Dicyclohexylcarbodiimide → 3-benzyl-4-fluorobenzyl (1RS, cis)-3-(Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropanecarboxylate

HRID 1199837Notes

Reaction equation

HRID 1199837 reaction equation
C1(N=C=NC2CCCCC2)CCCCC1.[Cl:16]/[C:17](/[C:27]([F:30])([F:29])[F:28])=[CH:18]\[C@@H:19]1[C@H:21]([C:22]([OH:24])=[O:23])[C:20]1([CH3:26])[CH3:25].[CH2:31]([C:38]1[CH:39]=[C:40]([CH:43]=[CH:44][C:45]=1[F:46])[CH2:41]O)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1>ClCCl.CN(C)C1C=CN=CC=1>[Cl:16]/[C:17](/[C:27]([F:28])([F:29])[F:30])=[CH:18]\[C@@H:19]1[C@H:21]([C:22]([O:24][CH2:41][C:40]2[CH:43]=[CH:44][C:45]([F:46])=[C:38]([CH2:31][C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)[CH:39]=2)=[O:23])[C:20]1([CH3:26])[CH3:25]

Participants

6

Reactant 3

HCID 10868DicyclohexylcarbodiimideHCID 11184106(1S-cis)-Cyhalothric acidHCID 138542813-Benzyl-4-fluorobenzyl alcohol

Product 1

HCID 867437673-benzyl-4-fluorobenzyl (1RS, cis)-3-(Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropanecarboxylateYield 36.5%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

A solution of dicyclohexylcarbodiimide (0.4 g) in dichloromethane (10 cm3) was added to a stirred mixture of (1RS, cis)-3-(Z-2-chloro,3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropanecarboxylic acid (0.54 g), 3-benzyl-4-fluorobenzyl alcohol (0.43 g), 4-dimethylaminopyridine (0.02 g) and dry dichloromethane (5 cm3), and the resultant mixture stirred at the ambient temperature (ca. 20° C.) for 18 hours. The reaction mixture was then heated to the reflux temperature for 3 hours, and subsequently cooled again. The precipitate which formed was removed by filtration, and the filtrate concentrated by evaporation of the solvent under reduced pressure. The residual oil was purified by column chromatography using a silica column eluted with a mixture of ethyl acetate (1 part by volume) and petroleum ether (boiling range 60°-80° C., 19 parts by volume), to yield 3-benzyl-4-fluorobenzyl (1RS, cis)-3-(Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropanecarboxylate (0.32 g).

Workup

  1. temperatureThe reaction mixture was then heated to the reflux temperature for 3 hours
  2. temperaturesubsequently cooled again
  3. customThe precipitate which formed
  4. customwas removed by filtration
  5. concentrationthe filtrate concentrated by evaporation of the solvent under reduced pressure
  6. customThe residual oil was purified by column chromatography
  7. washeluted with a mixture of ethyl acetate (1 part by volume) and petroleum ether (boiling range 60°-80° C., 19 parts by volume)

Sources & evidence

ORD record
ord-53fb8ab458444caba6012fc5c7d54fcf
Source dataset
uspto-grants-1990_02
Patent number
US04902814

Reaction notes

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