Les alcools sont des partenaires électrophiles attractifs pour des réactions de substitution nucléophile puisque l'eau est le seul sous-produit de la réaction en présence de nucléophiles protiques. Malgré le fait que la réaction soit fortement intéressante, la portée des transformations catalytique reste limitée à une combinaison spécifique alcool/nucléophile, ce qui rend l’emploi d’un ensemble général de conditions catalytiques fortement élusif. Cette thèse décrit le développement d'un système général de catalyse doux pour l'activation d'une large gamme d’alcools π-activés ainsi que d’alcools aliphatiques abordant ainsi les limitations clés dans le domaine. B(C6F6)3•H2O, un acide de Brønsted fort quand il est combiné avec le nitrométhane, a été découvert comme étant un système catalytique idéal pour la substitution chimiosélective d'alcools en présence de fonctionnalités et de groupements protecteurs sensibles aux conditions acides sans le compromis typique entre vitesse de réaction, réactivité substrat/nucléophile et quantité de catalyseur. Plus particulièrement, un effet co-catalytique de composés nitro est décrit pour la réaction d’azidation des alcools aliphatiques tertiaires en employant B(C6F6)3•H2O, permettant, pour la première fois, un turnover catalytique. Sur la base des investigations cinétiques, électroniques et spectroscopiques qui ont été menées, des agrégats de composés nitro et d’acides liés par des intéractions hydrogènes sont proposé comme étant l’espèce catalytiques responsables de la cinétique de la catalyse observée. L'utilité des nouvelles conditions catalytiques a été étendue au-delà de l'activation d'alcool et appliquée au clivage des liaisons fortes C-F dans les réactions de Friedel-Crafts défluorinatives de fluorures aliphatiques tertiaires. / Alcohols are attractive electrophilic partners for nucleophilic substitution reactions as water is the only by-product in a reaction with protic nucleophiles. Despite being a highly desirable reaction, the scope of useful catalytic transformations remains limited to specific alcohol-nucleophile pairs and a general set of catalytic conditions remains elusive. This thesis describes the development of a general and mild catalyst system for the activation of a broad range of π-activated and aliphatic alcohols to address key limitations in the field. B(C6F6)3•H2O, a strong Brønsted acid, when combined with nitromethane has been found as a widely useful catalyst system for chemoselective alcohol substitution in the presence of acid sensitive functionalities and protecting groups without the typical compromises in reaction rates, substrate/nucleophile scope and catalyst loading. In particular, a co-catalytic effect of nitro compounds is described for the B(C6F6)3•H2O catalyzed azidation of tertiary aliphatic alcohols, enabling catalyst turnover for the first time. On the basis of kinetic, electronic, and spectroscopic investigations, higher order hydrogen-bonded aggregates of nitro compounds and acids are proposed as kinetically competent Brønsted acid catalysts at the origin of the enhanced reactivity. The utility of the new catalytic conditions has been extended beyond alcohol activation and applied to the cleavage of strong C–F bonds in defluorinative Friedel-Crafts reactions of tertiary aliphatic fluorides.

La valorisation de la biomasse est une alternative intéressante aux ressources fossiles, et s'effectue fréquemment en catalyse hétérogène. L'élaboration de nouveaux catalyseurs est une tâche ardue qui peut être considérablement accélérée in silico. Cependant les molécules de la biomasse sont souvent complexes et hautement oxygénées, rendant ainsi les calculs plus difficiles et couteux en temps. Parmi ces composés, les polyols sont particulièrement importants. Nous avons développé des relations du type Brønsted-Evans-Polanyi (BEP) à partir d'une étude DFT menée sur une famille de monoalcools concernant les dissociations des liaisons C-H et O-H sur des catalyseurs métalliques (Co, Ni, Ru, Rh, Pd, Ir, Pt). Ces relations ont pour but de prédire l’énergie d’activation d’une étape élémentaire à partir de son énergie de réaction. La précision obtenue par ces modèles linéaires est supérieure à 0.10 eV pour l'échantillon considéré. Ces relations ont ensuite étaient appliquées aux étapes élémentaires de la déshydrogénation du glycérol, choisi comme polyol prototype. On observe une erreur moyenne inférieure à 0.10 eV et une erreur systématique de l'ordre de ± 0.10 eV sur Rh. Etant donné que la principale différence entre les monoalcools et le glycérol, vient des liaisons H intramoléculaires présentes dans celui-ci, nous avons mis en place des relations linéaires pour prédire la déshydrogénation des monoalcools assistée par l'eau. Ces nouvelles relations nous ont permis d'améliorer la prédiction sur le glycérol et même d'éliminer la déviation systématique dans le cas de la rupture de la liaison OH. Même si dans cette étude nous nous sommes focalisés sur la déshydrogénation du glycérol, des méthodes similaires pourraient être appliquées à d'autres polyols avec d'autres réactions chimiques, accélérant ainsi considérablement la recherche in silico de catalyseurs solides. Ce travail pave la route pour le développement de nouvelles techniques numériques pour aborder la question de la conversion de la biomasse. / Biomass valorization is an interesting alternative to fossil resources, which is frequently performed via heterogeneous catalysis. Designing new catalysts is a challenging task that can be significantly accelerated in silico. However, biomass molecules are often complex and highly oxygenated, hence rendering calculations more difficult and time consuming. Among these compounds, polyols are particularly important. We developed linear relations of the Brønsted-Evans-Polanyi (BEP) type from the DFT study of C-H or O-H bond dissociation elementary steps for a family of monoalcohol molecules on metallic catalysts (Co, Ni, Ru, Rh, Pd, Ir, Pt). Such relations aim at predicting activation energies from reaction energies. The accuracy of the obtained linear energy models is better than 0.10 eV on the sampling set. Then, the relations were applied for the prediction of the dehydrogenation elementary steps of glycerol, chosen as a prototype of polyalcohols, with an accuracy better than 0.10 eV and with a systematic error around ±0.10 eV for Rh. Keeping in mind that the main difference between glycerol and monoalcohols comes from intramolecular H-bonds present in the former, we designed linear relations for water-assisted dehydrogenation of monoalcohols. These new relations allowed us to improve the prediction on glycerol and to eliminate the systematic deviation in the case of OH bond breaking. Even if in this study we focused on glycerol dehydrogenation, similar methods may be applied to other polyols with other chemical reactions, and considerably speed up the computational design of solid catalysts. This work paves the way for the development of novel numerical techniques to address the issue of biomass conversion.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-01-04T13:24:36Z No. of bitstreams: 1 daniellelobojustopinheiro.pdf: 4869021 bytes, checksum: b4acfc12a41a6f83bf195e5947ae47cc (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-01-25T15:55:49Z (GMT) No. of bitstreams: 1 daniellelobojustopinheiro.pdf: 4869021 bytes, checksum: b4acfc12a41a6f83bf195e5947ae47cc (MD5) / Made available in DSpace on 2016-01-25T15:55:49Z (GMT). No. of bitstreams: 1 daniellelobojustopinheiro.pdf: 4869021 bytes, checksum: b4acfc12a41a6f83bf195e5947ae47cc (MD5) Previous issue date: 2015-03-31 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Carboidratos têm sido utilizados como organocatalisadores em síntese orgânica devido a sua quiralidade intrínseca. Neste trabalho foi sintetizado um novo organocatalisador aproveitando a estrutura da D-galactose como indutor de quiralidade. A síntese ocorreu em cinco etapas, a saber: proteção seletiva das hidroxilas das posições 1, 2, 3 e 4, seguida pela iodação da posição 6, substituição nucleofílica pelo grupo azido, redução à amina e por fim uma reação com anidrido ftálico. O rendimento global foi de 60 %. O organocatalisador foi testado na reação de adição de Michael entre o dibenzilideno acetona e a azalactona derivada da alanina. 20 mol% do catalisador conduziu ao produto com 57 % de rendimento e com total controle da régio- e diasteroseletividade. No escopo, vários produtos com funcionalização no esqueleto de dbas foram preparados e devidamente caracterizados pelas técnicas convencionais de análise. A determinação da estereoquímica relativa foi realizada através do uso de HPLC com fase estacionária quiral e foi atribuída como 1,2-anti após a comparação do tempo de retenção com um padrão já descrito na literatura. De maneira geral, é reportada, pela primeira vez, uma metodologia mais geral para a dessimetrização diasterosseletiva entre dbas e azalactonas catalisadas por ácido de Brønsted. / Carbohydrates have been used as organocatalysts in organic synthesis due to its inherent chirality. In this work, D-galactose was choose as a chiral pool in the catalyst design and it was prepared in five steps: selective ketalyzation of hydroxyl groups, following by an iodination and nucleophilic substitution in the presence of azide. To complete, reduction of the azide to amine and a coupling reaction with phthalic anhydride leading to the catalyst. Overall yield was 60 % for five steps. Then, the catalyst was adopted in the Michael addition reaction between dibenzylidene acetone and azalactone derivative of alanine. The product was obtained in 57% yield and with fully control of both regio- and diastereoselectivity. Next, various funcionalizated dbas were evaluated under the optimized reaction condition and the corresponding final products were fully characterized through conventional elemental analysis. The relative stereochemistry was assigned as being 1,2-anti by using chiral HPLC method. To this end, an authentic sample already described in the literature was prepared in order the retention time. In general, for the first time, a method more general to perform a diastereoselective dessymetrization of dbas in presence of azlactones by using a Brønsted acid as catalyst was described.

Durante o último século, diversas transformações envolvendo diazocompostos foram descobertas. Diazocompostos em presença de um átomo metálico como Rh, Cu, Au, entre outros, dão origem a um carbenóide o qual pode ser utilizado em diversos tipos de transformações. Dentre estas, podem ser destacadas as reações de ciclopropanação, rearranjos de Wolff, formação de ilídeos, reações de inserção C-H e reações de inserção X-H (sendo X= N, O, S, Se, halogênios, etc). As reações de inserção X-H, em especial as inserções de nitrogênio e oxigênio, tem sido muito estudadas nos últimos anos. Para se ter ideia do tamanho da importância dessas reações, as inserções N-H são atualmente usadas como etapa chave do processo da síntese do antibiótico Tienamicina, desenvolvido pela Merck. Recentemente, a primeira síntese total do Maecristal V, um produto natural muito promissor no combate ao câncer, evolveu em uma das etapas chave a reação de inserção O-H. Entretanto, a maior parte das metodologias para reações de inserção são descritas com a utilização de catálise metálica ou por reações fotoquímicas. A organocatálise tem se destacado nos últimos anos, o que pode ser notado pelo crescente número de publicações na área. Além das vantagem como, por exemplo, o menor custo, menor geração de resíduos, menor toxicidade, maior tolerância ao ar e umidade, entre outras. O presente trabalho demonstra uma nova metodologia para reações de inserção O-H, utilizando-se ácidos de Brønsted como organocatalisadores, especificamente um ácido fosfórico. Foram desenvolvidas duas metodologias, uma sem solvente com excesso de um álcool e outra utilizando solvente na presença de uma menor quantidade de álcool, fornecendo rendimentos entre 19-91%. Essas metodologias foram avaliadas em outras substâncias hidroxiladas, tais como, água, fenóis e silanóis, porém sem sucesso nesses casos. Por último, foram realizadas reações de inserção de metanol em alguns exemplos de um exemplo de α-aril-diazoéteres e em α-diazocetona, com rendimentos entre 50-96%, sendo possível mostrar a aplicabilidade do método. Por fim, foi estudada a inserção de metanol em β-ceto-α-diazoésteres, mas não houve sucesso nessa reação. / Over the last century, several transformations involving diazocompounds were discovered. Diazocompounds in the presence of metallic atoms such as Rh, Cu, Au, among others, lead to a carbenoid, which may be used in many kinds of transformations. Among them, we may hightlight cyclopropanation reactions, the Wolff rearrangement, formation of ylides, C-H and X-H insertion reactions (being X= N, O, S, Se, halogen, etc). The X-H insertion reactions, in special insertions of nitrogen and oxygen, have been extensively studied in the last years. To mention the importance of these reactions, a N-H insertion was used as the key step for the preparation of the antibiotic Tienamicene, developed by Merck. Recently, the first total synthesis of Maecristal V, a very promising natural product for cancer treatment, involved an O-H insertion reaction. Despite of that, most methodologies for insertion reactions are still described by metal catalysis or photochemistry reactions. Organocatalisys has been very popular in recent years, as may be seen by the growing number of publications in the area. Beyond this advantage, lower cost, less waste, less toxicity, increased tolerance to air and moisture are also encountered in organocatalysis. The present work demonstrates a new methodology for O-H insertion reaction, using Brønsted acids as the catalyst, specifically a phosphoric acid. Two methodologies were developed, one without solvent and with an excess of alcohol and other using solvent in presence of small amount of alcohol. Insertion reactions were performed in different alcohols, furnishing yields between 19-91%. These methodologies were evaluated with other hydroxylated substances, such as, water, phenols and silanols, but without success. Insertion reactions in the presence of methanol were carried out for some examples of α-aril-diazoesthers and with one example of a α-diazoketone (yields between 50-96%), showing the applicability of this method. Finally, the insertion of methanol in a β-keto-α-diazoesther was studied, but without success in this reaction.

Durante o último século, diversas transformações envolvendo diazocompostos foram descobertas. Diazocompostos em presença de um átomo metálico como Rh, Cu, Au, entre outros, dão origem a um carbenóide o qual pode ser utilizado em diversos tipos de transformações. Dentre estas, podem ser destacadas as reações de ciclopropanação, rearranjos de Wolff, formação de ilídeos, reações de inserção C-H e reações de inserção X-H (sendo X= N, O, S, Se, halogênios, etc). As reações de inserção X-H, em especial as inserções de nitrogênio e oxigênio, tem sido muito estudadas nos últimos anos. Para se ter ideia do tamanho da importância dessas reações, as inserções N-H são atualmente usadas como etapa chave do processo da síntese do antibiótico Tienamicina, desenvolvido pela Merck. Recentemente, a primeira síntese total do Maecristal V, um produto natural muito promissor no combate ao câncer, evolveu em uma das etapas chave a reação de inserção O-H. Entretanto, a maior parte das metodologias para reações de inserção são descritas com a utilização de catálise metálica ou por reações fotoquímicas. A organocatálise tem se destacado nos últimos anos, o que pode ser notado pelo crescente número de publicações na área. Além das vantagem como, por exemplo, o menor custo, menor geração de resíduos, menor toxicidade, maior tolerância ao ar e umidade, entre outras. O presente trabalho demonstra uma nova metodologia para reações de inserção O-H, utilizando-se ácidos de Brønsted como organocatalisadores, especificamente um ácido fosfórico. Foram desenvolvidas duas metodologias, uma sem solvente com excesso de um álcool e outra utilizando solvente na presença de uma menor quantidade de álcool, fornecendo rendimentos entre 19-91%. Essas metodologias foram avaliadas em outras substâncias hidroxiladas, tais como, água, fenóis e silanóis, porém sem sucesso nesses casos. Por último, foram realizadas reações de inserção de metanol em alguns exemplos de um exemplo de α-aril-diazoéteres e em α-diazocetona, com rendimentos entre 50-96%, sendo possível mostrar a aplicabilidade do método. Por fim, foi estudada a inserção de metanol em β-ceto-α-diazoésteres, mas não houve sucesso nessa reação. / Over the last century, several transformations involving diazocompounds were discovered. Diazocompounds in the presence of metallic atoms such as Rh, Cu, Au, among others, lead to a carbenoid, which may be used in many kinds of transformations. Among them, we may hightlight cyclopropanation reactions, the Wolff rearrangement, formation of ylides, C-H and X-H insertion reactions (being X= N, O, S, Se, halogen, etc). The X-H insertion reactions, in special insertions of nitrogen and oxygen, have been extensively studied in the last years. To mention the importance of these reactions, a N-H insertion was used as the key step for the preparation of the antibiotic Tienamicene, developed by Merck. Recently, the first total synthesis of Maecristal V, a very promising natural product for cancer treatment, involved an O-H insertion reaction. Despite of that, most methodologies for insertion reactions are still described by metal catalysis or photochemistry reactions. Organocatalisys has been very popular in recent years, as may be seen by the growing number of publications in the area. Beyond this advantage, lower cost, less waste, less toxicity, increased tolerance to air and moisture are also encountered in organocatalysis. The present work demonstrates a new methodology for O-H insertion reaction, using Brønsted acids as the catalyst, specifically a phosphoric acid. Two methodologies were developed, one without solvent and with an excess of alcohol and other using solvent in presence of small amount of alcohol. Insertion reactions were performed in different alcohols, furnishing yields between 19-91%. These methodologies were evaluated with other hydroxylated substances, such as, water, phenols and silanols, but without success. Insertion reactions in the presence of methanol were carried out for some examples of α-aril-diazoesthers and with one example of a α-diazoketone (yields between 50-96%), showing the applicability of this method. Finally, the insertion of methanol in a β-keto-α-diazoesther was studied, but without success in this reaction.

The synthesis of enantiomerically pure compounds is of vital importance. Most biologically active natural products are chiral and require asymmetric synthesis, chiral resolution, or the use of naturally chiral starting materials for their preparation. Organocatalytic enantioselective reaction methodology is a continuously growing area in organic chemistry. The use of organocatalysts as a potentially environmentally friendly alternative to metal catalysts is appealing to the pharmaceutical industry. In this dissertation an enantioselective Mannich reaction using an organocatalyst was investigated. The reaction was between a ß-keto ester and an imine electrophile catalyzed by vaulted biphenanthrol (VAPOL) phosphoric acid. The reaction resulted in products with high yields, but low to moderate enantioselectivity and diastereoselectivity. The development of the first Brønsted acid-catalyzed desymmetrization of meso-aziridines was also investigated. This is one of the first instances where a phosphoric acid has been used to catalyze a reaction that did not involve an imine. It was shown that the chiral VAPOL phosphoric acid was an excellent catalyst for the reaction resulting in high yields and enantioselectivities for the chiral ring opened products. It was also shown, for the first time, that a vaulted binaphthol (VANOL) phosphoric acid can also catalyze the ring-opening of meso-aziridines with comparable results to the VAPOL phosphoric acid in some cases. Mechanistic NMR studies were used to probe the reaction, and it is believed that evidence leads one to conclude that a unique mechanism for phosphoric acid-catalysis is followed. The products that can be obtained from this reaction, 1,2-diamines, are of high value for synthetic chemists. They have been used as chiral auxiliaries, ligands, and precursors to natural products.

This thesis focuses on the development of methods for the activation of the hydroxyl group in non-derivatized alcohols in substitution reactions. The thesis is divided into two parts, describing three different catalytic systems. The first part of the thesis (Chapter 2) describes nucleophilic allylation of amines with allylic alcohols, using a palladium catalyst to generate unsymmetrical diallylated amines. The corresponding amines were further transformed by a one-pot ring-closing metathesis and aromatization reaction to afford β-substituted pyrroles with linear and branched alkyl, benzyl, and aryl groups in overall moderate to good yields. The second part (Chapters 3 and 4) describes the direct intramolecular stereospecific nucleophilic substitution of the hydroxyl group in enantioenriched alcohols by Lewis acid and Brønsted acid/base catalysis. In Chapter 3, the direct intramolecular substitution of non-derivatized alcohols has been developed using Fe(OTf)3 as catalyst. The hydroxyl groups of aryl, allyl, and alkyl alcohols were substituted by the attack of O- and N-centered nucleophiles, to provide five- and six-membered heterocycles in up to excellent yields with high enantiospecificities. Experimental studies showed that the reaction follows first-order dependence with respect to the catalyst, the internal nucleophile, and the internal electrophile of the substrate. Competition and catalyst-substrate interaction experiments demonstrated that this transformation proceeds via an SN2-type reaction pathway. In Chapter 4, a Brønsted acid/base catalyzed intramolecular substitution of non-derivatized alcohols was developed. The direct intramolecular and stereospecific substitution of different alcohols was successfully catalyzed by phosphinic acid (H3PO2). The hydroxyl groups of aryl, allyl, propargyl, and alkyl alcohols were substituted by O-, N-, and S-centered nucleophiles to generate five- and six-membered heterocycles in good to excellent yields with high enantiospecificities. Mechanistic studies (both experiments and density functional theory calculations) have been performed on the reaction forming five-membered heterocyclic compounds. Experimental studies showed that phosphinic acid does not promote SN1 reactivity. Rate-order determination indicated that the reaction follows first-order dependence with respect to the catalyst, the internal nucleophile, and the internal electrophile. DFT calculations corroborated with a reaction pathway in which the phosphinic acid has a dual activation mode and operates as a bifunctional Brønsted acid/Brønsted base to simultaneously activate both the nucleophile and nucleofuge, resulting in a unique bridging transition state in an SN2-type reaction mechanism. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 4: Manuscript.</p>

Previous studies have successfully used near and supercritical water (SCW) for cracking and desulfurization of heavy crude oil and bio-oil, suppressing coke formation as a low-value by-product. Some of these studies benefited from using zeolite catalysts to increase the activity and selectivity toward targeted products; however, in depth studies are required to identify the role of water on zeolite catalysis under supercritical condition. Using three common zeolites, ZSM-5, HY, and β for supercritical water cracking of dodecane at 400°C, 24±2 MPa (in a 100 ml batch reactor), we showed that ZSM-5 is the only catalyst that partially retains its crystalline structure and activity under hydrothermal conditions. Further characterization of the ZSM-5 (used under 50/50 wt% SCW/dodecane feed) revealed 95% decrease in Brønsted acid site (BAS) density and 80% decrease in microporous area after 2 h reaction time. However, compared to the runs where SCW was absent, the apparent dodecane cracking rate constant in SCW decreased only by a factor of 2.6. Examining catalytic activity of ZSM-5 degradation products and re-using ZSM-5 showed that the unexpected activity cannot be ascribed to ZSM-5 degradation products. Using a group-type model, we showed that SCW accelerated gas and suppressed coke formations. Additionally a coke gasification pathway was suggested to account for formation of CO and CO2 in the presence of SCW. Additional experiments with two different ZSM-5 particle sizes suggested that dodecane cracking reaction is diffusion-limited in the absence of SCW and reaction-limited in its presence. Zero length chromatography of calcined and hydrothermally treated ZSM-5 showed 10 times greater apparent diffusivity for un-treated catalyst. This, according to Weisz-Prater analysis, suggested a 250 times greater dodecane surface concentration in the absence of SCW. We successfully optimized the water content of feed (5-15 wt%) to decrease the destructive effects of SCW on the structure, increase the selectivity toward BTEX products and eliminate coke formation.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22847号 / 工博第4787号 / 新制||工||1749(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 山子 茂, 教授 田中 一生, 教授 辻井 敬亘 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Previous studies have successfully used near and supercritical water (SCW) for cracking and desulfurization of heavy crude oil and bio-oil, suppressing coke formation as a low-value by-product. Some of these studies benefited from using zeolite catalysts to increase the activity and selectivity toward targeted products; however, in depth studies are required to identify the role of water on zeolite catalysis under supercritical condition. Using three common zeolites, ZSM-5, HY, and β for supercritical water cracking of dodecane at 400°C, 24±2 MPa (in a 100 ml batch reactor), we showed that ZSM-5 is the only catalyst that partially retains its crystalline structure and activity under hydrothermal conditions. Further characterization of the ZSM-5 (used under 50/50 wt% SCW/dodecane feed) revealed 95% decrease in Brønsted acid site (BAS) density and 80% decrease in microporous area after 2 h reaction time. However, compared to the runs where SCW was absent, the apparent dodecane cracking rate constant in SCW decreased only by a factor of 2.6. Examining catalytic activity of ZSM-5 degradation products and re-using ZSM-5 showed that the unexpected activity cannot be ascribed to ZSM-5 degradation products. Using a group-type model, we showed that SCW accelerated gas and suppressed coke formations. Additionally a coke gasification pathway was suggested to account for formation of CO and CO2 in the presence of SCW. Additional experiments with two different ZSM-5 particle sizes suggested that dodecane cracking reaction is diffusion-limited in the absence of SCW and reaction-limited in its presence. Zero length chromatography of calcined and hydrothermally treated ZSM-5 showed 10 times greater apparent diffusivity for un-treated catalyst. This, according to Weisz-Prater analysis, suggested a 250 times greater dodecane surface concentration in the absence of SCW. We successfully optimized the water content of feed (5-15 wt%) to decrease the destructive effects of SCW on the structure, increase the selectivity toward BTEX products and eliminate coke formation.