SYNTHESIS OF 1,2,3-TRIAZOLO-QUINOLIZIDINES BASED ON THE QUINOLIZIDINE ALKALOID LUPININE

The modification of the quinolysin alkaloid lupinine was carried out with the intro-duction of 1,2,3-triazolyl substituents for the hydroxymethylene group in the C-1 position of the quinolysin backbone. The reaction of lupinine with methanesulfochloride in the presence of triethylamine smoothly led to lupinine methanesulfonate, whose further reaction with sodium azide in DMFA led to lupinilazide. 1,3-Dipolar [4+2]-cycloaddition of the resulting azide to alkynes produced more stable 1,2,3-triazole compounds. The interaction of lupinilazide with 2-ethinylpyridine and with alcohols containing a terminal acetylene group (propargyl alcohol, 2-methylbut-3-in -2-ol or hex-5-in -1-ol) proceeded smoothly in the DMFA medium. The reactions were carried out in the presence of an aqueous solution of CuSO4 and sodium ascorbate in DMFA and allowed the corresponding 4-substituted (1S,9aR)-1H-1,2,3-triazol-1-yl to be synthesized with good yields)methyl)octahydro-1H-quinolysins. The results of studying the structural features of synthesized compounds by 1H - and 13C - NMR spectroscopy, as well as data from the two-dimensional COSY (1H-1H) and HMQC (1H-13C) spectra are presented. The values of chemical shifts, multiplicity and integral intensity of 1H and 13C signals in one-dimensional NMR spectra are determined. In the spectra of all synthesized new quinolizi-dinotriazoles, there is a peak of the fragmentary C10H17N ion (150-151 cu), corresponding to the cleavage of the molecule by the C-10 atom of the quinolizidine backbone.

Zum chemischen und photochemischen Abbau der Cyclodien-Insektizide Aldrin, Dieldrin, Endosulfan und weiterer Hexachlorbicyclo-[2.2.1]-hepten-Derivate / The Chemical and Photochemical Degradation of the Cyclodien-Insecticides Aldrin, Dieldrin, Endosulfan and other Hexachloronorbornene Derivatives

The conversion of the hexachloronorbornene-moiety of persistent cyclodiene pesticides has been studied by hydrolysis- and photolysis (UV) reactions. The chemical changes have been monitored by means of a microtitration method for chloride ions and electron capture gas chromatography. The 2,3-disubstituted hexachloronorborn-5-enes give a comparably easy loss of 1 mole chloride ions per mole compound if one of the substituents is a hydroxymethylene group, whereas with two carboxylic acid groups in the 2,3-position — that is chlorendic acid — or a further cycle or bicycle — that is endosulfanether or dieldrin — the compounds proved to be very stable. The alkaline stability of aldrin and dieldrin corresponds to their persistence in the ecosystem.

THE PAPILIONACEOUS ALKALOIDS: XXI. THE ALKALOIDS OF LUPINUS PILOSUS WALT. AND THE STRUCTURE OF TETRALUPINE

The alkaloidal extract from Lupinus pilosus Walt. was found to contain two alkaloids, one widely occurring one, d-lupanine, and one which had already been reported to occur in this plant, i.e., d-epilupinine, but no lupinine. The alkaloid tetralupine has been found by direct comparison of the bases and their corresponding salts and by their infrared absorption spectra to be identical with dl-epilupinine. A study of the infrared absorption spectra of lupinine and epi-lupinine leads to the same conclusion as the chemical evidence, i.e., that in the former the hydroxymethylene group occupies the axial position whereas in epilupinine this group is in the equatorial position.