This thesis describes the preparation of 4-chloro-2-trimethyl-stannyl-1-butene (8̲4̲) and its conversion into a number of structurally interesting and synthetically useful donor-acceptor reagents. Thus, transmetalation of (8̲4̲) with methyllithium produced 4-chloro-2-lithio-1-butene (9̲5̲), which reacted smoothly at -78°C in tetrahydrofuran with aldehydes, ketones and α,β-unsaturated N,N',N'-trimethylcarboxhydrazides to provide the addition products (1̲0̲8̲)-(̲1̲1̲3̲) and (̲1̲2̲8̲)-(̲1̲3̲0̲). When the reaction mixtures were treated with hexamethylphosphoramide and were then allowed to warm to room temperature, the 3-methylenetetrahydro-furan derivatives (̲1̲1̲4̲)-(̲1̲1̲9̲) and the 3-methylenecyclopentanecarboxylic acid derivatives (̲1̲3̲1̲)-(̲1̲3̲3̲) were produced in good yields. Treatment of reagent (̲9̲5̲) with 1 equiv of phenylthiocopper or cuprous cyanide provided solutions of the corresponding cuprate reagents (̲1̲7̲9̲) and (̲1̲8̲0̲). Conjugate addition of the latter species to the cyclic enones (̲1̲8̲1̲)-(̲1̲8̲6̲) afforded very good yields of the ketones (̲1̲8̲7̲)-(̲1̲9̲2̲), which, when treated with potassium hydride in tetrahydrofuran, provided the methylenecyclopentane annulation products (̲1̲̲9̲3̲)-(̲1̲9̲8̲), respectively. This methylenecyclopentane annulation method served as a key process in the total synthesis of two structurally interesting triquinane sesquiterpenoids, (±)-Δ⁹⁽¹²⁾ -capnellene (̲2̲0̲5̲) and (±)-pentalenene (̲2̲5̲1̲). Thus, copper bromide - dimethylsulfide catalyzed addition of the Grignard reagent (̲2̲3̲3̲) to 2-methyl-2-cyclopenten-1-one (̲1̲8̲4̲), followed by intramolecular alkylation of the resultant chloro ketone (̲1̲9̲0̲), gave the annulation product (̲1̲9̲6̲). This material was converted into the enone (̲2̲3̲1̲) , which was subjected to an annulation sequence identical with that used in the conversion of (̲1̲8̲4̲) into (̲1̲9̲6̲). Removal of the carbonyl group from the resultant product (̲2̲3̲2̲) provided (±)-Δ⁹⁽¹²⁾ capnellene (̲2̲0̲5̲). Transformation of the readily available keto acetal (̲2̲8̲̲7̲) into the enone (̲2̲8̲4̲), followed by subjection of the latter substance to the methylenecyclopentane annulation sequence, gave the tetracyclic keto olefin (̲2̲8̲5̲). Treatment of an acetic acid solution of this material with hydrogen in the presence of platinum metal produced a mixture of the epimeric ketones (2̲9̲8̲) and (2̲9̲9̲), which was converted into a mixture of (±)-pentalenene (2̲5̲1̲) and (±)-9-e̲p̲i̲-pentalenene (2̲6̲9̲), respectively. [Formula Omitted] / Science, Faculty of / Chemistry, Department of / Graduate

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Thesis (Ph. D.)--University of Wisconsin--Madison, 1982. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 426-461).

D.Sc. (Chemistry) / The Phosphate Development Corporation (FOSKOR) recovers apatite from foscorite ore by a process of froth flotation. Four reagents are used viz. sodium hydroxide, water-glass, nonylphenol tetraglycol ether (EMU) and a fatty acid. The fatty acid is mainly composed of a mixture of oleic and linoleic acid in a ratio of 1,2:1. The aim of this study was to investigate the influence of the first three above-mentioned reagents on the adsorption of oleic, linoleic and linolenic acids on apatite and The Phosphate Development Corporation (FOSKOR) recovers apatite from foscorite ore by a process of froth flotation ...

The preparation and synthetic utility of various β-trialkylstannyl-α,β-unsaturated carbonyl compounds is described. In this connection, treatment of tetrahydrofuran solutions of Me₃SnLi and n-Bu₃SnLi with one equivalent of PhSCu led to the in situ formation of PhS(Me-₃Sn)CuLi 72 and PhS (n-Bu₃Sn)CuLi 73, respectively. The latter reagents readily transferred, in a conjugate sense, the trialkyl-stannyl group to α,β-unsaturated carbonyl systems. In particular, these trialkylstannylcuprate reagents efficiently transformed β-iodo enones 4 into β-trialkylstannyl-α, β-unsaturated ketones 11, a new class of organotin derivatives. Likewise, treatment of the β-iodo enones 4_with Me₃SnCu • LiBr • SMe₂ 94, prepared by the reaction of Me₃SnLi with one equivalent of Me₂S*CuBr, gave the corresponding 6-trimethylstannyl enones in good yield. Two of these β-trialkylstannyl enones, β-trimetehyl-stannyl-2-cyclohexen-l-one 70 and β-tri-n-butylstannyl-2-cyclohexen-l-one, 74 were transformed into the vinylithium reagent 111. Sequential treatment of the enones 70 and 74 with lithium diisopropylamide and tert-butyldimethylsilyl chloride in the presence of hexamethylphosphoramide gave the enol silyl ethers 110 and 108, respectively. Transmetalation of the compounds 110 and 108 was accomplished by treatment of these substances with 1.1 equivalent of an alkyllithium reagent. Reaction of the resultant vinyllithium reagent 111 with electrophilic reagents proceeded smoothly to afford the corresponding substituted 1,3-cyclohexadienes in good yield. The reaction of PhS(Me₃Sn)CuLi 72 with various a, 6-acetylenic esters is also described. The course of the reaction could be controlled experimentally so as to produce, highly stereoselectively, either the (E) - or the (Z)-β-trimethylstannyl-α, β-unsaturated esters. Treatment (THF, -78°C) of PhS (Me₃Sn)CuLi 72 with a, β-acetylenic esters in the presence of a proton source (e.g., MeOH) gave the corresponding (E)-S-trimethylstannyl-a,g-unsaturated esters in good yield. Reaction of 7_2 with α,β-acetylenic esters at slightly higher temperatures (-48°C) in the absence of a proton source resulted in the formation of the corresponding (Z)-isomers. Reaction of ethyl (Z)-3 -tosyloxyacrylate 180 with Me₃SnCu*LiBr-SMe₂ 94 and n-Bu₃SnCu•LiBr*SMe₂ 181 gave the corresponding (Z)-β-trialkylstannylacrylates. Finally, two of the β-trimethylstannyl esters, ethyl (E)-3-trimethy1stanny1-2-butenoate 163 and ethyl (Z)-3-trimethylstannyl-2-butenoate 166, were converted into the geometrically isomeric trimethylstannyl dienes 184 and 185, respectively. Both of these substances underwent rapid and complete transmetalation when treated with 1.2 equivalents of methyllithium in tetrahydrofuran. The resultant 4-lithio-l,3-pentadienes (186 , 187) reacted smoothly with a variety of electrophiles to produce the corresponding substituted dienes (192 and 193). / Science, Faculty of / Chemistry, Department of / Graduate

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