Water → 2,2-Dimethyl-3-phenylcyclopropanecarbonitrile

HRID 1285520Notes

Reaction equation

HRID 1285520 reaction equation
[C:1]([C:3]1(C(OCC)=O)[CH:5]([C:6]2[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=2)[C:4]1([CH3:13])[CH3:12])#[N:2].C(=O)(O)[O-].[Na+].O>C(O)CCO>[CH3:12][C:4]1([CH3:13])[CH:5]([C:6]2[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=2)[CH:3]1[C:1]#[N:2]

Participants

5

Reactant 3

HCID 962WaterHCID 516892Sodium BicarbonateHCID 13429895Ethyl 1-Cyano-2,2-dimethyl-3-phenylcyclopropanecarboxylate

Product 1

HCID 134298982,2-Dimethyl-3-phenylcyclopropanecarbonitrileYield 95.5%

Reagents, catalysts & solvents 1

HCID 104421,3-PropanediolSolvent

Procedure

A mixture of 234 mg (0.96 mmole) of cyclopropanoid cyanoester 10 (produced in accordance with Example VIII), 174 mg (2.1 mmoles) of sodium bicarbonate, and 35 mg of water in 2.0 mL of 1,3-propanediol was heated at reflux, protected from atmospheric moisture, for 45 minutes. The product was isolated by diluting the cooled mixture with 25 mL of saturated brine and extraction with ether. The ether extracts were washed in successive order with 20 mL of 1:1 (v/v) 1M aqueous NaOH:saturated brine and 20 mL of 10% aqueous sodium chloride, dried over anhydrous magnesium sulfate, and filtered. Removal of the ether by evaporation at reduced pressure afforded 157 mg (95% yield) of nitrile 17 as a mixture of cis and trans stereoisomers, subsequently shown by NMR analysis (vinyl H absorption at approximately 5.0δ) to be accompanied by a minor amount (~10-15%) of ring-opened by-product.

Workup

  1. temperaturewas heated
  2. temperatureat reflux
  3. customThe product was isolated
  4. additionby diluting the cooled mixture
  5. extractionwith 25 mL of saturated brine and extraction with ether
  6. washThe ether extracts were washed in successive order with 20 mL of 1:1 (v/v) 1M aqueous NaOH
  7. dry with materialsaturated brine and 20 mL of 10% aqueous sodium chloride, dried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. customRemoval of the ether
  10. customby evaporation at reduced pressure

Sources & evidence

ORD record
ord-67a66320c90f47998d64811cf67715d6
Source dataset
uspto-grants-1986_01
Patent number
US04567265

Reaction notes

Loading…