Propyl chloroformate → tert.-butyl (1R,cis) 2,2-dimethyl-3(Z)-[2-bromo-2-propyloxycarbonyl-ethenyl]-cyclopropane-1-carboxylate

HRID 1154397노트

반응식

HRID 1154397 반응식
C([Li])CCC.[CH3:6][C:7]1([CH3:21])[C@@H:9]([CH:10]=[C:11]([Br:13])Br)[C@H:8]1[C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15].Cl[C:23]([O:25][CH2:26][CH2:27][CH3:28])=[O:24].P(O)(O)([O-])=O.[Na+]>CCCCCC.O1CCCC1.CCOCC>[CH3:21][C:7]1([CH3:6])[C@@H:9](/[CH:10]=[C:11](\[Br:13])/[C:23]([O:25][CH2:26][CH2:27][CH3:28])=[O:24])[C@H:8]1[C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15]

참가 물질

8

반응물 4

HCID 7998Propyl chloroformateHCID 12807744tert-butyl(1R,cis)2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropane-carboxylateHCID 23672064Monosodium phosphateHCID 178418339Butyllithium

생성물 1

HCID 86739795tert.-butyl (1R,cis) 2,2-dimethyl-3(Z)-[2-bromo-2-propyloxycarbonyl-ethenyl]-cyclopropane-1-carboxylate

시약·촉매·용매 3

HCID 3283Diethyl Ether용매HCID 8028Tetrahydrofuran용매HCID 8058Hexane용매

반응 조건

온도
-115 °C

실험 절차

50 ml of a solution of 16N butyllithium in hexane were added over 25 minutes at -115° C. to a solution of 28.3 g of tert-butyl (1R,cis) 2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropane-1-carboxylate in 120 ml of tetrahydrofuran and 120 ml of ether and after stirring the mixture at -115° C. for 15 minutes, 10 ml of n-propyl chloroformate were progressively added thereto. The mixture was stirred at -115° C. for 20 minutes, at -65° C. for one hour and was poured into an aqueous monosodium phosphate solution. The mixture was extracted with ether and the organic phase was washed with water, dried and evaporated to dryness under reduced pressure. The residue was chromatographed over silica gel and was eluted with a 95-5 cyclohexane-ethyl acetate mixture to obtain 3.52 g of tert.-butyl (1R,cis) 2,2-dimethyl-3(Z)-[2-bromo-2-propyloxycarbonyl-ethenyl]-cyclopropane-1-carboxylate and 3.16 g of the corresponding 3(E)-isomer.

후처리

  1. stirringThe mixture was stirred at -115° C. for 20 minutes, at -65° C. for one hour
  2. extractionThe mixture was extracted with ether
  3. washthe organic phase was washed with water
  4. customdried
  5. customevaporated to dryness under reduced pressure
  6. customThe residue was chromatographed over silica gel
  7. washwas eluted with a 95-5 cyclohexane-ethyl acetate mixture

출처 및 근거

ORD 기록
ord-57811a99d44647248fd6bbaac4ee9a3f
출처 데이터셋
uspto-grants-1984_12
특허 번호
US04489093

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