Hydrochloric Acid → HCID 131714993, compound

HRID 868307Notes

Reaction equation

HRID 868307 reaction equation
[NH2:1][C:2]1[C:7]([CH3:8])=[CH:6][C:5]([C:9]([C:13]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][CH:14]=2)([CH3:12])[C:10]#[N:11])=[C:4]([Cl:20])[CH:3]=1.Cl.[N:22]([O-])=O.[Na+].C([O-])(=O)C.[Na+].[C:31]([CH2:33][C:34]([NH:36][C:37](=[O:41])[O:38][CH2:39][CH3:40])=[O:35])#[N:32]>O.C(O)(=O)C>[CH2:39]([O:38][C:37](=[O:41])[NH:36][C:34](=[O:35])[C:33](=[N:22][NH:1][C:2]1[CH:3]=[C:4]([Cl:20])[C:5]([C:9]([C:13]2[CH:14]=[CH:15][C:16]([Cl:19])=[CH:17][CH:18]=2)([C:10]#[N:11])[CH3:12])=[CH:6][C:7]=1[CH3:8])[C:31]#[N:32])[CH3:40]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 23112N-CyanoacetylethylcarbamateHCID 517045Sodium AcetateHCID 21288227HCID 21288227, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 131714993HCID 131714993, compoundYield 74.1%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×

Procedure

To a stirred and cooled (5°-10° C.) mixture of 15.2 parts of 4-amino-2-chloro-α-(4-chlorophenyl)-α,5-dimethylbenzeneacetonitrile, 14.4 parts of concentrate hydrochloric acid and 125 parts of acetic acid was added dropwise, during a 30 minutes period, a solution of 3.5 parts of sodium nitrite in 15 parts of water at about 10° C. Upon completion, the whole was stirred for 30 minutes and then 10 parts of sodium acetate and 7.8 parts of ethyl (2-cyanoacetyl)carbamate were added, during a period of 2 hours, at room temperature. The reaction mixture was poured into 500 parts of water. The product was filtered off, washed with water and dissolved in dichloromethane. The organic layer was dried, filtered and evaporated. The residue was purified by column chromatography over silica gel using a mixture of trichloromethane and methanol (95:5 by volume) as eluent. The pure fractions were collected and the eluent was evaporated in vacuo. The residue was stirred in 2-propanol. The product was filtered off, washed with 2,2'-oxybispropane and dried, yielding 17.5 parts (74.1%) of ethyl[2-[[5-chloro-4-[1-(4-chlorophenyl)-1-cyanoethyl]-2-methylphenyl]hydrazono]-2-cyanoacetyl]carbamate (intermediate 44).

Workup

  1. temperaturecooled
  2. additionwas added dropwise, during a 30 minutes period
  3. customat about 10° C
  4. stirringUpon completion, the whole was stirred for 30 minutes
  5. filtrationThe product was filtered off
  6. washwashed with water
  7. dissolutiondissolved in dichloromethane
  8. customThe organic layer was dried
  9. filtrationfiltered
  10. customevaporated
  11. customThe residue was purified by column chromatography over silica gel using
  12. additiona mixture of trichloromethane and methanol (95:5 by volume) as eluent
  13. customThe pure fractions were collected
  14. customthe eluent was evaporated in vacuo
  15. stirringThe residue was stirred in 2-propanol
  16. filtrationThe product was filtered off
  17. washwashed with 2,2'-oxybispropane
  18. customdried

Sources & evidence

ORD record
ord-f464a9ea90ef4fd7b4d0c7b8de9056bc
Source dataset
uspto-grants-1988_10
Patent number
US04778887

Reaction notes

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