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

HRID 464450Notes

Reaction equation

HRID 464450 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].[Cl:33][C:34]([Cl:38])([Cl:37])[CH2:35]O>CN(C1C=CC=CN=1)C.C(Cl)Cl>[CH3:16][C:17]1([CH3:32])[C@@H:19]([C:20]#[C:21][C:22]([O:24][CH2:35][C:34]([Cl:38])([Cl:37])[Cl:33])=[O:23])[C@H:18]1[C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26]

Participants

6

Reactant 3

HCID 8259TrichloroethanolHCID 10868DicyclohexylcarbodiimideHCID 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 2

HCID 218852-DimethylaminopyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

A mixture of 6.2 g of dicyclohexylcarbodiimide, 7.15 g of tert.-butyl(1R,cis)2,2-dimethyl-3-(2-carboxyethynyl)-cyclopropane-carboxylate, 80 mg of dimethylaminopyridine and 35 ml of methylene chloride was stirred for 10 minutes and 4.5 g of 2,2,2-trichloroethanol were added thereto. The mixture was stirred for one hour and was filtered and the filtrate was washed with N hydrochloric acid and then with water until the wash water was neutral, dried and evaporated to dryness. The 14 g of oil residue were chromatographed over silica gel and eluted with a 97-3 benzeneethyl acetate mixture to obtain 9 g of tert.-butyl(1R,cis)2,2-dimethyl-3-[2,2,2-trichloroethoxycarbonyl-ethynyl]-cyclopropane-carboxylate melting at 70°-71° C.

Workup

  1. stirringThe mixture was stirred for one hour
  2. filtrationwas filtered
  3. washthe filtrate was washed with N hydrochloric acid
  4. customdried
  5. customevaporated to dryness
  6. customThe 14 g of oil residue were chromatographed over silica gel
  7. washeluted with a 97-3 benzeneethyl acetate mixture

Sources & evidence

ORD record
ord-47acb165439743e5bbb4b44331bcbf19
Source dataset
uspto-grants-1985_10
Patent number
US04547522

Reaction notes

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