Zur Kenntnis der Reaktionsfähigkeit des unsubstituierten Thiomorpholins und alkylsubstituierter Thiomorpholine. 3. Mitt

A new synthesis of thiomorpholine by ring closure of -chloro--aminodiethylene-sulfide with potassium hydroxide is reported. Numerous reactions of thiomorpholine (1) and, especially, 2-methyl-3-ethyl-thiomorpholine (2) are described such as acylation, diacylation (3–43), reactions with sulfonic acid chlorides (44–52), isocyanates (53–61, 70–75), diisocyanates (62–66, 76–78) and isothiocyanates (67–69, 79–82), alkylation reactions (83–111) and the synthesis of thiomorpholino-dithiocarbamates (112–121).

Teil der Dissertation,E. Wilms, Techn. Hochschule Aachen, 1971.     

Singularity-Free Two-Body Equation with Confining Interactions in Momentum Space

We are developing a covariant model for all mesons that can be described as quark-antiquark bound states in the framework of the Covariant Spectator Theory (CST) in Minkowski space. The kernel of the bound-state equation contains a relativistic generalization of a linear confining potential which is singular in momentum space and makes its numerical solution more difficult. The same type of singularity is present in the momentum-space Schrödinger equation, which is obtained in the nonrelativistic limit. We present an alternative, singularity-free form of the momentum-space Schrödinger equation which is much easier to solve numerically and which yields accurate and stable results. The same method will be applied to the numerical solution of the CST bound-state equations.     

Index theory for boundary value problems via continuous fields of -algebras

We prove an index theorem for boundary value problems in Boutet de Monvel's calculus on a compact manifold X with boundary. The basic tool is the tangent semi-groupoid generalizing the tangent groupoid defined by Connes in the boundaryless case, and an associated continuous field of C^*-algebras over [0,1]. Its fiber in =0, , can be identified with the symbol algebra for Boutet de Monvel's calculus; for ≠0 the fibers are isomorphic to the algebra of compact operators. We therefore obtain a natural map . Using deformation theory we show that this is the analytic index map. On the other hand, using ideas from noncommutative geometry, we construct the topological index map and prove that it coincides with the analytic index map.     

Temperature dependent thermodynamic model of the system H(+)-NH₄(+)-Na(+)-SO₄²⁻-NO₃⁻-Cl⁻-H₂O

A thermodynamic model of the system H(+)-NH?(+)-Na(+)-SO?2?-NO??-Cl?-H?O is parametrized and used to represent activity coefficients, equilibrium partial pressures of H?O, HNO?, HCl, H?SO?, and NH?, and saturation with respect to 26 solid phases (NaCl(s), NaCl·2H?O(s), Na?SO?(s), Na?SO?·10H?O(s), NaNO?·Na?SO?·H?O(s), Na?H(SO?)?(s), NaHSO?(s), NaHSO?·H?O(s), NaNH?SO?·2H?O(s), NaNO?(s), NH?Cl(s), NH?NO?(s), (NH?)?SO?(s), (NH?)?H(SO?)?(s), NH?HSO?(s), (NH?)?SO?·2NH?NO?(s), (NH?)?SO?·3NH?NO?(s), H?SO?·H?O(s), H?SO?·2H?O(s), H?SO?·3H?O(s), H?SO?·4H?O(s), H?SO?·6.5H?O(s), HNO?·H?O(s), HNO?·2H?O(s), HNO?·3H?O(s), and HCl·3H?O(s)). The enthalpy of formation of the complex salts NaNH?SO?·2H?O(s) and Na?SO?·NaNO?·H?O(s) is calculated. The model is valid for temperatures < or approximately 263.15 up to 330 K and concentrations from infinite dilution to saturation with respect to the solid phases. For H?SO?-H?O solutions the degree of dissociation of the HSO?? ion is represented near the experimental uncertainty over wide temperature and concentration ranges. The parametrization of the model for the subsystems H(+)-NH?(+)-NO??-SO?2?-H?O and H(+)-NO??-SO?2?-Cl?-H?O relies on previous studies (Clegg, S. L. et al. J. Phys. Chem. A 1998, 102, 2137-2154; Carslaw, K. S. et al. J. Phys. Chem. 1995, 99, 11557-11574), which are only partly adjusted to new data. For these systems the model is applicable to temperatures below 200 K, dependent upon liquid-phase composition, and for the former system also to supersaturated solutions. Values for the model parameters are determined from literature data for the vapor pressure, osmotic coefficient, emf, degree of dissociation of HSO??, and the dissociation constant of NH? as well as measurements of calorimetric properties of aqueous solutions like enthalpy of dilution, enthalpy of solution, enthalpy of mixing, and heat capacity. The high accuracy of the model is demonstrated by comparisons with experimentally determined mean activity coefficients of HCl in HCl-Na?SO?-H?O solutions, solubility measurements for the quaternary systems H(+)-Na(+)-Cl?-SO?2?-H?O, Na(+)-NH?(+)-Cl?-SO?2?-H?O, and Na(+)-NH?(+)-NO??-SO?2?-H?O as well as vapor pressure measurements of HNO?, HCl, H?SO?, and NH?.     

Benefits and Detriments of Gadolinium from Medical Advances to Health and Ecological Risks

Gadolinium (Gd)-containing chelates have been established as diagnostics tools. However, extensive use in magnetic resonance imaging has led to increased Gd levels in industrialized parts of the world, adding to natural occurrence and causing environmental and health concerns. A vast amount of data shows that metal may accumulate in the human body and its deposition has been detected in organs such as brain and liver. Moreover, the disease nephrogenic systemic fibrosis has been linked to increased Gd³⁺ levels. Investigation of Gd³⁺ effects at the cellular and molecular levels mostly revolves around calcium-dependent proteins, since Gd³⁺ competes with calcium due to their similar size; other reports focus on interaction of Gd³⁺ with nucleic acids and carbohydrates. However, little is known about Gd³⁺ effects on membranes; yet some results suggest that Gd³⁺ interacts strongly with biologically-relevant lipids (e.g., brain membrane constituents) and causes serious structural changes including enhanced membrane rigidity and propensity for lipid fusion and aggregation at much lower concentrations than other ions, both toxic and essential. This review surveys the impact of the anthropogenic use of Gd emphasizing health risks and discussing debilitating effects of Gd³⁺ on cell membrane organization that may lead to deleterious health consequences.     

Efficient Asymmetric Synthesis of Pumiliotoxin C via Intramolecular [4+2] Cycloaddition

An efficient asymmetric synthesis in nine steps of natural (−)‐pumiliotoxin C ( 1 ), a decahydroquinoline alkaloid found in the skin of Central American frog species, is presented. The enantiomerically pure starting material (S)‐norvalinol ( 3 ), obtained from commercial (S)‐norvaline, was cyclized in a one‐pot procedure to the tosylated aziridine 5 . Ring opening with propargylmagnesium bromide led to the acetylenic sulfonamide tosylamide 6 , free of the allenic isomer. Compound 6 was methylated on the acetylenic C‐atom, reduced, and deprotected with Na in liquid NH₃ to give the (E)‐configured unsaturated amine 8 , which was condensed with crotonaldehyde to the imine 9 and N‐acylated with isobutanoyl chloride to the key intermediate 2 . Intramolecular Diels‐Alder reaction furnished a diastereoisomeric mixture of N‐protected octahydroquinolines 10 . After catalytic hydrogenation and cleavage of the amide, natural 1 was obtained as the main product in 25% overall yield; 3.2% of its isomer 11 with the inverse configurations in position 4a, 5, and 8a was also isolated.     

Earnouts in mergers and acquisitions: A game-theoretic option pricing approach

This paper presents a valuation approach for merger and acquisition (M&A) deals employing contingent earnouts. It is argued that these transactions have option-like features, and the paper uses a game-theoretic option approach to model the value of such claims. More specifically, the paper examines the impact of uncertainty on the optimal timing of M&A using earnouts, and it also investigates the impact of uncertainty on the terms of the earnout. Optimal earnout and initial payment combinations are endogenously derived from the model, and testable hypotheses are developed. The theoretical contribution of this paper is a dynamic decision-making model of the invest-to-learn option generated upon investment in an acquisition. The paper also offers practical implications for the design of acquisitions employing earnouts.