- SELECTIVE OXIDATION OF ALCOHOLS BY K2FeO4-Al2O3-CuSO4*5H2O
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A solid mixture of K2FeO4, Al2O3 and CuSO4*5H2O efficiently oxidized allylic, benzylic, and saturated secondary alcohols to the corresponding aldehydes or ketones but did not oxidize saturated primary alcohols.
- Kim, Kwan Soo,Song, Yang Heon,Lee, Nam Ho,Hahn, Chi Sun
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- Vinylacidic Acid in the Reaction of Aza-Michael with 1-Ethylpyrazole
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Abstract: Commercial vinylacetic acid is a mixture of isomers of but-3-enoic andbut-2-enoic acids. It was shown that but-3-enoic acid undergoes isomerization inthe presence of a catalytic amount of 1-ethylpyrazole. The resulting Z- and E-isomersof but-2-enoic acid enter the aza-Michael reaction with pyrazole. The1H NMR analysis showed that by the end of theexperiment the ratio of unreacted Z- andE-isomers of but-2-enoic acid in thereaction mixture decreased by half (to 3 : 1), which pointed to a higherreactivity of the Z-isomer.
- Arzumanyan, A. M.,Attaryan, H. S.,Danagulyan, G. G.,Khachatryan, H. N.,Shahkhatuni, A. G.
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- Revisiting the Palladium-Catalyzed Carbonylation of Allyl Alcohol: Mechanistic Insight and Improved Catalytic Efficiency
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Although crotonic acid (CA) is in high demand due to its use in various industrial applications, the preparation of CA currently requires a multi-step process from the petrochemical cracking of ethane with a very low overall yield and poor selectivity. An atom economical, one-step, carbonylation of readily accessible allyl alcohol to CA is one of the attractive approaches. In this study, the direct carbonylative transformation of allyl alcohol to CA was analyzed in detail to detect the reaction intermediates and propose a reaction mechanism. Following the reaction mechanism, the process was optimized to synthesize CA via the direct carbonylation of allyl alcohol with improved efficiency and productivity (TON = 420) under mild reaction conditions using Pd-based catalytic systems.
- Jiang, Jianwei,Padmanaban, Sudakar,Yoon, Sungho
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- SEVERAL MECHANISMS IN THE ELIMINATION KINETICS OF ω-CHLOROCARBOXYLIC ACIDS IN THE GAS PHASE
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The kinetics of the gas-phase pyrolysis of ω-chlorocarboxylic acids were examined in a seasoned static reaction vessel and in the presence of at least twice the amount of the free radical inhibitor cyclohexene or toluene.In conformity with the available experimental data on rate determination, these reactions proved to be unimolecular and obeyed a first-order rate law.The presence of the primary chlorine leaving group in Cl(CH2)nCOOH (n=1-4) showed a change in mechanism from intramolecular displacement of the Cl leaving group by the acidic hydrogen of the COOH to anchimeric assistance of the carbonyl COOH to the C-Cl bond polarization in the transition state.This mechanistic consideration is nearly the same for the series of 2-, 3-, and 4-chlorobutyric acids.The chlorine atom at the 2-position of acetic, propionic and butyric acids is dehydrochlorinated through a prevailing reaction path involving a polar five-membered cyclic transition state.
- Chuchani, Gabriel,Martin, Ignacio,Rotinov, Alexandra,Dominguez, Rosa M.,Perez, Milogrados I.
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- FLAVONOIDS OF Thermopsis alterniflora. CROTONOYLTHERMOPSOSIDE AND CROTONOYLCOSMOSIIN - NEW ACYLATED FLAVONE GLYCOSIDES
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From the epigeal part of Thermopsis alterniflora Rgl. et Schmalh. (Fabaceae), in addition to formononetin, ononin, cynaroside, and rothindin, two new acylated flavone glycosides have been isolated and, on the basis of chemical transformations and spectral characteristics, their structures have been established as 4',5,7-trihydroxy-3'-methoxyflavone 7-O-(6"-O-crotonoyl-β-D-glucopyranoside) and 4',5,7-trihydroxyflavone 7-O-(6"-O-crotonoyl-β-D-glucopyranoside).
- Yuldashev, M. P.,Batirov, E. Kh.,Vdovin, A. D.,Malikov, V. M.,Yagudaev, M. R.
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- Straightforward Synthesis of 2-Alkenoic Acids from the Corresponding Saturated Aldehydes
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2-Alkenoic acids may be prepared in good yields from saturated aldehydes via α-selenenylation with 4-(phenylseleno)morpholine formed in situ, followed by hydrogen peroxide oxidation.The actual oxidizing agent is benzeneperseleninic acid which is formed in the reaction medium.
- Outurquin, Francis,Paulmier, Claude
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- Effect of the Reaction Products on the Rate of Oxidation of Crotonaldehyde
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Study of the oxidation of crotonaldehyde revealed an appreciable inhibitory effect of the products on the process. Analysis of the kinetic data obtained over a wide range of reaction conditions (c0 1.5-3.3 M, pO2 1-16 atm, T 293-309 K) showed that the overall oxidation process (with account taken of the inhibitory effect of the products) is described by the equation: WCA = kap* CCA (pO2 )°1.6 (1 + 0.17 Δ cCA τ)-1, where Kap* is the apparent rate constant, and Δ cCAτ is the decrease of the aldehyde concentration by a moment τ.
- Fedevich,Levush,Fedevich,Kit
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Read Online
- Ligand-controlled divergent dehydrogenative reactions of carboxylic acids via C–H activation
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Dehydrogenative transformations of alkyl chains to alkenes through methylene carbon-hydrogen (C–H) activation remain a substantial challenge. We report two classes of pyridine-pyridone ligands that enable divergent dehydrogenation reactions through palladium-catalyzed b-methylene C–H activation of carboxylic acids, leading to the direct syntheses of a,b-unsaturated carboxylic acids or g-alkylidene butenolides. The directed nature of this pair of reactions allows chemoselective dehydrogenation of carboxylic acids in the presence of other enolizable functionalities such as ketones, providing chemoselectivity that is not possible by means of existing carbonyl desaturation protocols. Product inhibition is overcome through ligand-promoted preferential activation of C(sp3)–H bonds rather than C(sp2)–H bonds or a sequence of dehydrogenation and vinyl C–H alkynylation. The dehydrogenation reaction is compatible with molecular oxygen as the terminal oxidant.
- Wang, Zhen,Hu, Liang,Chekshin, Nikita,Zhuang, Zhe,Qian, Shaoqun,Qiao, Jennifer X.,Yu, Jin-Quan
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p. 1281 - 1285
(2021/12/10)
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- Acrylonitrile Derivatives from Epoxide and Carbon Monoxide Reagents
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The present invention is directed to reactor systems and processes for producing acrylonitrile and acrylonitrile derivatives. In preferred embodiments of the present invention, the processes comprise the following steps: introducing an epoxide reagent and carbon monoxide reagent to at least one reaction vessel through at least one feed stream inlet; contacting the epoxide reagent and carbon monoxide reagent with a carbonylation catalyst to produce a beta-lactone intermediate; polymerizing the beta-lactone intermediate with an initiator in the presence of a metal cation to produce a polylactone product; heating the polylactone product under thermolysis conditions to produce an organic acid product; optionally esterifying the organic acid product to produce one or more ester products; and reacting the organic acid product and/or ester product with an ammonia reagent under ammoxidation conditions to produce an acrylonitrile product.
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Paragraph 0261-0265
(2019/01/15)
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- BIO-BASED METHACRYLIC ACID AND OTHER ALKENOIC-DERIVED MONOMERS VIA CATALYTIC DECARBOXYLATION
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A novel method for the catalytic selective decarboxylation of a starting material to produce an organic acid is disclosed. According to at least one embodiment, the method may include placing a reaction mixture into a reaction vessel, the reaction mixture including a solvent, a starting material, and a catalyst, subjecting the reaction mixture to a predetermined pressure and temperature, and allowing the reaction to continue for 1-3 hours. The starting material may be at least one of a dicarboxylic acid, a tricarboxylic acid, and an anhydride of a dicarboxylic or tricarboxylic acid. As an exemplary embodiment, itaconic acid may be a starting material and the organic acid may be methacrylic acid. The predetermined temperature may be 250° C. or less, and the reaction pressure may be less than 425 psi. Further, a polymerization inhibitor may be used.
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Paragraph 0054-0055; 0056-0057
(2018/04/26)
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- MANUFACTURING METHOD OF α,β-UNSATURATED CARBOXYLIC ACID
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PROBLEM TO BE SOLVED: To provide a manufacturing method which can get α,β-unsaturated carboxylic acid at a high yield by liquid phase oxidation of α,β-unsaturated aldehyde by oxygen or air with a handy metal catalyst under a mild reaction condition. SOLUTION: Preferably under a presence of organic solvent, α,β-unsaturated carboxylic acid is manufactured by oxidation of α,β-unsaturated aldehydes and oxygen or air under a presence of an iron salt catalyst and a catalyst of alkali metal salt of carboxylic acid. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0050-0052
(2018/10/16)
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- Reaction routes in catalytic reforming of poly(3-hydroxybutyrate) into renewable hydrocarbon oil
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Poly(3-hydroxybutyrate) or PHB is an energy storage material of microbial organisms and can be reformed into hydrocarbon oils rich with aromatic compounds. This work investigated the main reaction routes from PHB to the key intermediates and final hydrocarbons. The main sequential reactions under catalysis of phosphoric acid at moderate temperatures (200-230 °C) consist of: (1) decomposition of PHB into crotonic acid, a major monomeric intermediate, (2) deoxygenation of crotonic acid, and (3) combination of the deoxygenated molecules. The oxygen in PHB is removed as CO2 and H2O in stage (2), involving decarboxylation and ketonization of crotonic acid. The main aromatic compounds are formed in stage (3) from propylene and 2,3-dimethyl-2-cyclopenten-1-one as two key intermediates, the former from decarboxylation and the latter from ketonization of crotonic acid. The reaction routes reveal that the formation of aromatics is affected to a great extent by the concentrations of phosphoric acid and water in the reaction, which can be used to control the composition of hydrocarbon oil.
- Kang, Shimin,Yu, Jian
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p. 30005 - 30013
(2015/05/13)
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- Anticancer platinum complexes as non-innocent compounds for catalysis in aqueous media
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An efficient cyclization of alkyne-acids to enol-lactones catalyzed by anticancer platinum(ii) and platinum(iv) compounds is described. These compounds are not only DNA-binding complexes; they can also catalyze reactions in solvents such as acetone, methanol, water or blood plasma.
- Aleman, Jose,Del Solar, Virginia,Navarro-Ranninger, Carmen
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supporting information; experimental part
p. 454 - 456
(2010/04/30)
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- New reactions of anticancer-platinum complexes and their intriguing behaviour under various experimental conditions
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The anticancer platinum complexes here described react with organic substrates (such as acids, alkenes, alkynes) and catalyze transformations that can occur in biomolecules which contain unsaturated functions. We have analyzed the role of the platinum complexes in the observed reactions and studied the progress of the detected transformations upon variation of the reaction conditions. The Royal Society of Chemistry 2010.
- Aleman, Jose,Del Solar, Virginia,Cubo, Leticia,Quiroga, Adoracion G.,Navarro Ranninger, Carmen
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scheme or table
p. 10601 - 10607
(2011/01/05)
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- CuCl catalyzed oxidation of aldehydes to carboxylic acids with aqueous tert-butyl hydroperoxide under mild conditions
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Oxidation of aldehydes to the corresponding carboxylic acids can be performed highly efficiently at room temperature with 70% tert-butyl hydroperoxide (in water) in the presence of a catalytic amount of easily available ligand free CuCl in acetonitrile as solvent under very mild conditions. This oxidation protocol works well for various aldehydes including aliphatic aldehydes and aliphatic dialdehydes.
- Mannam, Sreedevi,Sekar
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p. 1083 - 1086
(2008/09/18)
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- SmI2-promoted intra- and intermolecular C-C bond formation with chiral N-acyl oxazolidinones
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The suitability of chiral oxazolidinones in the SmI2-mediated C-C bond generation between the imide functionality of an N-acyl oxazolidinone unit and an olefinic radical acceptor, in both inter- and intramolecular reactions, was investigated. It was shown that the products from an Evans asymmetric alkylation can undergo direct carbon-carbon bond formation with an acrylamide providing chiral acyclic ketones in reasonable yields. These examples represent the first transformation of such N-acyl oxazolidinones where this chiral auxiliary is removed under the conditions for ketone formation. 5-exo-trig Cyclization studies were also undertaken with the same type of substrates, providing trans-2,5-disubstituted cyclopentanones in yields of approx. 50%. However, attempts to cyclize heteroatom-containing equivalents were less rewarding.
- Taaning, Rolf H.,Thim, Laura,Karaffa, Jacob,Campa?a, Araceli G.,Hansen, Anna-Mette,Skrydstrup, Troels
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experimental part
p. 11884 - 11895
(2009/04/07)
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- Structure activity studies with xenobiotic substrates using carboxylesterases isolated from Arabidopsis thaliana
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Carboxylesterases (CXEs) catalyse the hydrolysis of xenobiotics and natural products radically altering their biological activities. Whereas the substrate selectivity of animal CXEs, such as porcine liver esterase (PLE) have been well studied, the respective enzymes in plants have yet to be defined and their activities determined. Using Arabidopsis thaliana (At) as a source, five representative members of the α/β hydrolase AtCXE family of proteins have been cloned, expressed and the purified recombinant proteins assayed for esterase activity with xenobiotic substrates. Two members, AtCXE5 and AtCXE18 were found to be active carboxylesterases, though AtCXE5 proved to be highly unstable as a soluble protein. AtCXE18 and the previously characterised S-formylglutathione hydrolase from Arabidopsis (AtSFGH) were assayed against a series of esters based on methylumbelliferone in which the acyl moiety was varied with respect to size and conformation. The same series was used to assay crude esterase preparation from Arabidopsis plants and the results compared with those obtained with the commonly used PLE. With straight chain esters, AtCXE18 behaved like PLE, but the Arabidopsis hydrolases proved less tolerant of branched chain acyl components than the mammalian enzyme. While none of the enzyme preparations accurately reflected all the activities determined with crude Arabidopsis protein extracts, the plant enzymes proved more useful than PLE in predicting the hydrolysis of the more sterically constrained esters.
- Cummins, Ian,Landrum, Marie,Steel, Patrick G.,Edwards, Robert
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p. 811 - 818
(2008/03/13)
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- Carboxylic acids from primary alcohols and aldehydes by a pyridinium chlorochromate catalyzed oxidation
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A facile and quantitative preparation of carboxylic acids by a pyridinium chlorochromate (PCC) catalyzed (2 mol%) oxidation of primary alcohols and aldehydes using 2.2 equivalents and 1.1 equivalents of H5IO 6, respectively, in acetonitrile is described here. Georg Thieme Verlag Stuttgart.
- Hunsen, Mo
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p. 2487 - 2490
(2007/10/03)
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- MANUFACTURING METHOD OF ISOMERIZED PRODUCT OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACID OR ESTER THEREOF
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PROBLEM TO BE SOLVED: To provide a method for selectively manufacturing an isomerized product of an ethylenically unsaturated monocarboxylic acid or esters thereof from the ethylenically unsaturated monocarboxylic acid or esters thereof without using a catalyst or an organic solvent. SOLUTION: The manufacturing method of the isomerized product of the ethylenically unsaturated monocarboxylic acid or esters thereof comprises transferring a double bond and selectively synthesizing a stereoisomer by causing the ethylenically unsaturated monocarboxylic acid or esters thereof to non-catalytically react in a reaction medium in a high temperature and high pressure state (a subcritical state or a supercritical state). Thus, the desired isomer is selectively manufactured in a short time in a one-step process without using the organic solvent. Moreover, waste or wastewater is hardly generated in the manufacturing processes.
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Page/Page column 6-8; 10
(2008/06/13)
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- METHOD FOR ISOMERIZING ORGANIC COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for isomerizing a compound bearing a hydrocarbon group having a carbon-carbon double bond which permits transfer of the carbon-carbon double bond of the compound without using a catalyst or an organic solvent. SOLUTION: The method for isomerizing the compound comprises transferring the position of the carbon-carbon double bond by causing the compound bearing the hydrocarbon group having the carbon-carbon double bond to non-catalytically react in a reaction medium in a high-temperature and high-pressure state. Thus, the isomer having the double bond transferred is obtained in a short time in one step by pressing the compound bearing the hydrocarbon group having the carbon-carbon double bond into high-temperature high-pressure water as a reaction site at a high speed. Neither waste nor wastewater to dispose of is discharged from the manufacturing processes.
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Page/Page column 6-7;11
(2008/06/13)
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- Hydration of propargylic alcohols by ruthenium catalysts, with dominant anti-Markovnikov regioselectivity, formation of α,β-unsaturated products and catalytic decarbonylation to 1-alkenes
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Ruthenium catalysts - water-soluble ruthenium sulfophthalocyanine and heterogeneous ruthenium hydroxyapatite complexes - proved to be effective for the hydration of propargylic alcohols in entirely aqueous media. 1-Phenyl-2-propyn-1-ol underwent an unprecedented catalytic hydration- decarbonylation-dehydration reaction, giving rise to styrene and carbon monoxide; 2-propyn-1-ol and 3-butyn-2-ol gave predominantly the products of anti-Markovnikov addition, together with products of hydration-dehydration (α,β-rearrangement) and, to a minor extent, the decarbonylation products, ethene or propene, respectively. Hydrations were also conducted in D2O, giving indications of the mechanism of the reactions and apparently ruling out the allenylidene route for the α,β- rearrangement. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- D'Alessandro, Nicola,Di Deo, Milena,Bonetti, Monica,Tonucci, Lucia,Morvillo, Antonino,Bressan, Mario
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p. 810 - 817
(2007/10/03)
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- Compositions of matter having bioactive properties
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Particles of coordinated complex comprising a basic, hydrous polymer and a capacitance adding compound, as well as methods for their production, are described. These complexes exhibit a high degree of bioactivity making them suitable for a broad range of applications through their incorporation into conventional vehicles benefiting from antimicrobial and similar properties.
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- Glucocorticoid receptor modulators
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The present invention provides non-steroidal compounds of formula I which are selective modulators (i.e., agonists and antagonists) of a steroid receptor, specifically, the glucocorticoid receptor. The present invention also provides pharmaceutical compositions containing these compounds and methods for using these compounds to treat animals requiring glucocorticoid receptor agonist or antagonist therapy. Glucocorticoid receptor modulators are useful to treat diseases, such as obesity, diabetes, inflammation and others as described below. The present invention also provides intermediates and processes for preparing these compounds. STR1
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- Tungsten(0) alkylidene complexes stabilized as pyridinium ylides: New aspects of their synthesis and reactivity
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The interaction of dihydropyridines with alkoxycarbene complexes of tungsten has been shown to lead to pyridinium ylid complexes: this transformation has now been applied to the synthesis of a hydroxyl-containing ylid complex by ring-opening of the pentacarbonyl (2-oxacyclopentylidene) tungsten(0) complex and to the synthesis of a series of chiral ylid complexes both from chiral and non-chiral carbene complexes by the use of dihydropyridines and dihydronicotines, respectively. The transfer of the alkylidene moiety of these complexes to nucleophilic olefins will be outlined and discussed. Especially relevant is the interaction of these pyridinium ylid complexes with unsaturated substrates such as dihydropyridines, enamines, and β-alkoxy bis(trimethyl-silyl) ketene acetals. This latter reaction leads to conjugated carboxylic acids, and has been be applied to a new synthesis of a honey bee pheromone, the queen substance.
- Rudler, Henri,Durand-Réville, Thomas
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p. 571 - 587
(2007/10/03)
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- (E)-Selective hydrolysis of (E,Z)-α,β-unsaturated nitriles by the recombinant nitrilase AtNIT1 from Arabidopsis thaliana
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From stereoisomeric α,β-unsaturated nitriles (E,Z)-1, the recombinant nitrilase AtNIT1 from Arabidopsis thaliana hydrolyses the (E)-isomers exclusively to the corresponding (E)-carboxylic acids (E)-2 with high specificity. The (E)-selectivity can also be utilised for the preparation of the isomerically pure nitriles (Z)-1. From (E,Z)-2-hydroxycinnamonitrile (E,Z)-3, the otherwise difficult obtainable (Z)-3 was prepared in 66% isolated yield. With β,γ-unsaturated (E,Z)-3-heptenenitrile (E,Z)-4, however, (E)-selectivity was not observed. AtNIT1 exhibits not only diastereoselectivity but also regioselectivity. From a mixture of the four isomers A-D of 3-(2-cyanocyclohex-3-enyl)propenenitrile 6, exclusively isomer D ((E)-cis-6) was hydrolysed to 3-(2-cyanocyclohex-3-enyl)propenoic acid (E)-cis-7, as stated by X-ray crystal structure. Only after complete conversion of D and high enzyme concentrations, isomer C ((E)-trans-6) was hydrolysed to a small extent.
- Effenberger, Franz,Osswald, Steffen
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p. 2581 - 2587
(2007/10/03)
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- Composition of matter having bioactive properties
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Particles of coordinated complex comprising a basic, hydrous polymer and a capacitance adding compound, as well as methods for their production, are described. These complexes exhibit a high degree of bioactivity making them suitable for a broad range of applications through their incorporation into conventional vehicles benefiting from antimicrobial and similar properties.
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- New insight into the mechanism of catalytic hydrogenation allows the structure of the key intermediate in asymmetric hydrogenation to be predicted
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An approach has been developed to determine the regioselectivity of hydrometalation in homogeneous and heterogeneous hydrogenation of alkenes. By studying the electronic effects on the orientation of hydrometalation it is found with palladium and rhodium that this key step is a two electron process that can occur by two modes (a Pd(δ*+-) H(δ-) or b Pd(δ-)- H(δ+)). This provides valuable information about the structure of the metal-alkyl intermediate and helps rationalise how chiral induction occurs.
- Yu, Jinquan,Spencer, Jonathan B.
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p. 15821 - 15832
(2007/10/03)
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- Synthesis of the Substituted Z-1-Bromo-1-alkenes and Arylacetylenes from 2,3-Dibromocarboxylic Acids
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Stereoselectivity was studied of simultaneous debromination-decarboxylation of dibrominated cinnamic and acrylic acids. The best selectivity in formation of Z-vinyl bromides was achieved with the use of organic nitrogen bases. The 1-bromo-1-alkenes were converted into the corresponding acetylenes.
- Matveeva,Erin,Kurz
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p. 1065 - 1067
(2007/10/03)
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- N-substituted cycloalkyl and polycycloalkyl α-substituted Trp-Phe- and phenethylamine derivatives
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Novel unnatural dipeptoids of α-substituted Trp-Phe derivatives useful as agents in the treatment of obesity, hypersecretion of gastric acid in the gut, gastrin-dependent tumors, colorectal tumors, or as antipsychotics are disclosed. Further the compounds are antianxiety agents, antiulcer agents, antidepressant agents, and are agents useful for preventing the withdrawal response produced by chronic treatment or use followed by chronic treatment followed by withdrawal from nicotine, diazepam, alcohol, cocaine, caffeine, or opiods. Also disclosed are pharmaceutical compositions and methods of treatment using the dipeptoids as well as processes for preparing them and novel intermediates useful in their preparation. An additional feature of the invention is the use of the subject compounds to prepare pharmaceutical and diagnostic compositions.
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- Activation of C-O and C-N Bonds in Allylic Alcohols and Amines by Palladium Complexes Promoted by CO2. Synthetic Applications to Allylation of Nucleophiles, Carbonylation, and Allylamine Disproportionation
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The direct activation of the C-O bonds in allylic alcohols catalyzed by palladium complexes has been accelerated by carrying out the reactions under CO2. On reaction with diethylamine, allyl alcohol can be converted into N,N-diethylallylamine in the presence of palladium complexes at room temperature under normal pressure of carbon dioxide. Allylation of various carbon nucleophiles such as β-keto esters and β-diketones can be achieved by using allylic alcohols directly in the presence of palladium complexes and CO2. Direct carbonylation of allylic alcohols into unsaturated carboxylic acids can be catalyzed by palladium complexes under the pressure of CO and CO2. Disproportionation of diallylamine into triallylamine and allylamine is also catalyzed by palladium complexes in the presence of CO2. On the basis of studies on the behavior of η3-allylpalladium hydrogencarbonate complexes with the nucleophiles, mechanisms are proposed to account for the palladium-catalyzed allylation processes influenced by CO2.
- Sakamoto, Masato,Shimizu, Isao,Yamamoto, Akio
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p. 1065 - 1078
(2007/10/03)
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- 4-substituted azetidinones as precursors to 2-substituted-3-carboxy carbapenem antibiotics and a method of producing them
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New 4-substituted azetidinones having the formulae I and II: STR1 wherein X is oxygen, sulfur or a moiety of the formula NR6 where R1, R2, R3, R4, R5 and R6 are defined hereafter, which are intermediates for the preparation of carbapenem and carbacephem antibacterials and processes for producing such antibacterials through the utilization of an acid mediated ring closure reaction.
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- N-SUBSTITUTED CYCLOALKYL AND POLYCYCLOALKYL ALPHA-SUBSTITUTED TRP-PHE- AND PHENETHYLAMINE DERIVATIVES
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Novel unnatural dipeptoids of α-substituted Trp-Phe derivatives useful as agents in the treatment of obesity, hypersecretion of gastric acid in the gut, gastrin-dependent tumors, or as antipsychotics are disclosed. Further the compounds are antianxiety agents, antiulcer agents, antidepressant agents, and are agents useful for preventing the withdrawal response produced by chronic treatment or use followed by chronic treatment followed by withdrawal from nicotine, diazepam, alcohol, cocaine, caffeine, or opiods. Also disclosed are pharmaceutical compositions and methods of treatment using the dipeptoids as well as processes for preparing them and novel intermediates useful in their preparation. An additional feature of the invention is the use of the subject compounds to prepare pharmaceutical and diagnostic compositions.
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- AMINO ACID DERIVATIVES CYCLIZED AT THE C-TERMINAL
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Novel α-substituted Trp dipeptoid derivatives cyclized at the C-terminal useful as agents in the treatment of obesity, hypersecretion of gastric acid in the gut, gastrin-dependent tumors, or as antipsychotics are disclosed. Further, the compounds are antianxiety agents and antiulcer agents. They are agents useful for preventing the response to the withdrawal from chronic treatment with or use of nicotine, diazepam, alcohol, cocaine, caffeine, or opioids. The compounds of the invention are also useful in treating and/or preventing panic attacks. Also disclosed are pharmaceutical compositions and methods of treatment using the compounds as well as processes for preparing them and novel intermediates useful in their preparation. An additional feature of the invention is the use of the compounds in diagnostic compositions.
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- Reactions of hydriodic acid with aldonolactones and n-alkanolactones. Interconversions between lactones and iodocarboxylic acids
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Aldonolactones containing from four to eight carbon atoms, and lactones of the related monohydroxy-n-alkanoic acids, were subjected to reaction with 57 percent hydriodic acid at 125 deg C.As in the classical studies of Kiliani, the reduction of D-glycero-D-ido-heptono-1,4-lactone yielded mainly γ-heptanolactone.Analogously, the corresponding γ-alkanolactones were obtained as major products from the 1,4-lactones of the D-xylono, D-allono-, and D-erythro-L-talo-octono configuration.Monoiodo-n-alkanoic acids were also formed in admixture with the lactones in all of these reactions.D-Erythrono-1,4-lactone was unique among the aldonolactones in that it led only to an acid, i.e., 3-iodo-n-butanoic acid.The latter was also the product of the non-reductive reaction of hydriodic acid with β-butyrolactone whereas, by contrast, γ-butyrolactone afforded 4-iodobutanoic acid.Among compounds in the five to eight carbon series, it was found that under conditions close to equilibrium the ratio of lactone to iodoacid decreased progressively with the length of the carbon chain; e.g., in the 4 h reactions of γ-valero, γ-capro, γ-heptano,- and γ-octanolactone, the ratios were 2.4, 1.2, 0.2, and 0.1, respectively.An accompanying characteristic of these reactions is a progression in the number of isomeric iodoacids formed.Whereas γ-valerolactone was accompanied by 4-iodopentanoic acid, there were two isomers (4- and 5-) of iodohexanoic acid, three monoiodo- (including 6-iodo-) heptanoic acids, and four (including 7-iodo-) octanoic acids.In all instances, the isomer substituted at the penultimate carbon was major.An interplay of several individual reactions, including ring-opening displacements, eliminations-additions, and rearrangements, as well as a probable influence of entropy changes on the lactone-acid equilibria, appear to account largely for these observations.
- Liu, Zhengchun,Granata, Alessandro,Shen, Xinhua,Perlin, Arthur S.
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p. 2081 - 2088
(2007/10/02)
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- Selective Debromination of Activated Vicinal Dibromides by Copper Promoted by Copper(II)
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A mild method for the conversion of vicinal dibromides to olefins by using a mixture of copper metal powder and copper(II)perchlorate is described.
- Vijayashree, N.,Samuuelson, Ashoka G.
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p. 559 - 560
(2007/10/02)
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- CINNAMOYLAMIDE DERIVATIVES
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A cinnamoylamide derivative of general formula:[wherein, (i) in case that R2 represents a methyl group and R3 represents a hydrogen atom, (R1)n represents a group selected out of 3-pentyl group, 4-pentyl group, 4-neopentyl group, 4-(2-ethylbutyl) group, 4-(2-methylpentyl) group, 2-fluoro-4-pentyloxy group, 4-butylthio group, 4-cyclobutylmethyl group, 4-cyclohexylmethyl group, 4-(4-phenylbutyl) group and 4-phenoxy group, and (ii) in case that R2 represents a hydrogen atom and R3 represents a methyl group, (R1)n represents a group selected out of 3-pentyl group and 4-phenethyl group] or non-toxic salts thereof possess an inhibitory activity on 5a-reductase, and therefore be useful for treating and/or preventing agent for alopecia, acnes or prostatic hypertrophy
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- CYCLIC HYDROCARBONS WITH AN AMINOALKYL SIDECHAIN
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Provided are cyclic hydrocarbons of Formula I with an aminoalkyl sidechain that are useful for treating phospholipase A2 mediated conditions, diabetes, and obesity.
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- A CATALYTIC ROLE OF Cu(II) FOR CONJUGATE ADDITION OF GRIGNARD REAGENTS. A COMPLETELY DIFFERENT BEHAVIOR FROM ORGANOCUPRATES
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Different from lithium dialkycuprates, Cu(II) catalyzed conjugate addition of Grignard reagents to allylic esters of α,β-unsaturated carboxylates has been effected in the presence of TMS-Cl, and the resulting allyl silyl keteneacetals further undergo rearrangement to afford 2-allyl 3-alkyl carboxylic acids in good yields.
- Aoki, Youji,Kuwajima, Isao
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p. 7457 - 7460
(2007/10/02)
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- Substituted 2,6-substituted pyridine compounds having herbicidal activity
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Disclosed herein are substituted pyridine-3-monocarboxylate compounds in which a substituent is bonded to the pyridine ring at the 5-position through an oxygen atom.
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- STEREOSELECTIVE SYNTHESIS OF (E)-α,β-UNSATURATED ACIDS FROM C,O,O-TRI(TRIMETHYLSILYL) KETENE ACETAL AND ALDEHYDS
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Aldehydes are converted into (E)-α,β-unsatured carboxylic acids by means of C,O,O-tri(trimethylsilyl) ketene acetal and a catalytic a mount of ZnBr2.
- Bellasoued, Moncef,Gaudemar, Marcel
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p. 4551 - 4554
(2007/10/02)
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- Iodide-promoted Debromination of Vicinal Dibromides. Part-I. In DMF
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The specific rate constants and the activation parameters ΔH*, ΔS* and ΔG*, for the iodide-induced debromination reaction of erythro-2,3-dibromo-3-phenylpropanoic acids (o-Cl, -F, -Br, -NO2, -CH3; m-OCH3, -F, -NO2, -CH3 and p-NO2, -F, -Cl, -CH3) and erythro-2,3-dibromobutanoic acid in dimethylformamide are reported.Ortho-substituted compounds were found to react faster than the unsubstituted ones irrespective of the nature of the substituent.Results indicate that the bromine attached to the α-carbon atom is attacked by I- and the transition state is between non-synchronous nearly E1 type and synchronous E2 type.
- Philip, V. J.,Mathai, I.M.,Raj, D. Joshwa Anthony,Jacob, G. Carol
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p. 350 - 353
(2007/10/02)
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- Quinolinium Dichromate - A New Reagent for Oxidation of Alcohols
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Quinolinium dichromate is shown to be a new oxidising agent for the selective oxidation of primary and secondary alcohols to aldehydes and ketones respectively.
- Balasubramanian, K.,Prathiba, V.
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p. 326 - 327
(2007/10/02)
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- Infrared Multiphoton Isomerization Reactions of Alkenes and Dienes
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The infrared multiphoton laser-induced unimolecular isomerization reactions of several simple alkenes, conjugated alkenes, and pentadienes have been investigated.Excitation of (E)-2-butene, pentene, and hexene results in contrathermodynamic E -> Z isomerization and fragmentation, the isomerization/fragmentation ratio decreasing with increasing chain length and increasing laser fluence.These results are in qualitative agreement with RRKM calculations for average reactant energies of 75-85 kcal/mol.In addition to products of C-C homolysis observed with all three alkenes, 1-butene and 1,3-butadiene are formed from (E)-2-butene. (E)-Crotononitrile undergoes laser-induced isomerization without fragmentation, resulting in quantitative conversion to the Z isomer.In contrast, (E)-methyl crotonate undergoes both isomerization and fragmentation, while (E)-ethyl crotonate undergoes essentially quantitative elimination of ethylene.Irradiation of (E)- or (Z)-1,3-pentadiene at low laser fluences results exclusively in E Z isomerization resulting in steady-state isomer ratios which depend upon the relative magnitude of the single photon cross sections of the two isomers.At higher fluences, both isomers are converted to cyclopentadiene and trace amounts of 1,4-pentadiene.Irradiation of 1,4-pentadiene results in efficient isomerization to (E)- and (Z)-1,3-pentadiene which reacts further to yield cyclopentadiene.The factors which govern these and related infrared multiphoton reactions are discussed.
- Lewis, Frederick D.,Teng, Peter,Weitz, Eric
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p. 2818 - 2826
(2007/10/02)
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