Acetic Acid → 1R-cis-Permethrinic acid

HRID 894296노트

반응식

HRID 894296 반응식
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]

참가 물질

6

반응물 2

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

생성물 1

HCID 6736471R-cis-Permethrinic acid수율 18%

시약·촉매·용매 3

HCID 23994Zinc촉매HCID 962Water용매HCID 3283Diethyl Ether용매3회

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-efcf069f61a741b7848e0e856eb2b437
출처 데이터셋
uspto-grants-1981_08
특허 번호
US04283341

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