Academic literature on the topic 'Decadiene-5,8ol-1(dimethyl-3,9 isopropyl-6)acetate|fin'

The analytical result by 80°С-based TD-GC/MS showed that 65 peaks were obtained from the helium volatiles from the fresh branches of Cinnamomum camphora and 60 chemical compounds were identified. The results showed that the main components were as: 1,3-Benzodioxole, 5-(2-propenyl)- (12.629%), Tricyclo[2.2.1.0(2,6)]heptane, 1,7-dimethyl-7-(4-methyl-3-pentenyl)-, (-)- (10.302%), 3-Cyclohexene-1-methanol, .alpha.,.alpha.4-trimethyl- (9.084%), Bicyclo[2.2.1] heptan-2-one, 1,7,7-trimethyl-, (1R)- (7.406%), Nerolidol (6.695%), Bicyclo[2.2.1]heptane, 2-methyl-3-methylene-2-(4-methyl-3-pentenyl)-, (1S-exo)- (6.017%), Bicyclo[2.2.1]heptan-2-one, 1,7,7-trimethyl-, (.+/-.)- (4.885%), Bicyclo[3.1.1]hept-2-ene, 2,6-dimethyl-6-(4-methyl-3-pentenyl)- (4.680%), Naphthalene, 1,2,3,5,6,8a-hexahydro-4,7-dimethyl-1-(1-methylethyl)-, (1S-cis)- (4.139%), 3-Cyclohexen-1-ol, 4-methyl-1-(1-methylethyl)-, (R)- (3.538%), Copaene (2.749%), Bicyclo[2.2.1] heptan-2-ol, 1,7,7-trimethyl-, (1S-endo)- (2.643%), Acetic acid, 1,7,7-trimethyl-bicyclo [2.2.1]hept-2-yl ester (2.536%), Cyclohexane, bromo- (2.530%), 1,6,10-Dodecatriene, 7,11- dimethyl-3-methylene-, (E)- (1.725%), Naphthalene, 1,2,3,4,4a,5,6,8a-octahydro-7-methyl-4- methylene-1-(1-methylethyl)-, (1.alpha.,4a.beta.,8a.alpha.)- (1.265%), Bicyclo[4.4.0]dec-1-ene, 2-isopropyl-5-methyl-9-methylene- (1.174%), (-)-Isosativene (1.149%), 11-Tetradecen-1-ol acetate (1.118%), .alpha.-Cadinol (1.061%), etc. The analytical result suggested that the helium volatiles from the fresh branches of C. camphora could be used as industrial materials of biomedicines, spicery and food industry.

A facile procedure for the preparation of 6-aryl-1,3-dimethyl-5H-pyrimido[4,5-b][1,4]diazepine2,4(1H,3H)-diones 8, 9 from 6-amino-5-arylideneamino-1,3-dimethyluracils 1, 2 and triethyl orthoacetate (3) in a two-step reaction via 6-aryl-8-ethoxy-6,7-dihydro-1,3-dimethyl-5H-pyrimido[4,5-b][1,4]diazepine-2,4(1H,3H)-diones 6, 7 is described. Condensation of 1 with diethoxymethyl acetate (10) resulted in the formation of (1,3-dimethyl-2,6-(1H,3H)-dioxopurin-7-yl)(phenyl)methyl acetate (11) and a small amount of 1,3-dimethyl-6-phenylpyrazino[2,3-d]pyrimidine-2,4(1H,3H)-dione (12). The structures of 6 and 11 were unambiguously confirmed by single-crystal X-ray diffraction analysis.

The seedlings of Oroxylum indicum were inoculated with plant growth promoting microbes (PGPMs) mainly, Glomus mosseae, Trichoderma harzianum and Pseudomonas putida both alone and consortium. The GCMS analysis of the methanolic root extract of inoculated seedlings of O. indicum showed that seedlings treated with mixed consortium of mycorrhizal fungi, bacteria and fungus showed the presence of maximum number of phytocompounds. The GC-MS analysis of control seedlings showed presence of 55 compounds where three new compounds were found i.e. 2-Cyclobutene-1-Carboxamide; Tetradecanoic Acid, 10, 13-dimethyl-, methyl ester; 1-methylene-2b-hydroxymethyl-3, 3-dimethyl-4b-(3-methylbut-2-enyl)-cy. 53 compounds were found in seedlings treated with mycorrhizae i.e., Glomus mosseae, and three new compounds were found i.e., 1-Ethyl-2-Hydroxymethylimidazole; Octadecanoic Acid, 11-Methyl-, methyl ester; 4-Methyl-1, 4-Heptadiene. The seedlings treated with bacteria i.e. Pseudomonas putida showed the presence of 52 compounds and three new compounds were found i.e. Meso-4, 5-octanediol; 1-ethyl-2-hydroxymethylimidazole; 2, 5-cyclohexadiene-1, 4-dione, 2, 5-dihydroxy-3-methyl-6-(1-methylethyl) - . A total of 56 compounds were present in seedlings treated with fungus i.e. Trichoderma harzianum and five new compounds were found i.e. 2-CyclohexeN-1-one, 2-Butyl-3-Methoxy; Methyl 12, 13-Tetradecadienoate; Methyl 6, 9, 12-hexadecatrienoate; 1, 9-Decadiyne; 1, 4-Naphthalenedione. The seedlings treated with dual consortium of mycorrhizae and bacteria showed the presence of 88 compounds and five new compounds were found i.e., N-(1-Methoxycarbonyl-1-methylethyl)-4-methyl-2-aza-1,3-dioxane;1-ethyl-2 hydroxy methylimidazole; Methyl 8-methyl-nonanoate; Naphthalene, 1,2,3,4,4a,5,6,8a-octahydro-4a,8-dimethyl; Methyl 12,13-tetradecadienoate. 152 compounds were present in seedlings treated with dual consortium of mycorrhizal fungi and fungus and ten new compounds were found to be present i.e. 1,9-Decadiyne; 3,7,11-Trimethyl-3-hydroxy-6,10-dodecadien-1-yl acetate; 3-Heptyne, 7-chloro; 3-Methyl-4-(methoxycarbonyl) hexa-2,4-dienoic acid; Benzo[c]cinnolin-2-amine ; Tetradecanoic acid, 10,13-dimethyl-,Methyl ester; Cis,cis-4,6-octadienol; 2-Cyclohexen-1-one, 2-butyl-3-methoxy; Methyl 12,13-tetradecadienoate; 2-Aminopyridazino(6,1-b) quinazolin-10-one. A total of 36 compounds were present in seedlings treated with dual consortium of bacteria and fungi and two new compounds were found i.e. [1,4] Dioxino [2,3-b]-1,4-dioxin, hexahydro-2,3,6,7 ; 1-Ethyl-2-hydroxymethylimidazole. The seedlings inoculated with mixed consortium of mycorrhizae, bacteria and fungus showed the presence of 213 compounds and fourteen new compounds were found i.e. 3,7,11-Tridecatrienenitrile, 4,8,12-Trimethyl; 1,9-Decadiyne; 2,6,10,14,18,22-Tetracosahexaene, 2,6,10,15,19,23-Hexamethyl-, (ALL-E) ; 1-Methylene-2b-hydroxymethyl-3,3-dimethyl-4b-(3-methylbut-2-enyl)-cy; 1,9-Decadiyne, Cyclobutane, 1,2-bis(1-methylethenyl)-, trans-, 3,7,11-Trimethyl-3-hydroxy-6,10-dodecadien-1-yl acetate, 5-Hydroxy-4-hydroxymethyl-1-(1-hydroxy-1-isopropyl)cyclohex-3-ene, 5,8,11,14-Eicosatetraenoic acid, methyl ester, (all-z)-, 1-Cyclohexyl-2-buten-1-ol (c,t) , 1-Oxetan-2-one, 4,4-diethyl-3-methylene-, Tetradecanoic acid, 10,13-dimethyl-, methyl ester, 2-Cyclohexen-1-one, 2-butyl-3-methoxy-, Methyl 12,13-tetradecadienoate, Heptacosanoic acid, 25-methyl-, methyl ester Hexadecanoic Acid, Methyl Ester; 2-Chloroethyl Linoleate; 9,12-Octadecadienoic Acid, Methyl Ester, (E,E); Butanoic acid, methyl ester; 4A,5,6,7,8,8A(4H) HexahydroBenzopyran-3-Carboxamide, 8A-Methoxy-4A-M,; Octadecanoic acid; Farnesene; Squalene; Myrcene; Naphthalene; Tetradecanoic Acid, Methyl Ester; Octadecanoic Acid, Methyl Ester; 1H-Cycloprop[E] Azulene, Decahydro-1,1,4,7-Tetramethyl-, [1AR-(1A].Alph ; Cyclohexane, 1-methyl-4-(1-methylethenyl)-, trans (Elemene); Cyclohexene, 1-methyl-4-(1-methylethenyl)-, (s)- (Limonene); were found to be present in this treatment.

Abstract Mannich reaction of 1,3-indandione-1-phenylhydrazone (1) or 1,3-diphenylhydrazone (5) withmorpholine or piperazine gave the Mannich base-phenylhydrazone 2 and 3 or the diphenylhydrazone6 and 7, respectively. Whereas, such reaction with 1 or 5 using primary amines affordedthe indeno[2,1-ƒ]-1,2,4-triazepin-6(2H)-one (4) or its 6-phenylhydrazone (8), respectively.Treatment of 5 with ammonium acetate and formalin afforded 9. The indeno[1,2-ƒ]-1,2,4,5-tetrazepin-10(2H)-one (11) was obtained from the 1,2-diphenylhydrazone 10 and formaldehyde.

A series of new compounds including p-bromo methyl pheno acetate [2]. N-( aminocarbonyl)–p-bromo pheno acetamide [3] , N-( aminothioyl) -p-bromo phenoacetyl amide [4], N-[4-(p-di phenyl)-1,3-oxazol-2-yl]-p-bromopheno acetamide [5],N-[4-p-di phenyl]-1,3-thiazol-2-yl-p-bromo phenoacet amide [6], p-bromopheno acetic acid hydrazide [7] , 1-N-(p-bromo pheno acetyl)-1,2-dihydro-pyridazin-3,6- dione [8], 1-N-(p-bromo pheno acetyl)-1,2-dihydro-phthalazin-3,8- dione[ 9], 1-(p-bromo pheno acetyl)-3-methylpyrazol-5-one [10] and 1-(p-bromo phenol acetyl)- 3,5-dimethyl pyrazole [11] have been synthesized. The prepared compounds were characterized by m.p.,FT-IR and 1H-NMR spectroscopy. Also ,the biological activity was evaluated .

Expoxidation of cholesta-5,8-dien-3?-yl acetate (1) with peracids takes place preferentially at the more highly substituted ?8-olefinic double bond to give: (a) with monoperphthalic acid, 8?,9?-epoxycholest-5-en-3?-yl acetate (2) (in 39 % yield) and 9?-hydroxy-5?,6?-epoxycholest-8(14)-en-3?-yl acetate (3) (in 30 % yield); and (b) with m-chloroperbenzoic acid, the 8?,9?-epoxide 2 (64 %) and 5?,6?-epoxy derivative 3 (20%). Some chemical transformations of the obtained epoxides are described.

The action of a tumor-promoting phorbol ester, 12-O-tetradecanoylphorbol 13-acetate (TPA), on isolated rat aortic and tail artery strips has been characterized. TPA (10−9 – 10−7 M) produced a graded contraction developing maximum tension over 30–40 min. The contraction was irreversible and was not relaxed by prolonged washing with physiologic saline. Relaxation occurred upon washing with Ca2+-free saline but readdition of Ca2+ restored response. TPA was without significant effect in rat tail arteries in physiologic saline but produced responses in saline containing elevated K+ (15 mM). The protein kinase C inhibitor, CP-46,665-1 (4-aminomethyl-1-[2,3-(di-n-decyloxy)n-propyl]-4-phenylpiperidine dihydrochloride) (5 × 10−5 M), blocked the response to TPA but was without effect on responses to Bay K 8644 (2,6-dimethyl-3-carbomethoxy-5-nitro-4-(2-trifluoromethylphenyl) 1,4-dihydropyridine), KCl, phenylephrine, and B-HT 920 (6-allyl-2-amino-5,6,7,8-tetrahydro-4H-thiazolo[4,5-d]azepin dihydrochloride). The calcium channel antagonist nifedipine and its analogue, 2,6-dimethyl-3,5-dicarbomethoxy-4-(3-cyanophenyl)-1,4-dihydropyridine, inhibited TPA responses with IC50 values of 9.28 × 10−9 and 1.96 × 10−7 M, respectively. Responses to Bay K 8644 in rat aorta were maximum in the presence of elevated KCl (10 mM), but TPA at concentrations of 10−9 and 3 × 10−9 M potentiated responses to Bay K 8644 in physiologic saline to levels approximating those in elevated K+ saline. TPA similarly potentiated responses to Ca2+ in Ca2+-free solution. In the presence of TPA, 10−8 and 3 × 10−8 M, responses to Ca2+ in nondepolarizing saline were potentiated to levels seen under depolarizing conditions. The present results suggest a relationship between protein kinase C and Ca2+ channel activation. However, alternative possibilities, including enhancement of the Ca2+ sensitivity of the contractile apparatus, may also contribute to the observed effects.

The treatment of salicylaldehyde 1 and derivatives 2-4 with triethyl phosphonoacetate 5 in refluxing toluene using piperidine acetate and β-alanine affords 3-diethyl phosphonocoumarins 6-9. By hydrogenation of the compounds 6-9, 3-diethylphosphono-3,4-dihydrocoumarins 10-13 have been obtained. The compounds 10-13 react with the aromatic aldehydes 14-18, under Wittig-Horner conditions, to give 3-alkyl-coumarins 19-24 in satisfactory yields. The reaction of 3-diethyl-phosphonolactones 25, 26 with isatin 27 and 5-bromoisatin 28, under similar reaction conditions, leads to 3-alkyl-α,β-unsaturated δ-lactones 29-31

An efficient synthesis of several A- and B-modified D-homo lactone androstane derivatives from 3?-hydroxy-17-oxa-D-homoandrost-5-en-16-one (1) is reported. 17-Oxa-Dhomoandrost- 4-ene-3,16-dione (2), obtained by the Oppenauer oxidation of compound 1, was converted via the unstable intermediate 3,16-dioxo-4,17-dioxa-D-homoandrostane- 5?-carboxaldehyde (3) to 17-oxa-D-homo-3,5-seco-4-norandrostan-5-one-3-carboxylic acid (4), which was also obtained directly from compound 2. Compound 1 was acetylated to give 17-oxa-D-homoandrost-5-en-16-on-3?-yl acetate (5) which was then oxidized with chromium(VI)-oxide in 50% acetic acid or with meta-chlorperbenzoic acid and chromium(VI)-oxide to yield compounds 6-8 and 5?-hydroxy-17-oxa-D-homoandrostane- 6,16-dion-3?-yl acetate (9), respectively. The oximination of compound 9 gave a mixture of 6(E)-hydroximino-5?-hydroxy-17-oxa-D-homoandrostan-16-on-3?-yl acetate (10) and 6(Z)-hydroximino-5?-hydroxy-17-oxa-D-homoandrostan-16-on-3?-yl acetate (11), the hydrolysis of which gave 6(E)-hydroximino-3?,5?-dihydroxy-17-oxa-D-homoandrostan- 16-one (12) and 6(Z)-hydroximino-3?,5?-dihydroxy-17-oxa-D-homoandrostan-16-one (13). 6-Nitrile-17-oxa-5,6-seco-D-homoandrostane-5,16-dion-3?-yl acetate (14) was obtained under the Beckmann fragmentation of compounds 10 and 11. Only pure and stable compounds (1, 2, 4, 5, 9 and 14) were tested in vitro on six malignant cell lines (MCF-7, MDA-MB-231, PC-3, HeLa, HT-29, K562) and one non-tumor MRC-5 cell line. Significant antiproliferative activity against MDA-MB-231 cells showed compounds 1, 5 and 9, while compound 2 exhibited a strong antiproliferative activity. Only compound 14 showed weak antiproliferative activity against MCF-7 cells. All tested compounds were not toxic on MRC-5 cells, whereas Doxorubicin was highly toxic on these cells.

In this work pyrazolin derivatives were prepared from the diazonium chloride salt of 4-aminobenzoic acid. Azo compounds were prepared from the reaction of an ethanolic solution of sodium acetate and calculated amount of active methylene compound namely, acetyl acetone to obtain the corresponding hydrazono derivative (1). Cyclocondensation reaction of compounds (1) with hydrazine hydrate and phenyl hydrazine in boiling ethanol affording the corresponding pyrazoline-5-one derivatives of 4-aminobenzoic acid (2,3). Then compound (3) was reacted with thionyl chloride to give the corresponding acid chloride derivative(4), followed by conversion into the corresponding acid hydrazide derivative (5) carboxylic acid thiosemicarbazide (11), esters (14,15), thioesters (16,17) and amides (18,19), when treated hydrazine hydrate, thiosemicarbazide, alcohols, alkylthiol and secondary amines in dry refluxing benzene; respectively. Schiff's bases (6-8) were prepared by refluxing of compound (5) with different aldehydes and ketons, then two compounds from the Schiff's bases were cyclized with ?-mercapto acetic acid to give (9 and 10). Furthermore, 1,2,4-triazole derivative (12) have been also prepared by refluxing thiosemicarbazide derivative with sodium hydroxide solution (4%) followed acidification of the result using (10%)hydrolic acid. Moreover, a thiadiazole derivative (13) has been prepared by treatment of thiosemicarbazide derivative with concentrated sulfuric acid as cyclyzing agent. Finally, oxadiazole derivative (20) has prepared by condensation of its acid hydrazide derivative with carbon disulfide in basic medium.

El presente libro ofrece un compendio de doce capítulos resultados de investigaciones en el ámbito de la educación inicial, básica, media y superior, en diferentes contextos educativos colombianos. En cuanto a la investigación en educación superior, se presentan seis trabajos: el capítulo 1 titulado Las estrategias de aprendizaje en estudiantes universitarios: estado del arte, presenta el resultado del ejercicio de investigación doctoral Las relaciones entre motivación, estilos y estrategias de aprendizaje en estudiantes de pregrado de la Corporación Universitaria Americana, en el que se aborda el aprendizaje y la función de los docentes en este proceso. El segundo capítulo: Instrumentos de evaluación de competencias profesionales en estudiantes universitarios: estado del arte, presenta los avances frente a la evaluación de competencias profesionales en estudiantes universitarios, enmarcado en el contexto de formación en licenciatura en pedagogía infantil haciendo un recuento de los conceptos de competencias profesionales, avances en la formación de profesionales de la educación y algunos estudios aplicados a población estudiantil para el desarrollo de competencias profesionales. El capítulo 3, Competencias transversales y aprendizaje basado en retos en estudiantes de administración de empresas: caso formulación de proyectos, muestra el análisis realizado a partir de las percepciones de los estudiantes frente a la aplicación de la metodología aprendizaje basado en retos –ABR, con el fin de determinar las competencias transversales desarrolladas en estudiantes de administración de empresas. Continuando con el ámbito de investigaciones en educación superior, el capítulo 9, Los estilos de aprendizaje de las estudiantes de Licenciatura en Pedagogía de la Primera Infancia: un estudio descriptivo, aborda la caracterización de los estilos de aprendizaje de las estudiantes de Licenciatura en Pedagogía de la Primera Infancia, con el fin de identificar aquellos estilos predominantes en esta población. Por su parte, el capítulo 10, Resignificación del saber pedagógico del maestro en la educación superior, ofrece el análisis de la concepción del maestro en los primeros siglos de nuestra era en contextos eclesiásticos, con el fin de identificar características que permitan la reconstrucción del saber pedagógico actual. Finalmente, en este ámbito, el capítulo 12, Influencia de las emociones en el aprendizaje virtual en educación superior, identifica el papel de las emociones en el contexto de aprendizaje virtual de estudiantes universitarios en la contingencia establecida por la pandemia Covid19. En el campo de la educación inicial, se presentan tres capítulos resultados de investigación. El capítulo 4, Evaluación de la competencia matemática temprana en primera infancia, muestra los resultados de investigación de un estudio de caso en el que se aplicó la prueba Early Numeracy Test Revisado (ENT-R) que evalúa las competencias matemáticas en niños de 4 y 5 años. El capítulo 6, El desarrollo de la competencia matemática temprana a partir de tecnologías de información y comunicación: diseño teórico de investigación, presenta un rastreo de las investigaciones que se han centrado en el desarrollo de la competencia matemáticas, consolidando el diseño teórico de investigación de un proyecto a realizar en el campo de la competencia matemática temprana (CMT); el capítulo 7, Desarrollo de habilidades investigativas en la primera infancia: diseño teórico de investigación y avances, evidencia la necesidad de un acercamiento por parte de los estudiantes al conocimiento de manera espontánea generando procesos de transversalización de diferentes áreas que se articulen al desarrollo de actividades de enseñanza. En el campo de las Tecnologías de la información y de la comunicación (TIC) aplicadas a la educación, se presentan dos capítulos. El capítulo 5, Programas y herramientas basadas en las TIC que facilitan los procesos de inclusión de las personas en situación de discapacidad y que se han implementado en Colombia en los procesos educativos en la última década, presenta un estudio documental de las investigaciones que se han realizado en la última década en Colombia y que utilizan alguna herramienta TIC en una población con una discapacidad determinada y se identifica la estrategia implementada por estos, encontrando que, a pesar de que se han inventado y se encuentran gratuitamente una gran cantidad de softwares especializados, las experiencias documentadas generalmente no hacen uso de estos. El capítulo 8. Propuesta b-learning significativo + IAD para medias técnicas del municipio de Medellín, expone una propuesta diseñada para el plan de desarrollo del municipio de Medellín, partiendo de la necesidad de este de ampliar la modalidad de media técnica a toda la educación media de la ciudad y los corregimientos. Pensando en eso, y teniendo en cuenta las condiciones pedagógicas, de infraestructura y la intencionalidad gubernamental de trabajar las áreas o disciplinas STEAM (Science, Technology, Engineering and Matemathics) para convertir a la ciudad en un gran símbolo de la innovación y entrar en concordancia con el proyecto Valle del software de la alcaldía. Finalmente, en el campo de las políticas públicas y la legislación educativa, el capítulo 11, Análisis histórico de la formulación de las políticas educativas en Colombia, describe las principales características de las políticas educativas en el contexto colombiano, con la finalidad de crear un conocimiento que permita tener un referente histórico para abordar la actualidad de las políticas educativas tanto en su formulación como en los mecanismo de evaluación que se tienen para medir el desempeño de la población que se está educando, para ello se realiza un somero análisis desde el año 1950 hasta el año 2007, resaltando los principales momentos históricos y los principales cambios en las políticas educativas para entender el contexto vigente.

Este libro es producto de los resultados obtenidos en la primera fase terminada del proyecto y línea de investigación denominada: “Análisis y Desarrollo de Indicadores para Medir el Crimen Económico y Responsabilidad Social Empresarial”, el cual ha sido financiado en su tercer periodo de desarrollo por la Corporación Universitaria Americana durante el periodo enero de 2016 y diciembre de 2018. El trabajo investigativo presentado aquí se basa en la experiencia de aproximadamente 6 años de investigaciones documentales y participaciones de los autores como ponentes en varios congresos internacionales en Latinoamérica, específicamente en: Brasil, Colombia, Costa Rica, Cuba, Chile, México y Venezuela. Esto ha permitido intercambiar interesantes puntos de vista con colegas expertos que se relacionan con el tema del crimen económico y la responsabilidad social empresarial, gubernamental y civil. Los antecedentes reflexivos que contiene este libro, se inician en el periodo 2009-2011 con cuatro trabajos presentados por Ibarra Alberto en trabajo conjunto con Echeverri Camilo: 1. Artículo del 2009: “Retrospectiva de la Responsabilidad Social Empresarial a través del Desarrollo del Pensamiento Económico”, Revista Universo Contabil de la Fundación Universitaria de Blumenau, Brasil; 2. La ponencia del 2009: “Correlación entre Información Empresarial y Objetivos Corporativos con base a la Responsabilidad Social Empresarial”, XIV Congreso Internacional de Contaduría, Administración e Informática en la UNAM, México; 3. La ponencia del 2010: “Algunos Fundamentos sobre la Responsabilidad Social en la Empresa Privada considerando el Desarrollo del Pensamiento Económico” , V Reunión Internacional de Gestión y Desarrollo sobre Responsabilidad Social y Emprendimiento, Universidad de Santa Catarina, Florianópolis, Brasil; 4. El artículo del 2011: “Índices para Medir Empresas Sostenibles con base a la Responsabilidad Social Empresarial vs Crimen Económico desde un Enfoque de la Teoría Behaviorista”, Revista Civilizar de Empresa y Economía de Universidad Sergio Arboleda, Bogotá, Colombia. El segundo periodo del desarrollo conceptual del trabajo de investigación comprende el periodo 2012-2014 con cuatro ponencias en congresos internacionales: 5. “La RSE como Estrategia de Crecimiento Económico”, XXV Congreso Latinoamericano de Estrategia, Universidad Metropolitana Castro Carazo, Costa Rica 2012. 6. “Análisis del Observatorio de la Globalización sobre Crimen Económico y Crisis de Cultura de Legalidad a Nivel Mundial (Soborno, Extorción, Corrupción y Fraude Empresarial)”, II Congreso The Global Compact de las Naciones Unidas 2012, Cámara de Comercio de Bogotá. 7. “Análisis Comparativo de los Indicadores e Informes de Crimen Financiero y Económico en el Mundo y Latinoamérica vs RSE.” XII International Finance Conference 2012, de American Academy of Financial Management, Universidad EAFIT Medellín, Colombia. 8. “Análisis del Crimen Financiero en Entornos de Crisis Financiera”. International Finance Conference 2014”, Universidad Nacional Autónoma de México. El tercer periodo comprende los años 2015-2016, y los autores trabajaron y presentaron 9 ponencias y un artículo de reflexión, donde gran parte de estos trabajos se llevaron a cabo en compañía de otros investigadores con excelente capacidad analítica sobre el tema. Entre estos académicos está la colaboración de Andrés Tibaquira y Alexander Castrillo. Los trabajos son: 9. “Estructuras Conceptuales del Crimen Económico y la RSE para desarrollar un Análisis Integral de Empresas Socialmente Responsables”, XXVIII Congreso Latinoamericano de Estrategia SLADE 2015, Universidad Pontificia Bolivariana, Medellín, Colombia. 10. “Desarrollo Sostenible con RSE versus Corrupción y Fraude Corporativo: Sus Indicadores e Índices de Medición”. Conferencia Magistral ante la Contraloría General de Medellín Colombia y Red de Transparencia”. 11. “Tres Intangibles Correlacionados con el Entorno Organizacional para Alcanzar Empresas Sostenibles y Éticas: Capital Social, Capital Intelectual y Responsabilidad Social”. XX Congreso Internacional de Contaduría, Administración e Informática 2015. Universidad Nacional Autónoma de México, 12. “Crimen Económico y Responsabilidad Social Empresarial”. Instituto Tecnológico Nacional de México, Conferencia Magistral ante el Consejo de Investigación. 13. “Análisis Internacional sobre el Crimen Económico por países”. Conferencista Magistral y Organizador Técnico del I Congreso Internacional de Crimen Económico y Fraude Financiero y Contable. Corporación Universitaria Remington, Medellín, Colombia. En el 2016, se presentaron las siguientes ponencias: 14. “Hacia Una Nueva Taxonomía del Delito y Crimen Económico”, II Congreso Internacional de Economía, Contabilidad y Administración”, Universidad de la Habana, Cuba.; 15. Ibarra Alberto y Tibaquira Andrés: “Hacia una Nueva Taxonomía del Delito y Crimen Económico para incrementar la RSE”. International Finance Conference 2016 Chile, Universidad de Valparaíso Chile y Universidad de Santiago de Chile. 16. Ibarra Mares Alberto y Tibaquira Cuervo Andrés: “Objetivos Empresariales Informales y su Influencia en Fraudes dentro del Sistema de Información Contable”, V Encuentro Internacional de Investigación y Espíritu Empresarial. Universidad Francisco de Paula Santander, Ocaña Santander Colombia. 17. Ibarra Alberto, Echeverri Camilo y Ramírez Carlos: “Antecedentes y Actualidad del Desarrollo del Gobierno Corporativo en Latinoamérica”, II Congreso Internacional de Crimen Económico y Fraude Financiero y Contable. Conferencista Magistral, Corporación Universitaria Remington, Medellín Colombia. 18. Ibarra Alberto, Pérez Luis Alfonso y Garzón Manuel (2015): “Código de ética empresarial para las Pymes: Marco de Referencia para la Sostenibilidad y Responsabilidad Social Empresarial (RSE)”. Revista Espacios. Venezuela. A partir de la experiencia adquirida, el objetivo de los autores en este trabajo fue sintetizar una serie de conceptos técnicos fundamentales sobre el crimen económico y sus principales componentes, con el fin de conformar una sólida taxonomía y metodología para medir las percepciones sobre los diferentes tipos de crimen económico en diferentes países de Latinoamérica, iniciando por Colombia, ello permitirá adaptar y mejorar algunos indicadores que se han estandarizado en el ámbito mundial para medir cualitativa y cuantitativamente las variables del crimen económico entre países, instituciones, sectores y personas. En el capítulo 1 y 2 se inicia con un análisis documental sobre cuáles son las principales variables que se toman en cuenta en la literatura especializada sobre este fenómeno económico negativo que registran las empresas, instituciones y países. Para ello, se partió de una taxonomía de 17 variables que proporcionaron información acerca de Transparencia Internacional (TI) y sobre el lenguaje del crimen económico para determinar ocho categorías o tipologías de crimen económico, a las cuales se les denominó taxonomía. En el capítulo 3 se da a conocer una muestra representativa de algunas de las principales organizaciones que se dedican al estudio y combate de delitos económicos y fraudes. Las primeras instituciones que incluimos por su prestigio y seriedad sobre el tema, fueron: Transparencia Internacional (TI), La Organización de las Naciones Unidas (ONU), PricewaterhouseCoopers (PWC), Ernst and Young (EY), KPMG y Deloitte and Touche. Además, consideramos datos y reportes del Fondo Monetario Internacional (FMI) y el Banco Mundial (BM). En los capítulos cuarto, quinto y sexto, analizamos respectivamente el crimen económico desde sus tres perspectivas o niveles: 1.) Por país, 2.) Por empresas, y 3.) Por personas. Por último, en el capítulo séptimo damos unas conclusiones que consideramos nos dan una primera visión para un análisis metodológico y con mayor rigor científico sobre el crimen económico En el capítulo séptimo incluimos las conclusiones finales basadas en el marco teórico sobre la teoría marginalista y teoría behaviorista, que nos permite fundamentar nuestras reflexiones y conclusiones. También adicionamos las ideas de Francis Fukuyama con respecto al concepto de confianza y capital social, que son componentes importantes de la ética y responsabilidad social empresarial. Incluimos además unas ideas sobre la teoría institucionalista que determina en gran medida el comportamiento de un individuo dependiendo del tipo de institución en dónde se desarrolla.

The genus Daphniphyllum consists of 25–30 species of evergreen trees and shrubs of south Asia. The leaves and roots are widely used in Chinese herbal medicine. About 250 alkaloids, many with complex polycyclic structures, have been isolated from these species. Of these, daphenylline 3 is unique in incorporating a benzene ring. Ang Li of the Shanghai Institute of Organic Chemistry envisioned (Nature Chem. 2013, 5, 679) a route to 3 based on the diastereoselective intramolecular Michael cyclization of 1 to 2. Following the work of Piers (J. Org. Chem. 1996, 61, 8439), the preparation of 1 began with the Birch reduction of 4, followed by hydrolysis. Epoxidation followed by elimination and acetylation led to the racemic acetate 5. Hydrolysis with pig liver esterase left one enantiomer of the acetate, that was transesterified with methoxide to give 6 in high ee. Mitsunobu coupling of 6 with the o-nitrobenzenesulfonamide 7 gave 8. After some experimentation, selective α¢-silylation was effected with TBDPSOTf, setting the stage for gold-catalyzed Conia cyclization to 9. Deprotection of the amine fol­lowed by acylation with 10 gave 1, that cyclized smoothly to 2 as a 10:1 ratio of diastereomers. The arene of 3 was constructed by converting 2 into the corresponding vinyl tri­flate. Pd-mediated coupling with 11 gave 12. Under irradiation with strict exclusion of oxygen, 12 cyclized to the dihydro aromatic, that on warming with DBU in the pres­ence of air was oxidized to 13. To close the last ring of 3, the ketone 13 was further oxidized to the enone 14. Desilylation of 14 followed by exposure to Ph3P/I2 gave the iodide 15, that was cyclized under reductive free radical conditions to 16. The hydrogenation of 16 under Pd catalysis delivered the incorrect diastereomer, perhaps because migration to the endocyclic alkene preceded reduction. This problem was solved by using the Crabtree Ir catalyst. Modified Krapcho decarbomethoxylation then gave 17, that was reduced to daphenylline 3.

The zaragozic acids, exemplified by Zaragozic Acid C 3, are picomolar inhibitors of cholesterol biosynthesis. Jeffrey S. Johnson of the University of North Carolina developed (J. Am. Chem. Soc. 2008, 130, 17281) an audacious silyl glyoxylate cascade approach to the oxygenated backbone fragment 1. Intramolecular aldol cyclization converted 1 to 2, setting the stage for the construction of 3. The lactone 2 includes five stereogenic centers, two of which are quaternary. The authors were pleased to observe that exposure of 4 to vinyl magnesium bromide 5 led, via condensation, silyl transfer, condensation, and again silyl transfer, to a species that was trapped with t-butyl glyoxylate 6 to give 7 as a single diastereomer. This one step assembled three of the stereogenic centers of 2, including both of the quaternary centers. The alcohol 7 so prepared was racemic, so the wrong enantiomer was separated by selective oxidation. Intramolecular aldol condensation of the derived α-benzyloxy acetate 1 then completed the construction of 2. Addition of the alkyl lithium 8, again as a single enantiomerically-pure diasteromer, to 2 gave the hemiketal 9. Exposure of 9 to acid initially gave a mixture of products, but this could be induced to converge to the tricyclic ester 10. To convert 10 to 11 , the diastereomer that was needed for the synthesis, two of the stereogenic centers had to be inverted. This was accomplished by exposure to t-BuOK/t-amyl alcohol, followed by re-esterification. The inversion of the secondary hydroxyl group was thought to proceed by retro-aldol/re-aldol condensation. Debenzylation of 11 followed by acetylation delivered 12, an intermediate in the Carreira synthesis of the zaragozic acids. Following that precedent, the ring acetates of 12 were selectively removed, leaving the acetate on the side chain. Boc protection was selective for the endo ring secondary hydroxyl, leaving the exo ring secondary hydroxyl available for condensation with the enantiomerically-pure acid 13. Global deprotection then completed the synthesis of Zaragozic Acid C 3. The key to the success of this synthesis of the complex spiroketal 3 was the assembly of 7 in one step as a single diastereomer from the readily-available building blocks 4, 5, and 6.

The cephalostatins and ritterazines, represented by cephalostatin 1 3, have the remarkable property of inducing apoptosis in apoptosis-resistant malignant cell lines. The total synthesis ( J. Am. Chem. Soc. 2010, 132, 275) of 3 by Matthew D. Shair of Harvard University required the practical preparation of the complex hexacyclic ketones 1 and 2. The preparation of 1 started with irradiation of commercial hecogenin acetate 4 to give the known aldehyde 5 . Reaction of 5 with N -phenyltriazolenedione 6 led to the ketal 7. Oxidative cleavage generated an aldehyde, which on reduction and allylation was converted to 8. Acid-mediated cyclization led to 9. The sidechain of 9 was removed, giving 10, which was selectively reduced, leading to 11. Intramolecular aldol condensation gave 12. The relative configuration of the spiroketal 1 was established by kinetic bromoetherification of the alcohol 13, followed by free radical reduction of the resulting tertiary bromide, and acid-catalyzed equilibration. The synthesis of 2 began with the inexpensive steroid 14. Following the Schönecker protocol, C-H functionalization led to the ketone 15. Pd-mediated coupling of the derived enol triflate with the alkyne gave 16, which was oxidized and cyclized to 17. Simmons-Smith conditions converted the dihydrofuran of 17 into the cyclopropane, which was again opened kinetically with Br (NBS) to set the relative configuration of the spiroketal. Free radical reduction followed by protection and oxidation then completed the preparation of 2. The coupling of 1 and 2 (not illustrated) to form the central pyrazine of 3 followed the precedent of Fuchs, combining the 2-azido ketone derived from 1 with the 2-amino methoxime derived from 2. Remarkably, tens of milligrams of 1 and of 2 were prepared, assuring a reasonable supply of 3 for further studies.

Disorazole C1 3, isolated from fermentation of the myxobacterium Sorangium cellu­losum, shows antifungal and anticancer activity. Amir H. Hoveyda of Boston College applied (J. Am. Chem. Soc. 2014, 136, 16136) recent advances in alkene metathesis from his group to enable the efficient assembly of 2 and so of 3. The ester 1 was assembled from the alcohol 11 and the acid 18. The preparation of 11 began with the enantioselective addition of 5 to 4 to give 6 and then 7, as described by Kalesse (Angew. Chem. Int. Ed. 2010, 49, 1619). Leighton allylation led to 8, that was then coupled with 9 to give 10 with high Z selectivity. Iodination of 10 followed by deprotection then completed the assembly of 11. The starting material for the acid 18 was the allylic alcohol 13. As reported by Cramer (Angew. Chem. Int. Ed. 2008, 47, 6483), exposure of the racemic alcohol 12 to vinyl acetate in the presence of Amano lipase PS converted one enantiomer to the acetate, leaving 13. Methylation of the secondary alcohol followed by acid-mediated removal of the t-butyl ester led to the acid 14, that was converted to the correspond­ing acyl fluoride and coupled with serine Me ester 15 to give 16. After cyclization to the oxazole 17, cross metathesis with five equivalents of 4-bromo-1-butene gave the homoallylic bromide, that was readily eliminated with DBU to give, after saponifica­tion, the acid 18. The cross metathesis of the coupled ester 1, a polyene, with 9 proceeded with remarkable selectivity to give 2, again as the Z geometric isomer. On exposure to the Heck catalyst Pd [(o-tolyl)3P]2, 2 dimerized efficiently. The deprotection was not straightforward, but conditions (H2SiF6, CH3OH, 4°C, 72 h) were found that deliv­ered 3 in 68% yield.

The sulfate ( + )-didemniserinolipid B 3, isolated from the tunicate Didemnum sp, has an intriguing spiroether core. A key step in the synthesis of 3 reported (Organic Lett. 2007, 9, 5357) by Steven D. Burke of the University of Wisconsin was the selective ring-closing metathesis of 1 to 2. The diol 6 that was used to prepare the ketal 1 was readily prepared from the inexpensive D-mannitol 4. Many other applications can be envisioned for the enantiomerically-pure diol 6 and for the monoacetate and bis acetate that are precursors to it. To set up the metathesis, the β, γ-unsaturated ketone 10 was needed. To this end, the keto phosphonate derived from the addition of the phosphonate anion 8 to the lactone 7 was condensed with phenyl acetaldehyde 9. The derived enone 10 was a 5:1 mixture of β, γ- and α, β-regioisomers. The diol 6 is C2 -symmetrical, but formation of the ketal 1 dissolved the symmetry, with one terminal vinyl group directed toward the styrene double bond, and the other directed away from it. On exposure to the first generation Grubbs catalyst, ring formation proceeded efficiently, to give 2. Williamson coupling with the serine-derived alcohol 11 then gave 12. To establish the secondary alcohol of 13 and so of 3, the more electron rich alkene of 12 was selectively epoxidized, from the more open face. Diaxial opening with hydride then gave 13. With 13 in hand, another challenge of selectivity emerged. The plan had been to attach the ester-bearing sidechain to 13 using alkene metathesis, then hydrogenate. As the side-chain of 3 contained an additional alkene, this had to be present in masked form. To this end, the α-phenylselenyl ester 14 was prepared. Alkene metathesis with 13 proceeded smoothly, this time using the second generation Grubbs catalyst. The unwanted alkene was then removed by reduction with diimide, and the selenide was oxidized to deliver the α, β-unsaturated ester.

The macrolactone leucascandrolide A 4, isolated from the calcareous sponge L. caveolata, has both cytotoxic and antifungal activity. The key step in the synthesis of 4 reported (J. Org. Chem. 2007, 72, 5784) by Scott D. Rychnovsky of the University of California, Irvine, was the stereoselective condensation of the aldehyde 1 with the allyl vinyl ether 2 to give 3. The cyclic ether of 1 was assembled from the crotyl addition product 5. Tandem Ru-catalyzed metathesis/hydrogenation converted 5 to the lactone 6. Reduction of 6 to the lactol followed by activation as the acetate gave 7, axial-selective condensation of which with the enol ether 8 delivered the enone 9. Diastereoselective Itsuno-Corey reduction of 9 followed by protecting group exchange and oxidation then gave 1, containing four of the eight stereogenic centers of leucascandrolide A 4. The vinyl ether 2 was readily prepared from the corresponding homoallylic alcohol. Condensation of 1 with 2 involved Lewis acid activation of the aldehyde, addition of the resulting carbocation to the vinyl ether, and cyclization with trapping by bromide ion. In this process, the other four of the eight stereogenic centers were assembled. Three of those centers were formed in the course of the reaction. While stereocontrol was not perfect, the route is pleasingly succinct, so practical quantities of diastereomerically pure 3 could be prepared. To complete the synthesis, the secondary alcohol of 3 was methylated. Selective desilyation of the primary alcohol followed by oxidation and desilylation then set the stage for the Mitsunobu macrolactonization. The intermediates in the Mitsunobu reaction are such that the lactonization can proceed with either inversion of absolute configuration at the secondary center, or retention. While the usually-employed Ph3P gave the lactone with retention of absolute configuration, Bu3P led to clean inversion. The last challenge was the establishment of the (Z) alkene of the side chain. This was accomplished using the Toru protocol. Coupling of the secondary bromide with the Cs salt 12 proceeded with inversion of absolute configuration, to give 13.

The total synthesis of lupeol was one of the crowning achievements of the Robinson annulation/ reductive alkylation approach to stereocontrolled polycarbocyclic construction developed by Gilbert Stork (J. Am. Chem. Soc. 1971, 93, 4945). It is a measure of the progress of organic synthesis since that time that E. J. Corey of Harvard University could devise (J. Am. Chem. Soc. 2009, 131, 13928) an enantioselective synthesis of (+)-lupeol 3 that could be carried out by a single colleague. The key step in the synthesis was the Lewis acid–mediated cyclization of 1 to 2. The preparation of 1 began with the enantioselective epoxidation of farnesol acetate 4. To this end, asymmetric dihydroxylation delivered the diol 5. Selective mesylation followed by exposure to dilute methoxide effected ring closure to the epoxide, but also removed the acetate, so this had to be reapplied. The synthesis of the aromatic portion of 1 started with the phenol 7. Protection as the very bulky triisopropylsilyl ether was important for the success of the subsequent cyclization, perhaps because it discouraged complexation of the Lewis acid with the aryl ether. Metalation followed by formylation delivered the aldehyde 8, which was reduced and carried on to the bromide 9. The derived Grignard reagent coupled smoothly with 6 under Li2CuCl4 catalysis. The cyclization of 1 to 2 proceeded with remarkable efficiency (43%!), for a reaction in which three new C-C bonds, four rings, and five new stereogenic centers were established. It is particularly noteworthy that the cyclization cleanly set the trans, anti, trans, anti tetra-cyclic backbone of (+)-lupeol 3. To complete the synthesis of 3, the less substituted alkene of 2 was selectively hydrogenated, then CH3 Li was added to give 10. Hydrolysis and dehydration yielded 11, which was reduced and equilibrated to 12. On brief exposure to MsCl/Et3 N, 13 cyclized to (+)-lupeol 3. It is a measure of the remarkable effi ciency of this synthesis of (+)-lupeol 3 that it provided suffi cient material to enable studies of the rearrangement of 3 under acidic conditions to other pentacyclic triterpenes, including, inter alia, germanicol, α -amyrin, δ -amyrin, and taraxasterol 14 .

Building on the Tanino synthesis of glycinoeclepin (Organic Highlights, January 3, 2011), the hatch-stimulating substance for the soybean cyst nematode, Keiji Tanino of Hokkaido University and Masaaki Miyashita, now at Kogakuin University, described (Nat. Chem. 2011, 3, 484) a convergent synthesis of solanoeclepin A 3, the hatch-stimulating substance for the potato cyst nematode. A key step in the synthesis was the diastereoselective Diels-Alder cyclization of 1 to 2. The starting point for the synthesis was the conjugate addition of 5 to 3-methyl cyclohexenone 4, followed by aldol condensation. The secondary acetate corresponding to 6 was readily resolved by lipase hydrolysis. The next challenge was the installation of the angular vinyl group. Enone transposition gave 7, to which vinyl Grignard added with high diastereocontrol, leading to the diol 8. TMSOTf-mediated epoxide rearrangement with concomitant 1,2 vinyl shift then delivered 9. Epoxidation followed by Stork cyclization completed the construction of the cyclobutane 10. The allylic alcohol 12 was enantiomerically pure, so the relative configuration of the sidechain cyclopropane could be set by the Charette protocol. Grieco dehydration of 14 then gave 16, a latent form of the cyclobutanone of 3. Condensation of the ketone 17 with 18 delivered the expected keto enamine, which rearranged nicely on exposure to Tf2O to the aldehyde 19. Diastereoselective addition of the furyl lithium 20 followed by Pd-catalyzed coupling with 21 then completed the assembly of the Diels-Alder substrate 1. The Me2AlCl-mediated intramolecular Diels-Alder cyclization of 1 led to 2 with remarkable diastereocontrol. Oxidation gave 22, that was further oxidized to the protected enol 23. Reduction, alkene cleavage, and protecting group manipulation then set the stage for the final oxidation of 24 to solanoeclepin A 3.

The Streptomyces metabolite (-)-FR182877 3 binds to and stabilizes microtubules, showing the same potency of anticancer activity as Taxol (paclitaxel). Masahisa Nakada of Waseda University assembled (Angew. Chem. Int. Ed. 2009, 48, 2580) the hexacyclic ring system of 3 by the tandem intramolecular Diels-Alder–intramolecular hetero Diels-Alder cyclization of 1, generating seven new stereogenic centers in a single step. The construction of the pentaene substrate 1 started with the known aldehyde 4, prepared by homologation of commercial ethyl 3-methyl-4-oxocrotonate. Addition of the propionyl oxazolidine anion 5 proceeded with high diastereocontrol, to give 6. The acyl oxazolidinone was not an efficient acylating agent, so it was converted to the Weinreb amide. Protection and deprotection then delivered the allylic acetate 7. The key step in the pentaene assembly was the carefully optimized Negishi-Wipf methylation of 8, followed by Pd-mediated coupling of the alkenyl organometallic so generated with the allylic acetate, to give 9. Condensation of the derived keto phosphonate 11 with the known aldehyde 12 then delivered the enone 13. The Nakada group has worked extensively on the intramolecular Diels-Alder reaction of substrates such as 1. They have shown that protected anti diols such as 1 cyclize with substantial diastereocontrol and in the desired sense. In contrast, cyclizations of protected syn diols proceed with poor diastereocontrol. The enone 13 was therefore reduced to the anti diol and protected, leading to 14 . Oxidation of 14 at room temperature led to a complex mixture, but slow oxidation at elevated temperature delivered 2 . Although the yield of 2 was not much better than if the reactions were carried out sequentially, first the intramolecular Diels-Alder cyclization, then the intramolecular hetero Diels-Alder cyclization, with the cascade protocol pure 2 was more readily separated from the reaction matrix. With 2 in hand, there was still the challenge of assembling the seven-membered ring. Cyclization was effected with an intramolecular Heck protocol. The two diastereomers of the allylic alcohol 15 cyclized with comparable efficiency. Ir-catalyzed alkene migration then converted the allylic alcohols to a mixture of ketones, which was equilibrated to give the more stable diasteromer.

The early promise for the biological activity of the derivatives of ingenol 3 has been borne out by the clinical efficacy of the derived angelate, recently approved by the US Food and Drug Administration for the treatment of actinic keratosis. Phil S. Baran of Scripps La Jolla envisioned (Science 2013, 341, 878) a route to 3 based on a rearrange­ment of 2, available by the Pauson–Khand cyclization of the allenyl alkyne 1. One of the partners for the preparation of 1 was available following the Sugai (Synlett 1997, 1297) procedure, by the Claisen rearrangement of triethyl orthopro­pionate 5 with the propargyl alcohol 4 to give 6. Reduction delivered a racemic mix­ture of alcohols. On exposure of the mixture to vinyl acetate and Pseudomonas cepacia lipase, the undesired enantiomer was selectively acetylated to 7, leaving residual 8 of high ee. IBX was found by the Scripps group to be effective at oxidizing 8 without racemization. The other component of 1 was prepared from the inexpensive (+)-3-carene 10. Chlorination followed by ozonolysis delivered 11, that was reduced to the enolate, then alkylated with methyl iodide. Exposure to LiHMDS gave a new enolate, that was added to the aldehyde 9 to give 12. Addition of ethynyl magnesium bromide to the now more open face of 12 proceeded with high diastereoselectivity. Selective silylation of the secondary alcohol followed by silylation of the tertiary alcohol set the stage for the Pauson–Khand cyclization. Following the Brummond protocol, 1 was cyclized to 2. Methyl magnesium bro­mide was added, again to the more open face of the ketone, to give a new tertiary alco­hol. Exposure to stoichiometric OsO4 converted the more available alkene to the cis diol, that was protected as its cyclic carbonate 13. A central challenge in the total synthesis of the ingenanes is the construction of the “inside–outside” skeleton. This was achieved by the pinacol rearrangement of 13 with BF3•OEt2, to give 14. All that remained to complete the synthesis was selective oxidation. Allylic oxi­dation with stoichiometric SeO2 installed the secondary alcohol, that was acety­lated to give 15. The other secondary alcohol was then freed, and dehydrated with the Martin sulfurane, to give 16. A last allylic oxidation completed the synthesis of ingenol 3.

Pregnancy as well as congenital deficiency in coagulation inhibitors are recognized as predisposing conditions to thrombosis. Thus, in women with a congenital deficiency, the risk of thrombosis associated to pregnancy is expected to be higher than in normal women (incidence of approximately 1°/..). We have investigated this risk in 16 women with congenital Antithrombin III (AT III) deficiency and in 31 with Protein C (PC) deficiency.In the 16 women with AT III deficiency, 30 pregnancies occured 3 of them were interrupted by provoked abortions and a deep vein thrombosis (DVT) or pulmonary embolism were observed in 2 patients after abortion. Of the 27 other pregnancies, in the absence of any anticoagulant treatment, 17 were complicated by thrombosis (62 %), either during pregnancy (n = 8) or in the post-partun period (n = 9).In the group of 31 women with PC deficiency, 82 pregnancies occured : 16 ended with a provoked abortion, followed by a DVT in one case. Out of the 66 other pregnancies, 17 (25 %) were associated with thrombosis, during pregnancy (n = 5) or in the post-partum (n = 12).Thus, pregnancy is a situation at high risk of thrombosis in PC deficient women, and even higher in AT III deficient ones. No standardized anticoagulant prophylaxis being available, various anticoagulant treatments (mainly SC heparin) were given at various doses, started at different moments of pregnancy to 6 AT III and 3 PC deficient women : 3 and O thrombosis occured respectively.In the post-partum, a thrombosis was observed in 1 of 4 AT III and 2 of 4 PC deficient women who received a treatment. Consequently, an efficient treatment remains to be determined.If a pregnancy is unwanted, estroprogestogens are contra-indicated but progestogen only treatments with chlormadinone acetate, levonorgestrel or low dose of norethisterone were given to 4 AT III and 6 PC deficient women who were simultaneously receiving AVK : no recurrence of thrombosis was observed afer 1 to 3 years of treatment.

Touqui et al (1986) have suggested that phosphorylation by protein kinase C of a 1ipomodulin-1 ike polypeptide extracted from platelets renders it inactive as an inhibitor of phospholipase A2. We have examined this suggestion by measuring thromboxane (Tx) B2 generation and cytosolic free calcium concentration ([Ca++]i) in stimulated, washed human platelets loaded with or without quin-2. Addition of thrombin (0.077, 0.23, 0.77, 2.3 and 7.7 nM) to control platelets produces a dose-related elevation of [Ca++]i (10±5, 50±7, 260±30, 550±25 and 1500±100 nM respectively) and generation of TxB2 (0, 9±4, 45±6, 194±10 and 375±30 pmoles/108 platelets respectively). Preincubation of platelets for 1 min with 1-oleoyl-2-acetyl-rac-glycerol (OAG, 22-198 μM), phorbol myristate acetate (PMA, 1.616 nM) or EGTA (2 mM) produces a marked inhibition of high and low dose thrombin (7.7 nM and 0.77 nM) or NaF (18 mM) induced elevation of [Ca++]i and TxB2 generation. Pretreatment of platelets with the protein kinase C inhibitor, H-7 (60 uM), prevented the inhibition of TxB2 formation induced by PMA (4.816 nM) or OAG (66-198 μM) in either thrombin (0.77 nM) or NaF (18 mM) stimulated platelets. When arachidonic acid (AA, 10 μM) is used as the stimulus, the Δ[Ca++]i is 190±15 nM and TxB2 generation is 35.9±2 pmoles/108 platelets. While pretreatment with 4.8 nM PMA obliterates the AA-induced Δ[Ca++]i and partially reduces (p< 0.05) the TxB2 generation to 27.8+3 pmoles/108 platelets. PMA and OAG pretreatment also inhibits TxB2 generation in thrombin-stimulated, non-quin-2-1oaded platelets. Thus, at least with intact, agonist- and NaF-stimulated platelets, activation of protein kinase C inhibits eicosanoid production.We thank the British Heart Foundation and Ciba-Geigy USA for financial support.

In recent years, a large number of nano-size semiconductors have been investigated for their potential applications in photovoltaic cells, optical sensor devices, and photocatalysts [1, 2, 3]. Nano-size semiconductor particles have many interesting properties due mainly to their size-dependent electronic and optical properties. Appropriately, many speciality of nanomaterials such as CdS and ZnS semiconductor particles, and other metal oxides such as ZnO and lithium-titanate oxide (LTO) have been prepared. However, most of them were prepared with toxic reactants and/or complex multistep reaction processes. Particularly, it is quite difficult to produce LTO nanoparticles, since it typically requires wearisome conditions such as very high temperature over 1000 °C, long producing times, and so on. To overcome such problems, various core/shell type nanocrystals were prepared through different methods such as the hydrothermal synthetic method, microwave, and sonochemistry. Also many coating methods on inorganic oxide nanoparticles were tried for the preparations of various core-shell type nanocrystals. Sonoluminescence (SL) is a light emission phenomenon associated with the catastrophic collapse of a gas bubble oscillating under an ultrasonic field [4]. Light emission of single bubble sonoluminescence (SBSL) is characterized by picosecond flashes of the broad band spectrum extending to the ultraviolet [5, 6]. The bubble wall acceleration has been found to exceed 1011 g at the moment of bubble collapse. Recently observed results of the peak temperature and pressure from the sonoluminescing gas bubble in sulfuric acid solutions [9] were accurately predicted by the hydrodynamic theory for sonoluminescence phenomena [7, 10, 11, 12], which provides a clue for understanding sonochemical reactions inside the bubble and liquid layer adjacent to the bubble wall. Sonochemistry involves an application of sonoluminescence. The intense local heating and high pressure inside the bubbles and liquid adjacent bubble wall from such collapse can give rise to unusual effects in chemical reactions. The estimated temperature and pressure in the liquid zone around the collapsing bubble with equilibrium radius 5 μm, an average radius of bubbles generated in a sonochemical reactor at a driving frequency of 20 kHz with an input power of 179 W, is about 1000 °C and 500 atm, respectively. At the proper condition, a lot of transient bubbles are generated and collapse synchronistically to emit blue light when high power ultrasound is applied to liquid, and it is called multibubble sonoluminescence (MBSL). Figure 1 shows an experimental apparatus for MBSL with a cylindrical quartz cell, into which a 5 mm diameter titanium horn (Misonix XL2020, USA) is inserted [13]. The MBSL facilitates the transient supercritical state [14].in the liquid layer where rapid chemical reactions can take place. In fact, methylene blue (MB), which is one of a number of typical textile dyestuffs, was degraded very fast at the MBSL condition while MB does not degrade under simple ultrasonic irradiation [13]. MBSL has been proven to be a useful technique to make novel materials with unusual properties. In our study, various metal oxides such as ZnO powder [15], used as a primary reinforcing filler for elastomer, homogeneous Li4Ti5O12 nanoparticles [16], used for electrode materials, and core/shell nanoparticles such as CdS coating on TiO2 nanoparticles [17] and ZnS coating on TiO2 nanoparticles [18], which are very likely to be useful for the development of inorganic dye-sensitized solar cells, were synthesized through a one pot reaction under the MBSL condition. Figure 2 shows the XRD pattern of ZnO nanoparticles synthesized from zinc acetate dehydrate (Zn(CH3CO2)2 · 2H2O, 99.999%, Aldrich) in various alcohol solutions with sodium hydroxide (NaOH, 99.99%, Aldrich) at the MBSL condition. The XRD patterns of all powers indicate hexagonal zincite. The XRD pattern for the ZnO nanoparticles synthesized is similar to the ZnO powder produced by a modified sol-gel process and subsequent heat treatment at about 600 °C [19] as shown in Fig.3. The average particle diameter of ZnO powder is about 7 nm. A simple sonochemical method for producing homogeneous LTO nanoparticles, as shown schematically in Fig. 4. First, LiOH and TiO2 nanoparticles were used to prepare LiOH-coated TiO2 nanoparticles as shown in Fig.5. Second, the resulting nanoparticles were thermally treated at 500 °C for 1 hour to prepare LTO nanoparticles. Figure 6 shows a high resolution transmission electron microscope image of LTO nanoparticles having an average grain size of 30–40 nm. All the nanoparticle synthesized are very pure in phase and quite homogeneous in their size and shape. Recently we succeeded in synthesizing a supported nickel catalyst such as Ni/Al2sO3, MgO/Al2O3 and LaAlO3, which turned out to be effective for methane decomposition [20]. Sonochemistry may provide a new way to more rapidly synthesize many specialty nanoparticles with less waste [21]. This clean technology enables the preparation of new materials such as colloids, amorphous particles [22], and various alloys.