Pyridine → 2-(4-Chlorophenyloxy)-2-methylpropyl 2-[4-(4-chlorophenyl)benzyloxy]-3,3,3-trifluoro-2-trifluoromethylpropionate

HRID 973304Notes

Reaction equation

HRID 973304 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:27]=[CH:26][C:11]([CH2:12][O:13][C:14]([C:22]([F:25])([F:24])[F:23])([C:18]([F:21])([F:20])[F:19])[C:15](Cl)=[O:16])=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.[Cl:28][C:29]1[CH:34]=[CH:33][C:32]([O:35][C:36]([CH3:40])([CH3:39])[CH2:37][OH:38])=[CH:31][CH:30]=1.N1C=CC=CC=1.C(Cl)(Cl)Cl>ClCCCl>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[CH:10][C:11]([CH2:12][O:13][C:14]([C:18]([F:19])([F:20])[F:21])([C:22]([F:23])([F:24])[F:25])[C:15]([O:38][CH2:37][C:36]([O:35][C:32]3[CH:31]=[CH:30][C:29]([Cl:28])=[CH:34][CH:33]=3)([CH3:40])[CH3:39])=[O:16])=[CH:26][CH:27]=2)=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 1049PyridineHCID 6212ChloroformHCID 191086602-(4-Chlorophenoxy)-2-methylpropan-1-olHCID 203144652-[4-(4-Chlorophenyl)benzyloxy]-3,3,3-trifluoro-2-trifluoromethylpropionyl chloride

Product 1

HCID 536972952-(4-Chlorophenyloxy)-2-methylpropyl 2-[4-(4-chlorophenyl)benzyloxy]-3,3,3-trifluoro-2-trifluoromethylpropionateYield 62.6%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent2×

Procedure

A solution of 2-[4-(4-chlorophenyl)benzyloxy]-3,3,3-trifluoro-2-trifluoromethylpropionyl chloride (3.16 g.) in 1,2-dichloroethane (10 ml.) is added, dropwise and below 10° C., to a stirred mixture of 2-(4-chlorophenyloxy)-2-methylpropanol (1.40 g.), pyridine (4.0 ml.), and 1,2-dichloroethane (10 ml.). The mixture is stirred at ambient temperature for 20 hours, then mixed with ice-water and chloroform. The organic phase is separated, and washed with 3N-hydrochloric acid and water. 0.4N-Aqueous potassium hydroxide (5 ml.) and ice are added, the mixture is shaken, and enough ether is added to cause the resulting emulsion to separate into two layers. The organic layer is washed with water, dried and evaporated. The residual oil (3.6 g.) is chromatographed in light petroleum (b.p. 60°-80° C.) on a column of silica gel (45 g.). The column is washed portionwise the solvent (2 l ) until no more material is eluted, and then with a mixture of light petroleum and ether (10:1, 200 ml.). This eluate is evaporated to give 2-(4-chlorophenyloxy)-2-methylpropyl 2-[4-(4-chlorophenyl)benzyloxy]-3,3,3-trifluoro-2-trifluoromethylpropionate (2.6 g.) as a syrup.

Workup

  1. customThe organic phase is separated
  2. washwashed with 3N-hydrochloric acid and water
  3. addition0.4N-Aqueous potassium hydroxide (5 ml.) and ice are added
  4. stirringthe mixture is shaken
  5. additionenough ether is added
  6. customto separate into two layers
  7. washThe organic layer is washed with water
  8. customdried
  9. customevaporated
  10. customThe residual oil (3.6 g.) is chromatographed in light petroleum (b.p. 60°-80° C.) on a column of silica gel (45 g.)
  11. washThe column is washed portionwise the solvent (2 l ) until no more material
  12. washis eluted
  13. additionwith a mixture of light petroleum and ether (10:1, 200 ml.)
  14. customThis eluate is evaporated

Sources & evidence

ORD record
ord-6e6f441a78104bbaa817215fc5e23366
Source dataset
uspto-grants-1977_10
Patent number
US04055595

Reaction notes

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