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

HRID 569518ノート

反応式

HRID 569518 の反応式
[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]

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8078Cyclohexane溶媒

反応条件

温度
-65 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-1e0645d9fb4a477ba6842b5639ca5152
出典データセット
uspto-grants-1988_03
特許番号
US04732903

反応ノート

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