PT107601B - VANÁDIO OXO-COMPLEX (8) WITH 8-HYDROXYCHINOLINE AND 2-HYDROXYBENZOYL HYDRAZONE DERIVATIVES AND ITS APPLICATION AS A CATALYST FOR PEROXIDATIVE OXIDIZATION, WITHOUT SIDE-ASSISTED AROID WASTE - Google Patents

VANÁDIO OXO-COMPLEX (8) WITH 8-HYDROXYCHINOLINE AND 2-HYDROXYBENZOYL HYDRAZONE DERIVATIVES AND ITS APPLICATION AS A CATALYST FOR PEROXIDATIVE OXIDIZATION, WITHOUT SIDE-ASSISTED AROID WASTE Download PDF

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PT107601B
PT107601B PT107601A PT10760114A PT107601B PT 107601 B PT107601 B PT 107601B PT 107601 A PT107601 A PT 107601A PT 10760114 A PT10760114 A PT 10760114A PT 107601 B PT107601 B PT 107601B
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catalyst
vanadium
peroxidative
assisted
oxidation
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PT107601A (en
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De Fátima Costa Guedes Da Silva Maria
José Latourrette De Oliveira Pombeiro Armando
Margarida Dias Ribeiro De Sousa Martins Luísa
Sutradhar Manas
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Cofac Coop De Formacao E Animacao Cultural Crl
Inst Superior Tecnico
Inst Superior De Engenharia De Lisboa
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Abstract

A INVENÇÃO REFERE-SE AO OXO-COMPLEXO DE VANÁDIO(V) COM LIGANDOS 8-HIDROXIQUINOLINA (HQH) E DERIVADO DE SALICILALDEÍDO-2-HIDROXIBENZOIL-HIDRAZONA (H2L) [VO(HQ)L] (1), (2-HIDROXI-N-[(2-OXIFENIL)METILENO]BENZENOCARBOHIDRAZONATO)(QUINOLIN-8-OLATO-N,O)-OXIDO-VANÁDIO(V), E AO SEU USO COMO CATALISADOR EFICIENTE E SELETIVO DA OXIDAÇÃO PEROXIDATIVA DE ÁLCOOIS SECUNDÁRIOS ÀS CETONAS CORRESPONDENTES, ASSISTIDA POR MICRO-ONDAS E SEM ADIÇÃO DE SOLVENTES. ESTE CATALISADOR É MUITO EFICAZ PERMITINDO RENDIMENTOS ATÉ 100% (QUANTITATIVOS) APÓS 30 MINUTOS DE REAÇÃO, E FREQUÊNCIAS DE CICLOS CATALÍTICOS, I.E., FREQUÊNCIAS DE ¿TURNOVER¿ (TOF), EXPRESSAS EM MOLES DE PRODUTO POR MOLE DE CATALISADOR E POR HORA, DE 3,6 X103 H-1.The invention relates to vanadium (V) oxide-complex with 8-hydroxyquinoline (HQH) and salicylaldehyde-2-hydroxybenzoyl-hydroxyzone (H2L) [VO (HQ) L] (2), (1), -N - [(2-OXYPHENYL) METHYLENE] BENZENOCARBOHYDRAZONATE) (QUINOLIN-8-OLATO-N, O) -ANANIDEOXIDE (V), AND ITS USE AS AN EFFICIENT AND SELECTIVE CATALYST OF PEROXIDATIVE OXIDATION TO THE CORROSOUND SUNDOSONAL CORDES , ASSISTED BY MICROWAVE AND WITHOUT ADDITION OF SOLVENTS. THIS CATALYST IS VERY EFFICIENT ALLOWING INCOME UP TO 100% (QUANTITATIVES) AFTER 30 MINUTES OF REACTION, AND CATALYTIC CYCLE FREQUENCY (TOF), EXPRESSED IN PRODUCT MOLES BY EHAL OF CATALYST 3.6 X103 H-1.

Description

DESCRIÇÃODESCRIPTION

Oxo-complexos de vanádio(IV-V) com ligandos derivados de salicilaldeido-2-hidroxibenzoil-hidrazona e 8-hidroxiquinolina ou 1,10-fenantrolina e sua aplicação como catalisadores para a oxidação peroxidativa, assistida por micro-ondas e sem adição de solvente, de álcoois secundários a cetonasVanadium (IV-V) oxo-complexes with ligands derived from salicylaldehyde-2-hydroxybenzoyl hydrazone and 8-hydroxyquinoline or 1,10-phenanthroline and their application as catalysts for microwave-assisted peroxidative oxidation solvent, from secondary alcohols to ketones

Campo da invenção:Field of the invention:

A presente invenção refere-se a complexos de vanádio(IV e V) com ligandos derivados de salicilaldeído-2-hidroxibenzoilhidrazona e 8-hidroxiquinolina ou 1,10-fenantrolina, e ao uso daqueles compostos como catalisadores eficientes e seletivos para a oxidação peroxidativa de álcoois secundários às cetonas correspondentes, assistida por micro-ondas e na ausência de solventes adicionados.The present invention relates to vanadium complexes (IV and V) with ligands derived from salicylaldehyde-2-hydroxybenzoylhydrazone and 8-hydroxyquinoline or 1,10-phenanthroline, and the use of such compounds as efficient and selective catalysts for peroxidative oxidation of secondary alcohols to the corresponding ketones, assisted by microwave and in the absence of added solvents.

Domínio técnico da invenção:Technical field of the invention:

Catálise, Micro-ondas, Química de Coordenação, Química OrgânicaCatalysis, Microwave, Coordination Chemistry, Organic Chemistry

A técnica anterior:The prior art:

Os produtos químicos funcionalizados com oxigénio, em particular as cetonas, estão na base de estratégias sintéticas industriais importantes, como solventes, precursores de polímeros e substratos para a síntese de produtos farmacêuticos, agroquímicos e fragrâncias [1-4].Oxygen-functionalized chemicals, in particular ketones, underlie important industrial synthetic strategies such as solvents, polymer precursors and substrates for the synthesis of pharmaceuticals, agrochemicals and fragrances [1-4].

Recentemente observa-se uma crescente preocupação na maximização da eficiência atómica e energética, eliminação da utilização de substâncias perigosas, redução do tempo reacional e do envolvimento de substâncias tóxicas (e.g., solventes orgânicos) e de resíduos de metais pesados nos vários métodos sintéticos conhecidos para a preparação de cetonas [5-10]. Assim, as oxidações seletivas, aeróbica [11-15] e peroxidativa [16-19], de álcoois secundários são consideradas como os métodos de síntese mais simples e úteis para a preparação de cetonas, bem como uma das transformações fundamentais na síntese orgânica contemporânea.Recently there has been increasing concern about maximizing atomic and energy efficiency, eliminating the use of hazardous substances, reducing reaction time and the involvement of toxic substances (eg organic solvents) and heavy metal residues in the various synthetic methods known to the preparation of ketones [5-10]. Thus, selective, aerobic [11-15] and peroxidative [16-19] oxidations of secondary alcohols are considered as the simplest and most useful synthesis methods for ketone preparation, as well as one of the fundamental transformations in contemporary organic synthesis. .

Existe também um grande interesse na conceção de catalisadores para oxidação utilizando metais que não sejam escassos nem apresentem um assinalável impacto ambiental, tal como o vanádio. Os oxo-complexos de vanádio são bons candidatos como catalisadores para reações de oxidação, e.g., de alcanos [20-23] . Também foi relatado o uso de polioxovanadatos para a oxidação com ácido p-toluenossulfónico de álcoois benzílicos aos compostos de carbonilo correspondentes [24]. No entanto, a utilização de vanádio para catalisar a oxidação peroxidativa de álcoois secundários é relativamente escassa [25-35]. Alguns sistemas dizem respeito à utilização de hidroperóxido de tercbutilo (TBHP) na presença de complexos de oxo-vanádio com bases de Schiff suportados em sílica [33] ou grafeno [34], ou de peróxido de hidrogénio numa mistura homogénea composta por vanadato, ácido, líquidos iónicos funcionalizados e TEMPO [35].There is also great interest in designing oxidation catalysts using metals that are not scarce or have a significant environmental impact, such as vanadium. Vanadium oxo-complexes are good candidates as catalysts for oxidation reactions, e.g. of alkanes [20-23]. The use of polyoxovanadates for p-toluenesulfonic acid oxidation of benzyl alcohols to the corresponding carbonyl compounds has also been reported [24]. However, the use of vanadium to catalyze peroxidative oxidation of secondary alcohols is relatively scarce [25-35]. Some systems concern the use of tert-butyl hydroperoxide (TBHP) in the presence of silica-based Schiff-based oxo-vanadium complexes [33] or graphene [34], or hydrogen peroxide in a homogeneous mixture of vanadate, acid , functionalized ionic liquids and TIME [35].

Persiste, assim, a necessidade de encontrar novos e eficientes sistemas sintéticos de cetonas que possam ultrapassar pelo menos algumas das relevantes limitações mencionadas acima.Thus, there remains a need to find new and efficient synthetic ketone systems that can overcome at least some of the relevant limitations mentioned above.

Descrição das figuras:Description of the figures:

FIG. 1 - Representação dos complexos de vanádio (no estado de oxidação IV ou V) com ligandos derivados de salicilaldeído-2hidroxibenzoil-hidrazona (H2L) e 8-hidroxiquinolina (hqH) ouFIG. 1 - Representation of vanadium complexes (in oxidation state IV or V) with ligands derived from salicylaldehyde-2hydroxybenzoylhydrazone (H2L) and 8-hydroxyquinoline (hqH) or

1,10-fenantrolina (phen) [VO(hq)L] (1), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(quinolin-8-olatoN,0)-oxido-vanádio(V) e [V0(phen)L] (2), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(1,10-fenantrolina)oxido-vanádio(IV);1,10-phenanthroline (phen) [VO (hq) L] (1), (2-hydroxy-N - [(2oxyphenyl) methylene] benzenecarbohydrazonate) - (quinolin-8-olatoN, 0) -oxide vanadium (V ) and [V0 (phen) L] (2), (2-hydroxy-N - [(2oxyphenyl) methylene] benzenecarbohydrazonate) - (1,10-phenanthroline) oxido vanadium (IV);

FIG. 2 - Representação das estruturas moleculares de difração de raios-X dos complexos 1(a) e 2(b);FIG. 2 - Representation of X-ray diffraction molecular structures of complexes 1 (a) and 2 (b);

FIG. 3 - Representação dos processos de sintese dos complexos de oxovanádio(IV-V) com ligandos derivados de salicilaldeido-2hidroxibenzoil-hidrazona (H2L) e 8-hidroxiquinolina (hqH) ou 1,10-fenantrolina (phen) [VO(hq)L] (1), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(quinolin-8-olatoN,0)-oxido-vanádio(V) e [V0(phen)L] (2), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(1,10-fenantrolina)oxido-vanádio(IV);FIG. 3 - Representation of the synthesis processes of oxovanadium (IV-V) complexes with ligands derived from salicylaldehyde-2hydroxybenzoylhydrazone (H 2 L) and 8-hydroxyquinoline (hqH) or 1,10-phenanthroline (phen) [VO (hq ) L] (1), (2-hydroxy-N - [(2oxyphenyl) methylene] benzenecarbohydrazonate) - (quinolin-8-olatoN, 0) -oxide vanadium (V) and [V0 (phen) L] (2) (2-hydroxy-N - [(2oxyphenyl) methylene] benzenecarbohydrazonate) - (1,10-phenanthroline) oxido vanadium (IV);

FIG. 4 - Oxidação peroxidativa de álcoois secundários às cetonas correspondentes, assistida por micro-ondas e na ausência de solventes ou aditivos, catalisada pelos complexos 1 e 2.FIG. 4 - Peroxidative oxidation of alcohols secondary to the corresponding ketones, assisted by microwaves and in the absence of solvents or additives, catalysed by complexes 1 and 2.

Descrição pormenorizada da invenção:Detailed Description of the Invention:

1. Objetivos e vantagens objetivo geral desta invenção consiste na obtenção de complexos de metais de transição capazes de atuar como catalisadores eficientes e seletivos da formação de cetonas por oxidação peroxidativa de álcoois secundários, e que apresentem, na sua esfera de coordenação, ligandos que não tenham ainda sido testados em estudos anteriores, na tentativa de estabelecer novos sistemas cataliticos para aquelas reações, assistidas por micro-ondas e isentos de solventes ou aditivos, com elevados rendimento e seletividade.1. Objectives and advantages The general objective of this invention is to obtain transition metal complexes capable of acting as efficient and selective catalysts of ketone formation by peroxidative oxidation of secondary alcohols, and which present, in their sphere of coordination, ligands which do not have been tested in previous studies in an attempt to establish new catalytic systems for those reactions, assisted by microwave and free of solvents or additives, with high yield and selectivity.

Para tal, foram selecionados os ligandos derivados de salicilaldeido-2-hidroxibenzoil-hidrazona hidroxiquinolina (hqH) e 1,10-fenantrolina (phen), como metal o desenvolveram-se no de oxidação IV ou âmbito dos novosFor this purpose, the ligands derived from salicylaldehyde-2-hydroxybenzoylhydrazone hydroxyquinoline (hqH) and 1,10-phenanthroline (phen) were selected as the metal developed in the oxidation IV or scope of the new

V) , seguintes complexos e os estudos objetivos de vanádio mais estado de oxidação IV ou V) com aqueles ligandos e aplicação destes novos complexos à oxidação catalítica de álcoois secundários em condições moderadas e de vista ambiental, com elevados rendimento e toleráveis do ponto seletividade.V), following complexes and objective studies of vanadium plus oxidation state IV or V) with those ligands and application of these new complexes to catalytic oxidation of secondary alcohols under moderate and environmentally friendly conditions, high yield and selectively tolerable.

Destes objetivos decorreu a obtenção, por um método simples, dos complexos de vanádio [VO(hq)L] (1), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(quinolin-8-olatoN,0)-oxido-vanádio(V) e [V0(phen)L] (2), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(1,10-fenantrolina)oxido-vanádio(IV). Além disso, nenhum sistema baseado num complexo de vanádio com os ligandos acima utilizados fora aplicado à oxidação peroxidativa de álcoois secundários.From these objectives it was possible to obtain, by a simple method, the vanadium complexes [VO (hq) L] (1), (2-hydroxy-N - [(2oxyphenyl) methylene] benzenocarbohydrazonate) - (quinolin-8-olatoN, 0 ) -oxide vanadium (V) and [V0 (phen) L] (2), (2-hydroxy-N - [(2oxyphenyl) methylene] benzenecarbohydrazonate) - (1,10-phenanthroline) oxido-vanadium (IV). In addition, no vanadium complex-based system with the above-used ligands had been applied to the peroxidative oxidation of secondary alcohols.

Como vantagens associadas a esta invenção, podem referir-se o recurso a catalisadores simples, ambientalmente toleráveis (de efeito poluente muito limitado), facilmente obtidos por vias simples (num só passo) e convenientes, recorrendo a materiais de partida disponíveis comercialmente e de baixo custo, permitindo o seu isolamento e purificação sem necessidade de recurso a técnicas sofisticadas.Advantages associated with this invention include the use of simple, environmentally tolerable (very limited pollutant effect) catalysts, readily obtainable by simple (one-step) and convenient use of low-cost, commercially available starting materials. allowing isolation and purification without the need for sophisticated techniques.

Outras vantagens residem na boa estabilidade destes catalisadores sob condições oxidantes e na sua solubilidade nos álcoois substratos, permitindo assim i) que o processo catalítico decorra na ausência de outros solventes e com pequenas quantidades de catalisador, e ii) eliminar a necessidade de agentes de transferência de fase.Other advantages lie in the good stability of these catalysts under oxidizing conditions and their solubility in the substrate alcohols, thus allowing i) the catalytic process to proceed in the absence of other solvents and with small amounts of catalyst, and ii) to eliminate the need for transfer agents. phase

desenvolvimento de processos químicos amigos do ambiente é atualmente considerado muito relevante e uma das vias mais eficientes é a substituição dos solventes orgânicos (devido, por exemplo, à sua toxicidade) por meios reacionais alternativos.The development of environmentally friendly chemical processes is currently considered very relevant and one of the most efficient ways is the replacement of organic solvents (due, for example, to their toxicity) by alternative reaction means.

Os álcoois testados foram o ciclohexanol e o 1-feniletanolThe alcohols tested were cyclohexanol and 1-phenylethanol.

em virtude do elevado interesse comercial because of the high commercial interest dos seus of yours produtos de products of oxidação oxidation [3] . [3] Além Beyond disso, o sistema catalítico que In addition, the catalytic system that é objeto is object da gives presente gift invenção invention recorre ao uso de micro-ondas, uses microwaves, que permitem that allow acelerar speed up

grandemente a reação e evitar o uso e solvente, e proporcionam um processo ecológico com significado em química verde, constituindo também uma vantagem do método desta invenção.greatly reaction and avoid use and solvent, and provide an environmentally significant process in green chemistry, also constituting an advantage of the method of this invention.

sistema catalítico da presente invenção constitui um sistema de elevadas atividade e seletividade, em condições moderadas (temperaturas até 80 °C) , e sem necessidade de cocatalisadores ou aditivos. Foram atingidos números de ciclos catalíticos, i.e., números de turnover (TON), expressos em moles de produto por mole de catalisador, até 1,8 x 103, frequências de ciclos catalíticos, i.e., frequências de turnover (TOF), expressas em moles de produto por mole de catalisador e por hora, até 3,6 x 103 h-1, e rendimentos até 100 % (quantitativos).The catalytic system of the present invention is a system of high activity and selectivity under moderate conditions (temperatures up to 80 ° C) and without the need for cocatalysts or additives. Catalytic cycle numbers, ie turnover numbers (TON), expressed in moles of product per mole of catalyst, up to 1.8 x 10 3 , catalytic cycle frequencies, ie turnover frequencies (TOF), expressed as moles of product per mole of catalyst per hour up to 3.6 x 10 3 h -1 and yields up to 100% (quantitative).

Tendo em conta as diversas vantagens acima mencionadas o sistema catalítico proposto parece bem atraente do ponto de vista económico e com potencial para ser aplicado industrialmente.In view of the various advantages mentioned above, the proposed catalytic system seems very economically attractive and potentially industrially applicable.

2. Caracteristicas inovadoras2. Innovative Features

A invenção em análise refere-se ao uso inovador de oxocomplexos de vanádio com ligandos derivados de salicilaldeido-2hidroxibenzoilhidrazona (H2L) e 8-hidroxiquinolina (hqH) ou 1,10fenantrolina (phen) [VO(hq)L] (1), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(quinolin-8-olatoN,O)-oxido-vanádio(V) e [VO(phen)L] (2), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(1,10-fenantrolina)oxido-vanádio(IV) como catalisadores para a oxidação peroxidativa de álcoois secundários às cetonas correspondentes.The present invention relates to the innovative use of vanadium oxocomplexes with ligands derived from salicylaldehyde-2hydroxybenzoylhydrazone (H 2 L) and 8-hydroxyquinoline (hqH) or 1,10phenanthroline (phen) [VO (hq) L] (1) , (2-hydroxy-N - [(2oxyphenyl) methylene] benzenecarbohydrazonate) - (quinolin-8-olatoN, O) -oxide vanadium (V) and [VO (phen) L] (2), (2-hydroxy- N - [(2oxyphenyl) methylene] benzenocarbohydrazonate) - (1,10-phenanthroline) oxide vanadium (IV) as catalysts for peroxidative oxidation of secondary alcohols to the corresponding ketones.

É de realçar que os próprios complexos de vanádio com os ligandos derivados de salicilaldeido-2-hidroxibenzoil-hidrazona (H2L) e 8-hidroxiquinolina (hqH) ou 1,10-fenantrolina (phen) [VO(hq)L] (1), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(quinolin-8-olatoN,O)-oxido-vanádio(V) e [VO(phen)L] (2), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(1,10-fenantrolina)oxido-vanádio(IV) são novos e a sua preparação envolve novas reações.It should be noted that the vanadium complexes themselves with the ligands derived from salicylaldehyde-2-hydroxybenzoylhydrazone (H 2 L) and 8-hydroxyquinoline (hqH) or 1,10-phenanthroline (phen) [VO (hq) L] ( 1), (2-hydroxy-N - [(2oxyphenyl) methylene] benzenecarbohydrazonate) - (quinolin-8-olatoN, O) -oxide vanadium (V) and [VO (phen) L] (2), (2- hydroxy-N - [(2oxyphenyl) methylene] benzenocarbohydrazonate) - (1,10-phenanthroline) oxide vanadium (IV) are new and their preparation involves new reactions.

A presente invenção reconhece, pela primeira vez, que os complexos daquele tipo catalisam eficientemente a oxidação peroxidativa de álcoois secundários às correspondentes cetonas, assistida por micro-ondas, sem requerer a presença de qualquer solvente orgânico, em condições suaves e ambientalmente toleráveis.The present invention recognizes for the first time that such complexes efficiently catalyze the peroxidative oxidation of microwave-assisted secondary alcohols without corresponding presence of any organic solvent under mild and environmentally tolerable conditions.

Os complexos de vanádio (no estado de oxidação IV ou V) desta invenção constituem, assim, os primeiros catalisadores com ligandos derivados de salicilaldeido-2-hidroxibenzoil-hidrazona (H2L) e 8-hidroxiquinolina (hqH) ou 1,10-fenantrolina (phen) [VO(hq)L] (1), (2-hidroxi-N-[(2 oxifenil)metileno]benzenocarbohidrazonato)-(quinolin-8-olatoN,0)-oxido-vanádio(V) e [V0(phen)L] (2), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(1,10-fenantrolina)oxido-vanádio(IV), ativos na oxidação peroxidativa, assistidaThe vanadium complexes (in oxidation state IV or V) of this invention thus constitute the first ligand catalysts derived from salicylaldehyde-2-hydroxybenzoylhydrazone (H 2 L) and 8-hydroxyquinoline (hqH) or 1,10- phenanthroline (phen) [VO (hq) L] (1), (2-hydroxy-N - [(2-oxyphenyl) methylene] benzenecarbohydrazonate) - (quinolin-8-olatoN, 0) -oxide vanadium (V) and [ V0 (phen) L] (2), (2-hydroxy-N - [(2oxyphenyl) methylene] benzenecarbohydrazonate) - (1,10-phenanthroline) oxido vanadium (IV), active in peroxidative, assisted oxidation

por micro-ondas, de by microwave, álcoois secundários secondary alcohols às at correspondentes matching cetonas. ketones. A invenção refere-se ainda à The invention further relates to the obtenção obtaining de in um novo a new tipo de kind of sistemas catalíticos, catalytic systems, baseados nos based on complexos complexes de in vanádio vanadium 1 e 2 e 1 and 2 and

no uso de micro-ondas, altamente ativos em tempos reacionais muito curtos (tipicamente 30 minutos) na preparação de cetonas por oxidação peroxidativa de álcoois secundários.in the use of microwaves, highly active at very short reaction times (typically 30 minutes) in the preparation of ketones by peroxidative oxidation of secondary alcohols.

De facto, os complexos de vanádio da presente invenção exibem uma atividade catalítica notável, sob condições moderadas (até 80 °C) e ambientalmente toleráveis, para aquela oxidação. São, assim, necessários apenas em muito pequenas quantidades, o que é favorável relativamente a outros exemplos acima descritos.Indeed, the vanadium complexes of the present invention exhibit remarkable catalytic activity under moderate (up to 80 ° C) and environmentally tolerable conditions for that oxidation. They are therefore only required in very small quantities, which is favorable in relation to other examples described above.

3. Descrição técnica3. Technical Description

A invenção consiste na obtenção de novos oxo-complexos de vanádio com ligandos derivados de salicilaldeido-2hidroxibenzoil-hidrazona (H2L) e 8-hidroxiquinolina (hqH) ou 1, 10-fenantrolina (phen) como catalisadores eficientes e seletivos da oxidação peroxidativa de álcoois secundários às cetonas correspondentes, assistida por micro-ondas e na ausência de solventes.The invention is to obtain novel vanadium oxo-complexes with ligands derived from salicylaldehyde-2hydroxybenzoylhydrazone (H 2 L) and 8-hydroxyquinoline (hqH) or 1,10-phenanthroline (phen) as efficient and selective catalysts of peroxidative oxidation. of secondary alcohols to the corresponding ketones, assisted by microwave and in the absence of solvents.

As sínteses dos catalisadores foram realizadas ao ar. Os solventes e os reagentes foram adquiridos comercialmente (Aldrich) e usados da forma como foram recebidos. Os espetros de e 51V foram efetuados em dimetilsulfóxido deuterado (DMSO-dg) com um espetrómetro de ressonância magnética nuclear (RMN) Bruker Avance II + 300 (UltraShield™ Magnet) ou Bruker 400The syntheses of the catalysts were performed in air. Solvents and reagents were purchased commercially (Aldrich) and used as received. E 51 V spectra were performed in deuterated dimethyl sulfoxide (DMSO-dg) with a Bruker Avance II + 300 (UltraShield ™ Magnet) or Bruker 400 Nuclear Magnetic Resonance Spectrometer (NMR).

UltraShield à temperatura ambiente. Os desvios químicos (δ) são expressos em ppm relativamente ao Si(Me)4 (protão) ou [VOCI3] (51V). Os espetros de infravermelhos (IV) foram traçados entre 4000 e 400 cm-1 num espetrofotómetro Bio-Rad FTS 3000MX ou Jasco FT/IR-430 em pastilhas de KBr sendo os números de onda dados em cm-1. A espetrometria de massa por electrospray foi realizada num instrumento ion-trap (Varian 500-MS LC Ion Trap Mass Spectrometer) com fonte de electrospray (ESI+-MS) . As soluções de etanol contendo os complexos foram continuamente introduzidas na fonte do espetrómetro de massa com um fluxo de 10 pL/min. A temperatura do gás secante foi mantida a 350 °C e o diazotoUltraShield at room temperature. Chemical shifts (δ) are expressed in ppm relative to Si (Me) 4 (proton) or [VOCI3] ( 51 V). Infrared (IR) spectra were plotted between 4000 and 400 cm -1 on a Bio-Rad FTS 3000MX or Jasco FT / IR-430 spectrophotometer on KBr pellets with the wave numbers given in cm -1 . Electrospray mass spectrometry was performed on an ion-trap instrument (Varian 500-MS LC Ion Trap Mass Spectrometer) with electrospray source (ESI + -MS). Ethanol solutions containing the complexes were continuously fed into the mass spectrometer source with a flow rate of 10 pL / min. The temperature of the drying gas was kept at 350 ° C and the diazote

usado como nebulizador a used as a nebulizer uma pressão de 35 psi. 0 e 1200. a pressure of 35 psi. 0 and 1200. varrimento sweep foi was efetuado entre m/z made between m / z = 100 = 100 Os espetros The spectrum de in absorção de UV-Vis UV-Vis absorption de in soluções solutions de in acetonitrilo de 1 1-acetonitrile (1,12 (1.12 x 10’5 M) e 2 (1,03 χx 10 ' 5 M) and 2 (1.03 χ 10’5 10 '5 M) em células M) in cells

de quartzo de 1,00 cm, foram traçados à temperatura ambiente num espetrofotómetro Lambda 35 UV-Vis (Perkin -Elmer) com varrimentos na região de 200 - 1000 nm à velocidade de 240 nm min-1.of 1.00 cm quartz were plotted at room temperature on a Lambda 35 UV-Vis (Perkin-Elmer) spectrophotometer with scans in the region of 200 - 1000 nm at a speed of 240 nm min -1 .

Os produtos dos testes catalíticos foram analisados por cromatografia em fase gasosa (GC) utilizando um cromatógrafo gasoso FISONS Instruments GC série 8000 com uma coluna capilar DB-624 (J&W) (detector FID) e o software Jasco-Borwin v.1.50. A temperatura de injeção foi de 240 0 C. A temperatura inicial foi mantida a 120 0 C durante 1 min, em seguida aumentada a 10 0 C / min até 200 0 C e mantida a esta temperatura durante 1 min. Foi utilizado hélio como gás de transporte. Análises de GC-MS foram realizadas utilizando um instrumento Perkin Elmer Clarus 600 C (hélio como gás de transporte) . A voltagem de ionização foi de 70 eV. A cromatografia gasosa foi realizada no modo de programação de temperatura, usando uma coluna SGE BPX5 (30 m x 0,25 mm χ 0,25 pm) . Os produtos reacionais foram identificados por comparação dos seus tempos de retenção com os compostos de referência conhecidos, e por comparação dos seus espetros de massa com os padrões de fragmentação obtidos a partir da biblioteca espetral NIST armazenada no programa de computador do espetrómetro de massa.Catalytic test products were analyzed by gas chromatography (GC) using a FISONS Instruments GC 8000 series gas chromatograph with a DB-624 (J&W) capillary column (FID detector) and Jasco-Borwin v.1.50 software. The injection temperature was 240 0 C. The initial temperature was maintained at 120 0 C for 1 min, then increased to 10 0 C / min to 200 0 C and maintained at this temperature for 1 min. Helium was used as a carrier gas. GC-MS analyzes were performed using a Perkin Elmer Clarus 600 C instrument (helium as carrier gas). The ionization voltage was 70 eV. Gas chromatography was performed in temperature programming mode using an SGE BPX5 column (30 mx 0.25 mm χ 0.25 pm). Reaction products were identified by comparing their retention times with known reference compounds, and by comparing their mass spectra with the fragmentation patterns obtained from the NIST spectral library stored in the mass spectrometer computer program.

A obtenção dos catalisadores [VO(hq)L] (1), (2-hidroxi-N[ (2-oxifenil)metileno]benzenocarbohidrazonato)-(quinolin-8olato-N,O)-oxido-vanádio(V) e [VO(phen)L] (2), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(1,10-fenantrolina)oxido-vanádio(IV) e a descrição do processo catalítico sãoObtaining the catalysts [VO (hq) L] (1), (2-hydroxy-N [(2-oxiphenyl) methylene] benzenecarbohydrazonate) - (quinolin-8olate-N, O) -oxide vanadium (V) and [ VO (phen) L] (2), (2-hydroxy-N - [(2oxyphenyl) methylene] benzenecarbohydrazonate) - (1,10-phenanthroline) oxido vanadium (IV) and the description of the catalytic process are

indicadas indicated com maior detalhe in greater detail através through de in alguns exemplos que some examples that são are meramente merely ilustrativos, não illustrative not sendo being de in caráter limitativo limiting character do of âmbito da scope of presente invenção. present invention. 3.1 Exemplo de sintese dos 3.1 Example of synthesis of complexos complexes de oxovanádio(IV-V) oxovanadium (IV-V) com with

ligandos derivados de salicilaldeido-2-hidroxibenzoil-hidrazona (H2L) e 8-hidroxiquinolina (hqH) ou 1,10-fenantrolina (phen) 1 eligands derived from salicylaldehyde-2-hydroxybenzoylhydrazone (H2L) and 8-hydroxyquinoline (hqH) or 1,10-phenanthroline (phen) 1 and

2.2.

[VO(hq)L] (1), (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(quinolin-8-olatoN,O)-oxido-vanádio (V) : A uma suspensão de H2L [0,256 g (1,00 mmol)]em 30 mL de acetonitrilo foram adicionados 0,265 g (1,00 mmol) de [VO(acac)2J e a mistura reacional foi submetida a refluxo durante 1 h num banho de óleo, ao ar. A esta mistura foram adicionados 0,145 g (1,00 mmol) de 8-hidroxiquinolina (hqH) e o refluxo foi continuado durante mais uma hora. A solução violeta escuro resultante foi filtrada e o filtrado foi mantido ao ar, formando-se um precipitado. Em seguida foram isolados cristais simples de qualidade para difração de raios-X, lavados três vezes com acetonitrilo frio e secos ao ar. Rendimento: 76%. 0 complexo 1 foi caracterizado por espetroscopia de IV, espetrometria de massa, análise elementar e difração de raios-X (Tabela 1). C23H16N3O5V requer: C, 59,37; H,[VO (hq) L] (1), (2-hydroxy-N - [(2oxyphenyl) methylene] benzenecarbohydrazonate) - (quinolin-8-olatoN, O) -oxide vanadium (V): To a suspension of H 2 L [0.256 g (1.00 mmol)] in 30 mL of acetonitrile was added 0.265 g (1.00 mmol) of [VO (acac) 2J] and the reaction mixture was refluxed for 1 h in an oil bath while stirring. air. To this mixture was added 0.145 g (1.00 mmol) of 8-hydroxyquinoline (hqH) and refluxing was continued for an additional hour. The resulting dark violet solution was filtered and the filtrate was kept in air to form a precipitate. Quality single X-ray diffraction crystals were then isolated, washed three times with cold acetonitrile and air dried. Yield: 76%. Complex 1 was characterized by IR spectroscopy, mass spectrometry, elemental analysis and X-ray diffraction (Table 1). C 23 H 16 N 3 O 5 V requires: C, 59.37; H,

3,47; N, 9,03. Encontrado: 59,28; H, 3,39; N, 8,91. IV (pastilha de KBr; crrh1) : 1599 v(C=N), 1257 v (C-O) enólica, 1103 v (N-N) , 9553.47; N, 9.03. Found: 59.28; H, 3.39; N, 8.91. IR (KBr pellet; crrh 1 ): 1599 v (C = N), 1257 v (CO) enolic, 1103 v (NN), 955

V(V=O). RMN: XH (DMSO-d6) ,V (V = O). NMR: X is H (DMSO-d 6) δ·. δ ·. 11,12 (s, 1H, 11.12 (s, 1H, OH), 8,59 OH) 8.59 (s, 2H, - (s, 2H, - CH=N), 8,26-6,78 (m, 14H, CH = N), 8.26-6.78 (m, 14H, c6h4 c 6 h 4 e C9H6NO) ; 51Vand C 9 H 6 NO); 51 V (DMSO-dg) , (DMSO-dg), δ·. - 478. δ ·. - 478. ESI+, m/z: 466 [1+H]+ (100ESI + , m / z: 466 [1 + H] + (100 %). %). Àmax (CH3CN/At max (CH 3 CN / nm, (ε, L nm, (ε, L M_1 cm-1) ) :M _1 cm -1 )): 552 (4,480), 331 (13,440), 552 (4.480), 331 (13.440), 273 273 (21,280), 240 (21.280), 240 (34,720). (34,720).

Tabela 1 - Comprimentos (Â) e ângulos de ligação (°) selecionados para o composto [VO(hq)L] (1).Table 1 - Lengths (Â) and bonding angles (°) selected for the compound [VO (hq) L] (1).

Comprimento de ligação Binding Length Nl-Vl Nl-Vl 2,090 (3) 2,090 (3) N3-V1 N3-V1 2,385 (3) 2,385 (3) Ol-Vl Ol-Vl 1,852 (3) 1.852 (3) 02—VI 02 — VI 1, 948 (3) 1,948 (3) 04—VI 04 — VI 1, 840 (3) 1,840 (3) O10-V1 O10-V1 1,580 (3) 1.580 (3) Ângulo de Angle of ligação Link 010-VI-04 010-VI-04 98, 68 (14) 98, 68 (14) 01-VI-NI 01-VI-NI 83,44 (12) 83.44 (12) OlO-Vl-Ol OlO-Vl-Ol 100,17 (15) 100.17 (15) 02—Vl—N1 02 — Vl — N1 75,38 (12) 75.38 (12) 04—Vl—01 04 — Vl — 01 96, 55 (12) 96, 55 (12) O10-V1-N3 O10-V1-N3 171,66(14) 171.66 (14) 010-VI-02 010-VI-02 95, 99 (14) 95, 99 (14) 04—Vl—N3 04 — Vl — N3 75,44 (11) 75.44 (11) 04—Vl—02 04 — Vl — 02 98,74 (12) 98.74 (12) 01—Vl—N3 01 — Vl — N3 86,51 (13) 86.51 (13) 01—Vl—02 01 — Vl — 02 155,76 (13) 155.76 (13) 02—Vl—N3 02 — Vl — N3 79,30 (12) 79.30 (12) O10-V1-N1 O10-V1-N1 102,94(14) 102.94 (14) N1-V1-N3 N1-V1-N3 82, 65 (12) 82, 65 (12) 04—Vl—N1 04 — Vl — N1 158,05 (13) 158.05 (13)

[VO(phen)L] (2) , (2-hidroxi-N-[(2oxifenil)metileno]benzenocarbohidrazonato)-(1,10-fenantrolina)oxido-vanádio(IV): Este complexo foi isolado na forma de cristais laranja avermelhados utilizando o procedimento adotado na preparação de mas com 1,10-fenantrolina (phen) em vez de 8hidroxiquinolina (hqH). Rendimento 72 %. 0 complexo 2 foi caracterizado por espetroscopia de IV, espetrometria de massa, análise elementar e difração de raios-X (Tabela 2). C26H18N4O4V requer: C,[VO (phen) L] (2), (2-hydroxy-N - [(2oxyphenyl) methylene] benzenecarbohydrazonate) - (1,10-phenanthroline) oxido-vanadium (IV): This complex was isolated as orange crystals using the procedure adopted in the preparation of but with 1,10-phenanthroline (phen) instead of 8hydroxyquinoline (hqH). Yield 72%. Complex 2 was characterized by IR spectroscopy, mass spectrometry, elemental analysis and X-ray diffraction (Table 2). C26H18N4O4V requires: C,

H, 3,62; N, 11,17. Encontrado: 61,96; H, 3,56;H, 3.62; N, 11.17. Found: 61.96; H, 3.56;

N, 11,09.N, 11.09.

v(C=N), 1252 v(C0)enólica,v (C = N), 1252 v (C0) enolic,

1056 V(N-N), 961 V(V=0). ESI+: m/z1056 V (NN), 961 V (V = 0). ESI + : m / z

Àmax (CH3CN/At max (CH 3 CN /

Tabela 2 - Comprimentos (Â) e ângulos de ligação (°)Table 2 - Lengths (Â) and bonding angles (°)

selecionados para o composto [VO(phen)L] selected for the compound [VO (phen) L] (2) . (2) . Comprimento Length de ligação binding Plano A Plan A Plano B Plan B Nl-Vl Nl-Vl 2,029 (10) 2,029 (10) N5-V2 N5-V2 2,005 (11) 2.005 (11) N3-V1 N3-V1 2,348 (11) 2,348 (11) N7-V2 N7-V2 2,316(11) 2,316 (11) N4-V1 N4-V1 2,157 (9) 2.157 (9) N8-V2 N8-V2 2,124 (11) 2,124 (11) Ol-Vl Ol-Vl 1, 927 (8) 1,927 (8) O4-V2 O4-V2 1, 999 (13) 1,999 (13) 02—VI 02 — VI 2,027 (9) 2,027 (9) O5-V2 O5-V2 2,001 (11) 2,001 (11) O10-V1 O10-V1 1,558 (9) 1,558 (9) O20-V2 O20-V2 1, 604 (10) 1,604 (10)

Ângulo de Angle of ligação Link O10-V1-O1 O10-V1-O1 103,1 (4) 103.1 (4) O20-V2-O5 O20-V2-O5 101,3 (5) 101.3 (5) 010-VI-02 010-VI-02 98,3 (4) 98.3 (4) O20-V2-O4 O20-V2-O4 99,5 (6) 99.5 (6) 01—Vl—02 01 — Vl — 02 155,9 (4) 155.9 (4) O5-V2-O4 O5-V2-O4 156,5 (4) 156.5 (4) O10-V1-N1 O10-V1-N1 107,5 (4) 107.5 (4) O20-V2-N5 O20-V2-N5 105,4 (5) 105.4 (5) 01—Vl—N1 01 — Vl — N1 86,4 (4) 86.4 (4) O5-V2-N5 O5-V2-N5 81, 9(5) 81.9 (5) 02—Vl—N1 02 — Vl — N1 76, 6 (4) 76.6 (4) O4-V2-N5 O4-V2-N5 82,2(5) 82.2 (5) 010-Vl-N4 010-Vl-N4 92,4 (5) 92.4 (5) O20-V2-N8 O20-V2-N8 94,5 (5) 94.5 (5) 01—Vl—N4 01 — Vl — N4 93, 0(3) 93.0 (3) O5-V2-N8 O5-V2-N8 96,0 (4) 96.0 (4) 02—Vl—N4 02 — Vl — N4 97,1 (3) 97.1 (3) O4-V2-N8 O4-V2-N8 93, 0(5) 93.0 (5) N1-V1-N4 N1-V1-N4 159,7 (5) 159.7 (5) N5-V2-N8 N5-V2-N8 160,0(5) 160.0 (5) 010-Vl-N3 010-Vl-N3 165,5 (4) 165.5 (4) O20-V2-N7 O20-V2-N7 166,7 (4) 166.7 (4) 01—Vl—N3 01 — Vl — N3 81,7 (3) 81.7 (3) O5-V2-N7 O5-V2-N7 82,3 (4) 82.3 (4) 02—Vl—N3 02 — Vl — N3 80,3 (4) 80.3 (4) O4-V2-N7 O4-V2-N7 79,9 (4) 79.9 (4) N1-V1-N3 N1-V1-N3 86,3 (4) 86.3 (4) N5-V2-N7 N5-V2-N7 87,8 (4) 87.8 (4) N4-V1-N3 N4-V1-N3 73,5 (4) 73.5 (4) N8-V2-N7 N8-V2-N7 72,3 (4) 72.3 (4)

3.2 Exemplos dos estudos de atividade catalítica3.2 Examples of catalytic activity studies

3.2.1 Oxidação peroxidativa assistida por micro-ondas de álcoois secundários às respetivas cetonas: Num tubo cilíndrico de pyrex do reator de micro-ondas CEM Discover foi colocado o substrato (álcool) (5 mmol), solução aquosa a 70% de hidroperóxido de terc-butilo (TBHP, 10 mmol) e 1-100 μπιοί (0,02 - 2 % mol vs. substrato) de catalisador 1 ou 2. O sistema foi fechado, colocado sob agitação e irradiação de micro-ondas durante 15-60 min., a 80 °C, à potência de 25 W. Após a reação, deixou-se a mistura reacional arrefecer até à temperatura ambiente.3.2.1 Microwave-assisted peroxidative oxidation of alcohols secondary to the respective ketones: In a cylindrical pyrex tube of the CEM Discover microwave reactor, the substrate (alcohol) (5 mmol), 70% aqueous hydroperoxide tert-butyl (TBHP, 10 mmol) and 1-100 μπιοί (0.02 - 2 mol% substrate) of catalyst 1 or 2. The system was closed, agitated and microwave irradiated for 15-60 µm. at 80 ° C at 25 W. After the reaction, the reaction mixture was allowed to cool to room temperature.

3.2.2 Análise por cromatografia gasosa: A mistura resultante da reação foi tratada com 5 mL acetonitrilo e 300 pL de padrão de3.2.2 Gas chromatographic analysis: The reaction mixture was treated with 5 mL acetonitrile and 300 µl of

interno internal (ex., benzaldeído). (eg benzaldehyde). Foi agitada durante 1 It was stirred for 1 0 min e, após 0 min and after repouso, rest foi retirada uma a amostra sample (1 pL) a partir da fase (1 pL) from phase orgânica organic e analisada por GC and analyzed by GC usando o using the método do padrão interno. internal standard method. Tabela Table 3 - Oxidação de 3 - Oxidation of álcoois secundários secondary alcohols selecionados selected catalisada pelos complexos 1 catalyzed by the complexes 1 e 2.a and 2. the Catalisador Substrato Substrate Catalyst Tempo Time Rendimento* Yield* TON c TON c reacional reactionary (%) (%) (TOF (h_1))d (TOF ( h_1 )) d (h) (H) 1 1 1-feniletanol 1-phenylethanol 0,5 0.5 99,3 99.3 497 (993) 497 (993) 1-feniletanol e 1-phenylethanol and 0,5 0.5 36, 3 36.3 1, 8xl03 (3, 6 x 103)1.8x10 3 (3.6x10 3 ) 1-feniletanol f 1-phenylethanol f 0,5 0.5 90, 9 90.9 46 (91) 46 (91) ciclohexanol cyclohexanol 0,5 0.5 30,3 30.3 151 (303) 151 (303) ciclohexanol e cyclohexanol and 0,5 0.5 12,3 12.3 615 (1,2 x 103)615 (1.2x10 3 ) ciclohexanol f cyclohexanol n 0,5 0.5 30,1 30.1 15 (30) 15 (30) 2 2 1-feniletanol 1-phenylethanol 0,5 0.5 86, 4 86.4 432 (863) 432 (863) ciclohexanol cyclohexanol 0,5 0.5 35,4 35.4 177 (354) 177 (354) a Condições reacionais: 5 a Reaction conditions: 5 mmol mmol de substrato, substrate, 10 pmol de 10 pmol of catalisador 1 ou 2 (0,2 % catalyst 1 or 2 (0.2% mol vs. mol vs. substrato), 10 substrate), 10 mmol de TBHP mmol TBHP (2 eq., (2 eq., 7 0 % em H2O) , 8070% in H 2 O), 80 °C, 30 ° C, 30 minutos com minutes with irradiação de irradiation of micro-ondas (25 W) . b Basemicrowave (25 W). b Base ado nas in the análises por analysis by cromatografia chromatography

100 de cetona por moles de álcool, 100% de gasosa, moles seletividade em todos os casos.100 ketone per mole of alcohol, 100% gas, mole selectivity in all cases.

c Número de ciclos catalíticos número de moles de cetona por mole de catalisador. d Frequência de ciclos catalíticos parêntesis) . e Foram utilizados 1 pmol (0,02 % mol vs. c Number of catalytic cycles number of moles of ketone per mole of catalyst. d Frequency of parenthesis catalytic cycles). e 1 pmol (0.02 mol% vs.

substrato) de 1. Foram utilizados 100 pmol (2 % mol vs.substrate) of 1. 100 pmol (2 mol% vs.

substrato)substrate)

Todos os catalisadores são notavelmente ativos e seletivos na oxidação por hidroperóxido de terc-butilo de álcoois secundários a cetonas, assistida por micro-ondas.All catalysts are remarkably active and selective in microwave-assisted tert-butyl hydroperoxide oxidation of ketone secondary alcohols.

De salientar ainda que aquelas atividade e seletividade notórias ocorrem na ausência de qualquer solvente adicionado, como ilustrado na Tabela 3.It is further noted that those noticeable activity and selectivity occur in the absence of any added solvent, as illustrated in Table 3.

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Claims (5)

REIVINDICAÇÕES Ia Complexos de vanádio(IV-V) com ligandos derivados de salicilaldeido-2-hidroxibenzoil-hidrazona e 8-hidroxiquinolina ou 1,10-fenantrolina caracterizados por apresentarem as seguintes fórmulas de estrutura:I vanadium complexes (IV-V) with salicylaldehyde-derived ligand 2-hydroxybenzoyl hydrazone and 8-hydroxyquinoline and 1,10-phenanthroline characterized by having the following structural formulas: 2a Uso dos compostos de fórmulas 1 e 2, caracterizado pela sua aplicação como catalisadores para a oxidação peroxidativa de álcoois secundários às respetivas cetonas.Use of the two compounds of formulas 1 and 2, characterized by its application as catalysts for the peroxidative oxidation of secondary alcohols to ketones respective. 3a Processo de oxidação peroxidativa de álcoois secundários às respetivas cetonas caracterizado pela utilização dos compostos de fórmulas 1 e 2 como catalisadores, e pela aplicação de irradiação de micro-ondas à mistura reacional.3 Process the peroxidative oxidation of secondary alcohols to ketones wherein the respective use of the compounds of formulas 1 and 2 as catalysts, and applying microwave radiation to the reaction mixture. 4a Processo de acordo com a reivindicação 3, caracterizado pela ausência de qualquer solvente orgânico ou outro aditivo.4 A process according to claim 3, characterized by the absence of any organic solvent or other additive. 5a Processo de acordo com as reivindicações 3 e 4, caracterizado pela aplicação de hidroperóxido de terc-butilo como agente oxidante.5 A process according to claims 3 and 4, characterized by the application of tert-butyl hydroperoxide as the oxidizing agent.
PT107601A 2014-04-14 2014-04-14 VANÁDIO OXO-COMPLEX (8) WITH 8-HYDROXYCHINOLINE AND 2-HYDROXYBENZOYL HYDRAZONE DERIVATIVES AND ITS APPLICATION AS A CATALYST FOR PEROXIDATIVE OXIDIZATION, WITHOUT SIDE-ASSISTED AROID WASTE PT107601B (en)

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