4-Chloroaniline → Ethyl 2-chloro-2-(2-(4-chlorophenyl)hydrazono)acetate

HRID 19755

Reaction equation

HRID 19755 reaction equation
[Cl:1][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1.[N:9]([O-])=O.[Na+].CC([O-])=O.[Na+].[Cl:18][CH:19](C(=O)C)[C:20]([O:22][CH2:23][CH3:24])=[O:21]>Cl.O.C(O)C>[Cl:18][C:19](=[N:9][NH:6][C:5]1[CH:7]=[CH:8][C:2]([Cl:1])=[CH:3][CH:4]=1)[C:20]([O:22][CH2:23][CH3:24])=[O:21]

Participants

8

Reactant 4

HCID 78124-ChloroanilineHCID 11858Ethyl 2-chloroacetoacetateHCID 517045Sodium AcetateHCID 23668193Sodium Nitrite

Product 1

HCID 2761323Ethyl 2-chloro-2-(2-(4-chlorophenyl)hydrazono)acetateYield 73.4%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
2.5 °C

Procedure

Part A: To a stirred solution of 4-chloroaniline (15.68 gram, 0.123 mol) in ice (30 ml) and concentrated hydrochloric acid (30 ml) is slowly added a solution of NaNO2 (9.0 gram, 0.13 mol) in water (16 ml) and the resulting solution is stirred for 1Hour at 0-5° C. and subsequently added to a cold mixture of NaOAc (32 gram, 0.39 mol), ethanol (520 ml) and ethyl 2-chloro-3-oxobutanoate (16.6 ml, 0.12 mol). After stirring the resulting mixture for 1 hour the formed precipitate is collected by filtration, washed with ethanol and dried in vacuo to give ethyl 2-chloro[(4-chlorophenyl)hydrazono]acetate (22.99 gram, 73% yield). Melting point: 147.5-149.5° C. 1H-NMR (200 MHz, CDCl3): 1.40 (t, J=7 Hz, 3H), 4.39 (q, J=7 Hz, 2H), 7.16 (br d, J=8 Hz, 2H), 7.30 (br d, J=8 Hz, 2H), 8.31 (br s, 1H).

Workup

  1. stirringAfter stirring the resulting mixture for 1 hour the formed precipitate
  2. filtrationis collected by filtration
  3. washwashed with ethanol
  4. customdried in vacuo

Sources & evidence

ORD record
ord-a821111b5cd14d5c9654f24ee869be1c
Source dataset
uspto-grants-2010_06
Patent number
US07745476B2

Linked notes

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