Poly(arylenenethynylene)s or PAEs are an interesting class of conjugated polymers that have potential uses in the field of thin film transistors, organic LEDs, sensors, and molecular wires. The field of PAEs have grown in recent years, however very few of its conjugated polymers have a heterocyclic motif contained within them. We have designed some conjugated heterocyclic polymers that contain quinoline, benzothidiazole, and quinoxaline. These polymers show interesting ionochromic and solvochromic effects as well as unusual solid state properties. Some of these polymers will demonstrate their ability to form fascinating nanostructures by use of either mesoporous discs or gold mediated nanotubes. Finally, we also have produced peralkynylated heterocyclic molecules for use in potential n-semiconductive devices. These molecules are not only aesthtically pleasing, but versatile molecules that could be used in conjugated PAEs.

Six bis(silyl)acetylenes with the following varied silicon substituents were prepared: I (Me, Me); II (H, H); III (Cl, H); IV (Cl, Cl); V (OMe, H); VI (OMe, OMe). While I and II may be prepared by the reaction of dilithio- or bis(bromomagnesium)-acetylide with appropriate chlorosilane, similar reactions designed to give III - VI give oligomers, YMe_2Si(C≡C-SiMe_2)_nY, VII, Y = Cl, OMe, as the major products indicating that the acetylenic functionality on silicon activates the chlorosilane toward nucleophilic substitution. Compounds III and IV were prepared by free radical chlorination of II. Methanolysis of III and IV gave quantitative yields of V and VI, respectively. In the presence of mineral acid, VI readily cyclized to give high yields of the cyclic siloxane octamethyl-4,9-dioxa-3,5,8,10-tetrasila-cyclodeca-1,6-diyne, VIII, and the analogous triyne, IX. It was determined that V and VI could be prepared directly from II in high yield by methanolysis with palladium catalyst. Vaska's complex also accomplished the conversion. I attempted to prepare bis(ethoxydimethylsilyl)acetylene by using of Wilkinson 's catalyst for hydrosilylation with acetaldehyde. The principal product of this reaction was 1-(dimethylsilyl)-3,5,5-trimethyl-4-oxa-3-silacyclopent-1-ene, XI.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work describes the synthesis of a series of twenty 4-[alkyl (aryl) (2-propinyl amino)-3-alken-2-ones], [R2C(O)CH=C(R1)N(R)(CH2C≡CH), where R2 = CF3, CCl3, CO2Et; R1 = Me, Et, Pr e R= Pr, Ph, Bn, 4-MeC6H4] obtained with 70-95% yield throught a reaction of 1,4-addition followed by substitution between propargylamines [NH(R)(CH2C≡CH), where R= Pr, Ph, Bn, 4-MeC6H4] and 4- alkoxy-3-alken-2-ones [R2C(O)CH=C(R1)(OMe), where R2 = CF3, CCl3, CO2Et, and R1= Me, Et, Pr], using acetonitrile as solvent, room temperature or under reflux, depending on substrates used. From the series of twenty 4-[alkyl(aryl) (2-propinylamino)]-3-alken-2-ones], nine were employed in cycloisomerization reactions using AgNO3 as catalyst and CHCl3 as solvent, at room temperature, which provided a series of eight 1,2-dihydropyridine 1-(R), 5-(C(O)R2) and 6-(R1) substituted with 70-90% yield, where R = Pr, Bn, Ph, 4-MeC6H4; R1 = Me, Et, Pr; R2 = CF3, CO2Et. In only one case the cycloisomerization reaction produced a five-membered heterocycle which was characterized as 4-methyl-1-propyl-3-trifluoroacetyl pyrrole. In this work was also studied the use of dimethylamino vinyl ketones [R4C(O)CH=CHNMe2, where R4= 4-FC6H4, 4-ClC6H4, 4-BrC6H4, 4-NO2C6H4] and terminal alkynes [R3C≡C-H, where R3= Pent, Ph], using BuLi as base, BF3.OEt2 as catalyst and THF as solvent furnishing a series of eninones with 65-80% yield. / Neste trabalho é descrita a síntese de uma série de vinte 4-[alquil(aril) (2-propinilamino)]-3-alquen-2-onas [R2C(O)CH=C(R1)N(R)(CH2C≡CH), onde R2= CF3,CCl3, CO2Et; R1= Me, Et, Pr e R= Pr, Ph, Bn, 4-MeC6H4] obtidas com rendimentos entre 70-95%, através de uma reação de adição-1,4 seguida de substituição, entre aminas propargílicas [NH(R)(CH2C≡CH), onde R= Pr, Ph, Bn, 4-MeC6H4] e 4-alcóxi-3-alquen-2-onas [R2C(O)CH=C(R1)(OMe), onde R2= CF3, CCl3, CO2Et, e R1= Me, Et, Pr] empregando acetonitrila como solvente e utilizando temperatura ambiente ou refluxo, dependendo dos substratos utilizados. A partir de vinte 4-[alquil(aril) (2- propinilamino)]-3-alquen-2-onas, nove foram empregadas em reações de cicloisomerização utilizando AgNO3 como catalisador e CHCl3 como solvente, empregando temperatura ambiente, o que forneceu uma série de oito 1,2-diidropiridinas 1-(R), 5-(C(O)R2) e 6-(R1) substituídas, com rendimentos entre 70-90% onde R= Pr, Bn, Ph, 4-MeC6H4; R1= Me, Et, Pr; R2 = CF3, CO2Et. Em somente um caso, a reação de cicloisomerização produziu um heterociclo de 5 membros, sendo caracterizado como 4-metil-1-propil-3-trifluoracetilpirrol. Neste trabalho também foi estudado o uso de β-dimetilamino vinil cetonas [R4C(O)CH=CHNMe2, onde R4= 4-FC6H4, 4-ClC6H4, 4-BrC6H4, 4-NO2C6H4] e alquinos terminais [R3C≡CH, onde R3 = Pent, Ph] em reações de acoplamento de organolítio via adição do tipo 1,4, utilizando BuLi como base, BF3.OEt2 como catalisador e THF como solvente para fornecer uma série de eninonas com rendimentos entre 65-80%.

Acetylenedicarboxylic acid monopotassium salt, ADCA-K, was polymerized by radiation induced solid-state and chemical initiator induced solution polymerization methods. Radiation induced solid-state polymerization was carried out by Co-60 g-radiation at room temperature. The powder polymer obtained was soluble in water but insoluble in common organic solvents. The solution polymerization initiated by benzoylperoxide was carried out in an oil bath at 90&deg / C. The polymer obtained was soluble in water but insoluble in dimethylsulfoxide. In the first stage of the polymerization, H2O, CO and/or CO2 gases were evolved and the polymerization was proceeded on the acetylene group. The polymers obtained were characterized by FT-IR, DSC, TGA-FTIR, NMR and DP-MS methods. The crystal structure effect on polymerization was investigated by X-Ray method. The monomer is monoclinic with a space group of C2/c. The unit cell parameters are a=795.4, b=1192.6, c=591.8 pm and b=105.40. Polymer showed a partial polycrystalline structure. The larger fraction of polymer has identical crystal structure to that of the monomer. Therefore, polymerization takes place a topotactic mechanism.

A novel hetero Diels-Alder reaction has been developed to facilitate the synthesis of annelated pyridines as models for pyridoacridine alkaloids. The key reaction is based on an intramolecular Diels-Alder reaction of an aza-1,3-butadiene with an appropriate dienophile, to yield the desired annelated pyridine. An extension of this methodology is to exploit the Eglinton copper (IT) dimerisation of terminal acetylenes. This allows for a unique double intramolecular hetero Diels-Alder reaction, where four new rings are formed in one step. This allows for a facile route to annelated bipyridines. Ultimately this methodology has led to an approach to the total synthesis of the natural product eilatin, a member of the class of compounds known as pyridoacridines.

A primeira parte deste trabalho trata da preparação de teluretos vinílicos funcionalizados, a partir da adição de tricloreto de p-metoxifenil telúrio a hidróxi alcinos e hidróxi alcinos protegidos. Observamos a formação de uma mistura de oxicloretos e dicloretos de aril telúrio. A redução, tanto dos oxicloretos como dicloretos de aril telúrio com tiossulfato de sódio levou a formação dos teluretos vinílicos correspondentes. A segunda parte do trabalho refere-se à síntese de sistemas enínicos e enediínicos. Para tanto, desenvolvemos uma nova metodologia que levam a esses compostos, baseado na reação de acoplamento de um telureto vinílico Z com acetilenos terminais catalisadas por PdCl2/CuI em trietilamina, usando como solvente metanol. Observamos que a reação ocorre com total retenção de configuração da ligação dupla sem interferir com os grupos hidroxilas presentes, tanto no telureto vinílico, quanto no alcino. / The first part of this work describes the synthesis of functionalized vinylic tellurides obtained from the addition of aryltellurium trichlorides to protected and unprotected hydroxy-alkynes attempting to determine the regio- and stereochemistry of the obtained tellurides. To that reaction, we observed the formation of a mixture of aryltellurium oxychlorides and dichlorides. The reduction of aryltellurium oxychlorides and dichlorides mixture with sodium thiosulfate yielded the desired vinylic tellurides. The second part of this work describes the synthesis of enyne and enedyine systems. To perform that reaction we developed a new methodology based on the coupling reaction of (Z)-vinylic tellurides and terminal alkynes catalyzed by PdCl2/CuI in triethylamine using methanol as solvent. The desired products were obtained with total retention of configuration of the double bond and the reaction conditions are compatible with hydroxy and carbonyl groups avoiding any protection step.

A primeira parte deste trabalho trata da preparação de teluretos vinílicos funcionalizados, a partir da adição de tricloreto de p-metoxifenil telúrio a hidróxi alcinos e hidróxi alcinos protegidos. Observamos a formação de uma mistura de oxicloretos e dicloretos de aril telúrio. A redução, tanto dos oxicloretos como dicloretos de aril telúrio com tiossulfato de sódio levou a formação dos teluretos vinílicos correspondentes. A segunda parte do trabalho refere-se à síntese de sistemas enínicos e enediínicos. Para tanto, desenvolvemos uma nova metodologia que levam a esses compostos, baseado na reação de acoplamento de um telureto vinílico Z com acetilenos terminais catalisadas por PdCl2/CuI em trietilamina, usando como solvente metanol. Observamos que a reação ocorre com total retenção de configuração da ligação dupla sem interferir com os grupos hidroxilas presentes, tanto no telureto vinílico, quanto no alcino. / The first part of this work describes the synthesis of functionalized vinylic tellurides obtained from the addition of aryltellurium trichlorides to protected and unprotected hydroxy-alkynes attempting to determine the regio- and stereochemistry of the obtained tellurides. To that reaction, we observed the formation of a mixture of aryltellurium oxychlorides and dichlorides. The reduction of aryltellurium oxychlorides and dichlorides mixture with sodium thiosulfate yielded the desired vinylic tellurides. The second part of this work describes the synthesis of enyne and enedyine systems. To perform that reaction we developed a new methodology based on the coupling reaction of (Z)-vinylic tellurides and terminal alkynes catalyzed by PdCl2/CuI in triethylamine using methanol as solvent. The desired products were obtained with total retention of configuration of the double bond and the reaction conditions are compatible with hydroxy and carbonyl groups avoiding any protection step.

(Doctoral Thesis, 2016, Mgr. Tomáš Faukner, IONIC POLYACETYLENE TYPE POLYMERS AND POLYMER NETWORKS BY CATALYST FREE QUATERNIZATION POLYMERIZATION) The composition and structure of a series of ionic π-conjugated poly(monosubstituted acetylene)s prepared via catalyst-free quaternization polymerization (QP) of 2-ethynylpyridine (2EP) activated with equimolar amount of alkyl halide [RX = ethyl bromide, ethyl iodide, nonyl bromide and haxadecyl (cetyl) bromide] as a quaternizing agent (QA) have been studied in detail. The performed QPs gave ionic polymers well soluble in polar solvents, with approximately half of pyridine rings quaternized, which implies that also non-quaternized monomers were involved in the process of QP. The configurational structure of polyacetylene main chains was suggested based on 1 H NMR, IR as well as Raman (SERS) spectral methods. The QPs in bulk gave more expected irregular cis/trans polymers while the QPs in acetonitrile solution gave high-cis polymers. A series of prepared symmetrical bi-pyridylacetylene based monomers has been polymerized via QP approach resulting into a series of new ionic π-conjugated poly(disubstituted acetylene) type materials. It is therefore obvious that the mechanism of quaternization activation frequently applied on monosubstituted...

4 ABSTRACT The synthesis has been described yielding a new type of rigid conjugated polymer networks which possess a high content of permanent micropores and macropores and exhibit high surface areas up to 1469 m2/g. The networks have been prepared via chain-growth coordination polymerization catalysed with insertion catalysts based on Rh complexes. This polymerization has been newly applied to bifunctional acetylenic monomers of diethynylarene type (1,4-diethynylbenzene, 1,3-diethynylbenzene and 4,4'-diethynylbiphenyl). The covalent structure of the networks consists of the polyacetylene main chains densely connected by arylene struts. The W and Mo metathesis catalysts have been revealed as inefficient for the synthesis of these networks. The increase in the polymerization temperature and time has been shown to affect positively the content and the diameter (up to 22 nm) of the mesopores in the networks. A mechanism has been proposed that explains the mesopores formation as a result of mutual knitting of small particles of the microporous polymer. The application of emulsion polymerization technique allowed to prepare texturally hierarchical polyacetylene networks possessing interconnected open macropores (diameter up to 4,8 μm) the walls of which exhibited micro/mesoporous texture. It was demonstrated...