Thesis (Ph. D.)--Oregon State University, 1982. / Typescript (photocopy). Includes bibliographical references (leaves 101-104). Also available on the World Wide Web.

Thesis (M.S.)--Oregon State University, 1985. / Typescript (photocopy). Includes bibliographical references (leaves 98-105). Also available on the World Wide Web.

Part I of the thesis describes four investigations of some of the neutral components of bark extractives. The petroleum ether extract of grand fir [Abies grandis (Dougl.) Lindl.] was found to contain two triterpene lactones. The first compound, cyclo-grandisolide, was shown by chemical and spectroscopic considerations and confirmed by X-ray analysis to be (2 3R)-3a-methoxy-9,19-cyclo-9β-lanost-24-ene-26 ,23-lactone (38) . The second component, epi-cyclograndisolide, was isomeric with the first and was assigned as (23S)-3α-methoxy-9,19-cyclo-9 β- lanost-24-ene-26,23-lactone (43). In the second investigation, three triterpenes of the chloroform extract of Pacific silver fir [A. amabilis (Dougl.) Forbes] were examined. The main component, abieslactone, was known and had been assigned as (23R)-3α-methoxylanosta-9(11),24—diene-26,23-lactone (30). Chemical and spectroscopic evidence is considered which indicates that assignment to be incorrect and abieslactone is tentatively re-assigned as (23R)-3a-methoxy-9β-lanosta-7,24-diene-26,23-lactone (81). A minor component, AA₃ was assigned on the basis of methylation studies as 3-desmethylabieslactone or (23R)-3α-hydroxy-9β-lanosta-7,24-diene-26,23-lactone (83). Oxidation of AA₃ gave a ketone identical to the second minor component, AA₂, which is then (23R)-3-oxo-9β-lanosta-7,24-diene-26,23-lactone (82). The third investigation concerns the structure of W₄, a triterpene ketone from the petroleum ether extract of Western white spruce [Picea glauca (Moench) Voss. var. albertiana (S. Brown) Sarg.]. The structure tentatively assigned on the basis of spectroscopic evidence is 3β-methoxy-8α-serrat-13-en-21-one (91). The fourth investigation was a chemosystematic study of the petroleum ether extract of Engelmann spruce [P. engelmannii Parry]. The presence of methoxyserratene derivatives known to be present in other members of the same genus were not detected in the present investigation. Part II of the thesis describes synthetic endeavors leading to possible bio-intermediates of indole alkaloids and the biosynthetic evaluation of one synthetic compound. Condensation of 3-ethylpyridine with 2-carboethoxy-3(β-chloroethyl)indole (60) followed by reduction gave N-[β{3(2-hydroxymethylindolyl)}ethyl]-3-ethy1-1,2,5,6-tetrahydropyridine (64). The benzoxymethyl derivative 65 of compound 64 was treated with potassium cyanide to give the cyanomethyl derivative 66 which could be hydroxyzed to N-[β{3(2-carbomethoxymethylindolyl)}ethyl]-3-ethyl-1,2,5,6-tetrahydropyridine (67). Alkylation of the compound with methyl formate followed by reduction of the resulating enol, gave 16,17-dihydrosecodin-17-ol (69). This compound was shown to be not, or very slightly, incorporated into the alkaloids of Vinca rosea L. plants. Attempts to oxidize the tetrahydropyridine 64 with mercuric acetate under various conditions failed to give detectable amounts of the corresponding pyridinium salt. In another synthetic sequence, condensation of the tryptophyl derivative 60 with 3-acetylpyridine ethylene ketal followed by the same sequence of reduction and homologation as employed before gave N-[β{3(2-carbomethoxy-methylindolyl)}ethyl]-3-acetyl-l,2,5,6-tetrahydropyridine (82). Attempts to oxidize 82 with mercurous acetate followed by hydrogenation failed to give the desired N-[β{3(2-carbomethoxymethylindolyl)}ethyl]-3-acetyl-l,4,5,6-tetrahydropyridine (83). In a second attempt to synthesize 83, the pyridinium chloride salt 84 from the condensation of 3-acetylpyridine with the tryptophyl derivative 60, was hydrogenated to N-[β{3(2-carboethoxyindolyl) }ethyl]-3-acetyl-l,4,5, 6-tetrahydropyridine (85). Reduction of 85 under a variety of conditions gave major amounts of N-[β{3(2-hydroxymethylindolyl)}ethyl]-3-acetylpiperi-dine (86) with only trace amounts of N-[β{3(2-hydroxymethylindoiy 1)}ethy1]-3-acety1-1,4,5,6-tetrahydropyridine (87) containing the necessary vinylogous amide chromophore. In a third approach to the synthesis of 83, methyl indole-2-carboxylate (88) was reduced and homologated as before to give methyl indole-2-acetate (92). Treatment of 92 with ethylene oxide and stannic.chloride gave methyl 3(β.-hydroxyethyl)indole-2-acetate (93). Treatment of the tryptophyl bromide derivative 94, produced by the action of phosphorous tribromide on hydrogenated to the vinylogous amide 83. More conveniently, treatment of 93 in 3-acetylpyridine with phosphorous tribromide and immediate hydrogenation gave 83 in better yield. / Science, Faculty of / Chemistry, Department of / Graduate

Part I of this thesis describes the structural elucidation of eleven triterpenes isolated from the benzene extract of Western white pine (Pinus monticbla Dougl.) bark. Chemical and detailed spectroscopic investigations revealed the presence of a common tetracyclic A9(ll)-lanostene skeleton in all of the investigated materials. Structural variations were found at the C3 position and in the side chain at C17. The following assignments have been made: compound I, 33~methoxy-5a-lanost-9(ll)-en-24S,25-diol (43); compound II, the corresponding 33-hydroxy derivative (51); compound III, 33-methoxy-5a-lanost-9(11)-en-24-one (59); compound IV, 33-methoxy-5a-lanost-9(11),25-dien-24S-ol (65); compound V, 3a-hydroxy-5a-lanost-9(ll),25-dien-24-ol (66); compound VI, 33-methoxy-5a-lanost-9(ll)-en-22,25-diol (70); compound VII, 33-methoxy-26,27-bis nor-5a-lanost-9(ll)-en-24-one (71). Compound VIII was shown to be the ethylidene derivative of 33-methoxy-5a-lanost-9(ll)-en-24S,25-diol (76) and compounds IX and X were assigned to structures (78) and (80), respectively. A novel dimeric steroidal structure (83) has been proposed for compound XI. Part II describes synthetic investigations which lead to the development of a sequence providing a synthon [(193) and (194)] for the synthesis of vobasine (78)- and sarpagine (77)-type alkaloids. 2-Amino-3-indolyl(3a)-propanol (121), obtained by lithium aluminum hydride reduction of L-tryptophan (106), was converted to its ditosylate (150). Treatment of the latter with cyanide ion provided 3-(N~tosylamino)-4-indolyl(3a)-butanonitrile (151) which was transformed to 3-(N-tosylamino)-4-indolyl(3a)-butanoic acid (152) by means of 30% sodium hydroxide solution. 3-Amino-4-indolyl(3a)-butanoi.c acid methyl ester (155) was obtained through reductive cleavage of (152), followed by Fischer esterification. Compound (155) could then be converted to 3-CN-.formylami.no)-4- (N-benzyl-indolyl)(3a)-butanoic acid methyl ester (163) by treatment with a mixture of formic acid and acetic anhydride followed by sodium hydride and benzyl bromide. Reaction with trifluoroacetic acid converted compound (163) to the tricyclic 3-carbomethoxymethyl-N -benzyl-3,4-dihydrocarboline (173) which upon condensation with 3-methylene-pentan-2-one (126) afforded the tetracyclic 2-oxo-3-ethyl-6-carbomethoxymethyl-l,2,3,4,6,7,12,12b-octahydro-(N-benzylindolo)(2,3-a)-quinolizine (175). The ethylene ketal (177) of the latter material was treated with diisopropyllithium amide and methyl chloroformate to provide 2-oxo-3-ethyl-6-dicarbomethoxymethyl-l,2,3,4,6,7, 12,12b-octahydro-(N-benzylindolo)(2,3-a)-quinolizine ethylene ketal (178), which possesses a highly activated acidic proton (C6a) in the side chain. A suitable leaving group at the C2 position, necessary for subsequent transannular cyclisation, was available through conversion of the tetracyclic ketone (175) to the corresponding C2cx-alcohol (181) and further transformation of the latter into various derivatives such as the acetate (182), the mesylate (183) and the p-nitrobenzoate (185). In order to allow generation of an exocyclic olefin at C3, the C2-olefin, 3-ethyl-6-carbomethoxymethyl-l,4,6,7,12,12b-hexahydro-(N-benzylindolo)(2,3-a)quinolizine (184), obtained via dehydration of the alcohol (181), was converted to 2,3-a-dihydroxy-3-ethyl-6-carbomethoxymethyl-l,2,3,4,6,7,12,12b-octahydro-(N-benzylindolo) (2,3-a)-quinolizine (186) by osmium tetroxide oxidation. Treatment of (186) with acetic anhydride or p-nitrobenzoyl chloride provided the diacetate (187) or the C2 mono p-nitrobenzoate (188), respectively. The 10-membered ring system, present in the vobasine skeleton, became availahle through reductive cleavage of the C/D ring junction in the tetracyclic alcohol (181), thus, affording 2a-hydroxy-3a-ethyl-N^-methyl-6-carhomethoxymethyl-l,2,3,4,6,7,12,12b,12b-nonahydro-(N-benzyl-indolo)(2,3-a)-12b,N^-seco-quinolizine (190). Acetic anhydride treatment of the ethylene ketal (177) provided two isomeric components, 2-oxo-3-ethyl-Nb-acetyl-6-carbomethoxymethyl-1,2,3,4,6,7,12,12b-octahydro-12b-acetoxy-(N-benzylindolo)(2,3-a)-12b,Nb-seco-quinolizine ethylene ketal (191a and b), also possessing the 10-membered ring skeleton. Furthermore, the latter materials enable an entry into the family of 2-acylindole alkaloids as well as members of the dimeric alkaloids such as voacamine (75). / Science, Faculty of / Chemistry, Department of / Graduate

This work follows successful research by staff members at Forintek Canada Corp. in modifying and extending phenol-formaldehyde (PF) plywood resins with powdered tree foliages and barks. In the present study, two urea-formaldehyde (UF) resins, one commercial and one laboratory synthesized, were modified at 15, 30 and 45% addition levels with finely ground white spruce [Picea glauca (Moench.) Voss] foliage or western hemlock [Tsuga heterophylla (Raf.) Sarg.] bark. Two five-ply Douglas-fir [Pseudotsuga mensiezii (Mirb.) Franco] test plywood panels (38 x 38 cm) were made at 32kg/l00 m² double glueline spread level, six and ten min pressing time at 149°C. The commercial and laboratory synthesized wheat flour extended UF resins were used as controls. Shear strengths and wood failure percentages were recorded for sets of test specimens after conditioning at 22°C and EMC of about 6% (Dry test), one vacuum pressure cycle, five vacuum pressure cycles and boiling cycle. Most formulations with the commercial UF resin containing foliage or bark yielded good bond quality (wood failure and shear strength) similar to the control when tested dry and after one vacuum pressure cycle. Following multi-cycle testing, one formulation containing foliage gave similar wood failure percentage to the control. Two formulations containing bark improved glue bond durability yielding 3 to 12% higher wood failure than the control. Results with the laboratory resin were not as good, showing bond quality lower than with the commercial UF formulation. No formulation survived boiling treatment implying that no modification among those used improved UF resin durability under conditions of high moisture and-temperature. Both UF resins were successfully extended by various foliage and bark additions. It was found that both materials can be used as partial substitutes for the conventional extender wheat flour up to the 40% level. This information may be of use to some developing countries that import wheat to flour-extended UF resins used to bond interior grade plywoods. Such countries could benefit by making use of local tree foliages or barks. / Forestry, Faculty of / Graduate

Shrubs are important as browse and cover for game animals and songbirds in the desert-shrub and chaparral plant communities in the Great Basin (Plummer, 1968). They also play a major role in soil binding and watershed maintenance (Colby and Weissert, 1975). Therefore, an understanding of the agents which affect the health and survival of the shrubs is important. Insects-have a great impact on the health and reproductive capacity of shrubs. Pollinators, defoliators, borers, etc. must be studied and known for proper management.

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4 pp. / Revised / This paper provides evidence of the infestation caused by pine bark beetles in Arizona. It provides information about their life history, and how to prevent and control them.