A presente Dissertação relata o estudo conformacional e das interações eletrônicas dos α-(etilsulfonil)-tioacetatos de fenila-para-substituídos X-Φ-S-C(O)-CH2-SO2-Et, sendo X substituintes atraentes, hidrogênio e doadores de elétrons, isto é, X= NO2 (1), Cl (2), Br (3), H (4), Me (5) e OMe (6) através da espectroscopia no Infravermelho, apoiada por cálculos ab initio e difração de Raio-X. Os dados obtidos indicaram a existência dos confôrmeros gauche1(s-trans) e um gauche2(s-cis), sendo este último bem mais estável do que o primeiro. Assim sendo, pode-se concluir que o componente de menor freqüência de maior intensidade da banda de carbonila corresponde ao confôrmero mais estável s-cis e o de maior freqüência de menor intensidade da banda da carbonila corresponde ao confôrmero s-trans menos estável. Diferentemente do que ocorre na maioria dos compostos carbonílicos α-heterossubstituídos, pode-se constatar que o aumento da polaridade do solvente origina uma população relativa gauche2(s-cis)/gauche1 (s-trans) praticamente constante em todas a série dos tioésteres estudados (1 )-(6). Este comportamento está de acordo com a menor basicidade dos tioésteres em relação às outras classes de compostos carbonílicos. Os dados dos cálculos ab initio indicam que: a) As interações orbitalar e eletrostática Oγ-(SO2)...........Cγ+(CO) estabilizam as conformações gauche2(s-cis) e gauche1(s-trans) praticamente na mesma extensão; b) A interação Oγ-(CO)...........Sγ+(SO2) estabiliza a conformação gauche2 (s-cis) em maior extensão do que a gauche1 (s-trans); c) A interação por ponte de hidrogênio Oγ-(CO)...........Hγ+(SO2Me)...........é mais forte no rotâmero gauche2(s-cis) do que no rotâmero gauche1 (s-trans). Os dados no Infravermelho indicam um aumento progressivo da população relativa gauche2(s-cis)/gauche1(s-trans) para os compostos de (1)-(6) em todos os solventes indo-se na posição para do grupo fenilsulfonila de substituintes atraentes a doadores de elétrons. Adicionalmente, constata-se no Infravermelho a ocorrência em CCl4 de deslocamentos de freqüência (Δν) mais negativos para o rotâmero gauche2(s-cis) do que o rotâmero gauche1(s-trans) dos compostos de (1)-(6), em relação aos tioacetatos de fenila correspondentes. Os dados no I.V. apoiam fortemente nos α-(etilsulfonil)-tioacetatos de fenila-para-substituídos (1)-(6) a ocorrência das interações orbitalares e eletrostáticas acima mencionados que estabilizam a conformação gauche2(s-cis) em maior extensão do que a gauche1(s-trans). Contrariamente ao nosso estudo anteriores de β-ceto-sulfonas, este comportamento pode ser atribuído à predominância das interações Oγ-(CO)...........Sγ+(SO2) e Oγ-(CO)...........Hγ+(SO2Me) sobre Oγ-(SO2)...........Cγ+(CO). De fato substituintes doadores de elétrons aumentam a densidade eletrônica sobre o átomo de oxigênio carbonílico, e desta forma facilitam as interações Oγ-(CO)...........Sγ+(SO2) e a Oγ-(CO).........Hγ+(SO2Me). Contrariamente, os substituintes em para atraente de elétrons diminuem a densidade eletrônica no átomo de oxigênio da carbonila e deste modo fazem com que a referida interação toma-se mais difícil de ocorrer. A análise por difração de Raio-X mono cristal dos α-etilsulfoniltioacetatos de fenila-(4) e de -para-metilfenila-(5) indicou que estes compostos no estado sólido encontram-se na conformação gauche2(s-cis), porém, ligeiramente distorcida em relação à mesma conformação presente no estado gasoso e em solução. A cela unitária do cristal é estabilizada pelo ganho de energia obtido tanto pelo acoplamento dos momentos de dipolos como também pela formação de ligações de hidrogênio intermoleculares Hγ+(orto)..........Oγ-(CO) e Hγ+(CH2CH3)...........Oγ(CO). / This thesis reports the conformational and electronic interaction studies of some p-substituted S-phenyl α-(ethylsulfonyl)-thioacetates Ph-SC(O)CH2SO2Et, being X electron-attracting, hydrogen and electron-donating para-substituents [X= NO2 (1), Cl (2), Br (3), H (4), Me (5) and OMe (6)], through IR spectroscopy supported by ab initio calculations and X-ray diffraction. The obtained data indicated the occurrence of two stable conformations i.e. the gauche2(s-cis) and the gauche1 (s-trans), being the former the most stable one. Therefore it may be concluded that the lower frequency more intense carbonyl doublet component is the most stable gauche2(s-cis) conformer while the higher frequency less intense doublet component is the least stable gauche1(s-trans) conformer. Differently from the majority of the α-heterosubstituted carbonyl compounds, the increasing polarity of the solvent effect originates an almost constant gauche2(s-cis)/gauche1(s-trans) population ratio for the whole series (1)-(6). This behaviour seems to be in line with the smaller basicity of the thioesters in comparison with the other classes of carbonyl compounds. The ab initio data indicate that: a) the Oγ-(SO2)..........Cγ+(CO) orbital and Coulombic interactions stabilise both the gauche2(s-cis) and gauche1 (s-trans) conformations almost to the same extent; b) the Oγ-(CO)..........Sγ+(SO2) interaction stabilises gauche2(s-cis) conformer into a greater extent than the gauche1(s-trans) conformer; e) the hydrogen bond interaction Hγ+(SO2Me)..........Oγ-(CO)) is slightly stronger for the gauche2(s-cis) conformer than that for the gauche1(s-trans) conformer. The IR data indicate that there is a progressive increase of the gauche2(s-cis)/gauche1(s-trans) population ratio for the whole series (1)-(6), on going at the para position of the phenylsulfonyl group, from electron attracting to electron donating substituents. Moreover there is, in carbon tetrachloride, a larger negative carbonyl frequency shifts (Δν) for the gauche2(s-cis)conformer of the title compounds (1)-(6) with respect to the gauche1(s-trans) conformer relative to the corresponding parent S-phenyl thioacetates (7)-(12). Therefore the IR data strongly support for the p-substituted S-phenyl α-(ethylsulfonyl)-thioacetate series the occurrence of the orbital and electrostatic interactions which stabilise the gauche2(s-cis) conformer into a larger extent than the gauche1(s-trans)conformer. Differently from the previously studied β-carbonyl-sulfones, this behaviour can be mainly ascribed to the predominance of the summing up of the Oγ-(CO)..........Sγ+(SO2) and Hγ+(SO2Me)..........Oγ-(CO) interactions over the Oγ-(SO2)..........Cγ+(CO) interaction. In fact, the electron donating para substituents increases the electron density on the carbonyl oxygen atom, and thus facilitates both the Oγ-(CO)..........Sγ+(SO2) and Hγ+(SO2Me)..........Oγ-(CO) interactions. On the other hand the electron attracting para substituents decreases the electron density on the carbonyl oxygen atom and thus make the referred interactions more difficult to occur. X-ray single crystal diffraction analyses for the S-phenyl-(4) and S-p-methylphenyl-(5), α-(ethylsulfonyl)-thioacetates indicated that these compouns exist in the solid state in a geometry which is reasonably close to the more stable gas and solution gauche2(s-cis) conformation. Furthermore in order to obtain the larger energy gain from the crystal packing, the slightly distorted gauche2(s-cis) geometry of compounds ( 4) and (5) is stabilised in the solid though dipole moment coupling along with the intermolecular Hγ+(o-Φ)..........Oγ-(CO) and Hγ+(CH2CH3)..........Oγ-(CO) hydrogen bond interactions.

A presente tese apresenta: 1. Revisão bibliográfica de reações de sulfenilação de compostos carbonílicos, nitrilas, compostos de fósforo e de enxofre. 2. Um estudo comparativo de sulfenilações de sulfonas benzílicas orto-, meta- e para-substituídas. São sintetizadas e caracterizadas oito sulfonas benzílicas monossulfeniladas e seis sulfonas benzílicas dissulfeniladas, todas inéditas. 3. Reações de decomposição térmica de sulfonas benzílicas orto- e meta-substituídas, conduzindo aos benzaldeídos orto- e meta-substituídos. 4. Reações de deuteração de α-metiltio Sulfonas benzílicas orto- e meta-substituídas, com obtenção de oito α-deutério sulfonas correspondentes inéditas. 5. Reações da decomposição térmica de sulfonas deuteradas orto- e meta-substituídas, conduzindo aos benzaldeídos deuterados correspondentes, com elevado índice de deuteração, sendo alguns deles inédito. / This thesis is presents: 1. A literature review on the sulfenylation reactions of carbonyl compounds, nitriles, as well as sulfur and phosphorus compounds. 2. A comparative study of the sulfenylation of ortho--, meta- e para-substituted benzyl sulfones is reported. Eight monosulfenylated and six disulfenylated new benzyl sulfones have been sinthesized. 3. Pyrolysis of ortho- and meta-substituted benzyl sulfones, leading to the corresponding benzaldehydes. 4. Deuteration reactions of α-methylthio ortho- and meta-substituted benzyl sulfones, leading to eight new α-deuterated corresponding sulfones. 5. Pyrolysis of deuterated ortho- and meta-substituted benzyl sulfones, yielding the corresponding 1-deuterio benzaldehydes of high isotopic purity, some of them not described in the literature.

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-05-09T20:05:40Z No. of bitstreams: 1 2016 - Melise Ferreira de Aguiar.pdf: 5763969 bytes, checksum: 9dcc7682d7ffab0b0a6ce4d1db704c10 (MD5) / Made available in DSpace on 2017-05-09T20:05:40Z (GMT). No. of bitstreams: 1 2016 - Melise Ferreira de Aguiar.pdf: 5763969 bytes, checksum: 9dcc7682d7ffab0b0a6ce4d1db704c10 (MD5) Previous issue date: 2016-12-12 / CAPES / Natural gas is extensively used in industries as well as in other sectors as an energy resource and, sometimes, it needs to undergo processes for the removal of impurities present in its composition. Among them are the sulfur compounds, which can cause damages to pipes and catalysts, making it necessary to develop and/or improve deep desulfurization methods. In this context, granular activated carbon was modified through two methods, oxidation using nitric acid, and impregnation using a ferric chloride solution. The resulting adsorbents were evaluated for their capacity of adsorbing seven sulfur compounds present in the synthetic natural gas sample, through their rupture curves. Afterwards, the adsorbents desorption was performed by using supercritical carbon dioxide under the conditions of 60?C at 100 bar, 150 bar and 200 bar. The results indicate that all the modification methods improved the sulfur compounds retention when compared to virgin activated carbon. The compound that had the greatest increase in the adsorption capacity after iron impregnation was the tert-butyl mercaptan (TBM), and with the activated carbon oxidized by HNO3 it was the dimethyl sulfide (DMS). Nevertheless, the supercritical conditions studied in the desorption stage were efficient only for the unmodified activated carbon. The adsorption capacities of both modified adsorbents after the regeneration were inferior to those capacities obtained in the first adsorption, then two hypotheses were investigated: (1) destruction of the newly created sites after regeneration; and (2) incomplete desorption in the studied supercritical conditions. Through other experiments it was proved that, after regeneration, there was no destruction of the newly created sites; therefore, further studies on the operating conditions are required in order to the modified adsorbents to achieve high regeneration capacities. / O g?s natural ? utilizado nas ind?strias e em outros setores como fonte de energia e necessita, por vezes, de processos de remo??o das impurezas presentes em sua composi??o. Dentre elas est?o os compostos de enxofre, que provocam danos em tubula??es e catalisadores, sendo necess?rio o desenvolvimento e/ou o aperfei?oamento de m?todos para a dessulfuriza??o profunda. Nesse contexto, um carv?o ativado granular foi modificado por meio de dois m?todos, oxida??o utilizando ?cido n?trico e por impregna??o usando uma solu??o de cloreto de ferro III, os adsorventes resultantes foram avaliados quanto ? sua capacidade para adsorver sete compostos de enxofre presentes em uma amostra de g?s natural sint?tica, atrav?s das curvas de rupturas. Posteriormente, foi realizada a dessor??o dos adsorventes utilizando di?xido de carbono supercr?tico nas condi??es de 60 ?C a 100 bar, 150 bar e 200 bar. Os resultados indicam que todos os m?todos de modifica??o melhoraram a reten??o dos compostos sulfurados individuais em compara??o com o carv?o ativado virgem. O composto que obteve maior aumento da capacidade de adsor??o ap?s a impregna??o com ferro foi o terc-butilmercaptana (TBM), e com o carv?o ativado oxidado pelo HNO3 foi o metiletilsulfeto (DMS). J? as condi??es supercr?ticas estudadas na etapa de dessor??o foram eficientes somente para o carv?o ativado n?o modificado. As capacidades de adsor??o dos dois adsorventes modificados ap?s a regenera??o foram inferiores aos obtidos na primeira adsor??o, ent?o duas hip?teses foram investigadas: (1) destrui??o dos novos s?tios criados ap?s a regenera??o; e (2) dessor??o incompleta nas condi??es supercr?ticas estudadas. Atrav?s de outros experimentos comprovou-se que n?o houve ? destrui??o dos novos s?tios criados ap?s a regenera??o, sendo necess?rio um estudo mais profundo em rela??o ?s condi??es operacionais, a fim de alcan?ar altas capacidades de regenera??o dos adsorventes modificados.

A presente tese apresenta uma nova síntese de vários vinil sulfóxidos, importantes dienófilos e aceptores de Michael, a partir de matéria prima facilmente disponível - álcoois ou haletos benzílicos. Dois passos novos nesta síntese, a sulfenilação de benzil i-propil sulfonas e o rearranjo de Ramberg-Bäcklund de α-metiltio sulfonas correspondentes resultantes da sulfenilação, são investigados. Os vinil sulfetos, obtidos neste último passo, podem ser também sintetizados por outros métodos. Uma grande variedade dos mesmos foi recolhida da literatura e agrupada em diversas classes, considerando as reações envolvidas. A falta de um \"review\" deste tipo na literatura toma a nossa revisão bibliográfica de grande utilidade. A síntese por nós desenvolvida pode ser apresentada pelo esquema abaixo indicado: (Veja esquema no arquivo PDF) Este esquema mostra que além das duas principais reações por nós já mencionadas, sulfenilação e rearranjo de Ramberg-Bäcklund, podem ser também destacadas diversas reações de oxidação de sulfetos que diferem no emprego de reagentes oxidantes e de condições experimentais. O esquema indica também que as tentativas de obtenção de vinil sulfóxidos pela oxidação prévia de sulfonas α-sulfeniladas aos sulfóxidos correspondentes e rearranjo de Ramberg-Bäcklund destes últimos, foram infrutíferas. Um número considerável de compostos novos foram por nós sintetizados, entre eles cinco benzil i-propil sulfonas, nove sulfonas sulfeniladas, quatro vinil sulfetos, três vinil sulfóxidos e cinco α-sulfinil sulfonas, além de quatro sulfetos intermediários. Além da parte sintética, a presente tese apresenta também uma discussão sobre as estabilidades e reatividades relativas de intermediários envolvidos nas duas reações investigadas: os α-sulfonil e α- metiltio α-sulfonil carbânions, destacando a influência do grupo metiltio. / This thesis presents a new synthesis of some vinyl sulfoxides, important dienophiles and Michael acceptors, starting from the easily available materials, benzylic alcohols or halides. Two new reaction steps of this synthesis, sulfenylation of benzyl i-propyl sulfones leading to the corresponding α-methylthio sulfones and Ramberg-Bäcklund rearrangement of the latter to give vinyl sulfides, are investigated. A great number of methods of synthesis of vinyl sulfides, described in the literature, were collected and selected according to the type of reaction which they envolve. It is noteworthy that such literature review could not be found in the literature. The scheme below shows the reaction steps of our synthesis of vinyl sulfides. (See scheme in file) It may be seen in the scheme that, beside the already mentioned two main reactions, sulfenylation and Ramberg-Bäcklund rearrangements, several oxidations of sulfides were also performed, which differ in oxidating reagents and experimental conditions. The scheme also indicates that the efforts to obtain the vinyl sulfoxides by previous oxidation of the α-sulfenylated sulfones to the corresponding sulfoxides and Ramberg-Bäcklund rearrangement of the latter, were unsuccessful. A considerable number of new compounds were synthesized, betwen them five benzyl i-propyl sulfones, nine α-sulfenylated sulfones, four vinyl sulfides, three vinyl sulfoxides, five sulfinyl sulfones, and four intermediate sulfides. The thesis presents also a discussion on the relative stability and reactivity of the reaction intermediates - α-sulfonyl and α-methylthio, α-sulfonyl carbanions, enhancing the influence of α-methylthio group.

S’ha estudiat la formació de sulfur d’hidrogen (H2S) i altres compostos de sofre volàtils lleugers com els mercaptans i disulfurs per part dels llevats durant la fermentació vínica. Es proposen mètodes per mesurar i evitar el problema de l’olor desagradable del H2S i els seus derivats, des de la vinya, el most, els llevats i el vi, i respectar les aromes pròpies de cada varietat. S’han analitzat diferents factors de la producció dels compostos de sofre, la descripció dels defectes associats, la formació dels sulfurs: anàlisi, identificació i quantificació dels sulfurs en vins, s’han identificat compostos com l’etil mercaptà, sulfur de dimetil i en menor quantitat el sulfur de dietil i el sulfur de metil. S’ha estudiat el moment de la formació en mostos model, i s’ha vist una o dues fases durant la fermentació on la producció de sulfur és alta. S’han estudiat les aromes típiques de varietats locals mitjançant l’anàlisi sensorial descriptiva. En un estudi de soques de llevat, s’ha observat que la majoria (60%) produeixen alguna quantitat de sulfurs durant la fermentació i que l’elecció de la soca és un factor important. S’han provat tres tipus de reg en vinya i s’ha vist que influeix en els estils dels vins i en els compostos nitrogenats dels mostos resultants. En vinya per la prevenció de l’oïdi es van fer tractaments alternatius sense sofre, per tal d’evitar la formació de sulfurs. Per a identificar el component genètic de la producció de H2S s’han comparat els transcriptomes de dues soques amb propietats enològiquessimilars, però diferent producció de H2S: UCD 522 (alta producció) i P29 (baixa producció). Les mostres es van extreure durant fermentacions en el moment de màxima producció de H2S. Degut a què no eren soques de laboratori es van fer tres tipus d’estudi del perfil de transcripció de les dues soques de llevat: un array basat en el cADN, un array basat en oligonucleòtids i un anàlisi per qRTPCR d’una selecció de transcripts. Els resultats foren similars amb les tres tècniques. Més del 90% dels gens no van mostrar diferències entre les dues soques. En canvi, la majoria dels gens relacionats amb la biosíntesi de la tiamina van tenir una sobreexpressió a la soca amb alta producció de H2S. Per contra, gens relacionats amb el catabolisme dels aminoàcids, una possible font de H2S, no van mostrar diferències d’expressió entre les dues soques. Això suggereix que, en les condicions estudiades, el metabolisme secundari com la biosíntesi de la tiamina i altres compostos amb sofre pot ser clau per explicar la producció de H2S per algunes soques de llevat durant la fermentació. En vins amb defectes de compostos de sofre volàtil s’han tractat amb citrat de coure i s’ha vist que podia ser una alternativa al sulfat de coure que s’ha fet servir tradicionalment.

We have described herein a convenient one-pot synthesis of lisulfides/diselenides from a-amino acids mediated by ammonium etrathiomolybdate in water. (Figure 1) (Figure) Figure 1 Transformation of α-amino acids into the corresponding tiiocyanates/selenocyanates/disulfides/diselenides Halo-de-amination of a-amino acids using HBr/NaNCte followed by treatment with ammonium tetrathiomolybdate (NH4)2]VloS4 jLb provided a general route for the the one-pot synthesis of chiral a,a' bis (dithio) carboxylic acids (Figure 1, 2b). The yields were moderate, limited mainly the moderate conversion of a-amino acids into the corresponding chiral a-bromides. It was possible to synthesize the 2-thiocyanto carboxylic acids from the corresponding a-amino acids by a similar strategy. Thus diazotization in the presence of KSCN yielded in the chiral 2-thiocyanto carboxylic acids in moderate yields (Figure 1, 3). Thiocyanato-de-amination thus afforded the thiocyanates which when treated with JJD provided the chiral disulfides (Figure 1, 4a). We could thus synthesize both enantiomers of the disulfide from a single enantiomer of the starting a-amino acid. (Figure 1, 4a,4b) Using a similar strategy we have also demonstrated an efficient method for the synthesis of chiral selenocyanates starting from a-amino acids, using selenocyanate anion as the nucleophile (Figure 1, 5). It is possible to demonstrate a one-pot synthesis of chiral diselenides by reductive coupling of selenocyanates using JJb. (Figure 1, 6) (for figure see the pdf file)

This diploma thesis is focused on changes in the content of ?-glutamyl- S-vinylcysteine (GVC), the anti-nutritional factor present in narbon beans (Vicia narbonensis). The samples were collected at different stages of growth and separated into individual parts. There were prepared 32 extracts after freeze-drying and homogenisation in which it was determined the quantity of GVC by HPLC. The levels of GVC at different developmental stages were influenced by climatic conditions during growth, mainly by temperature and precipitation. The results obtained were compared with data published previously in the literature. The highest content of GVC was found in the seeds of narbon beans, especially at early stages of growth. Surprisingly, no GVC was detected in other parts of narbon beans (stems, leaves, beans, and roots).

Há algum tempo, o laboratório de eletrossíntese orgânica do Instituto de Química vem estudando reações de halociclização na obtenção de compostos heterocíclicos de enxofre. No presente trabalho foram utilizados γ-δ e ;-δ-ε alquenil benzil sulfetos e realizados experimentos seguindo duas metodologias diferentes: a química (reações dos substratos com bromo) e a eletroquímica (reações dos substratos com bromo gerado eletroquimicamente). Os experimentos eletroquímicos são mais vantajosos porque dispensam a manipulação de bromo que, neste método, é gerado in situ através da oxidação eletroquímica de íons brometo. As misturas de reação obtidas nestes experimentos foram submetidas à oxidação com ácido m-cloro-perbenzóico ou oxone antes de isolar e caracterizar os produtos formados. Obteve-se resultados diferentes dependendo da metodologia empregada. Para os experimentos realizados com os 2-(1-ciclopentenil)-etilbenzil sulfeto (1a), 2-(1-cicloexenil)-etil-benzil sulfeto (1b) e (5-fenil-4pentenil)-benzil sulfeto (1c) em que foi utilizado bromo, os produtos principais foram os compostos heterocíclicos esperados a saber, hexa-hidro-3a-bromociclopenta[b]tiofeno-S-dióxido (6a), octa-hidro-3a-bromo-benzo[b]tiofeno-Sdióxido (6b) e 2-(1-bromo-1-fenilmetil)-tetra-hidro-tiofeno-S-dióxido (6c) respectivamente, porém o (3-metil-3-butenil)-benzil sulfeto (1d), nas mesmas condições, conduziu à (3,4-dibromo-3-metil-butil)-benzil sulfona (3d). Nos experimentos eletroquímicos, os resultados dependeram do eletrólito de suporte e do tipo de cela utilizados. Em cela dividida, utilizando Et4NClO4 na presença de pequenas quantidades de Et4NBr, o sulfeto (1b) forneceu como produto principal o composto heterocíclico (6b) e o sulfeto (1d) forneceu o perclorato de 3-bromo-3-metil-tetra-hidro-tiofeno-S-benzil sulfônio (4d). Quando apenas Et4NBr foi empregado o produto principai para o sulfeto (1b) foi o composto de adição de bromo à ligação dupla 2-(1,2-dibromocicloexil)-etil-benzil sulfona (7b). Este mesmo substrato fornece como produto principal a 2-(1,2-epóxi-1-cicloexil)-etil-benzil sulfona (11b) quando a eletrólise é realizada em cela não dividida. / The laboratory of organic electrosynthesis of the Instituto de Química has studied halocyclisation reactions to obtain of sulfur heterocyclic compounds. In the present work, γ-δ and δ-ε alkenyl benzyl sulfides were employed and experiments were carried out using two methodologies, a chemical (substrate reactions with bromine) and an electrochemical (substrate reactions with bromine generated electrochemically). The electrochemical experiments are more suitable because they avoid handling of bromine which is generated in situ by electrochemical oxidation. The crude reaction products were oxidized with m-chloroperbenzoic acid or oxone before their separation and characterization. Different results were obtained depending upon the methodology used. When 2-benzylthio-1-(1-cyclopentene)-ethane (1a), 2-benzylthio-1-(1-cyclo hexene)-ethane (1b) and 5-benzylthio-1-phenyl-1-pentene (1c) reacted with bromine the expected cyclic compounds hexahydro-3a-bromocyclopentan [b]thiophene-S-dioxide (6a), octahydro-3a-bromobenzo[b]thiophene-S-dioxide (6b) and 2-(1-bromo-1-phenylmethyl)tetrahydro-thiophene-S-dioxide (6c) respectively, were obtained, but (3-methyl-3-butenyl) benzyl sulfide (1d) yielded (3,4-dibromo-3-methylbutyl) benzyl sulfone (3d). In the electrochemical experiments, the structure of the products depends on the salt used as electrolyte and the type of cell used in the electrolyses. In a divided cell, when Et4NClO4 in the presence of small amounts of Et4NBr was employed, the main product from sulfide (1b) was compound (6b) whereas (3-methyl-3-butenyl) benzyl sulfide (1d) yielded 3-bromo-3-methyltetrahydrothiophene-S-benzyl sulfonium perchlorate (4d). Using only Et4NBr as electrolyte (1b) gave 2-(1,2-dibromocyclohexyl)ethyl benzyl sulfone (7b). The same substrate (1b) when electrolysed in an undivided cell, and otherwise same experimental conditions, afforded, as major product, 2-(1,2-epoxy-1-cyclohexyl)ethyl benzyl sulfone (11b).

Les composés soufrés sont répandus dans divers secteurs industriels comme la chimie. La conception et/ou l'optimisation des procédés impliquant ces composés nécessite de connaître leurs propriétés thermodynamiques (corps purs et mélanges). Etant donnée la complexité des mélanges et pour des raisons économiques, des modèles thermodynamiques « prédictifs » sont souvent privilégiés. Le développement et la validation de ces modèles nécessitent des données expérimentales. Notre étude bibliographique ciblant les sulfures (R-S-R'), les 1-mercaptans (R-SH) et leurs éventuels solvants (les n-alcanes et les 1-alcools) nous a permis de mettre en évidence un manque de données concernant ces composés. De plus nous avons également observé un manque de techniques expérimentales adaptés, et de ce fait le besoin de développer un nouveau dispositif expérimental.Au cours de cette thèse, nous avons conçu un dispositif expérimental innovant permettant la mesure des équilibres liquide-vapeur à des pressions comprises entre 0,1 et 10 bar. Ce dispositif est basé sur la méthode « statique-analytique ». Nous avons mis en place deux adaptations spécifiques aux échantillonneurs capillaires ROLSITM pour permettre l'échantillonnage à ces pressions. De nouvelles données des mélanges binaires et ternaires d'intérêt ont été ainsi mesurées.Le modèle thermodynamique prédictif choisi est PC-SAFT couplé avec une méthode de Contribution de Groupes (GC-PC-SAFT). Un terme polaire a été introduit. Le travail s'est focalisé sur l'étude de deux familles représentatives de composés soufrés : les sulfures et les 1-mercaptans. Le modèle GC-PC-SAFT a montré sa capacité de bien corréler et prédire les propriétés thermodynamiques des corps purs. L'ajustement des paramètres s'est appuyé sur les données de la littérature et celles obtenues par le nouvel équipement. Les diagrammes de phases des mélanges binaires (sulfure + n-alcane, sulfure + 1-alcool, 1-mercaptan + n-alcane et 1-mercaptan + 1-alcool) et ternaires (1-mercaptan + n-alcane + 1-alcool) ont été prédits. / Sulfur compounds are widespread in various industrial fields. Design and/or optimization of the processes involving these compounds require accurate knowledge of thermodynamic properties of the concerned mixtures. Considering the complexity of industrial mixtures and for economical reasons, one may look to thermodynamic models with predictive features. To develop and validate these models, a minimum number of experimental data are required. Our literature review on sulfides (R-S-R'), 1-thiols (R-SH) and their possible solvents (n-alkanes and 1-alkanols) has shown a lack of data and of adapted experimental method. This observation leads to the need of developing a new experimental apparatus.In this work, we designed an innovative experimental apparatus for vapor-liquid-equilibrium measurements in the pressure range of [0.1 – 10] bar. The new apparatus is based on the “static-analytic” method. The key improvements are the two adaptations made for ROLSITM capillary samplers to achieve phase sampling in this pressure range. After validating the newly developed apparatus, new data of binary and ternary mixtures of interest were measured in order to develop a new predictive thermodynamic model focusing on sulfur compounds.The proposed predictive model is the PC-SAFT equation of state combined with a group contribution method (GC-PC-SAFT). We incorporated a polar term into PC-SAFT and investigated two representative families of sulfur compounds: sulfides and 1-thiols. The GC-PC-SAFT model proved reliable in correlating and predicting thermodynamic properties of pure compounds. Model parameters were fitted to the data found in the literature, as well as to those obtained through the new apparatus. Phase diagrams of some binary (sulfide + n-alkane, sulfide + 1-alkanol, 1-thiol + n-alkane and 1-thiol + 1-alkanol) and ternary (1-mercaptan + n-alkane + 1-alcool) mixtures were predicted.

Le remplacement des solvants organiques classiques par une nouvelle génération de solvants moins toxiques, moins inflammables et moins polluants est un défi majeur pour l'industrie chimique. Les liquides ioniques, sels liquides qui satisfont ces critères, sont envisagés comme alternatives. Le but de ce travail est d'évaluer le comportement des liquides ioniques en présence de gaz à effet de serre (CO2, N2O et CH4) ou de composés organiques. Dans un premier temps, une étude théorique présente les performances du modèle thermodynamique PC-SAFT sur la représentation des équilibres liquide-vapeur de systèmes constitués de dioxyde de carbone et de liquide ionique. Ensuite, l'étude de la solubilité du méthane, du dioxyde de carbone et du protoxyde d'azote dans divers liquides ioniques a été effectuée sous basse ou haute pression. Ce travail propose un modèle basé sur le concept de contribution de groupes afin de prédire la constante d'Henry du CO2 dans les liquides ioniques. Enfin, une étude sur les équilibres liquide-vapeur des systèmes binaires rencontrés dans la désulfuration des essences a été effectuée. Les données expérimentales ont permis d'évaluer les performances de l'équation PC-SAFT à représenter les équilibres entre phases de systèmes {composés soufrés / aromatiques + liquide ionique} / The replacement of conventional organic solvents by a new generation of solvents less toxic, less flammable and less polluting is a major challenge for the chemical industry. Ionic liquids have been widely promoted as interesting substitutes for traditional solvents. The purpose of this work is to evaluate the behavior of ionic liquids in the presence of greenhouse gases (CO2, CH4 and N2O) or organic compounds. Firstly, a theoretical study presents the performance of the thermodynamic model PC-SAFT in the representation of vapor-liquid equilibrium of systems containing ionic liquids and carbon dioxide. Then, the solubility study of methane, carbon dioxide and nitrous oxide in various ionic liquids was performed at high or low pressure. The group contribution concept is proposed in this study in order to predict the Henry's law constant of carbon dioxide in ionic liquids. Finally, a study on the vapor-liquid equilibrium of binary systems encountered in gasoline desulfurization was carried out. Experimental data were used to evaluate the performance of PC-SAFT equation of state to represent phase equilibrium of systems {sulfur / aromatic compounds + ionic liquid}