Diethyl Ether → 2-Methyl-3-phenylbenzyl 3-(2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropanecarboxylate

HRID 1607366Notes

Reaction equation

HRID 1607366 reaction equation
[CH3:1][C:2]1([CH3:34])[CH:4]([CH:5](OC(=O)C)[C:6](Cl)([Cl:11])[C:7]([F:10])([F:9])[F:8])[CH:3]1[C:17]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[C:23]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C:22]=1[CH3:33])=[O:18].C(OCC)C.CCCCC>CN(C=O)C.[Zn]>[CH3:1][C:2]1([CH3:34])[CH:4]([CH:5]=[C:6]([Cl:11])[C:7]([F:8])([F:9])[F:10])[CH:3]1[C:17]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[C:23]([C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)[C:22]=1[CH3:33])=[O:18]

Participants

6

Reactant 3

HCID 3283Diethyl EtherHCID 8003PentaneHCID 13933704(2-Methyl-3-phenylphenyl)methyl 2,2-dimethyl-3-(1-acetoxy-2,2-dichloro-3,3,3-trifluoro-propyl)cyclopropanecarboxylate

Product 1

HCID 549012-Methyl-3-phenylbenzyl 3-(2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropanecarboxylateYield 95%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of 38.4 mg (0.074 mmol) of the stereoisomer [RF 0.39 (CH2Cl2 /hexane=1/1)] of (2-methyl-3-phenylphenyl)methyl 2,2-dimethyl-3-(1-acetoxy-2,2-dichloro-3,3,3-trifluoro-propyl)cyclopropanecarboxylate obtained in Example 11 and dissolved in 0.3 ml of DMF, 6 mg of zinc powder was added, and the mixture was stirred at 60° C. for 2.5 hours. After an addition of 2 ml of diethyl ether and 2 ml of pentane to the mixture, the inorganic salt was filtered off through a silica gel short column. The silica gel was washed with diethyl ether, and the organic layers were combined and concentrated under reduced pressure. The product was purified by thin layer chromatography (silica gel, dichloromethane/hexane=1/2) to obtain 29.8 mg of (2-methyl-3-phenylphenyl)methyl 2,2-dimethyl-3-(2-chloro-3,3,3-trifluoro-1-propenyl)cyclopropanecarboxylate as a colorless oily substance.

Workup

  1. filtrationthe inorganic salt was filtered off through a silica gel short column
  2. washThe silica gel was washed with diethyl ether
  3. concentrationconcentrated under reduced pressure
  4. customThe product was purified by thin layer chromatography (silica gel, dichloromethane/hexane=1/2)

Sources & evidence

ORD record
ord-1d450ce8d5fd45079b87b63cb33d67fd
Source dataset
uspto-grants-1989_09
Patent number
US04864052

Reaction notes

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