ChemInform Abstract: Synthesis Based on Cyclohexadienes. Part 16. Synthesis of Methyl 2,7-Dimethyltricyclo (5.2.2.01,5)undec-5-ene-6-carboxylates

Synthesis of methyl 2, 7-dimethyltricyclo{5.2.2.0(1,5}undec-5-en-6-carboxylates, the tricyclic skeleton present in (+)-allo-cedrol (1) is described using the Diels-Alder strategy. Thus, Birch reduction of the aromatic acid 8 gives 5, the methyl ester of which is isomerised with DBU to a 1:1 mixture of the dienes 6 and 4. Cycloaddition of this mixture with 2-chloroacrylonitrile followed by hydrolysis yields the ketone 60 having the tricyclo{5.2.2.0(1.5)}undec-5-ene framework. Similar reaction with methyl vinyl ketone affords the regioisomeric adducts 61 and 62.

Methanol electrooxidation on carbon-supported Pt-WO3−x electrodes in sulphuric acid electrolyte

Electrooxidation of methanol has been studied in sulphuric acid electrolyte at 60 degrees C on carbon-supported Pt-WO3-x, electrodes employing varying amounts of WO3-x,. It is found that the electrodes containing (3:1) Pt-WO3-x, composite catalyst exhibit a higher catalytic activity towards methanol electrooxidation than platinized carbon electrodes without WO3-x. In the light of the XPS and XRD data on the carbon-supported (3:1) Pt-WOx sample, it is speculated that the WOx is present in the form of an oxyhydroxide, which can promote surface oxy-species on platinum by proton transfer.

Enzymatic resolution of dioxygenated dicyclopentadienes: Enantiopure hydrindanes, hydroisoquinolones, diquinanes and application to a synthesis of (+)-coronafacic acid

A 5, 10-dioxygenated-tricyclo[5.2.1.0(2,6)]decane derivative 6 has yielded to efficient enzymatic resolution to provide a range of chiral building blocks, whose absolute configuration has been determined through a total synthesis of naturally occuring (+)-coronafacic acid. (C) 1999 Elsevier Science Ltd. All rights reserved.

Interaction of A beta peptide (1-40) with amino acid aluminium complexes: relevance to Alzheimer's disease

A beta (39-43 aminoacid residues) is the principal peptide component of amyloid deposits in Alzheimer's disease (AD). A beta peptide is derived from the amyloid precursor protein (APP) in which mutations give rise to many forms of familial AD. Aluminium is reported to play a key role in inducing conformational change in the synthetic beta-amyloid peptide (1-40)from alpha-helix to beta-pleated sheet, leading to aggregation and fibrillar formation. We have studied the interaction of amino acid-Al complexes such as D-Asp-Al and L-Glu-Al with A beta(1-40) in TFE/buffer (70% TFE and 30% H2O v/v pH 6.7) mixture using CD spectroscopy. The interaction of either of these amino acid complexes with A beta(1-40) results in loss of alpha-helical content and the peptide is more unstructured compared to free Al3+ in the solution. Our data strongly support the idea, that the Al3+ in the form of aminoacid-Al complexes is more effective in inducing random coil conformation in the A beta peptide than the free Al3+ present in the solution.

Chiral Mitsunobu reactions with (1S)-(+)-ketopinic acid: kinetic resolutions of secondary alcohols

Several secondary alcohols undergo the Mitsunobu reaction with triphenylphosphine, diethyl azodicarboxylate and (1S)-(+)-ketopinic acid (0.5 equiv. each relative to alcohol) in CH2Cl2 solution at -23degreesC, to furnish the chiral secondary alcohol and its ketopinate ester (d.e. >95%,). Chromatographic separation of these and subsequent hydrolysis of the ketopinate ester (KOH EtOH/0degreesC) provides the chiral secondary alcohol in overall yields of similar to75% and e.e. of similar to80%. When the above Mitsunobu reaction is performed with 1 equiv. of all the reactants. an effective dynamic kinetic resolution of the alcohol is observed in two cases, the ketopinate esters being isolated in 63 and 75% yields and >95% d.e. (C) 2002 Elsevier Science Ltd. All rights reserved.

Dendritic encapsulation of amino acid-metal complexes. Synthesis and studies of dendron-functionalized L-tyrosine-metal (Zn-II, Co-II) complexes

This paper describes the synthesis, characterization and studies of dendrimers possessing an amino acid-metal complex as the core. Using Frechet-type polyaryl ether dendrons, L-tyrosine-metal (Zn-II and Co-II) complex cored dendrimers of 0-4 generations were synthesized. The metal complexation of the tyrosine unit at the focal point of these dendrons took place smoothly, in excellent yields, even though the sizes of the dendrons increase as the generations advance. Spectrophotometric titrations with CoII metal ion confirmed the formation of a 2 : 1 dendritic ligand to metal complex and the existence of a pseudotetrahedral geometry at the metal centre is also inferred. Cyclic voltammetric studies of dendrimer-Co-II complexes showed that while the electron transfer of Co-II to Co-I was facile for generations 0-2, such a process was difficult with generations 3 and 4, indicating a rigid encapsulation of the metal ion centre by proximal dendron groups. Further reduction of Co-I to Co-0 and the corresponding oxidation processes appear to be limited by adsorption at the surfaces of the electrodes.

Volume Change behaviour in Calcitic Soil influenced with Sulphuric Acid using Artificial Neural Networks

This paper elucidates the methodology of applying artificial neural network model (ANNM) to predict the percent swell of calcitic soil in sulphuric acid solutions, a complex phenomenon involving many parameters. Swell data required for modelling is experimentally obtained using conventional oedometer tests under nominal surcharge. The phases in ANN include optimal design of architecture, operation and training of architecture. The designed optimal neural model (3-5-1) is a fully connected three layer feed forward network with symmetric sigmoid activation function and trained by the back propagation algorithm to minimize a quadratic error criterion.The used model requires parameters such as duration of interaction, calcite mineral content and acid concentration for prediction of swell. The observed strong correlation coefficient (R2 = 0.9979) between the values determined by the experiment and predicted using the developed model demonstrates that the network can provide answers to complex problems in geotechnical engineering.

Synthesis of 5-p-hydroxybenzyl-5,6-dihydro-2-naphthol, (+/-)-sequirin-d

A high-yield six-step synthesis of sequirin D (1a), a naturally occurring norlignan, is described. Michael addition of deoxyanisoin (2) to acrylonitrile gives a ketonitrile (3), which on Wolff–Kishner reduction is reduced and hyrolysed in situ to 4,5-bis-p-methoxyphenylpentanoic acid (4). Cyclodehydration of (4) with polyphosphoric acid, followed by borohydride reduction and dehydration furnishes di-O-methylsequirin D (1b) which affords on demethylation sequirin D (1a) in an overall yield from (2) of 60%. The key synthon (4) has also been prepared by three other routes.

Evidence of aggregation induced emission enhancement and keto-enol-tautomerism in a gallic acid derived salicylideneaniline gel

A novel salicylideneaniline type fluorescent organogelator based on a 3,4,5-(tri-dodecyloxy)benzoyl group immobilizes aromatic solvents. The resulting gels show enhancement in emission and thermochromic/non-photochromic behaviour during sol-to-gel transition.

Esterification of stearic acid with p-cresol over modified Indian bentonite clay catalysts

The esterification of stearic acid with p-cresol using modified Indian bentonite clay catalysts has been reported. The reaction was studied over exchanged clays, acid activated clays, exchanged acid activated clays, aluminium pillared clay, aluminium pillared acid activated clay, molecular sieve Al-MCM-41, zeolite H beta, ZrO2, S-ZrO2, p-TSA, montmorillonite K10, and montmorillonite KSF in o-xylene for 6 h. The catalysts were characterized by X-ray diffraction and surface area measurements. The acidity was determined by n-butylamine back-titration method and DRIFTS after pyridine adsorption. Acid activated Indian bentonite (AAIB) was found to be a better catalyst compared to other catalysts in the esterification of stearic acid with p-cresol.

Enantiospecific first total synthesis of (6S,7R)-silphiperfolan-6-ol

Enantiospecific first total synthesis of the angular triquinane sesquiterpene (65,7R)-silphiperfolan-6-ol has been accomplished, starting from 2-(3-isopropenyl-2-methylene-1-methylcyclopent-1-yl)acetic acid (readily available from (R)-limonene) employing an efficient, regioselective intramolecular rhodium carbenoid insertion into the CH bond of a tertiary methyl group as the key step. (C) 2012 Elsevier Ltd. All rights reserved.

Polymorphic Anhydrous Cocrystals of Gallic Acid and Acetamide from Methanol: Pointers toward a Stable Cocrystal Form

Polymorphic anhydrous cocrystals generated from a methanolic solution of gallic acid monohydrate and acetamide are shown to convert to the stable form II on complete drying, and the pathway to the stable form is explained on the basis of the variability in the hydrogen bonding patterns followed by theoretical calculations.

Chemoselective Schmidt Reaction Mediated by Triflic Acid: Selective Synthesis of Nitriles from Aldehydes

An excellent utility of Schmidt reaction of aldehydes to access corresponding nitriles in an instantaneous reaction is demonstrated. The reaction of aldehydes with NaN3 and TfOH furnishes the corresponding nitriles in near quantitative yields and tolerates a variety of electron-withdrawing and electron-donating substituents on the substrates. Formanilides, a common side product in Schmidt reaction, is not observed in this reaction. Besides these advantages, the salient feature of this reaction is that it exhibits a remarkable chemoselectivity, as acid and ketone functionalities are well tolerated under the reaction conditions. The reaction is easily scalable, high yielding, and nearly instantaneous.