Diethyl Ether → Methyl 2-(3-fluorophenyl)cyclopropanecarboxylate

HRID 2069183Notes

Reaction equation

HRID 2069183 reaction equation
[CH3:1]COCC.[F:6][C:7]1[CH:8]=[C:9](/[CH:13]=[CH:14]/[C:15]([O:17][CH3:18])=[O:16])[CH:10]=[CH:11][CH:12]=1.[N+](=C)=[N-]>CC([O-])=O.CC([O-])=O.[Pd+2].C(Cl)Cl>[F:6][C:7]1[CH:8]=[C:9]([CH:13]2[CH2:1][CH:14]2[C:15]([O:17][CH3:18])=[O:16])[CH:10]=[CH:11][CH:12]=1

Participants

6

Reactant 3

HCID 3283Diethyl EtherHCID 9550DiazomethaneHCID 13415099Methyl (E)-3-fluorocinnamate

Product 1

HCID 59414891Methyl 2-(3-fluorophenyl)cyclopropanecarboxylateYield 100%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6344DichloromethaneSolvent

Procedure

To a flame-dried round-bottom flask containing ether (50 mL) and CH2Cl2 (150 mL) was added 6 (900 mg, 5.0 mmol) and Pd(OAc)2 (5.80 mg) at 0° C. To this flask was added the freshly prepared diazomethane solution through a cannula, and then the reaction solution was slowly warmed to room temperature over a period of 30 min and allowed to stir at room temperature for an additional 2 h. The reaction mixture was washed with H2O (150 mL) and brine (150 mL) and dried over NaSO4. The solvent was removed by rotary evaporation to yield 7 as a colorless oil (965 mg, 5.0 mmol, 100%): 1H NMR (500 MHz, CDCl3) δ 1.30-1.35 (ddd, J=5.0, 7.0, 8.5 Hz, 1H), 1.60-1.66 (dt, J=5.0, 10.0 Hz, 1H), 1.90-1.94 (ddd, J=4.0, 5.0, 8.5 Hz, 1H), 2.51-2.54 (dt, J=2.5, 5.5 Hz, 1H), 3.74 (s, 3H), 6.70-6.80 (td, J=2.0, 10.0 Hz, 1H), 6.90-6.95 (m, 2H), 7.23-7.28 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 17.4, 24.4, 26.1, 52.3, 113.2, 113.4, 113.6, 113.8, 122.2, 130.1, 130.2, 142.9, 143.0, 164.2, 173.8; LCQ-MS (M+H+) calcd for C11H12FO2 195. found 195.

Workup

  1. washThe reaction mixture was washed with H2O (150 mL) and brine (150 mL)
  2. dry with materialdried over NaSO4
  3. customThe solvent was removed by rotary evaporation

Sources & evidence

ORD record
ord-d61b129119214ed4a5ec5997e4b39302
Source dataset
uspto-grants-2012_10
Patent number
US08299100B2

Reaction notes

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