Synthèse et étude de nouvelles molécules potentiellement polymérisables pour la fabrication de matériaux électroluminescents : analogues du 1,3,5 benzènetripyrrole, méthyle 3,5-bipyrrolebenzoate et 6,12-diméthyle-1,5-dipyrrolediazocane

Pyrroles are found in various natural products and in the chemical composition of certain drugs because of their interesting biological properties. Lipitor, Tolmetin and Amtolmetin are examples of drugs with 1,2,5-substituted pyrroles in their composition, in which biological activities have been certified. Moreover, pyrroles are used as precursors of semiconductor polymers, oligomers and dendrimers useful for the synthesis of electroluminescent materials used in devices, such as organic light-emitting diodes, field-effect transistors, solar and organic photovoltaic cells. We are interested in conjugated polymers based on pyrrole due to their optical properties, electrochemical and the conductivity produced by electron delocalization along their carbon chains. The overall objective of the work presented in this thesis is the synthesis of new molecules based on pyrrole for studying their electronic and electrochemical properties as well for the synthesis of conjugated polymers. Initially, we performed the synthesis of 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes, which may serve as precursors for the synthesis of conjugated dendrimers. Their synthesis was made in three steps starting from trimethyl 1,3,5-benzene-tricarboxylate which was converted to 1,3,5-tri-(pent-4-enoyl)benzene using vinylmagnesium bromide in a Grignard reaction catalyzed by copper cyanide. The olefins of 1,3,5-tri-(pent-4-enoyl)benzene were oxidized to produce 1,3,5-tri-(4-oxopentanoyl)benzene using a modified protocol of the Tsuji-Wacker reaction. Subsequent, Paal-Knorr condensation reactions on 1,3,5-tri-(4-oxopentanoyl)benzene with different amines were used to synthesize 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes with different N-substituents in yields between 44 and 60%. Incomplete reaction of vinylmagnesium bromide with trimethyl 1,3,5-benzenetricarboxylate gave the methyl-3,5-di(pent-4-enoyl)benzoate, which was converted to methyl-3,5-dipyrrolylbenzoate following the reaction of Tsuji- Wacker and Paal-Knorr with yields between 30 and 60%. The photochemical and electrochemical properties of the 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes and methyl-3,5-dipyrrolylbenzoates were studied in collaboration with the research group of professor William Skene. The results have shown that both types of pyrrole have potential for the synthesis of conjugated polymers and dendrimers used in the manufacture of electroluminescent materials. Following these encouraging results, we performed the synthesis of 6,12-dimethyl-1,5-dipyrrolediazocane. Methyl N-(Boc)-β-alaninate was converted to its corresponding homoallylic ketone, which was oxidized to N-(Boc)aminoheptan-3,6-dione. The Paal-Knorr condensation between N-(Boc)aminoheptan-3,6-dione and aminoheptan-3,6-dione hydrochloride gave 6,12-dimethyl-1,5-dipyrrolediazocane in 17% yield. In sum, we have synthesized and characterized seven new molecules, six of them having photochemical and electrochemical properties interesting for the synthesis of conjugated polymers and dendrimers. The latter offering potential as precursor for the conception of compounds of therapeutic interest.

N-Aryl stilbazolium dyes as sensitizers for solar cells

Eight new N-arylstilbazolium chromophores with electron donating –NR2 (R = Me or Ph) substituents have been synthesized via Knoevenagel condensations and isolated as their PF6− salts. These compounds have been characterized by using various techniques including 1H NMR and IR spectroscopies and electrospray mass spectrometry. UV–vis absorption spectra recorded in acetonitrile are dominated by intense, low energy π → π* intramolecular charge-transfer (ICT) bands, and replacing Me with Ph increases the ICT energies. Cyclic voltammetric studies show irreversible reduction processes, together with oxidation waves that are irreversible for R = Me, but reversible for R = Ph. Single crystal X-ray structures have been determined for three of the methyl ester-substituted stilbazolium salts and for the Cl− salts of their picolinium precursors. Time-dependent density functional theory calculations afford reasonable predictions of ICT energies, but greater rigour is necessary for –NPh2 derivatives. The four new acid-functionalized dyes give moderate sensitization efficiencies (ca. 0.2%) when using TiO2-based photoanodes, with relatively higher values for R = Ph vs Me, while larger efficiencies (up to 0.8%) are achieved with ZnO substrates.

Gas-phase reactions of aryl radicals with 2-butyne : an experimental and theoretical investigation employing the N-methyl-pyridinium-4-yl radical cation

Aromatic radicals form in a variety of reacting gas-phase systems, where their molecular weight growth reactions with unsaturated hydrocarbons are of considerable importance. We have investigated the ion-molecule reaction of the aromatic distonic N-methyl-pyridinium-4-yl (NMP) radical cation with 2-butyne (CH3C CCH3) using ion trap mass spectrometry. Comparison is made to high-level ab initio energy surfaces for the reaction of NMP and for the neutral phenyl radical system. The NMP radical cation reacts rapidly with 2-butyne at ambient temperature, due to the apparent absence of any barrier. The activated vinyl radical adduct predominantly dissociates via loss of a H atom, with lesser amounts of CH3 loss. High-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry allows us to identify small quantities of the collisionally deactivated reaction adduct. Statistical reaction rate theory calculations (master equation/RRKM theory) on the NMP + 2-butyne system support our experimental findings, and indicate a mechanism that predominantly involves an allylic resonance-stabilized radical formed via H atom shuttling between the aromatic ring and the C-4 side-chain, followed by cyclization and/or low-energy H atom beta-scission reactions. A similar mechanism is demonstrated for the neutral phenyl radical (Ph center dot)+2-butyne reaction, forming products that include 3-methylindene. The collisionally deactivated reaction adduct is predicted to be quenched in the form of a resonance-stabilized methylphenylallyl radical. Experiments using a 2,5-dichloro substituted methyl-pyridiniumyl radical cation revealed that in this case CH3 loss from the 2-butyne adduct is favoured over H atom loss, verifying the key role of ortho H atoms, and the shuttling mechanism, in the reactions of aromatic radicals with alkynes. As well as being useful phenyl radical analogues, pyridiniumyl radical cations may form in the ionosphere of Titan, where they could undergo rapid molecular weight growth reactions to yield polycyclic aromatic nitrogen hydrocarbons (PANHs).

A Simple and Convenient One Step Method for the Reductive Deoxygenation of Aryl Ketones to Hydrocarbons

A one step, clean and efficient, conversion of arylaldehydes, ketones and ketals into the corresponding hydrocarbon using ionic hydrogenation conditions employing sodium cyanoborohydride in the presence of two to three equivalents of BF3. OEt(2) is described.

Dialkyl (3-Aryl- 1,2,4-oxadiazol-5-yl)phosphonates: Synthesis and Thermal Behavior-Evidence for Monomeric Alkyl Metaphosphate

Dialkyl (3-aryl-l,2,4-oxadiazol-5-yl)phosphonate6sa -h have been obtained by 1,3-dipolar cycloaddition of arenenitrile oxides 5a-f to dialkyl phosphorocyanidates (4a and 4b) in yields ranging between 30% and 58%. A standardized method for obtaining cyanidates 4a and 4b has been established. The diethyl thiophosphorocyanidate (4c) is less reactive than 4a and 4b, only the 3-(4'-nitrophenyl) derivative 6i being obtainable. While the IR and NMFt spectra of 6a-i were unexceptional, their UV spectra showed evidence of conjugative interaction in high degrees between the phosphonate and heterocyclic moieties as well as a varying conjugative interaction between the heterocyclic and aryl moieties. The oxadiazoles 6a-h are thermally labile and yield trialkyl phosphates 7 as the only identifiable products. A mechanism based on the intermediacy of monomeric alkyl metaphosphate 11 in the formation of trialkyl phosphate was postulated, and supportive evidence in the form of trapping the metaphosphate with acetophenone has been obtained.

1H and 13C dynamic NMR studies of NN-diethyl N'-aryl thioureas

The variable temperature 1H and 13C NMR behaviour of two trisubstituted thioureas, namely N,N-diethyl N'-(2-thiazolyl) thiourea and N,N-diethyl N'-(3-pyridyl)thiourea has been investigated. The barrier to rotation of the diethylamino group has been obtained.

Synthesis and physico-chemical properties of diruthenium(III, II) tetra-aryl carboxylato compounds

Monochloro-tetra-μ-aryl-carboxylatodiruthenium(III, II) compounds Ru2Cl (O2CAr)4 (Ar = -C6H5; -C6H4-p-OCH3), are prepared and characterized. The compounds have magnetic moments that correspond to three unpaired spins per dimer. The Rusingle bondRu bond order is 2.5 and the ground electronic configuration is σ2π4δ2(δ*π*)3. The visible spectral band is observed at ca 450 nm along with a shoulder near 580 nm in DMF solution. The compounds undergo a one-electron Ru(III)Ru(II) → Ru(II)Ru(II) quasi-reversible reduction in DMF near 0.0 V vs sce.

Room temperature metathesis of aryl isocyanates and aromatic aldehydes catalyzed by group(IV) metal alkoxides: An experimental and computational study

Aromatic aldehydes and aryl isocyanates do not react at room temperature. However, we have shown for the first time that in the presence of catalytic amounts of group(IV) n-butoxide, they undergo metathesis at room temperature to produce imines with the extrusion of carbon dioxide. The mechanism of action has been investigated by a study of stoichiometric reactions. The insertion of aryl isocyanates into the metal n-butoxide occurs very rapidly. Reaction of the insertion product with the aldehyde is responsible for the metathesis. Among the n-butoxides of group(IV) metals, Ti((OBu)-Bu-n)(4) (8aTi) was found to be more efficient than Zr((OBu)-Bu-n)(4) (8aZr) and Hf((OBu)-Bu-n)(4) (8aHf) in carrying out metathesis. The surprisingly large difference in the metathetic activity of these alkoxides has been probed computationally using model complexes Ti(OMe)(4) (8bTi), Zr(OMe)(4) (8bZr) and Hf(OMe)(4) (8bHf) at the B3LYP/LANL2DZ level of theory. These studies indicate that the insertion product formed by Zr and Hf are extremely stable compared to that formed by Ti. This makes subsequent reaction of Zr and Hf complexes unfavorable.

N,N′-Bis(aryl)pyridine-2,6-dicarboxamide complexes of ruthenium: Synthesis, structure and redox properties

Reaction of five N,N′-bis(aryl)pyridine-2,6-dicarboxamides (H2L-R, where H2 denotes the two acidic protons and R (R = OCH3, CH3, H, Cl and NO2) the para substituent in the aryl fragment) with [Ru(trpy)Cl3](trpy = 2,2′,2″-terpyridine) in refluxing ethanol in the presence of a base (NEt3) affords a group of complexes of the type [RuII(trpy)(L-R)], each of which contains an amide ligand coordinated to the metal center as a dianionic tridentate N,N,N-donor along with a terpyridine ligand. Structure of the [RuII(trpy)(L-Cl)] complex has been determined by X-ray crystallography. All the Ru(II) complexes are diamagnetic, and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on the [RuII(trpy)(L-R)] complexes shows a Ru(II)–Ru(III) oxidation within 0.16–0.33 V versus SCE. An oxidation of the coordinated amide ligand is also observed within 0.94–1.33 V versus SCE and a reduction of coordinated terpyridine ligand within −1.10 to −1.15 V versus SCE. Constant potential coulometric oxidation of the [RuII(trpy)(L-R)] complexes produces the corresponding [RuIII(trpy)(L-R)]+ complexes, which have been isolated as the perchlorate salts. Structure of the [RuIII(trpy)(L-CH3)]ClO4 complex has been determined by X-ray crystallography. All the Ru(III) complexes are one-electron paramagnetic, and show anisotropic ESR spectra at 77 K and intense LMCT transitions in the visible region. A weak ligand-field band has also been shown by all the [RuIII(trpy)(L-R)]ClO4 complexes near 1600 nm.

Effect of substitution on molecular conformation and packing features in a series of aryl substituted ethyl-6-methyl-4-phenyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylates

The supramolecular structures of eight aryl protected ethyl-6-methyl-4-phenyl-2-thioxo-1,2,3,4 tetrahydropyrimidine-5-carboxyl ates were analyzed in order to understand the effect of variations in functional groups on molecular geometry, conformation and packing of molecules in the crystalline lattice. It is observed that the existence of a short intra-molecular C-H center dot center dot center dot pi interaction between the aromatic hydrogen of the aryl ring with the isolated double bond of the six-membered tetrahydropyrimidine ring is a key feature which imparts additional stability to the molecular conformation in the solid state. The compounds pack via the cooperative involvement of both N-H center dot center dot center dot S=C and N-H center dot center dot center dot O=C intermolecular dimers forming a sheet like structure. In addition, weak C-H center dot center dot center dot O and C-H center dot center dot center dot pi intermolecular interactions provide additional stability to the crystal packing.

Reversible double insertion of aryl isocyanates into the Ti-O bond of titanium(IV) isopropoxide

The insertion of phenyl isocyanate into titanium isopropoxide leads to the formation of a dimeric complex [Ti(O ' Pr)(2)(mu-O ' Pr){C6H5N(O ' Pr)CO}](2) (1) which has been structurally characterized. Reaction of titanium isopropoxide with two and more than 2 equiv. of phenyl isocyanate is complicated by competitive, reversible insertion between the titanium carbamate and titanium isopropoxide. The ligand formed by insertion of phenyl isocyanate into the titanium carbamate has been structurally characterized in its protonated form C6H5N{C(O ' Pr)O}C(O)N(H)C6H5 (3aH). Insertion into the carbamate is kinetically favored whereas insertion into isopropoxide gives the thermodynamically favored product. (c) 2004 Elsevier B.V. All rights reserved.