Hydrochloric Acid → Ethyl [2-[[4-[(4-chlorophenyl)cyanomethyl]-3-methoxyphenyl]hydrazono]-2-cyanoacetyl]carbamate

HRID 1165841

Reaction equation

HRID 1165841 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=2)[C:9]#[N:10])=[C:4]([O:18][CH3:19])[CH:3]=1.Cl.[N:21]([O-])=O.[Na+].C([O-])(=O)C.[Na+].[C:30]([CH2:32][C:33]([NH:35][C:36](=[O:40])[O:37][CH2:38][CH3:39])=[O:34])#[N:31]>O.C(O)(=O)C>[Cl:17][C:14]1[CH:15]=[CH:16][C:11]([CH:8]([C:9]#[N:10])[C:5]2[CH:6]=[CH:7][C:2]([NH:1][N:21]=[C:32]([C:30]#[N:31])[C:33]([NH:35][C:36](=[O:40])[O:37][CH2:38][CH3:39])=[O:34])=[CH:3][C:4]=2[O:18][CH3:19])=[CH:12][CH:13]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 23112N-CyanoacetylethylcarbamateHCID 517045Sodium AcetateHCID 230351864-Amino-alpha-(4-chlorophenyl)-2-methoxybenzeneacetonitrileHCID 23668193Sodium Nitrite

Product 1

HCID 86742407Ethyl [2-[[4-[(4-chlorophenyl)cyanomethyl]-3-methoxyphenyl]hydrazono]-2-cyanoacetyl]carbamate

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×

Procedure

To a stirred and cooled (5°-10° C.) mixture of 5.6 parts of 4-amino-α-(4-chlorophenyl)-2-methoxybenzeneacetonitrile, 6.2 parts of concentrated hydrochloric acid and 50 parts of acetic acid is added dropwise, during a 15 minutes period, a solution of 1.25 parts of sodium nitrite in 10 parts of water at about 10° C. Upon completion, the whole is stirred for 60 minutes and then 3.6 parts of anhydrous sodium acetate and 2.8 parts of ethyl (2-cyanoacetyl)carbamate are added and stirring is continued for 2 hours at room temperature. The reaction mixture is poured into 250 parts of water. The product is filtered off, washed with water and dissolved in a mixture of trichloromethane and methanol (90:10by volume). The organic layer is dried, filtered and evaporated. The residue is purified by column chromatography over silica gel using a mixture of trichloromethane and methanol (95:5 by volume) as eluent. The pure fractions are collected and the eluent is evaporated in vacuo, yielding ethyl [2-[[4-[(4-chlorophenyl)cyanomethyl]-3-methoxyphenyl]hydrazono]-2-cyanoacetyl]carbamate.

Workup

  1. temperaturecooled
  2. additionis added dropwise, during a 15 minutes period
  3. customat about 10° C
  4. stirringUpon completion, the whole is stirred for 60 minutes
  5. stirringstirring
  6. filtrationThe product is filtered off
  7. washwashed with water
  8. dissolutiondissolved in a mixture of trichloromethane and methanol (90:10by volume)
  9. customThe organic layer is dried
  10. filtrationfiltered
  11. customevaporated
  12. customThe residue is purified by column chromatography over silica gel using
  13. additiona mixture of trichloromethane and methanol (95:5 by volume) as eluent
  14. customThe pure fractions are collected
  15. customthe eluent is evaporated in vacuo

Sources & evidence

ORD record
ord-b9ca5530592a46908ad600bb5774f87d
Source dataset
uspto-grants-1990_03
Patent number
US04912106

Linked notes

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