1,2-Dichloroethane → N,1-dimethyl-5-nitro-1H-1,3-benzodiazol-2-amine

HRID 852949Notes

Reaction equation

HRID 852949 reaction equation
[CH3:1][NH:2][C:3]1[C:4]([NH2:12])=[CH:5][C:6]([N+:9]([O-:11])=[O:10])=[CH:7][CH:8]=1.[CH3:13][N:14]=[C:15]=S.C(Cl)CCl>N1C=CC=CC=1>[CH3:13][NH:14][C:15]1[N:2]([CH3:1])[C:3]2[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[CH:5][C:4]=2[N:12]=1

Participants

5

Reactant 3

HCID 111,2-DichloroethaneHCID 11167Methyl isothiocyanateHCID 34200251-N-methyl-4-nitrobenzene-1,2-diamine

Product 1

HCID 53396494N,1-dimethyl-5-nitro-1H-1,3-benzodiazol-2-amineYield 62.4%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
80 °C

Procedure

A solution of diamine 248 (1.88 g, 11.2 mmol) in pyridine (20 mL) was treated with methyl isothiocyanate (970 mg, 12.9 mmol) and the mixture was stirred at 80° C. for 30 minutes, cooled down to 15° C., treated with solid EDC (3.03 g, 15.8 mmol, 1.40 eq) and the heating continued at 80° C. for 16 h. After removal of pyridine in vacuo, the residue was purified by flash chromatography (eluent 5% MeOH in CH2Cl2) to afford the title compound 268 (1.44 g, 62% yield). 1H NMR: (CD3OD) δ (ppm): 8.12 (d, J=2.2 Hz, 1H), 7.94 (dd, J=2.2, 8.8 Hz, 1H), 7.04 (d, J=8.8 Hz, 1H), 4.44 (bs, 2H), 3.51 (s, 3H), 3.04 (s, 3H). LRMS: (calc.) 206.2; (obt.) 207.1 (MH)+.

Workup

  1. temperaturecooled down to 15° C.
  2. waitthe heating continued at 80° C. for 16 h
  3. customAfter removal of pyridine in vacuo
  4. customthe residue was purified by flash chromatography (eluent 5% MeOH in CH2Cl2)

Sources & evidence

ORD record
ord-3faec59ff25b48aa8f42812e6082df4e
Source dataset
uspto-grants-2007_08
Patent number
US07253204B2

Reaction notes

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