Methyl chloroformate → tert.-butyl(1R,cis)2,2-dimethyl-3-[2-(methoxy carbonyl)-ethynyl]-cyclopropane-carboxylate

HRID 464445노트

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HRID 464445 반응식
[CH3:1][C:2]1([CH3:16])[C@@H:4]([CH:5]=[C:6](Br)Br)[C@H:3]1[C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10].C([Li])CCC.Cl[C:23]([O:25][CH3:26])=[O:24].P(O)(O)([O-])=O.[Na+]>C1CCCCC1.O1CCCC1>[CH3:1][C:2]1([CH3:16])[C@@H:4]([C:5]#[C:6][C:23]([O:25][CH3:26])=[O:24])[C@H:3]1[C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10]

참가 물질

7

반응물 4

HCID 6586Methyl chloroformateHCID 12807744tert-butyl(1R,cis)2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropane-carboxylateHCID 23672064Monosodium phosphateHCID 178418339Butyllithium

생성물 1

HCID 12807746tert.-butyl(1R,cis)2,2-dimethyl-3-[2-(methoxy carbonyl)-ethynyl]-cyclopropane-carboxylate

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매HCID 8078Cyclohexane용매

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온도
-70 °C

실험 절차

55 g of tert-butyl(1R,cis)2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropane-carboxylate were introduced into 550 cm3 of tetrahydrofuran and the mixture was cooled to -70° C. 132 cm3 of a 20% solution of butyllithium in cyclohexane were added over 40 minutes to the mixture which was stirred for 30 minutes at -65° C. 12.5 cm3 of methyl chloroformate were then added thereto and after 2 hours reaction at -70° C., the temperature was allowed to rise again to -20° C. The mixture was poured into an aqueous solution of monosodium phosphate and the mixture was extracted with ether. The organic phase was washed, dried and evaporated to dryness under reduced pressure. 38.3 g of the residue were chromatographed over silica gel and was eluted with an 8-2 cyclohexane-ethyl acetate mixture to obtain 17.2 g of tert.-butyl(1R,cis)2,2-dimethyl-3-[2-(methoxy carbonyl)-ethynyl]-cyclopropane-carboxylate.

후처리

  1. customafter 2 hours reaction at -70° C.
  2. customto rise again to -20° C
  3. extractionthe mixture was extracted with ether
  4. washThe organic phase was washed
  5. customdried
  6. customevaporated to dryness under reduced pressure
  7. custom38.3 g of the residue were chromatographed over silica gel
  8. washwas eluted with an 8-2 cyclohexane-ethyl acetate mixture

출처 및 근거

ORD 기록
ord-041ef04e3009439f83e17c73be2b2c6d
출처 데이터셋
uspto-grants-1985_10
특허 번호
US04547522

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