2,2,2-Trifluoroethanol → 1,1-dimethylethyl (1R,cis) 2,2-dimethyl-3-[3-oxo-3-(2,2,2-trifluoroethoxy)-1-propynyl]-cyclopropane-carboxylate

HRID 569513Notes

Reaction equation

HRID 569513 reaction equation
[CH3:1][C:2]1([CH3:17])[C@@H:4]([C:5]#[C:6][C:7]([OH:9])=[O:8])[C@H:3]1[C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11].C1(N=C=NC2CCCCC2)CCCCC1.[CH2:33](O)[C:34]([F:37])([F:36])[F:35]>C(Cl)Cl.N1C=CC=CC=1>[CH3:1][C:2]1([CH3:17])[C@@H:4]([C:5]#[C:6][C:7](=[O:9])[O:8][CH2:33][C:34]([F:37])([F:36])[F:35])[C@H:3]1[C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11]

Participants

6

Reactant 3

HCID 64092,2,2-TrifluoroethanolHCID 10868DicyclohexylcarbodiimideHCID 13093787Tert.-butyl(1R,cis)2,2-dimethyl-3-(carboxy ethynyl)cyclopropane-carboxylate

Product 1

HCID 133900811,1-dimethylethyl (1R,cis) 2,2-dimethyl-3-[3-oxo-3-(2,2,2-trifluoroethoxy)-1-propynyl]-cyclopropane-carboxylateYield 65.1%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent2×

Procedure

4 g of the product of Step A and 3.5 g of dicyclohexylcarbodiimide were added to a solution of 20 ml of methylene chloride and 1 ml of pyridine and the reaction mixture was stirred for 1 hour. 2.15 g of trifluoroethanol and 5 ml of methylene chloride were then added to the mixture which was stirred at 20° C. for 16 hours and was filtered. The filtrate was rinsed with methylene chloride and the filtrate was evaporated to dryness. The residue was taken up in ether and the solution was washed with N hydrochloric acid, then with water and dried and evaporated to dryness. The 5 g of residue was chromatographed over silica gel and was eluted with a 95-5 benzene-ethyl acetate mixture to obtain 3.5 g of 1,1-dimethylethyl(1R,cis)2,2-dimethyl-3-[3-oxo-3-(2,2,2-trifluoroethoxy)-1-propynyl]-cyclopropane-carboxylate.

Workup

  1. stirringwas stirred at 20° C. for 16 hours
  2. filtrationwas filtered
  3. washThe filtrate was rinsed with methylene chloride
  4. customthe filtrate was evaporated to dryness
  5. washthe solution was washed with N hydrochloric acid
  6. dry with materialwith water and dried
  7. customevaporated to dryness
  8. customThe 5 g of residue was chromatographed over silica gel
  9. washwas eluted with a 95-5 benzene-ethyl acetate mixture

Sources & evidence

ORD record
ord-37fd190e206548c795dd707e15529dc8
Source dataset
uspto-grants-1988_03
Patent number
US04732903

Reaction notes

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