1,2-Dichloroethane → HCID 13505026, compound

HRID 1719256Notes

Reaction equation

HRID 1719256 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=O)[CH2:9][N:10]2[CH:14]=[N:13][CH:12]=[N:11]2)=[C:4]([Cl:16])[CH:3]=1.[Cl:17]P(Cl)(Cl)(Cl)Cl.ClCCCl.C(=O)([O-])[O-].[K+].[K+]>O.ClCCl>[Br:1][C:2]1[CH:7]=[CH:6][C:5](/[C:8](/[Cl:17])=[CH:9]\[N:10]2[CH:14]=[N:13][CH:12]=[N:11]2)=[C:4]([Cl:16])[CH:3]=1

Participants

7

Reactant 4

HCID 111,2-DichloroethaneHCID 11430Potassium CarbonateHCID 24819Phosphorus pentachlorideHCID 20267971HCID 20267971, compound

Product 1

HCID 13505026HCID 13505026, compoundYield 37%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of 20 parts of 1-(4-bromo-2-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone, 40 parts of pentachlorophosphorane and 300 parts of 1,2-dichloroethane was stirred and relfuxed overnight. 300 Parts of potassium carbonate and 650 parts of dichloromethane were added and water was added dropwise carefully till a volume of about 1500 parts. The aqueous phase was extracted with dichloromethane. The combined organic layers were washed with water, dried, filtered and evaporated. The residue was purified by reversed phase chromatography (HPLC) over LiChroprep RP 18 using a mixture of 75% of methanol containing 0.1% of N-(1-methylethyl)-2-propanamine and 25% of water containing 0.5% of ammonium acetate. The first fraction (E-isomer) was collected and the eluent was evaporated. The residue was crystallized from hexane at 0° C. The product was filtered off and dried in vacuo at 60° C., yielding 7.9 parts (37%) of (E)-1-[2-(4-bromo-2-chlorophenyl)-2 -chloroethenyl]-1H-1,2,4-triazole; mp. 84.0° C. (compound 44). The second fraction (Z-isomer) was collected and the eluent was evaporated. The residue was crystallized from hexane at 0° C. The product was filtered off and dried in vacuo at 60° C., yielding 0.36 parts of (Z)-1-[2-(4-bromo-2-chlorophenyl)-2-chloroethenyl]-1H-1,2,4-triazole; mp. 96.0° C. (compound 45).

Workup

  1. extractionThe aqueous phase was extracted with dichloromethane
  2. washThe combined organic layers were washed with water
  3. customdried
  4. filtrationfiltered
  5. customevaporated
  6. customThe residue was purified by reversed phase chromatography (HPLC) over LiChroprep RP 18 using
  7. additiona mixture of 75% of methanol containing 0.1% of N-(1-methylethyl)-2-propanamine and 25% of water containing 0.5% of ammonium acetate
  8. customThe first fraction (E-isomer) was collected
  9. customthe eluent was evaporated
  10. customThe residue was crystallized from hexane at 0° C
  11. filtrationThe product was filtered off
  12. customdried in vacuo at 60° C.

Sources & evidence

ORD record
ord-97df0faf6d054bbaa92042d22a3db609
Source dataset
uspto-grants-1985_09
Patent number
US04539325

Reaction notes

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