Trichloroethanol → tert.butyl(1R,cis)2,2-dimethyl-3-(2,2,2-trichloroethoxycarbonylethynyl)-cyclopropane-carboxylate

HRID 1719740Notes

Reaction equation

HRID 1719740 reaction equation
C1(N=C=NC2CCCCC2)CCCCC1.[CH3:16][C:17]1([CH3:32])[C@@H:19]([C:20]#[C:21][C:22]([OH:24])=[O:23])[C@H:18]1[C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26].CN(C1C=CC=CN=1)C.[Cl:42][C:43]([Cl:47])([Cl:46])[CH2:44]O>C(Cl)Cl>[CH3:16][C:17]1([CH3:32])[C@@H:19]([C:20]#[C:21][C:22]([O:24][CH2:44][C:43]([Cl:47])([Cl:46])[Cl:42])=[O:23])[C@H:18]1[C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26]

Participants

6

Reactant 4

HCID 8259TrichloroethanolHCID 10868DicyclohexylcarbodiimideHCID 218852-DimethylaminopyridineHCID 13093787Tert.-butyl(1R,cis)2,2-dimethyl-3-(carboxy ethynyl)cyclopropane-carboxylate

Product 1

HCID 13093790tert.butyl(1R,cis)2,2-dimethyl-3-(2,2,2-trichloroethoxycarbonylethynyl)-cyclopropane-carboxylateYield 81.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

6.2 g of dicyclohexylcarbodiimide were introduced into a solution of 7.15 g of tert.-butyl (1R,cis) 2,2-dimethyl-3-(2-carboxyethynyl)-cyclopropane-carboxylate and 80 mg of 4 dimethylamino-pyridine in 35 ml of methylene chloride and the reaction mixture was stirred for 10 minutes after which 4.5 g of 2,2,2-trichloroethanol were added. The mixture was stirred for 1 hour and was filtered. The filtrate was washed with N hydrochloric acid, then with water until neutral, dried and evaporated to dryness. The 14 g of oil residue were chromatographed over silica gel and eluted with a 97-3 mixture of benzene-ethyl acetate to obtain 9 g of tert.butyl (1R,cis) 2,2-dimethyl-3-(2,2,2-trichloroethoxycarbonylethynyl)-cyclopropane-carboxylate melting at 70°-71° C.

Workup

  1. additionwere added
  2. filtrationwas filtered
  3. washThe filtrate was washed with N hydrochloric acid
  4. dry with materialwith water until neutral, dried
  5. customevaporated to dryness
  6. customThe 14 g of oil residue were chromatographed over silica gel
  7. washeluted with a 97-3 mixture of benzene-ethyl acetate

Sources & evidence

ORD record
ord-73a79529b2d540a8815a75693732a4c8
Source dataset
uspto-grants-1985_09
Patent number
US04542142

Reaction notes

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