Diazomethane → Methyl 2-[4-(acetyloxy)phenyl]cyclopropane-1-carboxylate

HRID 1691522Notes

Reaction equation

HRID 1691522 reaction equation
[C:1]([O:4][C:5]1[CH:10]=[CH:9][C:8](/[CH:11]=[CH:12]/[C:13]([O:15][CH3:16])=[O:14])=[CH:7][CH:6]=1)(=[O:3])[CH3:2].[N+](=[CH2:19])=[N-].CN(N=O)C(N[N+]([O-])=O)=N.[OH-].[K+]>O1CCCC1.C(OCC)C.C(O)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:1]([O:4][C:5]1[CH:10]=[CH:9][C:8]([CH:11]2[CH2:19][CH:12]2[C:13]([O:15][CH3:16])=[O:14])=[CH:7][CH:6]=1)(=[O:3])[CH3:2]

Participants

9

Reactant 4

HCID 9550DiazomethaneHCID 14797Potassium HydroxideHCID 123984255226-78-3HCID 135436526N-Methyl-N'-nitro-N-nitrosoguanidine

Product 1

HCID 59364054Methyl 2-[4-(acetyloxy)phenyl]cyclopropane-1-carboxylateYield 97%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidCatalystHCID 167845palladium(II) acetateCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of methyl (2E)-3-[4-(acetyloxy)phenyl]acrylate (2.20 g, 10.0 mmol) in tetrahydrofuran (200 mL) was stirred under ice-cooling, and a solution of diazomethane, prepared from N-methyl-N′-nitro-N-nitrosoguanidine (50% water-containing product, 7.50 g, 51.0 mmol) and aqueous potassium hydroxide (6.28 g, 112 mmol) solution (10.5 mL), in diethyl ether (75 mL) and palladium(II) acetate (0.150 g, 0.668 mmol) were alternately added thereto over 10 min in small portions. The reaction mixture was stirred for 2 hr under ice-cooling, and acetic acid (3 drops) was added. The insoluble material was filtered off through celite, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane=5:95-40:60) to give the title compound (2.26 g, yield 97%) as a colorless oil.

Workup

  1. temperaturecooling
  2. temperaturecooling
  3. filtrationThe insoluble material was filtered off through celite
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. customThe residue was purified by silica gel column chromatography (ethyl acetate:hexane=5:95-40:60)

Sources & evidence

ORD record
ord-6d25ac095f1d490c9f04a384543a0daa
Source dataset
uspto-grants-2012_04
Patent number
US08153694B2

Reaction notes

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