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

HRID 35552

Reaction equation

HRID 35552 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 (90:10 by 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 (90:10 by 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-71c354cbd49542b2a5ed7741864d4e67
Source dataset
uspto-grants-1988_08
Patent number
US04767760

Linked notes

Loading…