Ammonium Chloride → HCID 23035203, 화합물

HRID 1710037노트

반응식

HRID 1710037 반응식
[CH3:1]C(=O)C.C(=O)=O.C[Li].[Cl:10][C:11]1[CH:16]=[C:15]([N:17]2[C:22](=[O:23])[NH:21][C:20](=[O:24])[CH:19]=[N:18]2)[CH:14]=[C:13]([Cl:25])[C:12]=1[CH:26]([C:30]1[CH:35]=[CH:34][C:33]([Cl:36])=[CH:32][CH:31]=1)[C:27](Cl)=[O:28].[Cl-].[NH4+]>O(CC)CC.O.[Cu]I.O1CCCC1>[Cl:25][C:13]1[CH:14]=[C:15]([N:17]2[C:22](=[O:23])[NH:21][C:20](=[O:24])[CH:19]=[N:18]2)[CH:16]=[C:11]([Cl:10])[C:12]=1[CH:26]([C:30]1[CH:35]=[CH:34][C:33]([Cl:36])=[CH:32][CH:31]=1)[C:27](=[O:28])[CH3:1]

참가 물질

9

반응물 4

HCID 25517Ammonium ChlorideHCID 18522661Acetone cardiceHCID 225573202,6-dichloro-alpha-(4-chlorophenyl)-4(4,5-dihydro-3,5-dioxo-1,2,4-triazin-2(3H)-yl)benzeneacetylchlorideHCID 178418348HCID 178418348, 화합물

생성물 1

HCID 23035203HCID 23035203, 화합물수율 18.8%

시약·촉매·용매 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 962Water용매HCID 3283Diethyl Ether용매HCID 8028Tetrahydrofuran용매2회

실험 절차

To a stirred and cooled (-70° C., 2-propanone/CO2 bath) solution of 5.7 parts of copper(I) iodide in 67.5 parts of tetrahydrofuran were added dropwise 37.5 parts of a methyllithium solution 1.6 M in 1,1'-oxybisethane during a period of 15 minutes under nitrogen atmosphere. Upon complete addition, stirring was continued for 30 minutes at this low temperature. A mixture of 4.45 parts of 2,6-dichloro-α-(4-chlorophenyl)-4-(4,5-dihydro-3,5-dioxo-1,2,4-triazin-2(3H)-yl)benzeneacetyl chloride and 22.5 parts of tetrahydrofuran was added dropwise during a period of 30 minutes at -65° C. Upon completion, stirring was continued first for 2 hours at -60° C. and then for 1 hour at -20° C. A saturated ammonium chloride solution in water was added dropwise (exothermic reaction). The precipitate was filtered off and from the filtrate, the organic layer was dried, filtered and evaporated. The residue was purified three times by column chromatography over silica gel: twice using a mixture of trichloromethane and methanol (95:5 and 98:2 by volume) and then a mixture of trichloromethane and ethyl acetate (92.5:7.5 by volume) as eluents. The pure fractions were collected and the eluent was evaporated in vacuo. The residue was stirred in acetonitrile. The product was filtered off, washed with 2,2'-oxybispropane and dried, yielding 0.8 parts (18.8%) of 2-[3,5-dichloro-4-[1-(4-chlorophenyl)-2-oxopropyl]phenyl]-1,2,4-triazine-3,5(2H,4H)-dione; mp. 208.4° C. (intermediate 42).

후처리

  1. additionUpon complete addition
  2. stirringstirring
  3. additionwas added dropwise during a period of 30 minutes at -65° C
  4. stirringUpon completion, stirring
  5. waitwas continued first for 2 hours at -60° C.
  6. waitfor 1 hour at -20° C
  7. custom(exothermic reaction)
  8. filtrationThe precipitate was filtered off and from the filtrate
  9. customthe organic layer was dried
  10. filtrationfiltered
  11. customevaporated
  12. customThe residue was purified three times by column chromatography over silica gel
  13. additiona mixture of trichloromethane and methanol (95:5 and 98:2 by volume)
  14. additiona mixture of trichloromethane and ethyl acetate (92.5:7.5 by volume) as eluents
  15. customThe pure fractions were collected
  16. customthe eluent was evaporated in vacuo
  17. stirringThe residue was stirred in acetonitrile
  18. filtrationThe product was filtered off
  19. washwashed with 2,2'-oxybispropane
  20. customdried

출처 및 근거

ORD 기록
ord-0783c8943cc54da7a724d0153db4b675
출처 데이터셋
uspto-grants-1990_08
특허 번호
US04952570

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