]([N+:21]([O-])=O)[CH:3]=1.C(O)(=O)C.CO>[Zn].C(Cl)Cl>[F: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])[S:14][C:10]=3[CH:9]=2)=[CH:19][CH:20]=1

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 887MethanolHCID 86681111HCID 86681111, compound

Product 1

HCID 86681110HCID 86681110, compoundYield 88.2%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
-10 °C

Procedure

To a stirred mixture of 4-fluoro-N-((2-(methylthio)benzo[d]thiazol-6-yl)methyl)-2-nitroaniline (1.18 g, 3.3 mmol) from the previous step, acetic acid (3 mL), MeOH (3 mL) and DCM (20 mL) at −10° C. was added portionwise zinc dust (1.7 g, 26 mmol). The reaction mixture was stirred at −10° C. for 0.5 h. The mixture was poured into ice-water and extracted with EtOAc (100 mL×3). The combined organic layers were washed sequentially with water, saturated aq NaHCO3 (100 mL×2), and brine (100 mL). The organic layer was separated, dried over Na2SO4, filtered, and concentrated under reduced pressure to afford 4-fluoro-N1-((2-(methylthio)benzo[d]thiazol-6-yl)methyl)benzene-1,2-diamine (0.93 g, yield 87%) as a yellow solid, which was not purified further. 1H NMR (300 MHz, CDCl3) δ 7.82 (d, J=8.4 Hz, 1H), 7.76 (s, 1H), 7.42 (dd, J=8.4, 1.8 Hz, 1H), 6.42-6.56 (m, 3H), 4.35 (s, 2H), 3.60 (br s, 2H), 2.79 (s, 3H); LCMS (ESI) m/z 320 (M+H)+.

Workup

  1. extractionextracted with EtOAc (100 mL×3)
  2. washThe combined organic layers were washed sequentially with water, saturated aq NaHCO3 (100 mL×2), and brine (100 mL)
  3. customThe organic layer was separated
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-91fbd75490964cda8afadb829ab1de2b
Source dataset
uspto-grants-2015_02
Patent number
US08952058B2

Reaction notes

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