Menthol → Ethyl 2-phenylcyclopropane-1-carboxylate

HRID 1682164

Reaktionsgleichung

Reaktionsgleichung von HRID 1682164
C=CC1C=CC=CC=1.[N+](=CC(OCC)=O)=[N-].[C:17]1([C@@H:23]2[CH2:25][C@H:24]2[C:26]([O:28][CH2:29][CH3:30])=[O:27])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.C1(C)CCC(C(C)C)C(O)C1.C1([C@@H]2C[C@H]2C([O-])=O)C=CC=CC=1>ClCCl>[C:17]1([CH:23]2[CH2:25][CH:24]2[C:26]([O:28][CH2:29][CH3:30])=[O:27])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Komponenten

7

Edukt 5

HCID 1254MentholHCID 7501StyreneHCID 12192Ethyl diazoacetateHCID 252496Ethyl trans-2-phenylcyclopropanecarboxylateHCID 6931403trans-2-Phenylcyclopropanecarboxylate

Produkt 1

HCID 316914Ethyl 2-phenylcyclopropane-1-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel3×

Versuchsvorschrift

To a mixture of styrene (2.15 g, 20.7 mmol) and Rh2 (4S-BNOX)4 (0.0113 g, 0.0131 mmol) in 5.0 mL of anhydrous dichloromethane was added, by syringe at room temperature, ethyl diazoacetate (0298 g, 2.62 mmol) in 3.0 mL of dichloromethane under nitrogen and at an addition rate of 0.8 mL/h (syringe pump). After addition was complete, the dichloromethane solution was passed through a plug of neutral alumina to separate the catalyst, and solvent and excess styrene were removed under reduced pressure. Gas chromatographic separation of the trans-isomer produced a material whose specific rotation was -6.4° which corresponded to an enantiomeric excess of the ethyl (1R,2R)-2-phenylcyclopropanecarboxylate. Conversion of the ethyl esters to the 1-menthyl esters by base hydrolysis, acid chloride formation, and esterification with (-)-menthol provided a gas chromatographically separable mixture that showed 25% enantiomeric excess for the (1R,2R)-enantiomer of the trans-2-phenylcyclopropanecarboxylate.

Aufarbeitung

  1. additionwas added, by syringe at room temperature
  2. additionAfter addition
  3. customto separate the catalyst, and solvent and excess styrene
  4. customwere removed under reduced pressure
  5. customGas chromatographic separation of the trans-isomer
  6. customproduced a material whose specific rotation
  7. customwas -6.4°
  8. customprovided a gas chromatographically separable mixture that

Quellen und Nachweise

ORD-Eintrag
ord-d0eb9353740b45878553496aa52e6f14
Quelldatensatz
uspto-grants-1992_12
Patentnummer
US05175311

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