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

HRID 464445ノート

反応式

HRID 464445 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][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]

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8078Cyclohexane溶媒

反応条件

温度
-70 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-041ef04e3009439f83e17c73be2b2c6d
出典データセット
uspto-grants-1985_10
特許番号
US04547522

反応ノート

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