Experimental and Theoretical Mechanistic Study on the Thermal Decomposition of 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline

The present paper is a continuation of comprehensive study regarding to synthesis and properties of pyrazoles and their derivatives. In its framework an experimental and theoretical studies of thermal decomposition of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline were performed. It was found, that the decompositions of the mentioned pyrazoline system in the solution and at the melted state proceed via completely different molecular mechanisms. These mechanisms have been explained in the framework of the Molecular Electron Density Theory (MEDT) with the computational level of B3LYP/6-31G(d). A Bonding Evolution Theory (BET) examination of dehydrochlorination of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline permits elucidation of the molecular mechanism. It was found, that on the contrary for most known HCl extrusion processes in solution, this reaction is realised via single-step mechanism.     

Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel–Crafts/Bradsher Cyclization Reaction

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T_decomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S₁ state by molecular oxygen.     

The Polyakov path integral over bordered surfaces

Following the general scheme of the convariant path integral quantization of gauge systems, two alternative formulations of the first quantized closed bosonic string in a position representation are presented. In both approaches the covariant path integral representations of the propagator and of the higher order off-shell amplitudes are constructed. For a wide class of gauges the explicit formulae for off-shell amplitudes are obtained. This paper is the continuation of our previous work where the corresponding problems in the open string case were considered [20].     

Generalized Einstein conditions on holomorphic Riemannian manifolds

Summary At first, a necessary and sufficient condition for a K?hler-Norden manifold to be holomorphic Einstein is found. Next, it is shown that the so-called (real) generalized Einstein conditions for K?hler-Norden manifolds are not essential since the scalarcurvature of such manifolds is constant. In this context, we study generalized holomorphic Einstein conditions. Using the one-to-one correspondence between K?hler-Norden structures and holomorphic Riemannian metrics, we establish necessary and sufficient conditions for K?hler-Norden manifolds to satisfy the generalized holomorphic Einstein conditions. And a class of new examples of such manifolds is presented. Finally, in virtue of the obtained results, we mention that Theorems 1 and 2 of H. Kim and J. Kim [10] are not true in general.     

Fibres of width 3 ordered sets

We show that in an ordered setP of width 3 there always exists a fibre (i.e., a subset intersecting each maximal nontrivial antichain) of size at most 11/18|P|. This improves previously known results.Research supported by Polish KBN Grant 2 2037 92 03.