Papierchromatographische Trennung von 1- und 2-Aminoanthrachinon

Ohne Zusammenfassung     

Ring nitrogen functionalization of 2-aminothiazol-4-acetic acid derivatives. I. Synthesis and properties of novel 2-aminothiazole N-oxides

Cyclization of thiocyanomethylketone oximes with hydroxylamine hydrochloride and oxidation of 2-aminothiazole derivatives with peracids are shown to afford the same products, which can be formulated either as 2-imino-3-hydroxy-2,3-dihydrothiazolines or 2-aminothiazole N-oxides. Compounds of this type bearing at position 4 an acetic or α-oxyiminoacetic residue are useful synthons for highly active β-lactam antibiotics; the problems connected with their preparation in a suitably protected form are examined. Scope and limitations of this previously unreported oxidation of the thiazole nucleus are discussed. All the products show limited stability in alkaline media: the 4-acetic derivatives, in addition, undergo a transposition to afford 4-methylidenethiazolidines. Possible types of isomerism and tautomerism are discussed in the light of the acquired spectral data. The uv and ir spectra of the compounds synthesized lend support to their formulation as 2-aminothiazole N-oxides.     

E.S.R. of hydrazoxyl radicals: Evidence for conformational isomers.

Thermolysis of azocarboxylates has been investigated by e.s.r. Experimental evidence for the existence of conformational isomerism in acylnitroxides has been obtained.     

Polyoxotungstate photoinduced alkylation of electrophilic alkenes by cycloalkanes

Alkyl radical obtained by irradiation of tetrabutylammonium decatungstate in acetonitrile in the presence of cycloalkanes (C5H10, C6H12, C7H14) are efficiently trapped by electrophilic alkenes (acrylonitrile, isopropylydenmalonitrile, isopropylydencyanoacetate) to give the corresponding alkylated aliphatic nitriles. The reaction can be carried out up to complete conversion of the alkene with reasonable (in most cases 60-65 %) yields. Addition of the radicals to the alkene is followed by electron transfer from reduced decatungstate regenerating the sensitizer (turn over number up to 60). Steady-state measurements, EPR evidence, deuteration experiments and attempted intramolecular trapping of the adduct radical support the mechanistic proposal.     

Number-theoretic properties of certain CR mappings

We first prove a uniqueness result for certain group-invariant CR mappings to hyperquadrics. For cyclic groups these mappings lead to a collection of polynomials ƒ_p,q (with integer coefficients) in two variables; here p and q are positive integers. We use the uniqueness result to prove some surprising number-theoretic results about the ƒ_p,q, in particular, ƒ_p,q is congruent to x^P + y^P modulo (p) (for P ≥ 2) if and only if p is prime. We also determine recurrence relations for these polynomials for q ≤ 3 and determine a functional equation for a generating function. Finally, we discuss the invariant polynomials that arise for certain representations of dihedral groups to illustrate the non-Abelian case.     

A Singular Parabolic Boundary Value Problem in Weighted <Emphasis Type="Italic">L</Emphasis><Superscript><Emphasis Type="Italic">p</Emphasis></Superscript>-spaces

We consider the operator ${\cal A}$ formally defined by ${\cal A}u(x)=\alpha(x)\Delta u(x)$ for any $x$ in a sufficiently smooth bounded open set $\Om\subset\R^N$ ($N\ge 1$), where $\alpha\in C(\ov\Omega)$ is a continuous nonnegative function vanishing only on $\partial\Omega$, and such that $1/\alpha$ is integrable in $\Omega$. We prove that the realization $A_p$ of ${\cal A}$, equipped with suitable nonlinear boundary conditions is an m-dissipative operator in suitably weighted $L^p(\Omega)$-spaces in the case where either $(p,N)\in (1,+\infty)\times\{1\}$ or $(p,N)=\{2\}\times\N$. Moreover, we prove that $A_p$ is a densely defined closed operator. We consider nonlinear boundary conditions of the following type: in the one dimensional case we take $\Omega=(0,1)$ and we assume that $u(j)=(-1)^j\beta_j(u(j))$ ($j=0,1$), $\beta_0$ and $\beta_1$ being nondecreasing continuous functions in $\R$ such that $\beta_0(0)=\beta_1(0)=0$; in the $N$-dimensional setting we assume that $(D_{\nu}u)_{|\partial\Omega}=-\beta(u_{|\partial\Omega})$, $\beta$ being a nondecreasing Lipschitz continuous function in $\R$ such that $\beta(0)=0$. Here $\nu$ denotes the unit outward normal to $\partial\Om$.     

Emergence of linear wave segments and predictable traits in saturated nonlinear media

We find the key behind the existence traits of asymptotic saturated nonlinear optical solitons in the emergence of linear wave segments. These traits, produced by the progressive relegation of nonlinear dynamics to wave tails, allow a direct and versatile analytical prediction of self-trapping existence conditions and simple soliton scaling laws, which we confirm experimentally in saturated-Kerr self-trapping observed in photorefractives. This approach provides the means to correctly evaluate beam tails in the saturated regime, which is instrumental in the prediction of soliton interaction forces.     

Unexpected stereochemistry in the lithium salt catalyzed ring expansion of nonracemic oxaspiropentanes. formal syntheses of (-)-(4R,5R)-muricatacin and the pheromone (R)-japonilure

[reaction: see text] The stereochemistry of the cyclobutanones 3, obtained by lithium salt catalyzed ring expansion of the optically pure oxaspiropentanes 2, depends not only on the lithium salt but also on the stereochemistry of 2. They constitute the starting material for the syntheses of the acetogenin (-)-(4R,5R)-muricatacin and the pheromone (R)-japonilure.     

Coarse-grained probabilistic automata mimicking chaotic systems

Discretization of phase space usually nullifies chaos in dynamical systems. We show that if randomness is associated with discretization dynamical chaos may survive and be indistinguishable from that of the original chaotic system, when an entropic, coarse-grained analysis is performed. Relevance of this phenomenon to the problem of quantum chaos is discussed.