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

HRID 1154397Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1154397
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]

Komponenten

8

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 3283Diethyl EtherLösungsmittelHCID 8028TetrahydrofuranLösungsmittelHCID 8058HexaneLösungsmittel

Reaktionsbedingungen

Temperatur
-115 °C

Versuchsvorschrift

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.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-57811a99d44647248fd6bbaac4ee9a3f
Quelldatensatz
uspto-grants-1984_12
Patentnummer
US04489093

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