Hydrazinecarboxylic acid, ethyl ester → ethyl N-[(E)-1-(4-chloro-2-methylphenyl)ethylideneamino]carbamate

HRID 857795Notes

Reaction equation

HRID 857795 reaction equation
[C:1]([O:5][CH2:6][CH3:7])(=[O:4])[NH:2][NH2:3].O.C1(C)C=CC(S(O)(=O)=O)=CC=1.[Cl:20][C:21]1[CH:26]=[CH:25][C:24]([C:27](=O)[CH3:28])=[C:23]([CH3:30])[CH:22]=1>C1(C)C=CC=CC=1>[Cl:20][C:21]1[CH:26]=[CH:25][C:24](/[C:27](=[N:3]/[NH:2][C:1]([O:5][CH2:6][CH3:7])=[O:4])/[CH3:28])=[C:23]([CH3:30])[CH:22]=1

Participants

5

Reactant 3

HCID 20064Hydrazinecarboxylic acid, ethyl esterHCID 521998p-Toluenesulfonic acid monohydrateHCID 123439381-(4-Chloro-2-methylphenyl)ethan-1-one

Product 1

HCID 145779288ethyl N-[(E)-1-(4-chloro-2-methylphenyl)ethylideneamino]carbamate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Ethyl carbazate (2.970 g, 28.53 mmol) and p-toluenesulfonic acid monohydrate (4.456 g, 28.53 mmol) were added to a stirred solution of 1-(4-chloro-2-methylphenyl)ethanone (4.81 g, 28.53 mmol) in toluene (50 mL). The mixture was heated to relux in a Dean-Stark apparatus. After 2 h the solution was evaporated and the viscous red-orange oil was purified by flash chromatography on silica (eluting with an EtOAc/hexanes gradient, 5–40% EtOAc). Ethyl (2E)-2-[1-(4-chloro-2-methylphenyl)ethylidene]hydrazine carboxylate was obtained as white crystals. MS m/z=255.6; 1H NMR (CDCl3, 400 MHz) δ 1.34 (t, J=6.8 Hz, 3H), 2.20 (s, 3H), 2.35 (s, 3H), 4.31 (q, J=6.8 Hz, 2H), 7.19 (m, 3H), 7.72 (s, 1H).

Workup

  1. temperatureThe mixture was heated
  2. customAfter 2 h the solution was evaporated
  3. customthe viscous red-orange oil was purified by flash chromatography on silica (
  4. washeluting with an EtOAc/hexanes gradient, 5–40% EtOAc)

Sources & evidence

ORD record
ord-4efbafb80cc645ceabc03f6fd8a7ed8d
Source dataset
uspto-grants-2006_12
Patent number
US07144899B2

Reaction notes

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