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

HRID 846861ノート

反応式

HRID 846861 の反応式
[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]

参加物

4

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

実験手順

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=).

後処理

  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

出典と根拠

ORDレコード
ord-d927f607f07b492aba18e76a04d08cb4
出典データセット
uspto-grants-1992_08
特許番号
US05138042

反応ノート

読み込み中…