Investigations of 2-alkyl-3-methoxypyrazines in three ladybug species and wine /

Investigations of 2-alkyl-3-methoxypyrazines (2-isopropyl-3-methoxypyra2ine, 2- secbutyl-3-methoxypyrazine and 2-isobutyl-3-niethoxypyrazine) in ladybug species {Coleoptera: Coccinellidae) and wine samples have been conducted. Headspace sampling coupled with gas chromatography-mass spectrometry was used to determine amounts of 2-alkyl-3-methoxypyra2ines in the ladybug species. Hippodamia convergens had the highest amount of alkybnethoxypyrazines, followed by Harmoma axyridis and the least in Coccinella septempunctata. Using a solvent extraction method, the precoccinelline alkaloid was found present in Hippodamia convergens and Coccinella septempunctata but not Harmonia axyridis. Steam distillation followed by a soHd phase extraction method as a sample preparation technique, enhanced detection while the isotope dilution method afforded accurate quantitation of the alkyknethoxypyrazines in the wine samples. Both ladybug-tainted and commercial wine samples were found to contain the 2- alkyl-3-methoxypyrazines. Wine samples prepared in 2001 generally contained higher levels than the corresponding 2003 samples. Levels of the 2-alkyl-3-methoxypyrazines found in the commercial wines ranged from a minimum value of 6 ng/L to 260 ±10 ng/L. Analyses revealed that for both ladybug species and wine samples, the 2- isopropyl-3-methoxypyrazine had the highest concentration, followed by 2-isobutyl- 3-methoxypyrazine and the least being the 2-secbutyl-3-methoxypyrazine. Possible contamination of the wine samples by ladybugs is thoroughly discussed. Furthermore, attempts to remove or reduce the levels of the alkylmethoxypyrazines with molecularly imprinted polymers from wine samples are presented in detail.

The impact of wine closure and packaging type, and light and temperature exposure on the concentration of 3-alkyl-2 -methoxypyrazines and other key constituents of wine

3-alkyl-2-methoxypyrazines (MPs) are grape- and insect-derived odor-active compounds responsible for vegetative percepts that are detrimental to wine quality when elevated. This study tested both the effect of closure/packaging types and light/temperature storage conditions on MPs (isopropyl-, secbutyl-, and isobutyl-MP) in wine. An MP-emiched wine rapidly (after 140 hours) and significantly decreased in MP concentration after natural and synthetic cork contact (immersion of closures in wine). This decrease was greatest with synthetic closures (70% - 89% reduction) and secbutyl-MP. Subsequently storage trials tested the effects of commercial closure/packaging options (natural cork, agglomerate cork, synthetic corks, screwcaps and TetraPak® cartons) on MPs in MP-emiched Riesling and Cabernet Franc over 18 months. Regardless of packaging, isobutyl-MP was the most altered from bottling. Notably, all MP levels tended to decrease to the greatest extent in TetraPak® cartons (~34% for all MPs) and there was evidence of contribution ofisoproyl- and secbutyl-MP from cork-based closures (i.e. ~30% increase in secbutyl-MP after 6 months) or from an unidentified wine constituent. To test the effects of various light/temperature conditions (light exposed at ambient temperature in three different bottle hues, light excluded at ambient temperature and light excluded at a "cellar" temperature (14°C)), MP-emiched Riesling and Cabernet Franc were also analyzed for MP concentrations over 12 months. MPs did not vary consistently with light or temperature. Other odorants and physico-chemical properties were tested in all wines during storage trials and closely agree with previous literature. These results provide novel insights into MPs during ageing, interactions with packaging and storage conditions, and assist in the selection of storage conditions/packaging for optimal wine quality.

Synthesis, properties and characterization of N-Alkyl substituted b-Diketiminato copper(I) Complexes

Le ligand nacnacxylH (xyl = C6Me2H3) et les ligands dikétimines N-alkyle substitués (nacnacCH(Me)PhH, nacnacBnH and nacnaciPrH) ont été préparés avec de bons rendements à l’exception du nacnaciPrH (23%) en utilisant un protocole en une étape et à l’aide d’un montage Dean-Stark. La réaction du S,S-nacnacCH(Me)PhH et du nacnacBnH avec le nBuLi dans le THF conduit au S,S-nacnacCH(Me)PhLi(THF) et au nacnacBnLi(THF). Les tentatives de bromation de ces composés par le N-bromosuccinimide conduisent plutôt aux ligands S,S-succnacnacCH(Me)PhH et succnacnacBnH (succ = succinimido) substitués par un groupement succinimido sur le carbone  La chloration par le N-chlorosuccinimide conduit au produit désiré, mais avec des impuretés. La réaction de ces ligands avec le CuOtBu (ou bien MesCu, où Mes = C6Me3H2, et une quantité catalytique de CuOtBu) en présence de bases de Lewis donne les (nacnacxylCu)2(-toluène), nacnacxylCuCNC6H3(Me)2, nacnacCH(Me)PhCuL (L = PPh3, PMe3, CNC6H3(Me)2, DMAP, lutidine, Py, MeCN), nacnacBnCuL (L = PPh3, CNC6H3(Me)2, styrène, trans-stilbene, phenylvinylether, acrylonitrile, diphenylacetylène), nacnaciPrCuL (L = PPh3, CNC6H3(Me)2, MeCN) et le succnacnacCH(Me)PhCuL (PPh3, CNC6H3(Me)2, pyridine). Tous ces complexes sont jaunes et sensibles à l’air et à l’humidité. En l’absence de fortes bases de Lewis, on n’observe pas de réaction entre les précurseurs de cuivre et les ligands N-alkyle substitués. Les études RMN des complexes dans le C6D6 ne présentent pas de complexe de toluène mais un mélange à l’équilibre du (nacnacxylCu)2(-C6D6) et nacnacxylCu(C6D6) dans une proportion de 2 pour 1. Alors que l’addition de plus de cinquante équivalents soit de THF, soit de toluène n’induit aucun changement des spectres RMN, l’addition de 2 équivalents de MeCN conduit instantanément au complexe nacnacxylCu(MeCN). De plus, le (nacnacxylylCu)2(-C6D6) ne se coordone ni ne réagit avec le N2O, même après avoir été chauffé à 60°C pendant treize jours. En présence de DPA (diphenylacétylène), la réaction du nacnacBnH avec le CuOtBu conduit au dimère ponté (nacnacBnCu)2(µ-DPA). L’addition d’un excès de DPA (10-12 équivalents) transforme le dimère ponté en complexe lié en position terminale nacnacBnCuDPA. Les nacnacRH (R = CH(Me)Ph et i-Pr) ne forment pas de complexe ni avec les oléfines ni avec le DPA. Une réactivité similaire a été observée avec les complexes de nacnacCH(Me)PhCu(NCMe) et nacnaci-PrCu(NCMe). Tandis que le complexe lié en position terminale par MeCN a été isolé et caractérisé, l’équilibre en solution nous laisse suspecter la formation d’un complexe d’acétonitrile ponté. Des études de réactivité comparatives ont été menées sur quelques complexes de cuivre. La Morpholine ne réagit pas avec le nacnacBnCu(acrylonitrile) contrairement à l’acrylonitrile libre. L’expérience de l’échange d’oléfine montre que l’acrylonitrile (une oléfine électro-attractrice) se lie plus fortement que les autres oléfines, mettant ainsi en évidence l’importance de la rétrodonation  face à la donation La rétrodonation est cependant faible comparée aux autres complexes de styrène structurellement caractérisés. Les complexes nacnacCH(Me)PhCuL (L = PPh3 et MeCN) ont été employés dans la cyclopropanation catalytique du styrène et dans l’addition conjuguée du ZnEt2 sur la 2-cyclohexénone, mais les résultats indiquent que le ligand dikétimine est éliminé avant son entrée dans le cycle catalytique. Par conséquent, il n’y a pas d’induction chirale. Les complexes tétra coordinées de cuivre avec les nacnacRCu(phen) (R = Bn, CH(Me)Ph et Phen = 1,10-phenanthroline, 2-Mes-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline (dmp) et 2,9-diphenyl-1,10-phenanthroline (dpp)) ont été synthétisés. Ces complexes sont d’une intense couleur bleue et des interactions d’empilement entre l’un des cycles phényle des ligands nacnac et la phénanthroline ont été observées dans les structures à l’état solide. Les mesures en absorption UV-visible ont été effectuées dans le toluène et les bandes MLCT sont déplacées vers le rouge par rapport à celles des complexes de cuivre et bisphénanthroline. Tous ces composés émettent à l’état solide mais les complexes 1,10-phenanthroline et 2-Mes-1,10-phenanthroline n’émettent pas en solution. Pour renforcer les interactions d’empilement , les nouveaux ligands nacnacRH (R = CH2C6H2(OMe)3, CH2C6F5) et leurs complexes de cuivre respectifs ont été préparés avec du dmp et dpp. Afin de permettre la comparaison, le nacnaciBuCu(dmp) a été synthétisé. Alors que les complexes dmp montrent une augmentation des interactions intramoléculaires - avec les substituants phényle du ligand dikétimine et de la phénanthroline, les complexes dpp ne révèlent pas de telles interactions. Les complexes perfluorés montrent, en absorption et en émission, un déplacement significatif vers le bleu, alors que les complexes substitués par un groupements isobutyle présentent des transitions déplacées vers le rouge. Alors que les intensités de luminescence et les durées de vie sont faibles, les déplacements réduits de Stokes et les pics étroits de luminescence comparables indiquent une réduction des distorsions de l’état excité.

Étude des poly(2-alkyl-2-oxazoline)s munis d'extrémités hydrophobes en solution aqueuse et à linterface eau/air

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

Design, synthèse et application en catalyse verte d’un ligand alkyl imidazolium β-cyclodextrine

Le 21e siècle est le berceau d’une conscientisation grandissante sur les impacts environnementaux des processus utilisés pour synthétiser des molécules cibles. Parmi les avancées qui ont marqué ces dernières décennies, il est également question de réduction de déchets, de conservation de l’énergie et de durabilité des innovations. Ces aspects constituent les lignes directrices de la chimie verte. De ce fait, il est impératif de développer des stratégies de synthèse dont les impacts environnementaux sont bénins. Dans ce mémoire nous présentons la synthèse, la caractérisation et l’étude des propriétés catalytiques en milieu aqueux d’un ligand composé d’une unité -cyclodextrine native, d’une unité imidazolium et d’une chaine alkyle à 12 carbones. Ce ligand hybride s’auto-assemble dans l’eau sous forme de micelles, permettant ainsi d’effectuer en sa présence des couplages de Suzuki-Miyaura dans l’eau, avec de bons rendements. La fonctionnalisation de la face primaire de la -cyclodextrine par un noyau alkyl-imidazolium, précurseur de ligand de type carbène N-hétérocyclique, a permis le développement d’un système catalytique vert et hautement recyclable. Dans un deuxième temps, nous présentons l’utilisation du même ligand hybride dans des couplages de Heck dans l’eau, démontrant ainsi la versatilité du ligand.

Second Order Fit for Mercuric Chloride Catalysed Solvolysis of Alkyl Chlorides in Aqueous DMSO Solvents

Kinetics of mercuric chloride catalysed solvolysis of l-butyl chloride, benzyl chloride. p-methylbenzyl chloride, l-phenylethyl chloride and triethylcarbinyl chloride have been studied in aq. DMSO, aq. acetonitrile and aq. ethanol. The kinetic data fit a second order rate equation in aq. DMSO. The calculated values of the second order rate coefficients increase in the case of aq. acetonitrile and aq. ethanol. The order in catalyst in 95%(v/v) aq. DMSO is less than unity.

Alkyl nitrates in outflow from North America over the North Atlantic during Intercontinental Transport of Ozone and Precursors 2004

This paper is based on alkyl nitrate measurements made over the North Atlantic as part of the International Consortium for Research on Atmospheric Transport and Transformation (ICARTT). The focus is on the analysis of air samples collected on the UK BAe-146 aircraft during the Intercontinental Transport of Ozone and Precursors (ITOP) project, but air samples collected on board the NASA DC-8 and NOAA WP-3D aircraft as part of a Lagrangian experiment are also used. The ratios between the alkyl nitrates and their parent hydrocarbons are compared with those expected from chemical theory. Further, a box model is run to investigate the temporal evolution of the alkyl nitrates in three Lagrangian case studies and compared to observations. The air samples collected during ITOP do not appear to be strongly influenced by oceanic sources, but rather are influenced by emissions from the N.E. United States and from Alaskan fires. There also appears to be a widespread common source of ethyl nitrate and 1-propyl nitrate other than from their parent hydrocarbons. The general agreement between the alkyl nitrate data and photochemical theory suggests that during the first few days of transport from the source region, photochemical production of alkyl nitrates, and thus ozone, had taken place. The observations in the more photochemically processed air masses are consistent with the alkyl nitrate production reactions no longer dominating the peroxy radical self/cross reactions. Further, the results also suggest that the rates of photochemical processing in the Alaskan smoke plumes were small.

Novel solid networks containing Sn-H as a greener replacement for soluble alkyl Sn-H reagents in radical assisted organic synthesis

DiGrignard reagents of the form XMg(CH2)(n)MgX, where X = Br or I and n = 6, 8, 10 or 12, were allowed to react with PhSnCl3 to produce highly cross-linked Ph-Sn polymeric networks. The Sn-H moiety was incorporated into these insoluble network polymers by treatment with Br-2 and NaBH4. Excellent accessibility of the Sn-H was displayed by these solvent penetrable but insoluble networks, giving them higher Sn-H loadings than all previously reported supported reagents. These reagents were totally regenerable in NaBH4 for radical assisted organic synthesis and no detectable leaching of the Sn into solution was observed during these reactions.

Fulvalene titanium and zirconium complexes: synthesis and NMR study of phosphanido-, alkyl-, and alkynyl-derivatives. X-ray crystal structures of [{Ti(η5−C5H5)(μ−PPH2)}2{μ−(η5−C5H4−η5−C5H4)}] and [{Zr(η5−C5H5)(μ−C≡CSiMe3)}2{μ−(η5−C5H4−η5−C5H4)}]

Reaction of with one or two equivalents of LiPPh2 afforded the new phosphanidometal(III) complexes . Reaction of 2 with LiC≡CSiMe3 led to the diamagnetic zirconium(III) alkynyl derivative [{Zr(C5H5)(μ−C≡CSiMe3)}2(μ−η5−C5H4−η5−C5H4], 7. Alkylation of 6 with LiCH2CMe2Ph gave [{Zr(η5−C5H5)(CH2CMe2Ph)2}2{μ−(η5−C5H4)}], 8. A detailed NMR study of complexes 3 and 4 allowed the observation of the spectral behaviour of the eight different fulvalene protons through their coupling to the 31P nucleus. The fluxional behaviour of complex 7 was studied by dynamic DNMR, and kinetic parameters for the σ-π-conversion of the alkynyl ligand were determined. The molecular structures of complexes 3 and 7 were determined by X-ray diffraction methods.

Tin–osmium cluster formation with a monomeric tin(II) alkyl: the formation, crystal structure and reactivity of [Os3(µ-H)SnR(CO)10], a formal stannyne complex of the osmium triangle {R = C(SiMe3)2C5H4N-2}

The monomeric tin(II) species SnR2{R = C(SiMe3)2C5H4N-2} reacts with [Os3(H)2(CO)10] in hexane to give [Os3(µ-H)SnR(CO)10]1 quantitatively; 1 is the first formal stannyne complex of the triosmium nucleus, in which the picoline nitrogen is coordinated to the tin atom, and which is itself also reactive, being a potential precursor to high nuclearity SnOs clusters.

Synthesis and evaluation of lipophilic BTBP ligands for An/Ln separation in nuclear waste treatment: the effect of alkyl substitution on extraction properties and implications for ligand design

Four new 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) ligands, which contain either additional alkyl groups on the pyridine rings or seven-membered aliphatic rings attached to the triazine rings, have been synthesized, and the effects of the additional alkyl substitution in the 4- and 4′-positions of the pyridine rings on their extraction properties with LnIII and AnIII cations in simulated nuclear waste solutions have been studied. The speciation of ligand 13 with some trivalent lanthanide nitrates was elucidated by 1H NMR spectroscopic titrations and ESI-MS. Although 13 formed both 1:1 and 1:2 complexes with LaIII and YIII, only 1:2 complexes were observed with EuIII and CeIII. Quite unexpectedly, both alkyl-substituted ligands 12 and 13 showed lower solubilities in certain diluents than the unsubstituted ligand CyMe4-BTBP. Compared to CyMe4-BTBP, alkyl-substitution was found to decrease the rates of metal-ion extraction of the ligands in both 1-octanol and cyclohexanone. A highly efficient (DAm > 10) and selective (SFAm/Eu > 90) extraction was observed for 12 and 13 in cyclohexanone and for 13 in 1-octanol in the presence of a phase-transfer agent. The implications of these results for the design of improved extractants for radioactive waste treatment are discussed.

Influence of diluent alkyl substitution on the extraction of Am(III) and Eu(III) by a 6,6'-bis(1,2,4-triazinyl)-2,2'-bipyridine ligand dissolved in alkylated cyclohexanone diluents

Several alkylated cyclohexanones were investigated as potential diluents for the selective extraction of Am(III) and Eu(III) from nitric acid solutions by the CyMe4-BTBP ligand. No significant extraction of either of the metal ions was observed for these diluents themselves. In the extractions from 1 M HNO3, 3-methylcyclohexanone and 4-methylcyclohexanone gave comparable results to cyclohexanone whereas in the extractions from 4 M HNO3, 2-methylcyclohexanone, 3-methylcyclohexanone and 4-methylcyclohexanone all gave superior results. For the monomethylated diluents, DAm and SFAm/Eu decreased in the order of alkyl substitution 2 > 4 ~ 3. However, alkyl substitution of cyclohexanone significantly slows down the extraction kinetics compared to cyclohexanone, and the position of alkyl substitution was found to play an important role in the solvents properties. 3-Methylcyclohexanone was identified as the most promising of the diluents.

The effect of alkyl substitution on the extraction properties of BTPhen ligands for the partitioning of trivalent minor actinides and lanthanides in spent nuclear fuels

Bis-triazinylphenanthroline ligands (BTPhens), which contain additional alkyl (n-butyl and sec-butyl) groups attached to the triazine rings, have been synthesized, and the effects of this alkyl substitution on their extraction properties with Ln(III) and An(III) cations in simulated nuclear waste solutions have been studied. The speciation of n-butyl-substituted ligand (C4- BTPhen) with some trivalent lanthanide nitrates was elucidated by 1 H-NMR spectroscopic titrations. These experiments have shown that the dominant species in solution were the 1:2 complexes [Ln(III)(BTPhen)2], even at higher Ln(III) concentrations, and the relative stability of 2:1 to 1:1 BTPhen-Ln(III) complexes varied with different lanthanides. As expected, sec-butylsubstituted ligand (sec-C4 BTPhen) showed higher solubility than C4-BTPhen in certain diluents. A greater separation factor (SFAm/Eu = ca. 210) was observed for sec-C4-BTPhen compared to C4-BTPhen (SFAm/Eu = ca. 125) in 1-octanol at 4 M HNO3 solutions. The greater separation factor may be due to the higher solubility of the 2:1 complex for sec-C4-BTPhen at the interface than the 1:1 complex of C4-BTPhen.