Polina I. Svirskaya

SYNTHESIS AND PHOTOCYTOTOXICITY OF SOME NEW SUBSTITUTED PHTHALOCYANINES

Abstract Some new, ring‐substituted phthalocyanines have been synthesized and underwent preliminary testing for photodynamic activity using the colony forming ability of Chinese hamster cells in culture as an endpoint. Using 4‐(3‐N, N‐diethylaminopropyl)phthalonitrile as a precursor, the previously unknown metal‐free 2,9,16,23‐tetra‐(3‐N, N‐diethylaminopropyl)phthalocyanine was prepared and converted to its zinc (II) and its cationic water‐soluble 2,9,16,23‐tetramethylammonium zinc (II) iodide derivatives. Other new phthalocyanine derivatives tested, include a 2,9,16,23‐tetra(2‐hydroxymethyl‐2‐methyIbutoxy)phthalocyaninato zinc (II) and 2,3,9,10,16,17,23,24‐octahydroxyphthalocyaninato zinc (II) derivatives. Boron tribromide cleavage of the newly prepared and fully characterized 2,3,9,10,16,17,23,24‐octamethoxyphthalocyanine gave the unstable metal‐free octahydroxyphthalocy‐anine, which could only be characterized by ultraviolet‐visible, NMR and IR spectroscopy.

A Stereoselective Synthesis of a Cis, Cis Conjugated Dienol, a Candidate Pheromone

Abstract There has been much interest recently focussed on the synthesis of geometrically pure conjugated diene alcohols, aldehydes and esters useful as sex pheromones and candidate sex attractants.1,2 A recent communication3 on the synthesis of all four geometrical isomers of some conjugated dienols by four different Wittig reactions prompts us to report our results on the synthesis of a cis, cis conjugated dienol, as the reported synthesis of this type of isomer yielded product of low geometrical purity.3 We describe below our stereo-selective synthesis of a cis, cis conjugated dienol

Syntheses of pure (9Z, 11Z), (9E, 11E), (9E, 11Z), and (9Z,11E)-9,11-hexadecadienals-possible candidate pheromones.

The title compounds were prepared by six different routes, and recommendations are given for the more convenient procedures in laboratory-scale syntheses. Modifications in the literature preparations of the 9E,11E and 9E,11Z isomers are described. Baseline separation of a prepared mixture of all four isomers of the (9Z, 11Z), (9E, 11E), (9E, 11Z), and (9Z, 11E)-9,11-hexadecadienals was achieved using GC methods with standard capillary columns. [13C]NMR spectroscopy of the alkene carbon atoms clearly differentiates between theZ,Z, E,E and eitherE,Z orZ,E isomers of the precursor dienols and thus of the dienals.

Syntheses of Unconjugated (Z,Z)-Diolefinic Insect Pheromones on Insoluble Polymer Supports

A 2% cross-linked styrene-divinylbenzene copolymer containing pendant trityl chloride groups was used as the solid support in the synthesis of (Z, Z)-3,13-octadecadien-1-yl acetate, a component of the sex attractant of the lesser peachtree borer,Synanthedon pictipes, the peachtree borer,Synanthedon exitiosa, and the cherry tree borer,Synanthedon hector. This solid-phase synthesis is compared with a similar synthetic approach in solution. The solid-phase synthesis of (Z, Z)-7,11-hexadecadien-1-yl acetate, a component of the pheromone of the pink bollworm moth,Pectinophora gossypiella is described.