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

HRID 1639429Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1639429
[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]

Komponenten

7

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittelHCID 8078CyclohexaneLösungsmittel

Reaktionsbedingungen

Temperatur
-65 °C

Versuchsvorschrift

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.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-8c9105a3d7b44914a22ff0a9673d73bd
Quelldatensatz
uspto-grants-1989_11
Patentnummer
US04883806

Notizen zur Reaktion

Wird geladen…