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Aromatic Ring (aromatic + ring)
Terms modified by Aromatic Ring Selected AbstractsReactions of 1,5-,-Cyclization of gem-Difluoro-Substituted Azomethine Ylides Involving an Aromatic Ring.CHEMINFORM, Issue 44 2006I. V. Voznyi Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] The First Samarium(II)-Mediated Aryl Radical Cyclization onto an Aromatic Ring.CHEMINFORM, Issue 10 2005Hiroaki Ohno Abstract For Abstract see ChemInform Abstract in Full Text. [source] Mono- and Multidecker Sandwich-Like Complexes of the Tetraazacyclobutadiene Aromatic Ring.CHEMINFORM, Issue 52 2004Jose M. Mercero Abstract For Abstract see ChemInform Abstract in Full Text. [source] Direct Introduction of CH2SMe Group in Aromatic Ring.CHEMINFORM, Issue 24 2004A. P. Zaraiskii No abstract is available for this article. [source] Samarium(II)-Promoted Radical Spirocyclization onto an Aromatic Ring.CHEMINFORM, Issue 5 2004Hiroaki Ohno Abstract For Abstract see ChemInform Abstract in Full Text. [source] Remarkably Slow Rotation about a Single Bond between an sp3 -Hybridised Carbon Atom and an Aromatic Ring without ortho SubstituentsCHEMISTRY - A EUROPEAN JOURNAL, Issue 9 2009Sarah Murrison Abstract Look, noorthosubstituents! A series of polycycles were prepared by using a three-component Joullié,Ugi reaction. The rate of rotation about the bond between a highly hindered bridgehead and a phenyl ring with no ortho substituents was measured, and was highly dependent on the substitution. Rotamer half-lives of up to 21,h at 298,K were observed (see figure). Rotamers resulting from this restricted rotation were isolated for the first time. A series of polycycles was prepared by using a three-component Joullié,Ugi reaction. The rate of rotation about the bond between a highly hindered bridgehead and a phenyl ring with no ortho substituents was measured by using, in general, variable-temperature HPLC. The rate of rotation was highly dependent on substitution and rotamer half-lives of up to 21,h at 298,K were observed. Insights into the effect of substitution on the rate of rotation were gleaned through electronic structure calculations on closely related derivatives. Rotamers resulting from restricted rotation about a bond between an sp3 -hybridised carbon atom and a phenyl ring with no ortho substituents were isolated for the first time, and the equilibration of the separated rotamers was followed by using analytical HPLC. It was demonstrated, for the first time, that a highly hindered environment for the sp3 -hybridised atom is sufficient for slow bond rotation about a single bond between sp3 - and sp2 -hybridised carbon atoms. [source] Structure,Activity Study on the Spatial Arrangement of the Third Aromatic Ring of Endomorphins 1 and 2 Using an Atypical Constrained C,TerminusCHEMMEDCHEM, Issue 3 2007Ye Yu Dr. Abstract The discovery of endomorphins (EMs) has opened the possibility of searching for new analgesics. However, the design of peptide analgesics has proven to be very difficult as a result of their conformational flexibility and a lack of clarity in structure,activity relationships (SAR). In EMs, the amino acid side chains exhibit considerable conformational flexibility, especially in the third aromatic ring, which is free to adopt a bioactive conformation. To resolve these problems, a series of C,terminus EM analogues, [Xaa4 -R]EMs, modified through the substitution of Phe4 with nonaromatic residues and termination with benzyl groups, were designed to generate conformational constrains of the third aromatic ring by amide bond and torsion angles (,4 and ,4) of Xaa4. Introduction of (S)-,-methyl or (S)/(R)-,-carboxamide on the methylene unit of the benzyl group was designed to produce an atypical topographical constraint (,5) of the third aromatic ring rotation. Interestingly, some EM derivatives, with elimination of the C-terminal carboxamide group and significant changes in the address sequence (Phe4 -NH2), still exhibited higher ,-opioid receptor (MOR) affinity than unmodified EMs. In contrast, some analogues with incorrectly constrained C,termini displayed very low affinity and pharmacological activities. Thus, our results indicate that these EM analogues, with atypical constrained C,termini, provide model compounds with potent MOR agonism. They also give evidence that the proper spatial orientation and conformational restriction of the third aromatic ring are crucial for the interaction of EMs with MOR. [source] A Haigh,Mallion-Based Approach for the Evaluation of the Intensity Factors of Aromatic RingsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 2 2006Cristiano Zonta Abstract A novel method for the determination of intensity factors of benzenoid systems based on the Haigh,Mallion (HM) theory has been developed. In this paper, the magnetic anisotropy generated by the ring-current effect in polycondensed arenes has been quantitatively calculated as nuclear independent chemical shieldings (NICSs) in a three-dimensional grid of points using the B3LYP/6-31G(d) method implemented in the Gaussian 98 program. The fitting of the calculated values to the HM model gives intensity factors for each ring. A comparison of the obtained values with Schleyer's NICS0 is given. The obtained intensity factors may find application in software using 1H NMR chemical shifts for structure determination.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] ChemInform Abstract: A New Method of Bromination of Aromatic Rings by an iso-Amyl Nitrite/HBr System.CHEMINFORM, Issue 38 2008Laurent Gavara Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Asymmetric Assembly of Aromatic Rings to Produce Tetra-ortho-Substituted Axially Chiral Biaryl Phosphorus Compounds.CHEMINFORM, Issue 36 2007Goushi Nishida Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Contra-Friedel,Crafts tert-Butylation of Substituted Aromatic Rings via Directed Metalation and Sulfinylation.CHEMINFORM, Issue 32 2006Jonathan Clayden Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] A New Regioselective Bromination of Activated Aromatic Rings.CHEMINFORM, Issue 22 2006Leonardo S. de Almeida Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Palladium-Catalyzed Sequential Alkylation,Alkenylation Reactions: Application Towards the Synthesis of Polyfunctionalized Fused Aromatic Rings.CHEMINFORM, Issue 44 2005Dino Alberico Abstract For Abstract see ChemInform Abstract in Full Text. [source] ChemInform Abstract: Merry-Go-Round Multiple Alkylation on Aromatic Rings via Rhodium Catalysis.CHEMINFORM, Issue 9 2001Kazuaki Oguma Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] The potential for estradiol and ethinylestradiol degradation in english riversENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 3 2002Monika D. Jürgens Abstract Water samples were collected in spring, summer, and winter from English rivers in urban/industrial (River Aire and River Calder, Yorkshire, UK) and rural environments (River Thames, Oxfordshire, UK) to study the biodegradation potential of the key steroid estrogen 17,-estradiol (E2) and its synthetic derivate ethinylestradiol (EE2). Microorganisms in the river water samples were capable of transforming E2 to estrone (E1) with half-lives of 0.2 to 9 d when incubated at 20°C. The E1 was then further degraded at similar rates. The most rapid biodegradation rates were associated with the downstream summer samples of the River Aire and River Calder. E2 degradation rates were similar for spiking concentrations throughout the range of 20 ng/L to 500 ,g/L. Microbial cleavage of the steroid ring system was demonstrated by release of radiolabeled CO2 from the aromatic ring of E2 (position 4). When E2 was degraded, the loss of estrogenicity, measured by the yeast estrogen screen (YES) assay, closely followed the loss of the parent molecule. Thus, apart from the transient formation of E1, the degradation of E2 does not form other significantly estrogenic intermediates. The E2 could also be degraded when incubated with anaerobic bed sediments. Compared to E2, EE2 was much more resistant to biodegradation, but both E2 and EE2 were susceptible to photodegradation, with half-lives in the order of 10 d under ideal conditions. [source] Non-Tethered Organometallic Phosphonate Inhibitors for Lipase Inhibition: Positioning of the Metal Center in the Active Site of Cutinase,,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2008Cornelis A. Kruithof Abstract Organometallic NCN-pincer complexes, bearing either a p -nitrophenyl phosphonate ester or a phosphonic acid group directly attached to the aromatic ring of the pincer complex, were synthesized. These compounds were tested as covalent inhibitors for the lipase cutinase. In a stoichiometric reaction of the NCN-pincer platinum phosphonate p -nitrophenyl ester 2 with cutinase, a 94,% conversion to the protein,pincer metal complex hybrid was obtained in 48 h. The NCN-pincer metal phosphonic acid derivatives (3, 4) appeared to be inactive as cutinase inhibitors. In contrast to our previous work which entails propyl tethered phosphonate esters connected to pincer metal complexes, the presented strategy allows positioning of metal complexes inside the active site of lipases. This opens up the possibility for fine-tuning the chemical environment (second coordination sphere) around a synthetic metal center inside the pocket of an enzyme for diagnostic and catalytic purposes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Cationic Iridium Complexes with Chiral Dithioether Ligands: Synthesis, Characterisation and Reactivity under Hydrogenation ConditionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2005Leticia Flores-Santos Abstract A series of cationic IrI complexes containing chiral dithioether ligands have been prepared in order to study the influence of the sulfur substituents and the metallacycle size on the acetamidoacrylate hydrogenation reaction. In the case of complexes 6, 7 and 10, a mixture of diastereomers is observed in solution due to the sulfur inversion processes. In contrast, this fluxional behaviour is efficiently controlled by using bicyclic ligands which inhibit the S-inversion in complexes 8 and 9. The solid-state structure of complex 10b shows only one diastereomer with the sulfur substituents in a relative anti disposition and in an overall configuration of SCSCSSSS at the coordinated dithioether ligand. Iridium complexes containing seven- and six-membered metallacycles (6b,d, 7b,c, 10a,b) react with the substrate through S-ligand substitution, and the rate of this substitution is related to the position of the fluorine atom on the aromatic ring. On the contrary, complexes containing a bismetallacycle (8 and 9) are not displaced by the substrate. The catalytic hydrogenation activity of complexes 8 and 9 is analysed in terms of the high stability of the corresponding dihydride complexes (13 and 14). In both cases, only two of the four possible diastereomeric dihydride species are formed in solution. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] The First Example of an Azaphenalene Profluorescent NitroxideEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 28 2007James P. Blinco Abstract The synthesis of the first example of an azaphenalene-based fused aromatic nitroxide TMAO, [1,1,3,3-tetramethyl-2,3-dihydro-2-azaphenalen-2-yloxyl, (5)], is described. This novel nitroxide possesses some of the structural rigidity of the isoindoline class of nitroxides, as well as some properties akin to TEMPO nitroxides. Additionally, the integral aromatic ring imparts fluorescence that is switched on by radical scavenging reactions of the nitroxide, which makes it a sensitive probe for polymer degradation.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] The Intramolecular Aromatic Electrophilic Substitution of Aminocyclopropanes Prepared by the Kulinkovich,de Meijere Reaction,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 21 2005Laurent Larquetoux Abstract This article describes new examples of intramolecular Kulinkovich,de Meijere reactions applied to carboxylic amides bearing an olefin moiety and an aromatic ring at a suitable position. Upon heating, the aminocyclopropanes thus obtained undergo intramolecular aromatic electrophilic substitution to afford polycyclic systems. Among the various starting materials prepared, best results are obtained from indole and phenol derivatives. In each case, a benzylic quaternary centre is introduced at the newly-formed ring junction. On one example, the efficiency of the cyclisation has been dramatically improved using a catalytic amount of para -toluenesulfonic acid. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Studies on the Origin of 1,5- anti Induction in Boron-Mediated Aldol ReactionsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 2 2004Bridget L. Stocker Abstract A model for the origin of selectivity in boron-mediated 1,5- anti -aldols is presented. This model involves ,-stacking between the boron enolate and a remote aromatic ring. A short, facile method for the synthesis of the C-12 to C-22 segment of peloruside A and its 1,5- anti -aldol coupling using the proposed model is also presented. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Tyr235 of human cytosolic phosphoenolpyruvate carboxykinase influences catalysis through an anion,quadrupole interaction with phosphoenolpyruvate carboxylateFEBS JOURNAL, Issue 23 2008Lakshmi Dharmarajan Tyr235 of GTP-dependent phosphoenolpyruvate (PEP) carboxykinase is a fully invariant residue. The aromatic ring of this residue establishes an energetically favorable weak anion,quadrupole interaction with PEP carboxylate. The role of Tyr235 in catalysis was investigated via kinetic analysis of site-directed mutagenesis-derived variants. The Y235F change lowered the apparent Km for PEP by about six-fold, raised the apparent Km for Mn2+ by about 70-fold, and decreased oxaloacetate (OAA)-forming activity by about 10-fold. These effects were due to an enhanced anion,quadrupole interaction between the aromatic side chain at position 235, which now lacked a hydroxyl group, and PEP carboxylate, which probably increased the distance between PEP and Mn2+ and consequently affected the phosphoryl transfer step and overall catalysis. For the Y235A and Y235S changes, an elimination of the favorable edge-on interaction increased the apparent Km for PEP by four- and six-fold, respectively, and the apparent Km for Mn2+ by eight- and six-fold, respectively. The pyruvate kinase-like activity, representing the PEP dephosphorylation step of the OAA-forming reaction, was affected by the substitutions in a similar way to the complete reaction. These observations indicate that the aromatic ring of Tyr235 helps to position PEP in the active site and the hydroxyl group allows an optimal PEP,Mn2+ distance for efficient phosphoryl transfer and overall catalysis. The Y235A and Y235S changes drastically reduced the PEP-forming and OAA decarboxylase activities, probably due to the elimination of the stabilizing interaction between Tyr235 and the respective products, PEP and pyruvate. [source] Exploring the primary electron acceptor (QA)-site of the bacterial reaction center from Rhodobacter sphaeroidesFEBS JOURNAL, Issue 4 2002Binding mode of vitamin K derivatives The functional replacement of the primary ubiquinone (QA) in the photosynthetic reaction center (RC) from Rhodobacter sphaeroides with synthetic vitamin K derivatives has provided a powerful tool to investigate the electron transfer mechanism. To investigate the binding mode of these quinones to the QA binding site we have determined the binding free energy and charge recombination rate from QA, to D+ (kAD) of 29 different 1,4-naphthoquinone derivatives with systematically altered structures. The most striking result was that none of the eight tested compounds carrying methyl groups in both positions 5 and 8 of the aromatic ring exhibited functional binding. To understand the binding properties of these quinones on a molecular level, the structures of the reaction center-naphthoquinone complexes were predicted with ligand docking calculations. All protein,ligand structures show hydrogen bonds between the carbonyl oxygens of the quinone and AlaM260 and HisM219 as found for the native ubiquinone-10 in the X-ray structure. The center-to-center distance between the naphthoquinones at QA and the native ubiquinone-10 at QB (the secondary electron acceptor) is essentially the same, compared to the native structure. A detailed analysis of the docking calculations reveals that 5,8-disubstitution prohibits binding due to steric clashes of the 5-methyl group with the backbone atoms of AlaM260 and AlaM249. The experimentally determined binding free energies were reproduced with an rmsd of ,,4 kJ·mol,1 in most cases providing a valuable tool for the design of new artificial electron acceptors and inhibitors. [source] Novel polyketides synthesized with a higher plant stilbene synthaseFEBS JOURNAL, Issue 13 2001Hiroyuki Morita The physiological function of the stilbene synthase (STS) from groundnut (Arachis hypogaea) is the formation of resveratrol. The enzyme uses 4-coumaroyl-CoA, performs three condensations with malonyl-CoA, and folds the resulting tetraketide into a new aromatic ring system. We investigated the capacity for building novel and unusual polyketides from alternative substrates. Three types of products were obtained: (a) complete reaction (stilbene-type), (b) three condensations without formation of an aromatic ring (CTAL-type pyrone derailment), and (c) two condensations (BNY-type pyrone derailment). All product types were obtained from 4-fluorocinnamoyl-CoA and analogs in which the coumaroyl moiety was replaced by furan or thiophene. Only type (b) and (c) products were synthesized from other 4-substituted 4-coumaroyl-CoA analogs (-Cl, -Br, -OCH3). Benzoyl-CoA, phenylacetyl-CoA, and medium chain aliphatic CoA esters were poor substrates, and the majority of the products were of type (c). The results show that minor modifications can be used to direct the enzyme reaction to form a variety of different and new products. Manipulation of the biosynthesis of polyketides by synthetic analogs could lead to the development of a chemical library of pharmaceutically interesting novel polyketides. [source] Conjugated Polymer Based on Polycyclic Aromatics for Bulk Heterojunction Organic Solar Cells: A Case Study of Quadrathienonaphthalene Polymers with 2% EfficiencyADVANCED FUNCTIONAL MATERIALS, Issue 4 2010Shengqiang Xiao Abstract Polycyclic aromatics offer great flexibility in tuning the energy levels and bandgaps of resulting conjugated polymers. These features have been exploited in the recent examples of benzo[2,1- b:3,4- b']dithiophene (BDT)-based polymers for bulk heterojunction (BHJ) photovoltaics (ACS Appl. Mater. Interfaces2009, 1, 1613). Taking one step further, a simple oxidative photocyclization is used here to convert the BDT with two pendent thiophene units into an enlarged planar polycyclic aromatic ring,quadrathienonaphthalene (QTN). The reduced steric hindrance and more planar structure promotes the intermolecular interaction of QTN- based polymers, leading to increased hole mobility in related polymers. As-synthesized homopolymer (HMPQTN) and donor,acceptor polymer (PQTN - BT) maintain a low highest occupied molecular orbital (HOMO) energy level, ascribable to the polycyclic aromatic (QTN) moiety, which leads to a good open-circuit voltage in BHJ devices of these polymers blended with PCBM ([6,6]-phenyl-C61 -butyric acid methyl ester; HMPQTN: 0.76,V, PQTN - BT: 0.72,V). The donor,acceptor polymer (PQTN - BT) has a smaller optical bandgap (1.6,eV) than that of HMPQTN (2.0,eV), which explains its current (5.69,mA,cm,2) being slightly higher than that of HMPQTN (5.02,mA,cm,2). Overall efficiencies over 2% are achieved for BHJ devices fabricated from either polymer with PCBM as the acceptor. [source] Luminescence Properties of Aminobenzanthrones and Their Application as Host Emitters in Organic Light-Emitting Devices,ADVANCED FUNCTIONAL MATERIALS, Issue 3 2007M.-X. Yu Abstract A series of aminobenzanthrone derivatives, possessing a keto and an amino group on the aromatic ring, are synthesized and their photoluminescence (PL) and electroluminescence (EL) properties are studied in detail. These compounds emit strongly in solution and in the solid state, with the emission maxima in the range of 528,668,nm resulting from charge-transfer transitions from the amino group to the keto moiety. The emission wavelength depends greatly on the polarity of the solvent. A red shift of nearly 100,nm is observed from n -hexane to dichloromethane for each of these compounds. The PL quantum yields of these molecules also depend tremendously on the solvent. The values are between 88 and 70,% in n- hexane and decrease as the polarity of the solvent increases. The single-crystal X-ray diffraction data reveal that the aminobenzanthrone planes of these molecules stack in the crystals in an antiparallel head-to-tail fashion. This strong dipole,dipole interaction accounts for the observed red-shifted emissions of the aminobenzanthrone molecules in powders and in films relative to those in nonpolar solvents. Electroluminescent devices using aminobenzanthrone derivatives as the host emitters or dopants emit orange to red light in the range 590,645,nm. High brightness, current efficiency, and power efficiency are observed for some of these devices. For example, the device using N -(4- t -butylphenyl)- N -biphenyl-3-benzanthronylamine as the emitter gives saturated red light with a current efficiency of 1.82,cd,A,1, brightness of 11,253,cd,m,2, and Commission Internationale de l'Éclairage (CIE) coordinates of (0.64,0.36); the device using N -(2-naphthyl)- N -phenyl-3-benzanthronylamine as the emitter gives orange,red light with a current efficiency of 3.52,cd,A,1, brightness of 25,000,cd,m,2, and CIE coordinates of (0.61,0.38). [source] Sensitized Lanthanide-Ion Luminescence with Aryl-Substituted N -(2-Nitrophenyl)acetamide-Derived ChromophoresHELVETICA CHIMICA ACTA, Issue 11 2009Michael Andrews Abstract The syntheses of the two tetraazamacrocyclic ligands L1 and L2 bearing a [(methoxy-2-nitrophenyl)amino]carbonyl chromophore, i.e., an N -(methoxy-2-nitrophenyl)acetamide moiety, together with their corresponding lanthanide-ion complexes are described. A combined spectroscopic (UV/VIS, 1H-NMR), structural (X-ray), and theoretical (DFT) investigation revealed that the absorption properties of the chromophores were dictated by the extent of electronic delocalisation, which in turn was determined by the position of the MeO substituent at the aromatic ring. X-Ray crystallographic studies showed that when attached to the macrocycle, both isomeric forms of the N -(methoxy-2-nitrophenyl)acetamide unit can participate in coordination, via the CO, to an encapsulated potassium cation. Luminescence measurements confirmed that such a binding mode also exists in solution for the corresponding lanthanide complexes (q ca. ,1), with the para -MeO derivative allowing longer wavelength sensitization (,ex 330,nm). [source] Structure,Activity Relationship in the Domain of Odorants Having Marine NotesHELVETICA CHIMICA ACTA, Issue 7 2007Jean-Marc Gaudin Abstract We synthesized or re-synthesized a large series of 2H -1,5-benzodioxepin-3(4H)-ones 9 (Scheme,1), 4,5-dihydro-1-benzoxepin-3(2H)-ones 10 (Schemes 3 and 4) and 5,6,8,9-tetrahydro-7H -benzocyclohepten-7-ones 11 (Schemes 5 and 6), since the lead compound for the olfactory note of perfumes based on marine accords is a well-known benzodioxepinone named Calone 1951® (9b). We meticulously described the odor profile of each synthesized compound and discussed relevant structure,odor relationships (Tables,1,3). In particular, we revealed a correlation between the conformation of the seven-membered ring and the activities of these compounds (Table,4 and Fig.,3). We also clarified the effect of the position and the size of the alkyl substituent at the aromatic ring. [source] Rate coefficients for the gas-phase reaction of hydroxyl radicals with the dimethylbenzaldehydesINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 9 2006Grainne M. Clifford Rate coefficients for the reactions of hydroxyl (OH) radicals with the dimethylbenzaldehydes have been determined at 295 ± 2K and atmospheric pressure using the relative rate technique. Experiments were performed in an atmospheric simulation chamber using gas chromatography for chemical analysis. The rate coefficients (in units of cm3 molecule,1 s,1) are: 2,3-dimethylbenzaldehyde, (25.9 ± 2.8) × 10,12; 2,4-dimethylbenzaldehyde, (27.5 ± 4.4) × 10,12; 2,5-dimethylbenzaldehyde, (27.6 ± 5.1) × 10,12; 2,6-dimethylbenzaldehyde, (30.7 ± 3.0) × 10,12; 3,4-dimethylbenzaldehyde, (24.6 ± 4.0) × 10,12; and 3,5-dimethylbenzaldehyde, (28.2 ± 2.5) × 10,12. The reactivity of the dimethylbenzaldehydes is compared with other aromatic compounds and it is shown that the magnitude of the OH rate coefficients does not depend significantly on the position of the CH3 substituent on the aromatic ring. The rate coefficient data are explained in terms of known mechanistic features of the reactions and the atmospheric implications are also discussed. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 563,569, 2006 [source] Ring Expansion versus Cyclization in 4-Oxoazetidine-2- carbaldehydes Catalyzed by Molecular Iodine: Experimental and Theoretical Study in ConcertADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2010Benito Alcaide Abstract Molecular iodine (10,mol%) efficiently catalyzes the ring expansion of 4-oxoazetidine-2-carbaldehydes in the presence of tert -butyldimethylsilyl cyanide, or allylic and propargylic trimethylsilanes to afford protected 5-functionalized-3,4-dihydroxypyrrolidin-2-ones with good yield and high diastereoselectivity, through a C3C4 bond cleavage of the ,-lactam nucleus. Interestingly, in contrast to the iodine-catalyzed reactions of 3-alkoxy-,-lactam aldehydes which lead to the corresponding ,-lactam derivatives (rearrangement adducts), the reactions of 3-aryloxy-,-lactam aldehydes under similar conditions gave ,-lactam-fused chromanes (cyclization adducts) as the sole products, through exclusive electrophilic aromatic substitution involving the C3 aromatic ring and the carbaldehyde. In order to support the mechanistic proposals, theoretical studies have been performed. [source] Band gaps and the possible effect on impact sensitivity for some nitro aromatic explosive materialsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 7 2009Hong Zhang Abstract The first principle density functional theory method SIESTA has been used to compute the band gap of several polynitroaromatic explosives, such as TATB, DATB, TNT, and picric acid. In these systems, the weakest bond is the one between an NO2 group and the aromatic ring. The bond dissociation energy (BDE) alone cannot predicate the relative sensitivity to impact of these four systems correctly. It was found that their relative impact sensitivity could be explained by considering the BDE and the band gap value of the crystal state together. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] | |||||||||||||||||||||||||||||||||||||||||||