3-chloro-4-[chloro(4-chlorophenyl)methyl]phenyl-1,2,4-triazine-3,5(2H,4H)-dione → Clazuril

HRID 1249370Notes

Reaction equation

HRID 1249370 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([N:17]2[C:22](=[O:23])[NH:21][C:20](=[O:24])[CH:19]=[N:18]2)[CH:5]=[CH:6][C:7]=1[CH:8](Cl)[C:9]1[CH:14]=[CH:13][C:12]([Cl:15])=[CH:11][CH:10]=1.[Cu](C#N)[C:26]#[N:27]>ClC(Cl)Cl.CO>[Cl:1][C:2]1[CH:3]=[C:4]([N:17]2[C:22](=[O:23])[NH:21][C:20](=[O:24])[CH:19]=[N:18]2)[CH:5]=[CH:6][C:7]=1[CH:8]([C:9]1[CH:14]=[CH:13][C:12]([Cl:15])=[CH:11][CH:10]=1)[C:26]#[N:27]

Participants

5

Reactant 2

HCID 225573573-chloro-4-[chloro(4-chlorophenyl)methyl]phenyl-1,2,4-triazine-3,5(2H,4H)-dioneHCID 178418260HCID 178418260, compound

Product 1

HCID 58901ClazurilYield 11.2%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6212ChloroformSolvent

Conditions

Temperature
180 °C

Procedure

A mixture of 12 parts of 2-[3-chloro-4-[chloro(4-chlorophenyl)methyl]phenyl]-1,2,4-triazine-3,5(2H,4H)-dione and 5.4 parts of copper cyanide was stirred and heated first for 3 hours at 130° C. and for 3 hours at 180° C. After cooling, the precipitated product was dissolved in a mixture of trichloromethane and methanol (90:10 by volume). The inorganic precipitate was filtered off and the filtrate was evaporated in vacuo. The residue was purified four times by column chromatography over silica gel using first a mixture of trichloromethane and acetonitrile (90:10 by volume), second a mixture of tetrachloromethane and methanol (93:7 by volume) and then twice a mixture of tetrachloromethane and acetonitrile (95:5 by volume) as eluent. The pure fractions were collected and the eluent was evaporated. The residue was further purified by column chromatography (HPLC) over silica gel using a mixture of trichloromethane and methanol (98:2 by volume) as eluent. The pure fractions were collected and the eluent was evaporated in vacuo. The residue was dried, yielding 1.3 parts (11.2%) of 2-chloro-α-(4-chlorophenyl)-4-(4,5-dihydro-3,5-dioxo-1,2,4-triazin-2(3H)-yl)benzeneacetonitrile; mp. 196.8° C. (compound 22).

Workup

  1. temperatureAfter cooling
  2. filtrationThe inorganic precipitate was filtered off
  3. customthe filtrate was evaporated in vacuo
  4. customThe residue was purified four times by column chromatography over silica gel using first
  5. additiona mixture of trichloromethane and acetonitrile (90:10 by volume), second
  6. additiona mixture of tetrachloromethane and methanol (93:7 by volume)
  7. additiontwice a mixture of tetrachloromethane and acetonitrile (95:5 by volume) as eluent
  8. customThe pure fractions were collected
  9. customthe eluent was evaporated
  10. customThe residue was further purified by column chromatography (HPLC) over silica gel using
  11. additiona mixture of trichloromethane and methanol (98:2 by volume) as eluent
  12. customThe pure fractions were collected
  13. customthe eluent was evaporated in vacuo
  14. customThe residue was dried

Sources & evidence

ORD record
ord-503cd09ba71d42f180bf41ce74a52d6c
Source dataset
uspto-grants-1986_12
Patent number
US04631278

Reaction notes

Loading…