Hydrochloric Acid → 2-[3,5-dichloro-4-[1-(4-chlorophenyl)-2-oxo-2-phenylethyl]phenyl)-1,2,4-triazine-3,5(2H,4H)-dione

HRID 35562ノート

反応式

HRID 35562 の反応式
[Cl-].[Cl-].[Cl-].[Al+3].[Cl:5][C:6]1[CH:11]=[C:10]([N:12]2[C:17](=[O:18])[NH:16][C:15](=[O:19])[CH:14]=[N:13]2)[CH:9]=[C:8]([Cl:20])[C:7]=1[CH:21]([C:25]1[CH:30]=[CH:29][C:28]([Cl:31])=[CH:27][CH:26]=1)[C:22](Cl)=[O:23].Cl>C1C=CC=CC=1>[Cl:20][C:8]1[CH:9]=[C:10]([N:12]2[C:17](=[O:18])[NH:16][C:15](=[O:19])[CH:14]=[N:13]2)[CH:11]=[C:6]([Cl:5])[C:7]=1[CH:21]([C:25]1[CH:30]=[CH:29][C:28]([Cl:31])=[CH:27][CH:26]=1)[C:22](=[O:23])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

参加物

5

反応物 3

HCID 313Hydrochloric AcidHCID 6451240Aluminum(III) ChlorideHCID 225573202,6-dichloro-alpha-(4-chlorophenyl)-4(4,5-dihydro-3,5-dioxo-1,2,4-triazin-2(3H)-yl)benzeneacetylchloride

生成物 1

HCID 230351932-[3,5-dichloro-4-[1-(4-chlorophenyl)-2-oxo-2-phenylethyl]phenyl)-1,2,4-triazine-3,5(2H,4H)-dione収率 13%

試薬・触媒・溶媒 1

HCID 241Benzene溶媒2 回

反応条件

温度
10 °C

実験手順

A mixture of 4.7 parts of aluminum trichloride and 67.5 parts of benzene was stirred in an ice bath till a temperature of ±10° C. A solution of 4.9 parts of 2,6-dichloro-α-(4-chlorophenyl)-4-(4,5-dihydro-3,5-dioxo-1,2,4-triazin-2(3H)-yl)benzeneacetylchloride in 22.5 parts of benzene was added dropwise during a period of 15 minutes at this low temperature (exothermic reaction). Upon complete addition, stirring was continued for 20 hours at room temperature. The reaction mixture was poured into 500 parts of ice water and the whole was acidified with concentrated hydrochloric acid. The product was extracted with trichloromethane. The extract was dried, filtered and evaporated. The residue was purified by filtration 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. The residue was further purified three times by column chromatography over silica gel using first a mixture of trichloromethane and methanol (97:3 by volume) and then a mixture of trichloromethane and methanol (99:1 by volume) and finally a mixture of trichloromethane and ethyl acetate (92.5:7.5 by volume) as eluent. The pure fractions were collected and the eluent was evaporated in vacuo. The residue was crystallized from 8 parts of ethanol. The product was filtered off, washed with 2,2'-oxybispropane and dried, yielding 0.7 parts (13.0%) of 2-[3,5-dichloro-4-[1-(4-chlorophenyl)-2-oxo-2-phenylethyl]phenyl]-1,2,4-triazine-3,5(2H,4H)-dione; mp. 143.0° C. (intermediate 41).

後処理

  1. additionUpon complete addition
  2. stirringstirring
  3. extractionThe product was extracted with trichloromethane
  4. customThe extract was dried
  5. filtrationfiltered
  6. customevaporated
  7. filtrationThe residue was purified by filtration over silica gel using
  8. additiona mixture of trichloromethane and methanol (95:5 by volume) as eluent
  9. customThe pure fractions were collected
  10. customthe eluent was evaporated
  11. customThe residue was further purified three times by column chromatography over silica gel using first
  12. additiona mixture of trichloromethane and methanol (97:3 by volume)
  13. additiona mixture of trichloromethane and methanol (99:1 by volume)
  14. additionfinally a mixture of trichloromethane and ethyl acetate (92.5:7.5 by volume) as eluent
  15. customThe pure fractions were collected
  16. customthe eluent was evaporated in vacuo
  17. customThe residue was crystallized from 8 parts of ethanol
  18. filtrationThe product was filtered off
  19. washwashed with 2,2'-oxybispropane
  20. customdried

出典と根拠

ORDレコード
ord-414cd77a59394cfeb330baef2d43ef01
出典データセット
uspto-grants-1988_08
特許番号
US04767760

反応ノート

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