Ethyl Acetate → 2-Fluoro-1-isocyanato-4-methoxybenzene

HRID 391708Notes

Reaction equation

HRID 391708 reaction equation
N/C(/C#N)=C(\N[C:7]([NH:9][C:10]1[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][C:11]=1[F:18])=[O:8])/C#N.FC1C=C(OC)C=CC=1N.C(Cl)(=O)OC(Cl)(Cl)Cl.CCOC(C)=O>C1(C)C=CC=CC=1>[F:18][C:11]1[CH:12]=[C:13]([O:16][CH3:17])[CH:14]=[CH:15][C:10]=1[N:9]=[C:7]=[O:8]

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 10426DiphosgeneHCID 37563832-Fluoro-4-methoxyanilineHCID 57474840(Z)-1-(2-Amino-1,2-dicyanovinyl)-3-(2-fluoro-4-methoxyphenyl)urea

Product 1

HCID 189810662-Fluoro-1-isocyanato-4-methoxybenzene

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

(Z)-1-(2-Amino-1,2-dicyanovinyl)-3-(2-fluoro-4-methoxyphenyl)urea. In a 100 mL round-bottomed flask was added 2-fluoro-4-methoxyaniline (0.79 g, 5.60 mmol) and trichloromethyl carbonochloridate (0.68 mL, 5.60 mmol) in toluene (6 mL) to give a purple suspension. The mixture was then stirred at 110° C. for 3 h. Upon heating, the suspension becomes a homogeneous solution. After 3 h, no starting material remained (TLC, 3:1 hex/EtOAc). The reaction mixture was concentrated to afford 2-fluoro-1-isocyanato-4-methoxybenzene (0.936 g, 5.6 mmol, quant.) as a green oil. The intermediate 2-fluoro-1-isocyanato-4-methoxybenzene (0.936 g, 5.6 mmol) was then dissolved in acetonitrile (20 ml) and reacted with 2,3-diaminomaleonitrile (0.605 g, 5.60 mmol) according to General Procedure A. The product was filtered to give the title compound (1.36 g, 88%). MS (ESI) m/z 276.3[M+1]+.

Workup

  1. customto give a purple suspension
  2. temperatureUpon heating
  3. waitAfter 3 h
  4. concentrationThe reaction mixture was concentrated

Sources & evidence

ORD record
ord-5e3a6766429e4f1c9ed48360326c7a38
Source dataset
uspto-grants-2013_02
Patent number
US08383634B2

Reaction notes

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