Halothiation as a Method for Oxidation of Primary Halides and Terminal Olefins to Aldehydes

The richly varied reactivity of the aldehyde group frequently imparts pivotal importance to this functionality in organic synthesis. This fact has resulted in the development of several methods for the elaboration of this structural unit from a variety of precursors.² The report delineates the feasibility of two new couplementary approaches which proceed under mild conditions and demonstrate the utility of “halothiation” as applied to the oxidation of primary halides and terminal olefins. We were led to investigate this approach as a direct consequence of our interest in the Ramberg-Bäcklund rearrangement³ where the preliminary step often involves α-chlorination of the sulfide substrate.⁴ Halothiation is defined by us as a three-step transformation involving introduction of an ArS moiety, directed α-chlorination of the resulting sulfide, and hydrolysis. In principle, of course, the ArSCH₂-unit is uniquely an aldehyde synthon and attention is therefore focused specifically on it at this time.     

Thermal Characterization of Polybutadiyne

Butadiyne was thermally polymerized from the vapor phase onto substrate polyethylene, poly(vinylidene fluoride), polytetrafluoro-ethylene, and fluorinated ethylene propylene films at 20°C. The reaction is characterized as an initial absorption of monomer into the film followed by polymerization in the condensed state. A postpolymerization thermal reaction of the polybutadiyne pendant ethynyl groups was conducted over a 120 to 470°C temperature range with a subsequent surface electrical resistivity decrease to 7 × 10¹¹ ohm/square. The reaction of the pendant acetylenic groups was monitored by DSC and IR spectroscopy and found to be more complex than an intramolecular conversion of an acetylenic polyene to a polyacene structure.     

The structure of events triggered by direct photons in π− p, π+ p andpp collisions at 280 GeV/c

The structure of events associated with the production of direct photons in π^? p, π⁺ p andpp reactions of 280 GeV/c has been studied using data from the WA 70 experiment at the CERN SPS. Results are presented on the distributions of the fractional momenta of the colliding partons and on the fragmentation of the recoil jet and a comparison is made with predictions using the structure functions of Duke and Owens in the Lund Monte Carlo with string fragmentation.     

Double prompt photon production at high transverse momentum byπ − on protons at 280 GeV/c

A search for pairs of highp _T prompt photons produced in hydrogen by a 280 GeV/c incidentπ ^- beam has been carried out using a fine-grained electromagnetic calorimeter and the Omega spectrometer at the CERN SPS. Clear evidence for the existence of such events is found with a six standard deviation signal forp _T >3.0 GeV/c. The cross-sections are consistent with beyond leading order QCD calculations. A discussion on the determination of α _s is also presented.     

Compact complex homogeneous manifolds with large automorphism groups

Let X be a compact complex homogeneous manifold and let Aut(X) be the complex Lie group of holomorphic automorphisms of X. It is well-known that the dimension of Aut(X) is bounded by an integer that depends only on n=dim X. Moreover, if X is K?hler then dimAut (X)≤n(n+2) with equality only when X is complex projective space. In this article examples of non-K?hler compact complex homogeneous manifolds X are given that demonstrate dimAut(X) can depend exponentially on n. Let X be a connected compact complex manifold of dimension n. The group of holomorphic automorphisms of X, Aut(X), is a complex Lie group [3]. For a fixed n>1, the dimension of Aut(X) can be arbitrarily large compared to n. Simple examples are provided by the Hirzebruch surfaces F _m , m∈N, for which dimAut(F _m )=m+5, see, e.g. [2, Example 2.4.2]. If X is homogeneous, that is, any point of X can be mapped to any other point of X under a holomorphic automorphism, then the dimension of the automorphism group of X is bounded by an integer that depends only on n, see [1, 2, 6]. The estimate given in [2, Theorem 3.8.2] is roughly dimAut(X)≤(n+2) ⁿ . For many classes of manifolds, however, the dimension of the automorphism group never exceeds n(n+2). For example, it follows directly from the classification given by Borel and Remmert [4], that if X is a compact homogeneous K?hler manifold, then dimAut(X)≤n(n+2) with equality only when X is complex projective space P ⁿ . It is an old question raised by Remmert, see [2, p. 99], [6], whether this same bound applies to all compact complex homogeneous manifolds. In this note we show that this is not the case by constructing non-K?hler compact complex homogeneous manifolds whose automorphism group has a dimension that depends exponentially on n. The simplest case among these examples has n=3m+1 and dimAut(X)=3m+3 ^m , so the above conjectured bound is exceeded when n≥19. These manifolds have the structure of non-trivial fiber bundles over products of flag manifolds with parallelizable fibers given as the quotient of a solvable group by a discrete subgroup. They are constructed using the original ideas of Otte [6, 7] and are surprisingly similar to examples found there. Generally, a product of manifolds does not result in an automorphism group with a large dimension relative to n. Nevertheless, products are used in an essential way in the construction given here, and it is perhaps this feature that caused such examples to be previously overlooked. Oblatum 13-X-97 & 24-X-1997     

Hydrodynamics of a bounded vertical film with nonlinear surface properties

The drainage of a thin liquid film with an insoluble monolayer down a vertical wall is studied. Lubrication theory is used to develop a model where the film is pinned at the top with a given thickness and the film drains into a bath at the bottom. A nonlinear equation of state is used for the surface tension and the surface viscosity is a nonlinear function of the surfactant concentration; these are appropriate for some aqueous systems. The three partial differential equations are solved via discretization in space and then the resulting differential algebraic system is solved. Results are described for a wide range of parameters, and the conditions under which the free surface is immobilized are discussed.     

Determination of total polyvinylpyrrolidone (PVP) in ophthalmic solutions by size exclusion chromatography with ultraviolet-visible detection

A straightforward size exclusion chromatography (SEC) method was developed and validated for the determination of total polivinylpyrrolidone (PVP) in ophthalmic solutions using the unusual combination of size exclusion chromatography (SEC), ultraviolet-visible detection and quantitation of an analyte peak that elutes in the total exclusion volume of the column. Samples of opthalmic solutions are diluted with water and injected onto a TSKgel G1000PW, 7.5 mm i.d. × 30 cm, 12 μm column at 50°C, with 80:20 0.1M sodium acetate-methanol mobile phase and UV detection at 220 nm. Validation was successful for a stability indicating pharmaceutical method, with parameters including specificity, accuracy, linearity, and precision within typical pharmaceutical acceptance criteria. A stress study with acid, base, peroxide, heat, and light indicates that there is no interference from drug, product, or excipients.     

Generation and reactivity of bis(2,6-diethylphenyl)germanium(II)

The title intermediate ($\text{3a}$) is produced on photolysis of hexakis(2,6-diethyl-phenyl)cyclotrigermane ($\text{1}$) or bis(2,6-diethylphenyl)bis(trimethylsilyl)germane ($\text{4}$) as evidenced by trapping experiments, and thermally dimerizes to tetrakis(2,6-diethyl-phenyl)digermene ($\text{2a}$). Diarylgermylenes such as $\text{3a}$ do not form stable triethylamine adducts (e.g. $\text{5a}$) as has been previously reported.     

Characterization of inclusion complexes of betamethasone-related steroids with cyclodextrins using high-performance liquid chromatography

HPLC was used to study the inclusion complexes formed between various beta- and gamma-cyclodextrins and a series of corticosteroids related to betamethasone. Apparent association constants were measured in acetonitrile-water for a set of 13 steroids. An increase in the stability of the steroid-cyclodextrin complex is observed at lower concentrations of acetonitrile. The effects of the nature of the halide at the 9-position, the location of a double bond within the C-ring, substitution at the 9- and 11-positions, and modification of the D-ring of the steroid backbone were studied. The 11- and 17-positions were found to be critically involved in the inclusion process. Larger apparent association constants were obtained with gamma-cyclodextrin (gamma-CD) than with beta-cyclodextrin (beta-CD) due to the increased diameter of the gamma-CD cavity. Van't Hoff plots were constructed to examine the thermodynamic properties of the inclusion process. Plots constructed using retention factors were found to be nonlinear when gamma-CD was present in the mobile phase. This is due to an increase in the strength of the inclusion complex as temperature decreases. Plots constructed using apparent association constants were linear, indicating that the mechanism of inclusion does not change over the range of temperatures studied (10 to 80 degrees C). Enthalpy-entropy compensation was observed for 11 of the 13 steroids studied. The usefulness of cyclodextrins to achieve the separation of steroids in HPLC is discussed and a practical application for the analysis of a steroid and three potential impurities is described.