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

HRID 1154397ノート

反応式

HRID 1154397 の反応式
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]

参加物

8

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒HCID 8058Hexane溶媒

反応条件

温度
-115 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-57811a99d44647248fd6bbaac4ee9a3f
出典データセット
uspto-grants-1984_12
特許番号
US04489093

反応ノート

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