Cyclopropanecarbonyl chloride → Ethyl 4-(cyclopropanecarbonyl)benzoate

HRID 72988

Reaction equation

HRID 72988 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH:11]=[CH:10][C:9]([Zn]I)=[CH:8][CH:7]=1)=[O:5])[CH3:2].[CH:14]1([C:17](Cl)=[O:18])[CH2:16][CH2:15]1>C1COCC1.Cl[Pd](Cl)(P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH:14]1([C:17]([C:9]2[CH:10]=[CH:11][C:6]([C:4]([O:3][CH2:1][CH3:2])=[O:5])=[CH:7][CH:8]=2)=[O:18])[CH2:16][CH2:15]1

Participants

5

Reactant 2

HCID 77637Cyclopropanecarbonyl chlorideHCID 178469117HCID 178469117, compound

Product 1

HCID 24724092Ethyl 4-(cyclopropanecarbonyl)benzoateYield 78.4%

Reagents, catalysts & solvents 2

HCID 178479802HCID 178479802, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

(4-Ethoxycarbonylphenyl)-iodo-zinc (20 mL of 0.5 M in THF, 10.0 mmol) was added over 10 min to dichloro-bis(triphenylphosphoranyl)palladium (211 mg, 0.3 mmol) in THF (20 mL) under an atmosphere of nitrogen at 0° C. The reaction mixture was stirred for 15 minutes, cyclopropanecarbonyl chloride (941 mg, 817 μL, 9.0 mmol) was added dropwise at 0° C. and stirred for 2 hours. The reaction mixture was quenched with 1M HCl (20 mL), extracted with ethyl acetate (2×50 mL). The organic layer was washed sequentially with sat. aq. NaHCO3 (5 mL) and brine solution (50 mL), dried over MgSO4 and purified by silica gel column chromatography using 0-30% EtOAc/hexanes as eluent to give ethyl 4-(cyclopropanecarbonyl)benzoate (1.54 g, 71%) as a pale yellow oil. ESI-MS m/z calc. 218.0. Found 219.3 (M+1)+; Retention time: 1.57 minutes (3 min run).

Workup

  1. stirringstirred for 2 hours
  2. customThe reaction mixture was quenched with 1M HCl (20 mL)
  3. extractionextracted with ethyl acetate (2×50 mL)
  4. washThe organic layer was washed sequentially with sat. aq. NaHCO3 (5 mL) and brine solution (50 mL)
  5. dry with materialdried over MgSO4
  6. custompurified by silica gel column chromatography

Sources & evidence

ORD record
ord-6a3194c2b1bd4f3480dc376d7f732f5c
Source dataset
uspto-grants-2014_09
Patent number
US08828996B2

Linked notes

Loading…