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Synthesis of naturally occurring diene and trienes by Te/Li exchange on (1Z,3Z)-butyltelluro-4-methoxy-1,3-butadiene

DABDOUB, Miguel J.; DABDOUB, Vania B.; BARONI, Adriano C. M.; HURTADO, Gabriela R.; BARBOSA, Sandro L.
Fonte: PERGAMON-ELSEVIER SCIENCE LTD Publicador: PERGAMON-ELSEVIER SCIENCE LTD
Tipo: Artigo de Revista Científica
Português
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26.14%
(1Z,3Z)-Butyltelluro-o-4-methoxy-1,3-butadiene 2 was obtained by the hydrotelluration of(Z)-1-methoxy-but-1-en-3-ynes 1. The butadienyllithium 3 obtained by the Te/Li exchange reaction in the (1Z,3Z)-1-butyltelluro-4-methoxy-1.3-butadiene 2 reacted with aldehydes to form the corresponding alcohols 4a-d with total retention of configuration. The alcohols formed undergo hydrolysis, resulting in the alpha,beta,gamma,delta-unsaturated aldehydes of (E,E) configuration, which are precursors of trienes obtained from natural sources. The products of this reaction were employed in the synthesis of methyl-(2E,4E)-decadienoate 7, which is a component of the flavor principles of ripe Bartlett pears. Performing the Wittig reaction of the methyl triphenylphosphorane with the deca-(2E,4E)-dienal 5a, we were able to synthesize the undeca-(1,3E,5E)-triene 6a. This compound is a sex-pheromone component of the marine brown algae Fucus serratus, Dictyopteris plagiograma, and Dictyopteris australis. Performing the Wittig reaction of methyl triphenylphosphorane with the octa-(2E,4E)-dienal 5c, the nona-(1,3E,5E)-triene 6b was synthesized. The compound obtained is a sex-pheromone component of the marine brown alga Sargassum horneri. The octa-( 1,3E,5E)-triene 6c was easily obtained from hepta-(2E...

[(13)C(2)]- Acetaldehyde Promotes Unequivocal Formation of 1,N(2)-Propano-2 `-deoxyguanosine in Human Cells

GARCIA, Camila Carriao M.; ANGELI, Jose Pedro F.; FREITAS, Florencio P.; GOMES, Osmar F.; OLIVEIRA, Tiago F. de; LOUREIRO, Ana Paula M.; MASCIO, Paolo Di; MEDEIROS, Marisa H. G.
Fonte: AMER CHEMICAL SOC Publicador: AMER CHEMICAL SOC
Tipo: Artigo de Revista Científica
Português
Relevância na Pesquisa
35.99%
Acetaldehyde is an environmentally widespread genotoxic aldehyde present in tobacco smoke, vehicle exhaust and several food products. Endogenously, acetaldehyde is produced by the metabolic oxidation of ethanol by hepatic NAD-dependent alcohol dehydrogenase and during threonine catabolism. The formation of DNA adducts has been regarded as a critical factor in the mechanisms of acetaldehyde mutagenicity and carcinogenesis. Acetaldehyde reacts with 2`-deoxyguanosine in DNA to form primarily N(2)-ethylidene-2`-deoxyguanosine. The subsequent reaction of N(2)-ethylidenedGuo with another molecule of acetaldehyde gives rise to 1,N(2)-propano-2`-deoxyguanosine (1,N(2)-propanodGuo), an adduct also found as a product of the crotonaldehyde reaction with dGuo. However, adducts resulting from the reaction of more than one molecule of acetaldehyde in vivo are still controversial. In this study, the unequivocal formation of 1,N(2)-propanodGuo by acetaldehyde was assessed in human cells via treatment with [(13)C(2)]-acetaldehyde. Detection of labeled 1,N(2)-propanodGuo was performed by HPLC/MS/MS. Upon acetaldehyde exposure (703 mu M), increased levels of both 1,N(2)-etheno-2`-deoxyguanosine (1,N(2)-epsilon dGuo), which is produced from alpha,beta-unsaturated aldehydes formed during the lipid peroxidation process...

Preparation of alpha,beta-Unsaturated Diazoketones Employing a Horner-Wadsworth-Emmons Reagent

PINHO, Vagner D.; BURTOLOSO, Antonio C. B.
Fonte: AMER CHEMICAL SOC Publicador: AMER CHEMICAL SOC
Tipo: Artigo de Revista Científica
Português
Relevância na Pesquisa
56.37%
A new method for the preparation of alpha,beta-unsaturated diazoketones from aldehydes and a Horner-Wadsworth- Emmons reagent is reported. The method was applied to the short synthesis of two substituted pyrrolidines.; FAPESP (Research Supporting Foundation of the State of Sao Paulo); Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP); CNPq; Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Exploring the intrinsic polar [4?+?2+] cycloaddition reactivity of gaseous carbosulfonium and carboxonium ions

Basher, Muftah M.; Corilo, Yuri E.; Sparrapan, Regina; Benassi, Mario; Augusti, Rodinei; Eberlin, Marcos N.; Riveros, Jose M.
Fonte: WILEY-BLACKWELL; HOBOKEN Publicador: WILEY-BLACKWELL; HOBOKEN
Tipo: Artigo de Revista Científica
Português
Relevância na Pesquisa
25.99%
Gas-phase reactions of model carbosulfonium ions (CH3-S+?=?CH2; CH3CH2-S+?=?CH2 and Ph-S+?=?CH2) and an O-analogue carboxonium ion (CH3-O+?=?CH2) with acyclic (isoprene, 1,3-butadiene, methyl vinyl ketone) and cyclic (1,3-cyclohexadiene, thiophene, furan) conjugated dienes were systematically investigated by pentaquadrupole mass spectrometry. As corroborated by B3LYP/6-311?G(d,p) calculations, the carbosulfonium ions first react at large extents with the dienes forming adducts via simple addition. The nascent adducts, depending on their stability and internal energy, react further via two competitive channels: (1) in reactions with acyclic dienes via cyclization that yields formally [4?+?2+] cycloadducts, or (2) in reactions with the cyclic dienes via dissociation by HSR loss that yields methylenation (net CH+ transfer) products. In great contrast to its S-analogues, CH3-O+?=?CH2 (as well as C2H5-O+?=?CH2 and Ph-O+?=?CH2 in reactions with isoprene) forms little or no adduct and proton transfer is the dominant reaction channel. Isomerization to more acidic protonated aldehydes in the course of reaction seems to be the most plausible cause of the contrasting reactivity of carboxonium ions. The CH2?=?CH-O+?=?CH2 ion forms an abundant [4?+?2+] cycloadduct with isoprene...

Avaliação e identificação de toxicidade em efluente da fabricação de resinas de poliester.; Toxicity identification evaluation of polyester resin manufacturing wastewater.

Roberto Augusto Caffaro Filho
Fonte: Biblioteca Digital da Unicamp Publicador: Biblioteca Digital da Unicamp
Tipo: Tese de Doutorado Formato: application/pdf
Publicado em 05/06/2008 Português
Relevância na Pesquisa
56.37%
Os processos industriais são geradores de uma ampla variedade de contaminantes que estão presentes nas águas residuarias. A seleção de processos de tratamento baseia-se nas características do efluente a ser tratado. Neste trabalho investigou-se um efluente tóxico da fabricação de resinas de poliéster. Existem poucas informações na literatura sobre este tipo de água residuaria. Procedeu-se a caracterização do efluente, efetuando-se a avaliação e identificação de constituintes tóxicos presentes no mesmo por meio de uma abordagem orientada por toxicidade. Foi utilizado bioensaio respirometrico em lodo ativado para avaliar a toxicidade do efluente bruto. Então, foram efetuados tratamentos físicos e químicos para fracionamento do efluente, e apos cada um deles, realizou-se o mesmo bioensaio. Dessa maneira, avaliou-se qual técnica de fracionamento foi a mais efetiva na redução da toxicidade. A maior redução de toxicidade foi observada apos o fracionamento do efluente por arraste com ar em pH 11 (62,5 %). Este resultado demonstrou que uma fração significativa da toxicidade do efluente para lodos ativados era causada por compostos orgânicos volatilizados em pH 11. Isso indica que o tratamento do efluente por arraste com ar em pH básico pode ter impacto positivo em um tratamento biológico aeróbio subseqüente. Uma vez determinado o tipo de compostos no efluente que provocam efeitos tóxicos (Compostos Organicos Volateis - COVs)...

Exploring the intrinsic polar [4?+?2+] cycloaddition reactivity of gaseous carbosulfonium and carboxonium ions

Basher, Muftah M.; Corilo, Yuri E.; Sparrapan, Regina; Benassi, Mario; Augusti, Rodinei; Eberlin, Marcos N.; Riveros, Jose M.
Fonte: Wiley-Blackwell; Hoboken Publicador: Wiley-Blackwell; Hoboken
Tipo: Artigo de Revista Científica
Português
Relevância na Pesquisa
25.99%
Gas-phase reactions of model carbosulfonium ions (CH3-S+?=?CH2; CH3CH2-S+?=?CH2 and Ph-S+?=?CH2) and an O-analogue carboxonium ion (CH3-O+?=?CH2) with acyclic (isoprene, 1,3-butadiene, methyl vinyl ketone) and cyclic (1,3-cyclohexadiene, thiophene, furan) conjugated dienes were systematically investigated by pentaquadrupole mass spectrometry. As corroborated by B3LYP/6-311?G(d,p) calculations, the carbosulfonium ions first react at large extents with the dienes forming adducts via simple addition. The nascent adducts, depending on their stability and internal energy, react further via two competitive channels: (1) in reactions with acyclic dienes via cyclization that yields formally [4?+?2+] cycloadducts, or (2) in reactions with the cyclic dienes via dissociation by HSR loss that yields methylenation (net CH+ transfer) products. In great contrast to its S-analogues, CH3-O+?=?CH2 (as well as C2H5-O+?=?CH2 and Ph-O+?=?CH2 in reactions with isoprene) forms little or no adduct and proton transfer is the dominant reaction channel. Isomerization to more acidic protonated aldehydes in the course of reaction seems to be the most plausible cause of the contrasting reactivity of carboxonium ions. The CH2?=?CH-O+?=?CH2 ion forms an abundant [4?+?2+] cycloadduct with isoprene...

Organocatalysis and asymmetric catalysis : new applications of ferrocenylphosphines and nitromethane addition to conjugated substrates

Pereira, Susana Isabel Dinis
Fonte: Universidade de Aveiro Publicador: Universidade de Aveiro
Tipo: Tese de Doutorado
Português
Relevância na Pesquisa
16.14%
A presente dissertação centrou-se em duas areas de investigação distintas: o estudo de novas aplicações de ferrocenilfosfinas e a adição conjugada de nitrometano a substratos conjugados. Tendo em conta êxito do grupo do Prof. Carretero no desenvolvimento e uso de 1-fosfino-2-sulfenilferrocenos (ligandos Fesulphos) enquanto catalizadores quirais, propusemo-nos estudar a possibilidade de as ferrocenil dialquilfosfinas, compostos estáveis ao ar e ricos em electrões graças à sua estrutura ferrocénica, constituírem bons catalizadores para a reacção de Morita-Baylis- Hillman (RMBH). Adicionalmente, a elevada estabilidade destes sólidos cristalinos também constitui uma grande vantagem sobre as trialquilfosfinas comerciais, conhecidas pela sua elevada sensibilidade à oxidação pelo contacto com o ar e, nalguns casos, carácter pirofórico. Esta reacção geradora de ligações C-C entre alquenos activados e nucleófilos de carbono contendo um átomo de carbono sp2 deficiente em electrões tem frequentemente associados problemas de baixa reactividade e rendimentos dependentes do tipo de substracto utilizado. Durante o nosso estudo confirmámos que as ferrocenil diarilfosfinas e as ferrocenil dialquilfosfinas são, de facto...

Formação de adutos exocíclicos com bases de DNA: implicações em mutagênese e carcinogênese

Loureiro,Ana Paula M.; Di Mascio,Paolo; Medeiros,Marisa H. G.
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/09/2002 Português
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35.99%
A number of ring-extended DNA adducts resulting from reaction of alpha,beta-unsaturated aldehydes, or their epoxides, with DNA bases have been characterized in recent years. These adducts can lead to miscoding during DNA replication which, if not repaired, result in mutations that can contribute to cancer development. Recently, the use of ultrasensitive methods allowed the detection of background levels of etheno DNA adducts in tissues of untreated animals and humans suggesting the existence of endogenous sources of reactive intermediates. In this review, we briefly summarize the recent advances in the chemistry of these DNA lesions.

Clean and atom-economic synthesis of alpha-phenylselenoacrylonitriles and alpha-phenylseleno- alpha,beta-unsaturated esters by knoevenagel reaction under solvent-free conditions

Perin,Gelson; Jacob,Raquel G.; Botteselle,Giancarlo V.; Kublik,Emerson L.; Lenardão,Eder J.; Cella,Rodrigo; Santos,Paulo César Silva dos
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/08/2005 Português
Relevância na Pesquisa
46.22%
A simple, clean and efficient method has been developed for the synthesis of alpha-phenylselenoacrylonitriles and alpha-phenylseleno-alpha,beta-unsaturated esters by a one-pot reaction of aldehydes with phenylselenoacetonitrile or ethyl(phenylseleno)acetate respectively, in the presence of a solid supported catalyst (KF/Al2O3), without any solvent.

Fast and efficient method for reduction of carbonyl compounds with NaBH4 /wet SiO2 under solvent free condition

Zeynizadeh,Behzad; Behyar,Tarifeh
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/12/2005 Português
Relevância na Pesquisa
26.14%
Reduction of structurally different carbonyl compounds such as aldehydes, ketones, alpha,beta-unsaturated enals and enones, alpha-diketones and acyloins were accomplished efficiently by sodium borohydride in the presence of wet SiO2 (30% m/m) under solvent free condition. The reactions were performed at room temperature or 75-80 ºC with high to excellent yields of the corresponding products. The chemoselective reduction of aldehydes over ketones was achieved successfully with this reducing system.

Synthesis and reactivity of alpha-phenylseleno-beta-substituted styrenes: preparation of (Z)-allyl alcohols, (E)-alpha-phenyl-alpha,beta-unsaturated aldehydes and alpha-aryl acetophenones

Lenardão,Eder J.; Cella,Rodrigo; Jacob,Raquel G.; Silva,Thiago B. da; Perin,Gelson
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/10/2006 Português
Relevância na Pesquisa
86.67%
A new and efficient method was developed to prepare alpha-phenylseleno-beta-substituted styrenes by reaction of diethyl alpha-phenylseleno benzylphosphonate with NaH and aldehydes. Selenium-lithium exchange by reaction with n-BuLi yielded the vinyl lithium species, which were captured with several electrophiles, like aldehydes and DMF, affording exclusively (Z)-allyl alcohols, and (E)-alpha-phenyl-alpha-beta-unsaturated aldehydes, respectively in good yields. The hydrolysis of the vinyl selenides in presence of TiCl4 allowed the corresponding alpha-aryl acetophenones.

Detoxication of base propenals and other alpha, beta-unsaturated aldehyde products of radical reactions and lipid peroxidation by human glutathione transferases.

Berhane, K; Widersten, M; Engström, A; Kozarich, J W; Mannervik, B
Tipo: text
Publicado em 15/02/1994 Português
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56.34%
Radiation and chemical reactions that give rise to free radicals cause the formation of highly cytotoxic base propenals, degradation products of DNA. Human glutathione transferases (GSTs; RX:glutathione R-transferase, EC 2.5.1.18) of classes Alpha, Mu, and Pi were shown to promote the conjugation of glutathione with base propenals and related alkenes. GST P1-1 was particularly active in catalyzing the reactions with the propenal derivatives, and adenine propenal was the substrate giving the highest activity. The catalytic efficiency of GST P1-1 with adenine propenal (kcat/Km = 7.7 x 10(5) M-1.s-1) is the highest so far reported with any substrate for this enzyme. In general, GST A1-1 and GST M1-1, in contrast to GST P1-1, were more active with 4-hydroxyalkenals (products of lipid peroxidation) than with base propenals. The adduct resulting from the Michael addition of glutathione to the alkene function of one of the base propenals (adenine propenal) was identified by mass spectrometry. At the cellular level, GST P1-1 was shown to provide protection against alpha, beta-unsaturated aldehydes. GST P1-1 added to the culture medium of HeLa cells augmented the protective effect of glutathione against the toxicity of adenine propenal and thymine propenal. No protective effect of the enzyme was observed in the presence of the competitive inhibitor S-hexylglutathione. GST P1-1 introduced into Hep G2 cells by electroporation was similarly found to increase their resistance to acrolein. The results show that glutathione transferases may play an important role in cellular detoxication of electrophilic alpha...

Human neutrophils employ the myeloperoxidase-hydrogen peroxide-chloride system to convert hydroxy-amino acids into glycolaldehyde, 2-hydroxypropanal, and acrolein. A mechanism for the generation of highly reactive alpha-hydroxy and alpha,beta-unsaturated aldehydes by phagocytes at sites of inflammation.

Anderson, M M; Hazen, S L; Hsu, F F; Heinecke, J W
Tipo: text
Publicado em 01/02/1997 Português
Relevância na Pesquisa
66.72%
Reactive aldehydes derived from reducing sugars and lipid peroxidation play a critical role in the formation of advanced glycation end (AGE) products and oxidative tissue damage. We have recently proposed another mechanism for aldehyde generation at sites of inflammation that involves myeloperoxidase, a heme enzyme secreted by activated phagocytes. We now demonstrate that human neutrophils employ the myeloperoxidase-H202-chloride system to produce alpha-hydroxy and alpha,beta-unsaturated aldehydes from hydroxy-amino acids in high yield. Identities of the aldehydes were established using mass spectrometry and high performance liquid chromatography. Activated neutrophils converted L-serine to glycolaldehyde, an alpha-hydroxyaldehyde which mediates protein cross-linking and formation of Nepsilon-(carboxymethyl)lysine, an AGE product. L-Threonine was similarly oxidized to 2-hydroxypropanal and its dehydration product, acrolein, an extremely reactive alpha,beta-unsaturated aldehyde which alkylates proteins and nucleic acids. Aldehyde generation required neutrophil activation and a free hydroxy-amino acid; it was inhibited by catalase and heme poisons, implicating H202 and myeloperoxidase in the cellular reaction. Aldehyde production by purified myeloperoxidase required H202 and chloride...

In vivo absorption, metabolism, and urinary excretion of alpha,beta-unsaturated aldehydes in experimental animals. Relevance to the development of cardiovascular diseases by the dietary ingestion of thermally stressed polyunsaturate-rich culinary oils.

Grootveld, M; Atherton, M D; Sheerin, A N; Hawkes, J; Blake, D R; Richens, T E; Silwood, C J; Lynch, E; Claxson, A W
Tipo: text
Publicado em 15/03/1998 Português
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35.99%
Thermal stressing of polyunsaturated fatty acid (PUFA)- rich culinary oils according to routine frying or cooking practices generates high levels of cytotoxic aldehydic products (predominantly trans-2-alkenals, trans,trans-alka-2,4-dienals, cis,trans-alka-2, 4-dienals, and n-alkanals), species arising from the fragmentation of conjugated hydroperoxydiene precursors. In this investigation we demonstrate that typical trans-2-alkenal compounds known to be produced from the thermally induced autoxidation of PUFAs are readily absorbed from the gut into the systemic circulation in vivo, metabolized (primarily via the addition of glutathione across their electrophilic carbon-carbon double bonds), and excreted in the urine as C-3 mercapturate conjugates in rats. Since such aldehydic products are damaging to human health, the results obtained from our investigations indicate that the dietary ingestion of thermally, autoxidatively stressed PUFA-rich culinary oils promotes the induction, development, and progression of cardiovascular diseases.

Effects of cigarette smoke and its constituents on the adherence of polymorphonuclear leukocytes.

Bridges, R B; Hsieh, L; Haack, D G
Tipo: text
Publicado em /09/1980 Português
Relevância na Pesquisa
35.99%
The in vitro effects of the water-soluble fraction of whole cigarette smoke (WSF) and two alpha, beta-unsaturated aldehydes of cigarette smoke (acrolein and crotonaldehyde) on polymorphonuclear leukocyte (PMNL) adherence were determined with nylon fiber columns. Each of these cigarette smoke constituents caused a dose-dependent inhibition of PMNL adherence. However, at least fivefold higher concentrations of these agents were necessary to inhibit adherence as compared with those necessary to achieve the same level of inhibition of PMNL chemotaxis. Furthermore, inhibition of adherence by WSF could be differentiated from its effects on chemotaxis in that reduced glutathione completely protected chemotaxis from the effects of WSF but only afforded partial protection to PMNL adherence. These data suggest that the inhibitory effects of WSF, acrolein, and crotonaldehyde on PMNL chemotaxis are not due to their inhibition of adherence. Finally, although PMNL adherence is considered to be an integral part of the chemotactic mechanism, differentiation between these two PMNL functions may be possible, since some inhibitors of chemotaxis do not have corresponding inhibitory effects on adherence.

Substrate specificity of an aflatoxin-metabolizing aldehyde reductase.

Ellis, E M; Hayes, J D
Tipo: text
Publicado em 01/12/1995 Português
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25.99%
The enzyme from rat liver that reduces aflatoxin B1-dialdehyde exhibits a unique catalytic specificity distinct from that of other aldo-keto reductases. This enzyme, designated AFAR, displays high activity towards dicarbonyl-containing compounds with ketone groups on adjacent carbon atoms; 9,10-phenanthrenequinone, acenaphthenequinone and camphorquinone were found to be good substrates. Although AFAR can also reduce aromatic and aliphatic aldehydes such as succinic semialdehyde, it is inactive with glucose, galactose and xylose. The enzyme also exhibits low activity towards alpha,beta-unsaturated carbonyl-containing compounds. Determination of the apparent Km reveals that AFAR has highest affinity for 9,10-phenanthrenequinone and succinic semialdehyde, and low affinity for glyoxal and DL-glyceraldehyde.

Identification of cardiac oxidoreductase(s) involved in the metabolism of the lipid peroxidation-derived aldehyde-4-hydroxynonenal.

Srivastava, S; Chandra, A; Ansari, N H; Srivastava, S K; Bhatnagar, A
Tipo: text
Publicado em 01/02/1998 Português
Relevância na Pesquisa
25.99%
The aim of this study was to identify the cardiac oxidoreductases involved in the metabolism of 4-hydroxy-2-trans-nonenal (HNE), an alpha,beta unsaturated aldehyde generated during the peroxidation of omega-6 polyunsaturated fatty acids. In homogenates of bovine, human and rat ventricles the primary pyridine coenzyme-linked metabolism of HNE was associated with NADPH oxidation. The NADPH-dependent enzyme catalysing HNE reduction was purified to homogeneity from bovine heart. The purified enzyme displayed kinetic and immunological properties identical with the polyol pathway enzyme aldose reductase (AR), and catalysed the reduction of HNE to its alcohol 1,4-dihydroxynonene (DHN), with a Km of 7+/-2 microM. In the presence of NADP the enzyme did not catalyse the oxidation of DHN. During catalysis, HNE did not cause inactivation of AR. Nevertheless when the apoenzyme was incubated with HNE a dissociable complex was formed between the enzyme and HNE, followed by irreversible loss of activity. Inactivation of the enzyme by HNE was prevented by NADP. Partial modification of the enzyme with HNE led to a 17-fold increase in the KHNEm and Kglyceraldehydem, and the HNE-modified enzyme had a 500-fold higher IC50 for sorbinil than for the reduced enzyme...