Acetic Acid → 1-[2-(2,4-Dichlorophenyl)-pentylidene]-2-methoxycarbonylhydrazine

HRID 637513Notes

Reaction equation

HRID 637513 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[CH:9]([CH2:12][CH2:13][CH3:14])[C:10]#[N:11].[CH3:15][O:16][C:17]([NH:19]N)=[O:18].C(O)(=O)C.[H][H]>[Ni].C(O)C.C(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[CH:9]([CH2:12][CH2:13][CH3:14])[CH:10]=[N:11][NH:19][C:17]([O:16][CH3:15])=[O:18]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 80519Methyl carbazateHCID 33245222-(2,4-Dichlorophenyl)pentanenitrileHCID 178418361HCID 178418361, compound

Product 1

HCID 545461481-[2-(2,4-Dichlorophenyl)-pentylidene]-2-methoxycarbonylhydrazine

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 702EthanolSolventHCID 6212ChloroformSolvent

Procedure

11.0 g of Raney nickel are added to a solution of 22.8 g (0.1 mol) of 2-(2,4-dichlorophenyl)-valeronitrile, 9.0 g (0.1 mol) of hydrazinecarboxylic acid methyl ester and 6.0 g (0.1 mol) of acetic acid in 200 ml of 95% aqueous ethanol, and the mixture is hydrogenated at room temperature under a normal pressure of hydrogen for 6.5 hours. Filtration and crystallisation yield 23.3 g (77% of theory) of the above product, which after recrystallisation from methanol has a melting point of 165°-166° C. and gives the following analytical data: IR spectrum (CHCl3) in cm-1 : 1750, 1718; 1H-NMR spectrum (250 MHz, CDCl3) 8.0 (bs, 1H, HN); 7.41 (d, J=2, 1H, H--Ar); 7.28 (s, 1H, HC=N--); 7.23 (dAB xd, JAB =8, J=2, 1H, H--Ar); 7.16 (dAB, JAB =8, 1H, H--Ar); 4.11 (q, J=7, 1H, HC(2)); 3.80 (s, 3H, H3CO--); 2.02-1.68 (m, 2H, H2C(3)); 1.40-1.10 (m, 2H, H2C (4)); 0.88 (t, J=7, 3H, H3C); mass spectrum: 304/302 (M+).

Workup

  1. filtrationFiltration and crystallisation yield 23.3 g (77% of theory) of the above product, which
  2. customafter recrystallisation from methanol
  3. customgives the following analytical data

Sources & evidence

ORD record
ord-2f88eb99ff594118867f9514131a8b54
Source dataset
uspto-grants-1985_12
Patent number
US04556717

Reaction notes

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