P-Toluenesulfonylhydrazide → 1,2-Di-(methoxycarbonyl)-4-ethylidene-cyclohexane

HRID 846861Notes

Reaction equation

HRID 846861 reaction equation
[C:1]([C:4]1[CH2:5][CH:6]([C:14]([O:16][CH3:17])=[O:15])[CH:7]([CH2:12][CH:13]=1)[C:8]([O:10][CH3:11])=[O:9])(=O)[CH3:2].S(NN)(C1C=CC(C)=CC=1)(=O)=O>C(O)C>[CH3:11][O:10][C:8]([CH:7]1[CH2:12][CH2:13][C:4](=[CH:1][CH3:2])[CH2:5][CH:6]1[C:14]([O:16][CH3:17])=[O:15])=[O:9]

Participants

4

Reactant 2

HCID 15303P-ToluenesulfonylhydrazideHCID 13453483Dimethyl 1,2,3,6-tetrahydro-4-acetyl-phthalate

Product 1

HCID 540253811,2-Di-(methoxycarbonyl)-4-ethylidene-cyclohexaneYield 80%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

17 g of dimethyl 1,2,3,6-tetrahydro-4-acetyl-phthalate, prepared as described in Example 1, was refluxed in anhydrous ethanol with 14.6 g of tosylhydrazine. After removal of the solvent, 24 g of dimethyl 1,2,3,6-tetrahydro-4-(1-tosylhydrazono-ethyl)-phthalate (IV) crystallized from water: m.p. 162°-163° C. m/z 408 (M+.). This compound was dissolved in chloroform, and treated at 0° C. with 14 ml of catechol borane. Sodium acetate was added to the reaction mixture, which was then refluxed. After washing with water, the solvent was evaporated off and the residue was purified by chromatography on a column of silica gel giving 10 g of the title compound (yield 80%): m/z 226 (M+.); PMR (CDCl3): inter alia δ 1.6 (d, J=8 Hz, CH3 --CH=), 5.3 (q, J=8 Hz, CH3 --CH=).

Workup

  1. customAfter removal of the solvent, 24 g of dimethyl 1,2,3,6-tetrahydro-4-(1-tosylhydrazono-ethyl)-phthalate (IV)
  2. customcrystallized from water
  3. dissolutionThis compound was dissolved in chloroform
  4. additiontreated at 0° C. with 14 ml of catechol borane
  5. additionSodium acetate was added to the reaction mixture, which
  6. temperaturewas then refluxed
  7. washAfter washing with water
  8. customthe solvent was evaporated off

Sources & evidence

ORD record
ord-d927f607f07b492aba18e76a04d08cb4
Source dataset
uspto-grants-1992_08
Patent number
US05138042

Reaction notes

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