p-Toluenesulfonic acid → 4-(4-chlorophenyl)-5-(2,4-dichlorophenyl)-2,2-dimethyl-4-(1H-1,2,4-triazol-1-yl)methyl-1,3-dioxolane

HRID 65024Notes

Reaction equation

HRID 65024 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([OH:25])([CH2:19][N:20]2[CH:24]=[N:23][CH:22]=[N:21]2)[CH:9]([C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][C:12]=2[Cl:18])[OH:10])=[CH:4][CH:3]=1.CO[C:28](OC)([CH3:30])[CH3:29].C1(C)C=CC(S(O)(=O)=O)=CC=1.C(=O)([O-])O.[Na+]>CC(C)=O.CN(C)C=O.[Cl-].[Zn+2].[Cl-].C(Cl)Cl>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2([CH2:19][N:20]3[CH:24]=[N:23][CH:22]=[N:21]3)[CH:9]([C:11]3[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][C:12]=3[Cl:18])[O:10][C:28]([CH3:30])([CH3:29])[O:25]2)=[CH:4][CH:3]=1

Participants

9

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 64952,2-DimethoxypropaneHCID 516892Sodium BicarbonateHCID 202350372-(4-chlorophenyl)-1-(2,4-dichlorophenyl)-3-(1H-1,2,4-triazol-1-yl)-1,2-propanediol

Product 1

HCID 137270184-(4-chlorophenyl)-5-(2,4-dichlorophenyl)-2,2-dimethyl-4-(1H-1,2,4-triazol-1-yl)methyl-1,3-dioxolaneYield 20%

Reagents, catalysts & solvents 4

HCID 3007855ZincchlorideCatalystHCID 180AcetoneSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 500 mg of 2-(4-chlorophenyl)-1-(2,4-dichlorophenyl)-3-(1H-1,2,4-triazol-1-yl)-1,2-propanediol in a mixture of 20 ml of acetone and 1 ml of dimethylformamide are added 2 ml of 2,2-dimethoxypropane, 100 mg of p-toluenesulfonic acid and about 50 mg of zinc chloride, and the resultant mixture is refluxed for 68 hours. The reaction mixture is poured into cold aqueous sodium hydrogencarbonate solution, and the mixture is shaken with methylene chloride. The organic layer is washed with water, dried over anhydrous sodium sulfate and concentrated. The residue is chromatographed on a column of silica gel, which is eluted with benzene and ethyl acetate (1:1 v/v). The eluate is concentrated and the residue is washed with isopropyl ether to give 110 mg of 4-(4-chlorophenyl)-5-(2,4-dichlorophenyl)-2,2-dimethyl-4-(1H-1,2,4-triazol-1-yl)methyl-1,3-dioxolane as crystals melting at 141° to 142° C. The yield is 20%.

Workup

  1. washThe organic layer is washed with water
  2. dry with materialdried over anhydrous sodium sulfate
  3. concentrationconcentrated
  4. customThe residue is chromatographed on a column of silica gel, which
  5. washis eluted with benzene and ethyl acetate (1:1 v/v)
  6. concentrationThe eluate is concentrated
  7. washthe residue is washed with isopropyl ether

Sources & evidence

ORD record
ord-e894c45f2e7a49f8854aec7befac582f
Source dataset
uspto-grants-1986_09
Patent number
US04612322

Reaction notes

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