Stereochemical Analysis of an Aromatic Triplet Di-π-methane Rearrangement

It is shown that (−)-(S)-N,N-dimethyl-2-(1′-methylallyl)aniline ((−)-(S)- 4 ), on direct irradiation in MeCN at 20°, undergoes in its lowest-lying triplet state an aromatic di-π-methane (ADPM) rearrangement to yield (−)-(1′R,2′R)- and (+)-(1′R,2′S)-N,N-dimethyl-2-(2-methylcyclopropyl)aniline ((−)-trans- and (+)-cis- 7 ) in an initial trans/cis ratio of 4.71 ± 0.14 and in optical yields of 28.8 ± 5.2% and 15 ± 5%, respectively. The ADPM rearrangement of (−)-(S)- 4 to the trans- and cis-configurated products occurs with a preponderance of the path leading to retention of configuration at the pivot atom (C(1′) in the reactant and C(2′) in the products) for (−)-trans- 7 and to inversion of configuration for (+)-cis- 7 , respectively. The results can be rationalized by assuming reaction paths which involve the occurrence of discrete 1,4- and 1,3-diradicals (cf. Schemes 10, 12, and 13). A general analysis of such ADPM rearrangements which allows the classification of these photochemical reactions in terms of borderline cases is presented (Scheme 14). It is found that the optical yields in these ‘step-by-step’ rearrangements are determined by the first step, i.e. by the disrotatory bond formation between C(2) of the aromatic moiety and C(2′) of the allylic side chain leading to the generation of the 1,4-diradicals. Moderation of the optical yields can occur in the ring closure of the 1,3-diradicals to the final products, which may take place with different trans/cis-ratios for the individual 1,3-diradicals. Compounds (−)-trans- 7 as well as (+)-cis- 7 easily undergo the well-known photochemical trans/cis-isomerization. It mainly leads to racemization. However, a small part of the molecules shows trans/cis-isomerization with inversion of configuration at C(1′), which is best explained by a photochemical cleavage of the C(1′)–C(3′) bond.     

A novel (E,E)-dioxime and its mono-, di- and trinuclear complexes bearing tetradentate octyl sulfanyl phenylamino substituents. Synthesis,characterization and electrochemical properties of its transition metal complexes

A new vic-dioxime, 13,14-bis-(hydroxyimino)-9,12,15,18-diazadithiaoctacosane, has been synthesized from 2-octylsulfanylaminobenzene and (E,E)-dichloroglyoxime. Mononuclear transition metal complexes of Ni^II, Cu^II, Co^II and Fe^II have been prepared and were found to have a metal–ligand ratio of 1:2. The synthesis of di- and trinuclear complexes was achieved with U^IVO₂ and Cu^II depending on the stoichiometry of the reactants. The complexes were characterized by elemental analysis, ¹H-n.m.r., u.v.–vis, i.r., f.a.b.-m.s. and by cyclic voltammetry.     

Phenolic compounds from the aerial parts of Clematis viticella L. and their in vitro anti-inflammatory activities*

Phytochemical investigations on the EtOH extract of Clematis viticella led to the isolation of six flavonoid glycosides, isoorientin (1), isoorientin 3′-O-methyl ether (2), quercetin 7-O-α-L-rhamnopyranoside (3), quercetin 3,7-di-O-α-L-rhamnopyranoside (4), manghaslin (5) and chrysoeriol 7-O-β-D-glucopyranoside (6), one phenylethanol derivative, hydroxytyrosol (7), along with three phenolic acids, caffeic acid (8), (E)-p-coumaric acid (9) and p-hydroxybenzoic acid (10). The structures of the isolates were elucidated on the basis of NMR and HR-MS data. All compounds were isolated from C. viticella for the first time. Compounds 7 and 8 showed significant anti-inflammatory activity at 100 μM by reducing the release of NO in LPS-stimulated macrophages comparable to positive control indomethacin. Compounds 3 and 7 exhibited anti-inflammatory activity through lowering the levels of TNF-α while 1, 3 and 5 decreased the levels of neopterin better than the positive controls.     

A boundary-value problem for Hamilton-Jacobi equations in hilbert spaces

We study a Hamilton-Jacobi equation in infinite dimensions arising in optimal control theory for problems involving both exit times and state-space constraints. The corresponding boundary conditions for the Hamilton-Jacobi equation, of mixed nature, have been derived and investigated in [19], [2], [5], and [15] in the finite-dimensional case. We obtain a uniqueness result for viscosity solutions of such a problem and then prove the existence of a solution by showing that the value function is continuous.The work of P. Cannarsa was partially supported by the Italian National Project Equazioni Differenziali e Calcolo delle Variazioni. H. M. Soner's work was supported by National Science Foundation Grant DMS-90-02249.     

Die Sechseck-n-Waben in der Ebene,welche von n Kreisbüscheln erzeugt werden

In this paper, the problem of determining the pencils of circles which form a hexagonal n-web in E₂, is completely solved. It is well-known that n pencils of circles orthogonal to a fixed circle form a hexagonal n-web. Therefore, the main problem is the determination of all circle pencils which form a hexagonal n-web and which do not cut a fixed circle orthogonally. In this connection the following results have been obtained: The number of hexagonal 4-webs is six, whereas the number of hexagonal 5-webs is two.Finally, after having proved that the number of hexagonal 6-webs is one, it is shown that, for n7, there exist no circle pencils forming a hexagonal n-web without being orthogonal to a fixed circle.     

Immobilization of Mercuric reductase from aPseudomonas putida strain on different activated carriers

Mercuric reductase was isolated fromPseudomonas putida KT2442::mer-73 and immobilized on Chromatographic carriers activated by various methods. The immobilization methods for covalent coupling were compared with regard to preservation of enzymatic activity and coupling yields. Highest yields were obtained with carriers bearing the most reactive functional groups. Best results were achieved with tresyl chloride-activated carriers. The optimum binding conditions were found at pH 8. Application of the immobilized mercuric reductase for continuous treatment of Hg(II)-containing water was examined in a fixed bed reactor. Space-time yields up to 510 nmol/min-mL were attained. The kinetics of immobilized enzyme systems were not diffusion-controlled.     

Crystal structure of an unsymmetrical Schiff base, immobilization of its cobalt and manganese complexes on a silica support, and catalytic studies

An unsymmetrical tetradentate Schiff base (H₂L) was synthesized by the reaction of 3-methoxysalicylaldehyde, o-phenylenediamine, and salicylaldehyde in EtOH. H₂L was characterized by single-crystallographic X-ray analysis. Its Co(II) and Mn(III) complexes ([CoL] and [MnLCl]) were prepared and immobilized on 3-aminopropyltriethoxysilane functionalized silica gel. The immobilized materials were found to be efficient catalysts for epoxidation of styrene in the presence of tert-BuOOH in acetonitrile at 40 °C. The catalysts can be reused several times without significant loss of performance.     

Synthesis,characterization and catalytic activity of peripherally tetra‐substituted Co(II) phthalocyanines for cyclohexene oxidation

New 3,3‐diphenylpropoxyphthalonitrile (5) was obtained from 3,3‐diphenylpropanol (3) and 4‐nitrophthalonitrile (4) with K₂CO₃ in DMF at 50 °C. The novel cobalt(II) phthalocyanine complexes, tetrakis‐[2‐(1,4‐dioxa‐8‐azaspiro[4.5]dec‐8‐yl)ethoxy] phthalocyaninato cobalt(II) (2) and tetrakis‐(3,3‐diphenylpropoxy)phthalocyaninato cobalt(II) (6) were prepared by the reaction of the phthalonitrile derivatives 1 and 5 with CoCl₂ by microwave irradiation in 2‐(dimethylamino)ethanol for at 175 °C, 350 W for 7 and 10 min, respectively. These new cobalt(II)phthalocyanine complexes were characterized by spectroscopic methods (IR, UV–visible and mass spectroscopy) as well as elemental analysis. Complexes 2 and 6 are employed as catalyst for the oxidation of cyclohexene using tert‐butyl hydroperoxide (TBHP), m‐chloroperoxybenzoic acid (m‐CPBA), aerobic oxygen and hydrogen peroxide (H₂O₂) as oxidant. It is observed that both complexes can selectively oxidize cyclohexene to give 2‐cyclohexene‐1‐ol as major product, and 2‐cyclohexen‐1‐one and cyclohexene oxide as minor products. TBHP was found to be the best oxidant since minimal destruction of the catalyst, higher selectivity and conversion were observed in the products. Copyright © 2012 John Wiley & Sons, Ltd.