P-Anisidine → 3-(2,5-Dichlorophenyl)-4-(4-methoxyphenyl)-5-[4-(octyloxy)phenyl]-4H-1,2,4-triazole

HRID 11187

Reaction equation

HRID 11187 reaction equation
C(Cl)Cl.CN(C=O)C.[Cl:9][C:10]1[CH:36]=[CH:35][C:34]([Cl:37])=[CH:33][C:11]=1[C:12]([NH:14][NH:15][C:16](=O)[C:17]1[CH:22]=[CH:21][C:20]([O:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])=[CH:19][CH:18]=1)=O.[CH3:38][O:39][C:40]1[CH:45]=[CH:44][C:43]([NH2:46])=[CH:42][CH:41]=1.P(Cl)(Cl)Cl>ClC1C=CC=CC=1Cl>[Cl:9][C:10]1[CH:36]=[CH:35][C:34]([Cl:37])=[CH:33][C:11]=1[C:12]1[N:46]([C:43]2[CH:44]=[CH:45][C:40]([O:39][CH3:38])=[CH:41][CH:42]=2)[C:16]([C:17]2[CH:22]=[CH:21][C:20]([O:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])=[CH:19][CH:18]=2)=[N:15][N:14]=1

Participants

6

Reactant 4

HCID 7732P-AnisidineHCID 24387Phosphorus trichlorideHCID 219820862,5-dichloro-N'-[4-(octyloxy)benzoyl]benzohydrazideHCID 22350042dichloromethane N,N-dimethylformamide

Product 1

HCID 219821043-(2,5-Dichlorophenyl)-4-(4-methoxyphenyl)-5-[4-(octyloxy)phenyl]-4H-1,2,4-triazoleYield 34%

Reagents, catalysts & solvents 1

HCID 72391,2-DichlorobenzeneSolvent

Conditions

Temperature
180 °C

Procedure

Into a 1L round-bottomed flask fitted with a mechanical stirrer, reflux condenser and nitrogen inlet were introduced 2,5-dichloro-N′-[4-(octyloxy)benzoyl]benzohydrazide (40 g, 0.09146 mole, 1 equivalent), p-anisidine (67.60 g, 0.5487 mole, 6 equivalents) and 300 mL 1,2-dichlorobenzene. Mechanical stirring resulted in partial solvation of the solids. Phosphorus trichloride (12.56 g, 0.0146 mole, 1 equivalent) was added and the contents of the flask heated at 180° C. for 12 hrs. The solvent was distilled off under a light vacuum and the residue transferred to a 2L flask with 1L of a 1:1 acetone/heptane mixture. The solid material was filtered off and dissolved in acetone. Enough heptane was added to precipitate a purple-colored oily sludge. Heptane dilution of a test sample of the acetone/heptane layer ensured that the oily sludge had been completely precipitated. The acetone/heptane layer was decanted off and diluted further with a large excess of heptane to precipitate a white solid. This was filtered off, dissolved in acetone and re-precipitated with heptane. Filtration and drying gave 3-(2,5-dichlorophenyl)-4-(4-methoxyphenyl)-5-[4-(octyloxy)phenyl]-4H-1,2,4-triazole (8) (16.25 g, 34% yield).

Workup

  1. temperaturereflux condenser and nitrogen inlet
  2. customresulted in partial solvation of the solids
  3. distillationThe solvent was distilled off under a light vacuum
  4. filtrationThe solid material was filtered off
  5. dissolutiondissolved in acetone
  6. additionEnough heptane was added
  7. customto precipitate a purple-colored oily sludge
  8. customhad been completely precipitated
  9. customThe acetone/heptane layer was decanted off
  10. additiondiluted further with a large excess of heptane
  11. customto precipitate a white solid
  12. filtrationThis was filtered off
  13. dissolutiondissolved in acetone
  14. customre-precipitated with heptane
  15. filtrationFiltration
  16. customdrying

Sources & evidence

ORD record
ord-62b08a787a1c47d9ad468eaa7c37bca6
Source dataset
uspto-grants-2006_08
Patent number
US07094902B2

Linked notes

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