3-Furanmethanol → Methyl (3-furyl)methyl 2-vinylcyclopropane-1,1-dicarboxylate

HRID 1702219Notes

Reaction equation

HRID 1702219 reaction equation
[CH:1]([CH:3]1[CH2:5][C:4]1([C:10]([O:12][CH3:13])=[O:11])[C:6]([O:8][CH3:9])=[O:7])=[CH2:2].[O:14]1[CH:18]=[CH:17][C:16](CO)=[CH:15]1>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:1]([CH:3]1[CH2:5][C:4]1([C:10]([O:12][CH2:13][C:16]1[CH:17]=[CH:18][O:14][CH:15]=1)=[O:11])[C:6]([O:8][CH3:9])=[O:7])=[CH2:2]

Participants

7

Reactant 2

HCID 204493-FuranmethanolHCID 104649921,1-Dimethyl 2-ethenylcyclopropane-1,1-dicarboxylate

Product 1

HCID 13137097Methyl (3-furyl)methyl 2-vinylcyclopropane-1,1-dicarboxylateYield 57.4%

Reagents, catalysts & solvents 4

HCID 785HydroquinoneCatalystHCID 6116Calcium AcetateCatalystHCID 9798523Di-n-butyl diacetoxy tinCatalystHCID 887MethanolSolvent

Procedure

Dimethyl 2-vinylcyclopropane-1,1-dicarboxylate (79.5 g; 0.432 mol) was combined with 21.2 g (0.216 mol) (3-furyl)carbinol and heated to 165°-183° C. in the presence of 1.0 g hydroquinone, 1.0 g calcium acetate and 0.75 g dibutyltin diacetate. When the transalcoholysis was essentially complete, as determined by the amount of methanol recovered, heating was terminated. Gas chromatographic analysis of the reaction mixture confirmed that essentially all of the (3-furyl)carbinol was consumed. The reaction mixture was diluted with an equal volume of ethyl ether, filtered to remove insoluble catalyst residue and vacuum distilled to recover 31 g (57.4% yield) crude methyl (3-furyl)methyl 2-vinylcyclopropane-1,1-dicarboxylate. B.p. 97°-105° C. at 0.018 mm Hg. Infrared and nuclear magnetic resonance spectra were consistent with the desired structure.

Workup

  1. customrecovered
  2. temperatureheating
  3. customwas terminated
  4. customwas consumed
  5. additionThe reaction mixture was diluted with an equal volume of ethyl ether
  6. filtrationfiltered
  7. customto remove insoluble catalyst residue and vacuum
  8. distillationdistilled

Sources & evidence

ORD record
ord-f8147c682f2e4055b22855b4454c0ae4
Source dataset
uspto-grants-1983_04
Patent number
US04380656

Reaction notes

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