Benzene → 1-(6'-Methoxycarbonyl-n-hex-2-enyl)-4-methyl-1,2,4-triazolidine-3,5,-dione

Reaktionsgleichung

[CH3:1][N:2]1[C:6](=[O:7])[NH:5][NH:4][C:3]1=[O:8].[C:9]([OH:17])(=[O:16])[CH2:10][CH2:11][CH2:12][CH2:13][CH:14]=[CH2:15].[CH:18]1C=CC=CC=1>>[CH3:18][O:16][C:9]([CH2:10][CH2:11][CH2:12][CH:13]=[CH:14][CH2:15][N:4]1[C:3](=[O:8])[N:2]([CH3:1])[C:6](=[O:7])[NH:5]1)=[O:17]

Komponenten

Edukt 3

HCID 241Benzene2×

HCID 707056-Heptenoic acid

HCID 1777354-Methyl-1,2,4-triazolidine-3,5-dione

Produkt 1

HCID 538819771-(6'-Methoxycarbonyl-n-hex-2-enyl)-4-methyl-1,2,4-triazolidine-3,5,-dione

Versuchsvorschrift

Dinitrogen tetroxide was bubbled through a suspension of 4-methyl-1,2,4-triazolidine-3,5-dione (23.0 g, 0.2 mol) in dichloromethane (250 ml) cooled to 0° C., until a clear, homogenous deep red solution was obtained. This solution was then dried (Na2SO4), filtered, and the filtrate evaporated at room temperature in vacuo to give 4-methyl-1,2,4-triazolidine-3,5-dione (m.p. 105° decomp). To the 4-methyl-1,2,4-triazolidine-3,5-dione (23.0 g, 0.2 mol) dissolved in benzene (200 ml) was added dropwise hept-6-enoic acid (23.0 g, 0.18 mol) in benzene (100 ml) and the resultant solution boiled under reflux in an atmosphere of nitrogen, until a pale yellow solution had been obtained (in 1 hr). The resultant solution was evaporated in vacuo and the residue dissolved in a 10% solution of acetyl chloride in methanol (300 ml). This solution was boiled at reflux for 5 hr, stirred at room temperature overnight and then evaporated in vacuo. The residue (44 g) was chromatographed on silica gel (Merck Kieselgel 60, 900 g) using chloroform; methanol as eluant (0-5% methanol), to afford 1-(6'-methoxycarbonyl-n-hex-2-enyl)-4-methyl-1,2,4-triazolidine-3,5,-dione (19.1 g) m.p. 55-7.