Phenyl chloroformate → 1,1-dimethylethyl(1R,cis)2,2-dimethyl-3-[3-oxo-3-phenoxy-1-propynyl]-cyclopropane-carboxylate

HRID 1719737노트

반응식

HRID 1719737 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][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)=[O:24].P(O)(O)([O-])=O.[Na+]>O1CCCC1.C1CCCCC1>[CH3:1][C:2]1([CH3:16])[C@@H:4]([C:5]#[C:6][C:23](=[O:24])[O:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@H:3]1[C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10]

참가 물질

7

반응물 4

HCID 15891Phenyl chloroformateHCID 12807744tert-butyl(1R,cis)2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropane-carboxylateHCID 23672064Monosodium phosphateHCID 178418339Butyllithium

생성물 1

HCID 539041751,1-dimethylethyl(1R,cis)2,2-dimethyl-3-[3-oxo-3-phenoxy-1-propynyl]-cyclopropane-carboxylate

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매HCID 8078Cyclohexane용매

반응 조건

온도
-65 °C

실험 절차

A solution of 25 g of 1,1-dimethylethyl (1R,cis) 2,2 dimethyl-3-(2',2'-dibromovinyl)-cyclopropane-carboxylate in 250 ml of tetrahydrofuran was admixed with 48 ml of a 20% solution of butyllithium in cyclohexane with stirring at -65° C. and the mixture was stirred for one hour at -65° C. 9.6 ml of phenyl chloroformate were added to mixture which was then stirred at -65° C. for one hour. The temperature was allowed to return to room temperature while the stirring was maintained and the mixture was poured into a saturated aqueous solution of monosodium phosphate. The mixture was extracted with ether and the ether phase was washed with water and dried. The 24.6 g of oil residue was chromatographed over silica gel and was eluted with a 9-1 cyclohexane ethyl acetate mixture to obtain 14.4 g of 1,1-dimethylethyl (1R,cis) 2,2-dimethyl-3-[3-oxo-3-phenoxy-1-propynyl]-cyclopropane-carboxylate.

후처리

  1. stirringthe mixture was stirred for one hour at -65° C
  2. stirringwas then stirred at -65° C. for one hour
  3. customto return to room temperature while the stirring
  4. temperaturewas maintained
  5. extractionThe mixture was extracted with ether
  6. washthe ether phase was washed with water
  7. customdried
  8. customThe 24.6 g of oil residue was chromatographed over silica gel
  9. washwas eluted with a 9-1 cyclohexane ethyl acetate mixture

출처 및 근거

ORD 기록
ord-7a38a19695994d10ad910abc23b87fd1
출처 데이터셋
uspto-grants-1985_09
특허 번호
US04542142

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