Cyclopropanecarbonyl chloride → Ethyl 4-(cyclopropanecarbonyl)benzoate

HRID 713073

Reaction equation

HRID 713073 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-68a84cabc4444674870de6c805b18ff4
Source dataset
uspto-grants-2015_11
Patent number
US09181273B2

Linked notes

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