Chemisorption Synthesis of the Ion-Polymeric Heteronuclear Gold(III)–Bismuth(III) Complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9])n Based on [Bi2{S2CN(C3H7)2}6]: 13C MAS NMR,Supramolecular Structure,and Thermal Behavior

Russian Journal of Coordination Chemistry - Chemisorption synthesis on the basis of the binuclear compound [Bi2{S2CN(C3H7)2}6] (I) and preparative isolation of the ion-polymeric heteronuclear...     

Structural Conformation of a Novel Piperidine-4-One Derivative: 1-Acryloyl-3-Methyl-2,6-Dip-Tolylpiperidine-4-One

Abstract  

The novel 3-methyl-2,6-dip-toylpiperidine-4-one was acylated by 3-chloropropanoychloride and subjected for dehydrohalogenation. The synthesized compound was characterized by spectroscopic techniques and finally confirmed by X-ray diffraction studies. The molecule crystallizes in the monoclinic crystal class in the space group C ₂/c with cell parameters a = 18.538(2) ?, b = 9.9050(1) ?, c = 22.954(2) ?, β = 94.486(8)° and Z = 8. The piperidine ring adopts a twist boat conformation.     

Existence and Limiting Behavior of Trajectories Associated with P0-equations

Given a continuous P₀-function F : Rⁿ Rⁿ, we describe a method of constructing trajectories associated with the P₀-equation F(x) = 0. Various well known equation-based reformulations of the nonlinear complementarity problem and the box variational inequality problem corresponding to a continuous P₀-function lead to P₀-equations. In particular, reformulations via (a) the Fischer function for the NCP, (b) the min function for the NCP, (c) the fixed point map for a BVI, and (d) the normal map for a BVI give raise to P₀-equations when the underlying function is P₀. To generate the trajectories, we perturb the given P₀-function F to a P-function F(x, ); unique solutions of F(x, ) = 0 as varies over an interval in (0, ) then define the trajectory. We prove general results on the existence and limiting behavior of such trajectories. As special cases we study the interior point trajectory, trajectories based on the fixed point map of a BVI, trajectories based on the normal map of a BVI, and a trajectory based on the aggregate function of a vertical nonlinear complementarity problem.     

Kinetic and mechanistic studies of oxidation of arginine,histidine, and threonine in alkaline medium by N-chloro-N-sodio-p-toluenesulfonamide

The kinetics of oxidation of arginine, histidine, and threonine by chloramine-T (CAT) have been investigated in alkaline medium at 35°C. The rates are first order in both [CAT] and [amino acid] and inverse fractional order in [OH^?] for arginine and histidine. The rate is independent of [OH^?] for threonine. Variation of ionic strength and addition of the reaction product, p-toluenesulfonamide, or Cl^? ions had no effect on the rate. A decrease of the dielectric constant of the medium by adding methanol decreased the rate with arginine, while the rates increased with histidine and threonine. The solvent isotope effect was studied using D₂O. (k_obs)/(k_obs) was found to be 0.55 and 0.79 for arginine and histidine, respectively. The reactions were studied at different temperatures, and activation parameters have been computed. The oxidation process in alkaline medium, under conditions employed in the present investigations, has been shown to proceed via two paths, one involving the interaction of RNHCl (formed rapidly from RNCl^?), with the amino acid in a slow step to form monochloroamino acid, which subsequently interacts with another molecule of RNHCl in a fast step to give the products, p-toluenesulfonamide (RNH₂), and the corresponding nitrile of the amino acid (R'CN). The other path involves the interaction of RNCl^? with the amino acid in a similar way to give RNH₂ and R'CN. Mechanisms proposed and the derived rate laws are consistent with the observed kinetics. The rate constants predicted using the derived rate laws, as [OH^?] varies, are in excellent agreement with the observed rate constants, thus justifying these rate laws and hence the proposed mechanistic schemes.     

Hopf-Lax type formula for non monotonic autonomous Hamilton Jacobi equations

We give an explicit formula for a solution of Hamilton-Jacobi equation u_t+H(u,Du)=0 in with initial condition u(x,0)=u₀(x), where p H(u,p) is convex, positively homogeneous of degree one and the Hamiltonian H need not satisfy the monotonicity condition in u.     

A concise synthetic strategy to functionalized chromenones via [5+1] heteroannulation and facile C-N/C-S/C-O bond formation with various nucleophiles

A highly efficient strategy to 2,3-substituted chromen-4H-ones has been developed. The methodology involves unexpected intramolecular heteroannulation of readily accessible substituted 2-hydroxy-ω-nitroacetophenone with carbon disulfide in the presence K₂CO₃ followed by methylation with methyl iodide. These chromenones were further reacted with various nucleophiles such as amines, thiols, and alkoxide resulting in the facile C-N, C-S, and C-O bond formation. The scope and generality have been discussed.     

Errata: On semidefinite linear complementarity problems

We correct an error in the statement of Theorem 8 in [1]. Received: January 3, 2001 / Accepted: February 26, 2001?Published online May 18, 2001