PART I: THE PHOTOCHEMICAL REACTIONS OF REISSERT COMPOUNDS TOWARDS APORPHINE SYNTHESIS. PART II: SYNTHESES AND ANALYSES OF DICYANOQUINODIMETHANES FOR LASER INDUCED SECOND HARMONIC GENERATION

Part I of this work describes a general photochemical cyclization of two series of 1-(2-halobenzyl)-isoquinoline Reissert compounds (see Tables 2 and 4 in dissertation). Reissert compounds 83*, 120* and 121* were alkylated with a number of 2-halobenzyl halides to furnish the 1-(2-halobenzyl)-isoquinoline-1-carbonitriles. Photocyclization of the 1-(2-halobenzyl)-1,2,3,4-tetrahydroisoquinoline-1-carbonitriles (see Table 5 in dissertation) furnished the aporphine precursors. Additionally, a number of the aporphine precursors were transformed by pyrrolysis into N-benzoyl-6a,7-dehydroaporphines in quantitative yield. The irradiation of the corresponding 1-(2-halobenzyl)-1,2-dihydroisoquinoline-1-carbonitriles (see Table 2 in dissertation) unexpectedly furnished a new class of alkaloid, namely the isopavines. The isopavine structure was confirmed by conversion of isopavine 111* to the derivative 113* by treatment with methanolic potassium hydroxide. Additionally, the photoproduct 111* was verified by X-ray structural analysis. The isopavines were isolated in 26-83% yield. Part II of this work describes the syntheses and analyses of a new class of compounds, dicyanoquinodimethanes, for laser-induced second harmonic generation. The synthesis began with the transformation of a number of aminoacids to furnish vicinal aminoalcohols and vicinal diamines. The vicinal aminoalcohols and diamines were then condensed with tetracyanoquinodimethane 7** to give the dicyanoquinodimethanes (see Table 10 in dissertation) in 56-97% yield. The dicyanoquinodimethanes so prepared were subjected to the 1060 nm laser input upon which they produced the second harmonic beam. Dicyanoquinodimethane 47** produced the second harmonic beam comparable to that reported for the substituted pyridine 74** when exposed to a laser beam. In addition, the requirement for a noncentrosymmetric unit cell structure was confirmed by the observation that optically active dicyanoquinodimethane 42** produced excellent second harmonic beam. Racemic dicyanoquinodimethanes 56** gave no observable result. The X-ray structure determination showed 42** to be noncentrosymmetric whereas 56** was centrosymmetric. Part II of this work also describes an improved alternate procedure for synthesizing arylmalononitriles. Arylmalononitriles (see Table 12 in dissertation) were synthesized in a one step procedure by treating arylacetonitriles with lithium diisopropylamide and 2-chlorobenzyl thiocyanate. Arylmalononitriles were isolated in 77-100% yield. *See Part I in dissertation for illustration. **See Part II in dissertation for illustration