A new strategy for the alpha-vinylation of ketones: Application to an enantioselective synthesis of sesquiterpene (+)-alpha-elemene

A new, simple and preparatively useful protocol for the construction of a-vinyl ketones, particularly those bearing a quaternary carbon centre, from the corresponding alkenes has been devised. Our four-step strategy consists of dichloroketene addition, base catalysed ring contraction to 'push-pull' cyclopropane esters, reduction and eliminative cyclopropane fragmentation to unravel the a-vinyl ketone moiety. The generality of this approach has been demonstrated with a few representative olefins and good regio- and stereocontrol has been observed. As an application of this methodology, an enantioselective synthesis of sesquiterpene hydrocarbon (+)-alpha-elemene (42) from R-(+)-limonene (43) has been accomplished.

Hot deformation and microstructural evolution in an alpha(2)/O titanium aluminide alloy Ti-25Al-15Nb

Deformation processing and microstructural development of an alpha(2)/O aluminide alloy Ti-25Al-15Nb (at.%) was studied in the temperature range of 950 to 1200 degrees C and strain rate range of 10(-3) to 100 s(-1). Regions of processing and instability were identified using dynamic materials model. Dynamic recrystallization (DRX) of alpha(2)/O phase and p phase were seen to occur in the region of 950 to 1050 degrees C/0.001 to 0.05 s(-1) and 1125 to 1175 degrees C/0.001 to 0.1 s(-1), respectively. Unstable flow was seen to occur in the region of 1050 to 1190 degrees C/10 to 100 s(-1). Thermal activation analysis showed that DRX of alpha(2)/O and beta was controlled by cross-slip.

On the existence of a nickel hydroxide phase which is neither alpha nor beta

A novel phase of nickel hydroxide with an average interlayer spacing 5.4-5.6 Angstrom has been synthesized which is neither ct nor beta type but is an interstratification of both. It ages to the beta form in strong alkali. These observations have implications on the dissolution-reprecipitation mechanism suggested for the alpha-->beta transformation of nickel hydroxide.

Processing map for the hot working of near-alpha titanium alloy 685

Using a dynamic materials model, processing and instability maps have been developed for near-alpha titanium alloy 685 in the temperature range 775-1025 degrees C and strain-rate range of 0.001-10 s(-1) to optimise its hot workability. The alloy's beta-transus temperature lies at about 1020 degrees C. The material undergoes superplasticity with a peak efficiency of 80% at 975 degrees C and 0.001 s(-1), which are the optimum parameters for alpha-beta working. The occurrence of superplasticity is attributed to two-phase microduplex structure, higher strain-rate sensitivity, low flow stress and sigmoidal variation between log flow stress and log strain rate. The material also exhibits how localisation due to adiabatic shear-band formation up to its beta-transus temperature with strain rates greater than 0.02 s(-1) and thus cracking along these regions. (C) 1997 Published by Elsevier Science S.A.

A Change in the 3(10)- to alpha-Helical Transition Point in the Heptapeptides Containing Sulfur and Selenium

Crystal structures of three heptapeptides Boc-Ala-Leu-Aib-XXX-Ala-Leu-Aib-OMe (where XXX = methionine in peptide A, selenomethionine in peptide B, and S-benzyl cysteine in peptide C) reveal mixed 3(10)-/alpha-helical conformations with R factors of 6.94, 5.79, and 5.98, respectively. All the structures were solved in the P2(1)2(1)2(1) space group. 3(10)- to a-helical transitions are observed in all of these peptides. The helices begin as a 3(10)-helical segment at the N-terminus and then transit for peptides A and C at residue Aib(3) carbonyl (O(3)), while for peptide B the transition occurs at residue Leu(2) carbonyl oxygen (O(2)). There are water molecules associated in the crystal of each of these peptides and they form different types of hydrogen bonding patterns in each crystal. The observations suggest that 3(10)- to alpha-helical transition is sequence dependent in these short heptapeptide sequences.

Role of two consecutive alpha,beta-dehydrophenylalanines in peptide structure: Crystal and molecular structure of Boc-Leu-Delta Phe-Delta Phe-Ala-Phe-NHMe

An N-alpha-protected model pentapeptide containing two consecutive Delta Phe residues, Boc-Leu-Delta Phe-Delta Phe-Ala-Phe-NHMe, has been synthesized by solution methods and fully characterized. H-1-nmr studies provided evidence for the occurrence of a significant population of a conformer having three consecutive, intramolecularly II-bonded beta-bends in solution. The solid state structure has been determined by x-ray diffraction methods. The crystals grown from aqueous methanol are orthorhombic, space group P2(1)2(1)2(1),, a = 11.503(2), b = 16.554(2), c = 22.107(3) Angstrom, V = 4209(1) Angstrom,(3) and Z = 4. The x-ray data were collected on a CAD4 diffractometer using CuKalpha radiation (lambda = 1.5418 Angstrom). The structure was determined using direct methods and refined by full-matrix least-squares procedure. The R factor is 5.3%. The molecule is characterized by a right handed 3(10)-helical conformation ((phi) = -68.2 degrees (psi) = -26.3 degrees), which is made up of two consecutive type III beta-bends and one type I beta-bend. In the solid state the helical molecules are aligned head-to-tail, thus forming long rod like structures. A comparison with other peptide structures containing consecutive Delta Phe residues is also provided. The present study confirms that the -Delta Phe-Delta Phe-sequence can be accommodated in helical structures. (C) 1997 John Wiley & Sons, Inc.

Stereocontrolled synthesis of (+/-)-alpha-pinguisene and (+/-)-pinguisenol

Total synthesis of (+/-)-alpha-pinguisene 1 and (+/-)-pinguisenol 2, employing an orthoester Claisen rearrangement and an intramolecular diazo ketone cyclopropanation reaction for the stereospecific construction of vicinal quaternary carbon atoms, is described.

Structural characterization and chain dynamics of poly(alpha-methylstyrene peroxide) by NMR spectroscopy

Poly(alpha-methylstyrene peroxide) has been synthesized and characterized spectroscopically. The H-1 and C-13 NMR spectra are shown to reveal the stereochemical features and the endgroups in the peroxide chain. The preliminary studies on the chain dynamics of the polyperoxide chain has been done by measuring the spin-lattice relaxation times (T-1) of the main chain as well as the side chain carbons. It has been shown from the dependence of the spin-lattice relaxation times that the polyperoxide chain is more flexible compared to the corresponding hydrocarbon-backbone analog.

Theory of coexisting charge and spin-density waves in (TMTTF)(2)Br, (TMTSF)(2)PF6 and alpha-(BEDT-TTF)(2)MHg(SCN)(4)

We discuss a recently formulated microscopic theory of the unusual coexistence of spin density waves (SDWs) and charge density waves (CDWs) that has been seen in recent experiments on (TMTTF)2Br, (TMTSF)2PF6 and α-(BEDT-TTF)2MHg(SCN)4.

Theory of coexisting charge and spin-density waves in (TMTTF)(2)Br, (TMTSF)(2)PF6, and alpha-(BEDT-TTF)(2)MHg(SCN)(4)

Recent experiments indicate that the spin-density waves (SDWs) in (TMTTF)(2)Br, (TMTSF)(2)PF6, and alpha-(BEDT-TTF)(2)MHg(SCN)(4) are highly unconventional and coexist with charge-density waves (CDWs). We present a microscopic theory of this unusual CDW-SDW coexistence. A complete understanding requires the explicit inclusion of strong Coulomb interactions, lattice discreteness, the anisotropic two-dimensional nature of the lattice, and the correct hand filling within the starting Hamiltonian. [S0031-9007(99)08498-7].

Zinc-substituted alpha-nickel hydroxide as an electrode material for alkaline secondary cells

Double hydroxides of the formula, Ni1-xZn2x (OH)(2) (CO3)(x). nH(2)O (x = 0.1 to 0.25) having the same structure as that of alpha-nickel hydroxide have been synthesized by partial substitution of zinc for nickel. The hydroxide having the composition x = 0.25 exhibits prolonged stability in 6 M KOH. Pasted electrodes comprising this material are rechargeable with a stabilized reversible discharge capacity of 410 +/- 15 mAh g(-1) of nickel even under suboptimal conditions of electrode fabrication. This compares favorably with the capacity values achieved for beta-nickel hydroxide (221 mAh g(-1)', This work; 297 mAh g(-1), Delahaye-Vidal and Figlarz;(1) 456 mAh g(-1), theoretical). (C) 1999 The Electrochemical Society. S0013-4651(98)01-071-4. All rights reserved.

A ring closing metathesis-based approach to (+/-)-herbertene, (+/-)-alpha-herbertenol, (+/-)-beta-herbertenol and (+/-)-herbertenediol

An efficient methodology for the synthesis of the aromatic sesquiterpenes (+/-)-herbertene, (+/-)-alpha-herbertenol, (+/-)-beta-herbertenol (+/-)-herbertenediol and (+/-)-alpha-cuparenone, employing a combination of Claisen rearrangement and ring closing metathesis reactions, is described.

High-pressure kinetics of oxidative copolymerization of styrene with alpha-methyl styrene

This is the first report on the study carried out on high-pressure free-radical initiated oxidated copolymerization of styrene (STY) with alpha-methylstyrene (AMS) at various temperatures (45-65degreesC) at constant pressure (100 psi) and then at various pressures (50-300 psi) keeping the temperature (50degreesC) constant. The compositions of the copolyperoxides obtained from the H-1 NMT spectra were utilized to determine the reactivity ratios of the monomers. The reactivity ratios indicate that STY forms an ideal copolyperoxide with AMS and the copolyperoxide is richer in AMS. The effect of temperature and oxygen pressure in the reactivity ratios of the monomers was studied. The rates of copolymerization (R-p) were used to determine the overall activation energies (E-a) and activation volume (DeltaV(#)) of copolymerization. The unusually higher values of the DeltaV(#) may be due to the pressurizing fluid oxygen which itself is a reactant in the copolymerization, the side reactions, and the chain-transfer reactions occuring during copolymerizations.

Pressure-induced phase transitions in alpha-ZrMo2O8

We report high-pressure Raman, infrared (IR), and optical-absorption spectra of alpha-ZrMo2O8 (trigonal) up to 38 GPa at room temperature. The spectroscopic studies are consistent with diffraction results that show that alpha-ZrMo2O8 transforms into delta-ZrMo2O8 (monoclinic) at about 1 GPa and the delta phase converts to the epsilon phase (trielinic) at about 2.0 GPa. Optical-absorption measurements give an estimate of the band gap of about 0.6 eV at the lowest pressure. Band-gap changes with pressure are confirmed with visual observations. ZrMo2O8 changes from transparent at 5 GPa to yellow at 10 GPa, red at 18 GPa, and at about 30 GPa it becomes opaque.