Competing Pathways in the Photogeneration of Didehydrotoluenes from (Trimethylsilylmethyl)aryl Sulfonates and Phosphates

The scope of the photochemical generation of α,n‐didehydrotoluene diradicals from aryl sulfonates and phosphates and their chemistry are explored. The thermally inaccessible α,2‐ and α,4‐ intermediates are efficiently obtained by irradiation of ortho‐ and para‐(trimethylsilylmethyl)phenyl triflates through heterolytic splitting of the ester anion from the substrate in the triplet state. Triplet phenyl cations are formed and the loss of trimethylsilyl cation from them affords the desired diradicals (³Me₃SiCH₂C₆H₄‐OZ→³Me₃SiCH₂C₆H₄⁺→ ^? CH₂C₆H₄ ^? ). Triplet sensitization is required, for which acetone is used throughout. Direct irradiation leads, on the contrary, to photo‐Fries fragmentation (¹Me₃SiCH₂C₆H₄O‐Z→Me₃SiCH₂C₆H₄O ^? +Z ^? ). With mesylates, where ester cleavage is less convenient, a further competition from the triplet is direct desilylation. Didehydrotoluenes are also obtained from the corresponding phosphates, although with poor efficiency.     

聚芳醚酮类聚合物晶体结构醚酮等效性的研究

半结晶的聚芳醚酮类聚合物 ( PAEKs)因其性能优异而在机械、航天等高技术领域中得到广泛应用 .有关其晶体结构的研究亦有许多文献报道[1～ 11] ,而醚基与酮基在晶体结构方面是否等效一直存在争议 .虽然醚酮等效性的观点已被广泛接受 [4～ 8] ,但对于聚合物主链中含联苯基团的 PAEKs的醚酮等效性的研究则复杂得多 .文献 [1 ]报道醚酮等效性在主链含有联苯基团时不再成立 .本文首次发现醚酮等效性在主链含有联苯基团时在适当条件下仍可成立 ,并对聚芳醚酮类聚合物晶体结构的醚酮等效性问题进行了系统阐述 .1　实验部分　　样品联苯聚醚酮 …     

Shear-induced Stabilization of the Nematic Phase in a Side Group-containing Poly (aryl ether ketone) Copol ymer

IntroductionPolarized optical microscopes (POM) are commonly used to identify liquid crystalline tex-tures. However, it is often found problematic to employ this technique in investigating themesophase transition of polymeric materials due to their higher viscosities. Rheological mea-surements at this juncture could provide us with valuable information about the mesophase- transition of liquid crystalline polymers[1]. Accordingly, there have been some rheological in-vestigations reported on …     

Disorder in condensed matter systems: proton spin lattice relaxation study of the mixed systems of betaine phosphate and glycine phosphite, BPxGPI(1-x)

Proton NMR relaxation measurements have been carried out in the mixed system of antiferroelectric (AFE) betaine phosphate (BP) and ferroelectric (FE) glycine phosphite (GPI), BPxGPI(1-x), at 11.4 and 23.3 MHz from 300 to 100 K for x=0.3, 0.4, 0.5, 0.6, 0.7 and 0.8. The temperature dependence of spin lattice relaxation (SLR) time follows the BPP model in the parent compounds, while the Larmor frequency dependence of T1 in the mixed system is rather unusual. The T1 curve exhibits different slopes for the low-temperature wings at the two frequencies, which is a clear experimental evidence of the presence of different methyl groups with different activation energies (Ea), indicating disorder. For x=0.3 and 0.4, biexponential recovery of magnetization has been observed below 190 K, showing that the degree of disorder varies with the concentration. The temperature dependence of relaxation time data has been interpreted in terms of NH3, trimethyl ammonium and methyl group reorientations.     

Characterizations of self-combustion reactions (SCR) for the production of nanomaterials used as advanced cathodes in Li-ion batteries

In this work, self-combustion reactions (SCR) for the preparation of important cathode materials for rechargeable Li-ion batteries were investigated by thermal analytical tools (DSC, ARC, TGA), electron microscopy, XRD, various spectroscopies (MS, Raman, FTIR) and elemental analysis by ICP. The systems studied include solutions containing metal nitrates at the right stoichiometry and sucrose as a fuel, for the preparation of LiMn_0.5Ni_0.5O₂ (layered), LiMn_1.5Ni_0.5O₄ (spinel), LiMn_0.33Ni_0.33Co_0.33O₂ (layered), and LiMn_0.4Ni_0.4Co_0.2O₂ (layered). Similar products, which do not depend on the atmosphere of the processes (air or inert) were obtained by spontaneous SCR and the gradual heating of the same solutions by DSC, ARC, and TGA. The reactions involve the partial caramelization of sucrose, complicated by red-ox reactions with the nitrates that form solid products, whose organic part is finally decomposed around 400 °C. The presence of cobalt ions has a stabilizing effect, which is expressed by the low dissolution rates of Li ions from the solid products thus formed, into aqueous solutions. The reaction mechanisms are discussed herein.     

Oscillatory reactions in the lactic acid/acidic bromate system with a tetraazamacrocyclic nickel(ii) complex as catalyst

Summary  Vezetéknév     

Preparation,characterization and catalytic activity of a nano-Co(II)-catalyst as a high efficient heterogeneous catalyst for the selective oxidation of ethylbenzene,cyclohexene, and benzyl alcohol

This paper reports the preparation of a nano-Co(II)-catalyst (NCC) by anchoring of Co ions on immobilized bipyridylketone over the nano-sized SiO₂/Al₂O₃ mixed oxides. The nano-Co(II)-catalyst has been characterized by elemental analysis, BET, FT-IR, DR UV–vis and SEM. The catalytic activity of the catalyst towards the oxidation of ethylbenzene, cyclohexene, and benzylalcohol to different chemically and pharmaceutically important products were evaluated with tert-butyl hydroperoxide (TBHP) in the absence of solvent. Under optimized conditions, the nano-catalyst proved highly selective towards the acetophenone, 2-cyclohexene-1-one and benzaldehyde as reaction products, with excellent conversion rates.     

The high temperature transition of polyethylene into a Condis phase,described on the basis of the cluster-entropy hypothesis (CEH)

On the basis of atomistic calculations a rotator model of the high temperature Condis phase of polyethylene is proposed. Its cooperative statistical treatment (using CEH for the lateral packing of chains) explains the first order transition from the all-trans crystal as well as the transition dataT _t ,S _t ,V _t . We found that the normal melting (i. e. at pressures below the triple point) is also governed by the onset of the Condis phase.This abbreviation was introduced by B. Wunderlich [1], to describe conformationally disordered oligomer or polymer crystals.Dedicated to Professor Dr. R. Kosfeld on the occasion of his 60th birthday.     

Tandem oxidative isocyanide-based cycloaddition reactions in the presence of MIL-101(Cr) as a reusable solid catalyst

The tandem oxidative three-component synthesis of two types of the heterocycles such as furans and imidazopyridines, via isocyanides [1+4] cycloaddition reactions in the presence of MIL-101(Cr) under aerobic conditions are reported. When the 4-toluenesulfonylmethyl isocyanide was used, an unexpected [3+2] cycloaddition reaction of isocyanides with aldehydes accomplished and dihydrophenyloxazoles and phenyloxazoles produced. These syntheses were successfully carried out using a wide scope of the substrates.     

PEG350-based di-(2-pyridyl)methylamine as a ligand in the Pd-catalyzed water Suzuki-Miyaura reaction of aryl chlorides

The synthesis of new hydrosoluble PEG-based ligand derived from di-(2-pyridyl)methylamine has been developed. The catalytic performance of this ligand is demonstrated in Suzuki-Miyaura reactions between aryl chlorides and arylboronic acids and using water as solvent.     

Catalytic activity of Mn(III) and Fe(III) complexes of meso-tetra(n-propyl)porphyrin in oxidation of olefins: Meso-alkyl substituent in comparison with the alkenyl and aryl ones

Catalytic activity of Mn(III) and Fe(III) complexes of meso-tetra(n-propyl)porphyrin, MnT(n-Pr)P(X) and FeT(n-Pr)P(X) (X = Cl, SCN, OAc) in oxidation of olefins with tetra-n-butylammonium periodate at room temperature has been studied. The influence of different parameters including the molar ratio of catalyst to imidazole, type of counter ion (X) and oxidative stability of metalloporphyrins on the efficiency of the catalysts was investigated. The results of competitive oxidation of cis- and trans-stilbene suggest the presence of a high-valent Mn-oxo as the predominant oxidant species in equilibrium with a six coordinate complex, MnT(n-Pr)P(ImH)(IO₄) in the case of MnT(n-Pr)P(OAc). An unusual preference for trans-stilbene over cis-stilbene was observed in the reaction catalyzed by FeT(n-Pr)P(OAc). Control reaction indicated a significant cis- to trans-isomerization (81%) in oxidation of cis-stilbene catalyzed by FeT(n-Pr)P(OAc) which may explain the observed unusual cis to trans-stilbene oxide ratio. While oxidation of cyclooctene and styrene led to the exclusive formation of the corresponding epoxides, oxidation of cyclohexene gave 2-cyclohexe-1-ol and cyclohexene oxide as the products. However, the results of this study clearly demonstrate the key role played by the group substituted at the meso positions of metalloporphyrins on their catalytic activity, apart from the electron-donating or electron-withdrawing properties of the substituents.     

Oxidative decarboxylation of cyclohexanecarbaldehyde in the presence of cyclooctane catalyzed by a binculear manganese(IV) complex

On heating, a Mn^IV complex initiates oxidation of cyclohexanecarbaldehyde with atmospheric oxygen in MeCN resulting in the formation of cyclohexanecarboxylic acid and considerable amounts of oxidative decarboxylation products (cyclohexane, cyclohexanol, and cyclohexanone). Cyclooctanol and cyclooctanone are also formed in the presence of cyclooctane. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2385–2387, November, 1998.     

Spectroscopy of Ru(II) polypyridyl complexes used as intercalators in DNA: Towards a theoretical study of the light switch effect

The absorption spectroscopy of [Ru(phen)₂dppz]²⁺ and [Ru(tap)₂dppz]²⁺ (phen = 1,10-phenanthroline, tap = 1,4,5,8-tetraazaphenanthrene; dppz = dipyridophenazine) complexes used as molecular light switches by intercalation in DNA has been analysed by means of Time-Dependent Density Functional Theory (TD-DFT). The electronic ground state structures have been optimized at the DFT (B3LYP) level of theory. The absorption spectra are characterized by a high density of excited states between 500 nm and 250 nm. The absorption spectroscopy of [Ru (phen)₂dppz]²⁺ in vacuum is characterized by metal-to-ligand-charge-transfer (MLCT) transitions corresponding to charge transfer from Ru(II) either to the phen ligands or to the dppz ligand with a strong MLCT () absorption at 411 nm. In contrast, the main feature of the lowest part of the vacuum theoretical spectrum of [Ru(tap)₂dppz]²⁺ between 522 nm and 400 nm is the presence of various excited states such as MLCT (), ligand-to-ligand-charge-transfer LLCT () or intra-ligand IL () states. When taking into account solvent corrections within the polarizable continuum model (PCM) approach (H₂O, CH₃CN) the absorption spectrum of [Ru(tap)₂dppz]²⁺ is dominated by a strong absorption at 388 nm (CH₃CN) or 390 nm (H₂O) assigned to a ¹IL () corresponding to a charge transfer from the outside end of the dppz ligand to the site of coordination to Ru(II). These differences in the absorption spectra of the two Ru(II) complexes have dramatic effects on the mechanism of deactivation of these molecules after irradiation at about 400 nm. In particular, the electronic deficiency at the outside end of the dppz ligand created by absorption to the ¹IL state will favour electron transfer from the guanine to the Ru(II) complex when it is intercalated in DNA.     

One-pot synthesis of aryl alkyl thioethers and diaryl disulfides using carbon disulfide as a sulfur surrogate in the presence of diethylamine catalyzed by copper(I) iodide in polyethylene glycol (PEG200)

A copper catalyzed one-pot protocol for the preparation of aryl alkyl thioethers and diaryl disulfides using carbon disulfide as the sulfur source and diethylamine in polyethylene glycol (PEG200) is described.     

Carbon monoxide as a reagent: A report on the role of N-heterocyclic carbene (NHC) ligands in metal-catalyzed carbonylation reactions

This report is a focused and critical essay on the effectiveness of M–NHC catalysts in reactions that specifically utilize carbon monoxide as a C1-carbon source. NHC ligands are touted as excellent trialkylphosphine (PR₃) mimics and are purported to improve existing phosphine based catalysts. One premise for using NHCs is that the need for excess ligand could be obviated in certain reactions. If true, then reactions involving CO as a reagent should be improved when a M–NHC complex is employed. Herein is a compilation of results that feature CO as a reagent in reactions such as: hydroformylation, hydroaminomethylation, carbonylation of aryl halides, oxidative carbonylation of amino and phenolic compounds, and the copolymerization of alkenes and CO. The aim of the report is to highlight reactions in which the ancillary NHC ligand is beneficial, detrimental, ineffective, or inconclusive in promoting the desired chemistry.     

Ion-pair formation in the ionic liquid 1-ethyl-3-methylimidazolium bis(triflyl)imide as a function of temperature and concentration.

The structures and ion-pair formation in the ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide are studied by a combination of FTIR measurements and DFT calculations. We could clearly distinguish imidazolium cations that are completely H-bonded to anions from those that are single H-bonded in ion pairs. Ion-pair formation already occurs in the neat IL and rises with temperature. Ion-pair formation is strongly promoted by dilution of the IL in chloroform. In these weakly polar environments ion pairs H-bonded via C(2)H are strongly favored over those H-bonded via C(4,5)H. This finding is in agreement with DFT (gas phase) calculations, which show a preference for ion pairs H-bonded via C(2)H as a result of the acidic C(2)H bond.     

Co2(CO)8 as a convenient in situ CO source for the direct synthesis of benzamides from aryl halides (Br/I) via aminocarbonylation

A fast, mild, and functional group tolerant method for the direct synthesis of benzamides from aryl halides (Br, I) via aminocarbonylation, using solid Co₂(CO)₈ as a convenient CO source, has been demonstrated. The developed method is applicable to a wide variety of 1° and cyclic and acyclic 2° amines. Nitro substituted (o, m and p) aryl halides have easily been converted to the corresponding benzamides, without the reduction of the nitro group, in high yields using this in situ carbonylation methodology under microwave irradiation.