2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → Methyl-(2-methyl-thiazolo[4,5-h]quinazolin-8-yl)-(3-nitro-phenyl)-amine

HRID 2102792Notes

Reaction equation

HRID 2102792 reaction equation
[CH3:1][N:2]([C:12]1[N:21]=[CH:20][C:19]2[CH2:18][CH2:17][C:16]3[N:22]=[C:23]([CH3:25])[S:24][C:15]=3[C:14]=2[N:13]=1)[C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([N+:9]([O-:11])=[O:10])[CH:4]=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C1(C)C=CC=CC=1>[CH3:1][N:2]([C:12]1[N:21]=[CH:20][C:19]2[CH:18]=[CH:17][C:16]3[N:22]=[C:23]([CH3:25])[S:24][C:15]=3[C:14]=2[N:13]=1)[C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([N+:9]([O-:11])=[O:10])[CH:4]=1

Participants

4

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 11451037Methyl-(2-methyl-4,5-dihydro-thiazolo[4,5-h]quinazolin-8-yl)-(3-nitro-phenyl)-amine

Product 1

HCID 11268167Methyl-(2-methyl-thiazolo[4,5-h]quinazolin-8-yl)-(3-nitro-phenyl)-amineYield 68%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Under dry conditions, a mixture of methyl-(2-methyl-4,5-dihydro-thiazolo[4,5-h]quinazolin-8-yl)-(3-nitro-phenyl)-amine (16 mg, 0.045 mmol) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (10.2 mg, 0.045 mmol) in dry toluene (2 mL) was heated under reflux for 16 h. The solvent was evaporated under vacuum and the residue was purified by flash column chromatography (10% EtOAc:hexane) to afford the title product as a yellow solid (10 mg, 68%). mp 209-210° C. Anal. RP-HPLC: tR 23.4 min (10-70% MeCN, purity 98%). 1H-NMR (CDCl3): δ 9.09 (s, 1H, Py-H), 8.41 (t, 1H, J 2.3, Ph-H), 8.09 (ddd, 1H, J 8.2, 2.3, 1.0, Ph-H), 7.85 (d, 1H, J 8.7, Ph-H), 7.79 (ddd, 1H, J 8.2, 2.3, 1.0, Ph-H), 7.72 (d, 1H, J 8.7, Ph-H), 7.58 (t, 1H, J 8.2, Ph-H), 3.78 (s, 3H, N—CH3), 2.94 (s, 3H, Me). 13C-NMR (CDCl3): δ 171.04, 161.09, 158.53, 157.16, 148.54, 148.04, 146.25, 131.74, 129.31, 125.29, 121.01, 119.85, 119.30, 116.97, 38.39, 20.48 missing 1 quat signal. MS (ESI+): m/z 352.08 (M+H)+.

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 16 h
  3. customThe solvent was evaporated under vacuum
  4. customthe residue was purified by flash column chromatography (10% EtOAc:hexane)

Sources & evidence

ORD record
ord-ed06486bed274b629e6228b45c807cae
Source dataset
uspto-grants-2009_08
Patent number
US07576091B2

Reaction notes

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