Pyridine → (S)alpha-cyano-3-phenoxy-benzyl (1R,cis) 2,2-dimethyl-3-[(Z) 3-(2,2,2trifluoroethoxy)-3-oxo-1-propenyl]-cyclopropane-carboxylate

HRID 569515Notes

Reaction equation

HRID 569515 reaction equation
[CH3:1][C:2]1([CH3:18])[C@@H:4](/[CH:5]=[CH:6]\[C:7](=[O:14])[O:8][CH2:9][C:10]([F:13])([F:12])[F:11])[C@H:3]1[C:15]([OH:17])=[O:16].N1C=CC=CC=1.C1(N=C=NC2CCCCC2)CCCCC1.O[C@@H:41]([C:44]1[CH:49]=[CH:48][CH:47]=[C:46]([O:50][C:51]2[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=2)[CH:45]=1)[C:42]#[N:43]>C(Cl)Cl>[CH3:1][C:2]1([CH3:18])[C@@H:4](/[CH:5]=[CH:6]\[C:7]([O:8][CH2:9][C:10]([F:13])([F:11])[F:12])=[O:14])[C@H:3]1[C:15]([O:17][C@H:41]([C:42]#[N:43])[C:44]1[CH:49]=[CH:48][CH:47]=[C:46]([O:50][C:51]2[CH:52]=[CH:53][CH:54]=[CH:55][CH:56]=2)[CH:45]=1)=[O:16]

Participants

6

Reactant 4

HCID 1049PyridineHCID 10868DicyclohexylcarbodiimideHCID 9837437(2S)-2-hydroxy-2-(3-phenoxyphenyl)acetonitrileHCID 13390085(1R,cis)2,2-dimethyl-3-[(Z)3-oxo-3-(2,2,2-trifluoroethoxy)-1-propenyl]-cyclopropane-carboxylic acid

Product 1

HCID 13188366(S)alpha-cyano-3-phenoxy-benzyl (1R,cis) 2,2-dimethyl-3-[(Z) 3-(2,2,2trifluoroethoxy)-3-oxo-1-propenyl]-cyclopropane-carboxylateYield 57.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

1.3 g of (1R,cis)2,2-dimethyl-3-[(Z)3-oxo-3-(2,2,2-trifluoroethoxy)-1-propenyl]-cyclopropane-carboxylic acid, 0.1 ml of pyridine and 15 ml of methylene chloride were mixed with agitation and then 1.05 g of dicyclohexylcarbodiimide were added thereto. A solution of 1.35 g of (S)α-hydroxy-3-phenoxy-benzene-acetonitrile in 5 ml of methylene chloride were then added to the mixture which was stirred for 5 hours at ambient temperature and then was filtered. The filter was rinsed with methylene chloride and 2N hydrochloric acid was added to the filtrate. The decanted organic phase was washed with water, dried and evaporated to dryness. The oil residue was chromatographed over silica gel and was eluted with 95-5 cyclohexane-ethyl acetate mixture to obtain 1.33 g of (S)α-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-[(Z)3-(2,2,2-trifluoroethoxy)-3-oxo-1-propenyl]-cyclopropane-carboxylate with a specific rotation of [α]D20 =+42°±2° (c=0.7% in benzene).

Workup

  1. filtrationwas filtered
  2. washThe filter was rinsed with methylene chloride and 2N hydrochloric acid
  3. additionwas added to the filtrate
  4. washThe decanted organic phase was washed with water
  5. customdried
  6. customevaporated to dryness
  7. customThe oil residue was chromatographed over silica gel
  8. washwas eluted with 95-5 cyclohexane-ethyl acetate mixture

Sources & evidence

ORD record
ord-52b7667dd8144e7fa35f988f8fef7e4c
Source dataset
uspto-grants-1988_03
Patent number
US04732903

Reaction notes

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