Hydrochloric Acid → HCID 131720911, compound

HRID 355360Notes

Reaction equation

HRID 355360 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([CH:9]([C:12]2[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][CH:13]=2)[C:10]#[N:11])=[C:4]([Cl:19])[CH:3]=1.Cl.[N:21]([O-])=O.[Na+].C([O-])(=O)C.[Na+].[CH2:30]([O:32][C:33](=[O:40])[NH:34][C:35](=[O:39])[CH2:36][C:37]#[N:38])[CH3:31]>O.C(O)(=O)C>[CH2:30]([O:32][C:33](=[O:40])[NH:34][C:35](=[O:39])[C:36](=[N:21][NH:1][C:2]1[CH:3]=[C:4]([Cl:19])[C:5]([CH:9]([C:12]2[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][CH:13]=2)[C:10]#[N:11])=[C:6]([Cl:8])[CH:7]=1)[C:37]#[N:38])[CH3:31]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 23112N-CyanoacetylethylcarbamateHCID 517045Sodium AcetateHCID 15068435(4-Amino-2,6-dichlorophenyl)(4-chlorophenyl)acetonitrile2×HCID 23668193Sodium Nitrite

Product 1

HCID 131720911HCID 131720911, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×

Procedure

To a stirred and cooled (5-10 degrees C) mixture of 15.2 parts of 4-amino-2,6-dichloro-α-(4-chlorophenyl)-benzeneacetonitrile (intermediate 2), 14.4 parts of concentrate hydrochloric acid and 125 parts of acetic acid is added dropwise, during a 30 minutes period, a solution of 3.5 parts of sodium nitrite in 15 parts of water at about 10 degrees C. Upon completion, the whole is stirred for 30 minutes and then 10 parts of sodium acetate and 7.8 parts of ethyl(2-cyanoacetyl)carbamate are added, during a period of 2 hours, at room temperature. The reaction mixture is poured into 500 parts of water. The product is filtered off, washed with water and dissolved in dichloromethane. 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. The residue is stirred in 2-propanol. The product is filtered off, washed with 2,2'-oxybispropane and dried, yielding ethyl[2-[[3,5-dichloro-4-[(4-chlorophenyl)cyanomethyl]phenyl]hydrazono]-2-cyanoacetyl]carbamate (intermediate 3).

Workup

  1. temperaturecooled
  2. additionis added dropwise, during a 30 minutes period
  3. customat about 10 degrees C
  4. stirringUpon completion, the whole is stirred for 30 minutes
  5. filtrationThe product is filtered off
  6. washwashed with water
  7. dissolutiondissolved in dichloromethane
  8. customThe organic layer is dried
  9. filtrationfiltered
  10. customevaporated
  11. customThe residue is 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 are collected
  14. customthe eluent is evaporated in vacuo
  15. stirringThe residue is stirred in 2-propanol
  16. filtrationThe product is filtered off
  17. washwashed with 2,2'-oxybispropane
  18. customdried

Sources & evidence

ORD record
ord-0d95f4f2b70444fb9f1b10efe3ac07a5
Source dataset
uspto-grants-1998_11
Patent number
US05830893

Reaction notes

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