Hydroquinone → Methyl (5-benzyl-3-furyl)methyl 2-vinylcyclopropane-1,1-dicarboxylate

HRID 1702218Notes

Reaction equation

HRID 1702218 reaction equation
[CH2:1]([C:8]1[O:12][CH:11]=[C:10]([CH2:13][OH:14])[CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH:15]([CH:17]1[CH2:19][C:18]1([C:24](OC)=[O:25])[C:20]([O:22][CH3:23])=[O:21])=[CH2:16].C1(C=CC(O)=CC=1)O>C([O-])(=O)C.[Ca+2].C([O-])(=O)C.C([O-])(=O)C.C([O-])(=O)C.C([Sn+2]CCCC)CCC.CO>[CH:15]([CH:17]1[CH2:19][C:18]1([C:24]([O:14][CH2:13][C:10]1[CH:9]=[C:8]([CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[O:12][CH:11]=1)=[O:25])[C:20]([O:22][CH3:23])=[O:21])=[CH2:16]

Participants

7

Reactant 3

HCID 785HydroquinoneHCID 104649921,1-Dimethyl 2-ethenylcyclopropane-1,1-dicarboxylateHCID 123643963-Furanmethanol, 5-(phenylmethyl)-

Product 1

HCID 13137096Methyl (5-benzyl-3-furyl)methyl 2-vinylcyclopropane-1,1-dicarboxylateYield 35%

Reagents, catalysts & solvents 3

HCID 6116Calcium AcetateCatalystHCID 9798523Di-n-butyl diacetoxy tinCatalystHCID 887MethanolSolvent

Procedure

Twenty grams (0.106 mol) (5-benzyl-3-furyl)carbinol was charged to a stirred glass reactor with 39 g (0.212 mol) dimethyl 2-vinylcyclopropane-1,1-dicarboxylate, 0.5 g hydroquinone, 0.5 g calcium acetate and 0.38 g dibutyltin diacetate and heated. After the temperature reached about 165° C., methanol began to distill from the reaction mixture and was collected by means of a suitable condenser-trap arrangement. When the transalcoholysis was essentially complete (3.2 g methanol collected; reaction temperature 182° C.) heating was terminated. Excess dimethyl 2-vinylcyclopropane-1,1-dicarboxylate was removed by distillation and the resulting crude light brown oil worked up to recover 12.6 g (35% yield) methyl (5-benzyl-3-furyl)methyl 2-vinylcyclopropane-1,1-dicarboxylate. B.p. 160°-162° C. at 0.018 mm Hg; nD21 1.5335. Infrared and nuclear magnetic resonance spectra were consistent with the desired structure.

Workup

  1. temperatureheated
  2. customreached about 165° C.
  3. distillationto distill from the reaction mixture
  4. customwas collected by means of a suitable condenser-trap arrangement
  5. custom(3.2 g methanol collected; reaction temperature 182° C.)
  6. temperatureheating
  7. customwas terminated
  8. customExcess dimethyl 2-vinylcyclopropane-1,1-dicarboxylate was removed by distillation

Sources & evidence

ORD record
ord-51012afcab2847dcba55530772637148
Source dataset
uspto-grants-1983_04
Patent number
US04380656

Reaction notes

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