Acetic Acid → 1R-cis-Permethrinic acid

HRID 894296ノート

反応式

HRID 894296 の反応式
C(O)(=O)C.[CH3:5][C:6]1([CH3:17])[C@H:11]2[C@@H:7]1[C@H:8]([C:13](Cl)([Cl:15])[Cl:14])[O:9][C:10]2=[O:12]>CCOCC.O.[Zn]>[Cl:14][C:13]([Cl:15])=[CH:8][C@H:7]1[C@@H:11]([C:10]([OH:12])=[O:9])[C:6]1([CH3:5])[CH3:17]

参加物

6

反応物 2

HCID 176Acetic AcidHCID 10538220(1R,4R,5S)-6,6-dimethyl-2-oxo-4-trichloromethyl-3-oxabicyclo[3.1.0]hexane

生成物 1

HCID 6736471R-cis-Permethrinic acid収率 18%

試薬・触媒・溶媒 3

HCID 23994Zinc触媒HCID 962Water溶媒HCID 3283Diethyl Ether溶媒3 回

実験手順

To a suspension of finely divided zinc dust (0.81 g, 1.23 mmole) in acetic acid (0.99 g, 1.64 mmole) and 4 ml of ether was added, under nitrogen, a solution of (1R,4R,5S)-6,6-dimethyl-2-oxo-4-trichloromethyl-3-oxabicyclo[3.1.0]hexane (0.50 g, 1.84 mmole) from Example IA.8.(a) in 4 ml of ether. The reaction was monitored by glpc. When the glpc results indicated almost complete conversion, the reaction mixture was diluted with additional ether and water, filtered through Celite filter aid, and the organic layer was separated, dried, and evaporated to a yellow oil which was chromatographed on two 20×20 cm preparative tlc plates with CH2Cl2 as eluent. The slow running acid band was removed, extracted with CH2Cl2, and the extract was filtered and evaporated to afford (1R,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid (68 mg, 18% isolated yield). The optical rotation of the acid prepared in a second identical run was measured; [α]D31 =+6.2 (hexane).

後処理

  1. additionwas added, under nitrogen
  2. customWhen the glpc results
  3. filtrationfiltered through Celite
  4. filtrationfilter aid
  5. customthe organic layer was separated
  6. customdried
  7. customevaporated to a yellow oil which
  8. customwas chromatographed on two 20×20 cm preparative tlc plates with CH2Cl2 as eluent
  9. customThe slow running acid band was removed
  10. extractionextracted with CH2Cl2
  11. filtrationthe extract was filtered
  12. customevaporated

出典と根拠

ORDレコード
ord-efcf069f61a741b7848e0e856eb2b437
出典データセット
uspto-grants-1981_08
特許番号
US04283341

反応ノート

読み込み中…