p-Toluenesulfonic acid → Methyl 1-(spiro[benzo[d][1,3]dioxole-2,1'-cyclobutane]-5-yl)cyclopropanecarboxylate

HRID 1908387Notes

Reaction equation

HRID 1908387 reaction equation
[CH3:1][O:2][C:3]([C:5]1([C:8]2[CH:13]=[CH:12][C:11]([OH:14])=[C:10]([OH:15])[CH:9]=2)[CH2:7][CH2:6]1)=[O:4].CC1C=[CH:19][C:20](S(O)(=O)=O)=[CH:21][CH:22]=1.C1(=O)CCC1>C1(C)C=CC=CC=1>[C:19]12([O:14][C:11]3[CH:12]=[CH:13][C:8]([C:5]4([C:3]([O:2][CH3:1])=[O:4])[CH2:7][CH2:6]4)=[CH:9][C:10]=3[O:15]1)[CH2:20][CH2:21][CH2:22]2

Participants

5

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 14496CyclobutanoneHCID 59129280Methyl 1-(3,4-dihydroxyphenyl)cyclopropanecarboxylate

Product 1

HCID 59129386Methyl 1-(spiro[benzo[d][1,3]dioxole-2,1'-cyclobutane]-5-yl)cyclopropanecarboxylateYield 461%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 1-(3,4-dihydroxy-phenyl)-cyclopropanecarboxylic methyl ester (1.0 g, 4.8 mmol) in toluene (30 mL) was added TsOH (0.10 g, 0.50 mmol) and cyclobutanone (0.70 g, 10 mmol). The reaction mixture was heated at reflux for 2 h before being concentrated under vacuum. The residue was purified by chromatography on silica gel (petroleum ether/ethyl acetate 15:1) to give methyl 1-(spiro[benzo[d][1,3]dioxole-2,1′-cyclobutane]-5-yl)cyclopropanecarboxylate (0.6 g, 50%). 1H NMR (CDCl3 300 MHz) δ 6.78-6.65 (m, 3H), 3.62 (s, 3H), 2.64-2.58 (m, 4H), 1.89-1.78 (m, 2H), 1.56-1.54 (m, 2H), 1.53-1.12 (m, 2H).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 2 h
  3. concentrationbefore being concentrated under vacuum
  4. customThe residue was purified by chromatography on silica gel (petroleum ether/ethyl acetate 15:1)

Sources & evidence

ORD record
ord-bc68aa5467a84a00933e662ccd4d115f
Source dataset
uspto-grants-2013_12
Patent number
US08598181B2

Reaction notes

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