Réactivité de spirochromènes et de mérocyanines azahétérocycliques vis-à-vis de quelques agents nucléophiles

Under the action of nucleophile reagents such as water, hydrogen sulfide and sodium borohydride, the saturated azaheterocyclic spirochromenes are opened either on the azaheterocyclic side or on the benzopyran side or on both parts simultaneously. The merocyanines are either partially reduced or decomposed by the sodium borohydride.     

Asymmetric Synthesis of α-Aminophosphonic Acids by Cycloaddition of N-Glycosyl-C-dialkoxyphosphonoylnitrones

Addition of dialkyl phosphites to the nitrone 6 , formed in situ from the oxime 5 and formaldehyde gave the hydroxylamines 7 (86%) and 8 (88%), which reacted with p-benzoquinone in the presence of ethylene via the C-dialkoxyphosphonoylnitrones 9 and 10 to yield the cycloaddition products 11 – 14 (80–85%) with a diastereoselectivity of about 50%. The cycloaddition products were transformed into the monoisopropylidene derivatives 15 – 18 and the diacetates 19 – 22 . Comparison of the NMR spectra and the specific rotations of the compounds 19 – 22 with those of the corresponding α-ammo-acid derivatives 23 – 26 of known configuration indicated preferential formation of the L -isomers. The cycloaddition products were transformed in good yield into the L -α-aminophosphonic acids 29 , 30 , 36 , and 39 .     

Capillary electrophoretic chiral separations using cyclodextrin additives: III. Peak resolution surfaces for ibuprofen and homatropine as a function of the pH and the concentration of β-cyclodextrin

Our recent extended peak resolution equation of capillary electrophoresis has been combined with the multiple equilibria-based electrophoretic mobility model of chiral separations to describe peak resolution as a function of the composition of the background electrolyte (pH and the β-cyclodextrin concentration) and a function of the operating variables (effective portion of the applied potential, dimensionless electroosmotic flow coefficient). Using the previously determined model parameters, the resolution surfaces were calculated for a Type I chiral separation (ibuprofen), and a Type III chiral separation (homatropine). In Type I separations resolution can be obtained only over a narrow pH range in the vicinity of the pK_a value, and above a minimum value, the concentration of β-cyclodextrin plays a lesser role. In Type III separations, the pH- and β-cyclodextrin concentration-dependent resolution surface has two lobes, on which the migration order of the enantiomers is opposite. This can be an advantage in trace component analysis. In both Type I and Type III separations, peak resolution varies strongly with the dimensionless electroosmotic flow coefficient when its value is changed in the − 1 to 1 range. The loci of the pH-dependent and the β-cyclodextrin concentration-dependent resolution maxima do not shift significantly when the dimensionless electroosmotic flow coefficient is changed. This fact provides the analyst with an additional resolution enhancement tool that does not alter the selectivity of the separation. The utility of the model and its theoretical predictions has been demonstrated by comparing measured and calculated R_s values for ibuprofen and homatropine.     

A parallel implementation of the COLUMBUS multireference configuration interaction program

Summary In this work a parallel implementation of the COLUMBUS MRSDCI program system is presented. A coarse grain parallelization approach using message passing via the portable toolkit TCGMSG is used. The program is very well portable and runs on shared memory machines like the Cray Y-MP, Alliant FX/2800 or Convex C2 and on distributed memory machines like the iPSC/860. Further implementations on a network of workstations and on the Intel Touchstone Delta are in progress. Overall, results are quite satisfactory considering the complexity and the prodigious requirements, especially the I/O bandwidth, of MRCI programs in general. For our largest test case we obtain a speedup of a factor of 7.2 on an eight processor Cray Y-MP for that section of the program (hamiltonian matrix times trial vector product) which has been parallelized. The speedup for one complete diagonalization iteration amounts to 5.9. An absolute speed close to 1 GFLOPS is found. Results for the iPSC/860 show that ordinary disk I/O is certainly not sufficient in order to guarantee a satisfactory performance. As a solution for that problem, the implementation of a fully asynchronous distributed-memory model for certain data files is in preparation. On leave from: Bereich Informatik, Universität Leipzig, Augustusplatz 10/11, O-7010 Leipzig, Germany     

Fluorescence from the second excited singlet of aromatic thioketones in solution

The spectral characteristics and the quantum yield of the fluorescence from the second excited singlet state S₂ of the aromatic thioketone molecules xanthione (XS) and thioxanthione (TXS) have been determined in solution at room temperature and 77 K. In 3-methylpentane, the measured quantum yields are φ_f (295 K) = 5.1 × 10^?3 and φ_f(77 K) = 1.0 × 10^?2 for XS, and φ_f (295 K) = 1.5 × 10^?3 and φ_f (77 K) = 2.5 × 10^?3 for TXS. Using the Strickler-Berg expression for the radiative lifetime, the decay rate of S₂ is derived. It is concluded that internal conversion S₂ ? S₁ is the dominating deactivation channel of S₂ with k^{77 K}_nr(S₂ ? S₁) = 1.0 × 10¹⁰ s^?1 for XS and k^{77 K}_nr (S₂→S₁) = 2.2 × 10¹⁰ s^?1 for TXS. Between 295 and 77 K, φ_f increases by a factor of about 2 following an Arrhenius type expression. This temperature dependence of φ_f is considered to be intramolecular in nature and is attributed to a temperature sensitive rate constant k_nr(S₂?S₁) with an activation energy of 190 ± 20 cm^?1 and a frequency factor k′_nr = 3 × 10¹⁰ s^?1 for the XS molecule in 3-methylpentane.     

Synthesis of the branched-chain sugar aceric acid: a unique component of the pectic polysaccharide rhamnogalacturonan-II

Described herein is the synthesis of 3-C-carboxy-5-deoxy-L-xylose (aceric acid), a rare branched-chain sugar found in the complex pectic polysaccharide rhamnogalacturonan-II. The key synthetic step in the construction of aceric acid was the stereoselective addition of 2-trimethylsilyl thiazole to 5-deoxy-1,2-O-isopropylidene-alpha-L-erythro-pentofuran-3-ulose (2), which was prepared from L-xylose. The thiazole group was efficiently converted into the required carboxyl group via conventional transformations. Aceric acid was also synthesized by dihydroxylation of a 3-C-methylene derivative of 2 followed by oxidation of the resulting hydroxylmethyl group. The C-2 epimer of aceric acid was also synthesized using thiazole addition chemistry, starting from L-arabinose.     

GC–MS analysis of phenolic compounds in fuels after conversion to trifluoroacetate esters

The GC–MS characteristics of trifluoroacetate esters of phenolic compounds are discussed. Linear temperature programmed retention indices and total ion current MS response factors of over 120 phenolic esters are reported. The main GC advantages from analysis of trifluoroacetate esters as compared to plain phenols are enhanced volatility and improved resolution. For example, the elution temperature of a given phenol is typically 50 °C greater than that of the corresponding trifluoroacetate ester. Also, while retention of compounds with two trifluoroacetate groups is only moderately greater than mono esters, underivatized dihydroxy compounds are very difficult to elute from any GC column. Complete resolution of isomeric C₀-, C₁- and C₂-alkylphenol esters is readily achieved on conventional fused silica GC columns; resolution of the corresponding underivatized compounds requires specialized GC columns with low temperature limits. In general, mass spectra of trifluoroacetate esters are more characteristic of a given structure than those of the corresponding phenols and may be more rigorously interpreted towards structural elucidation. A table in the report summarizes some of the more important spectral features used in compound identification. Example applications in analysis of coal-, shale- and petroleum-derived materials are presented. Selected ion monitoring is used to determine individual phenolic components in whole distillates; reconstructed ion chromatograms are used to illustrate distributions of selected species as a function of fuel storage and thermal stress.     

A potential-function reduction algorithm for solving a linear program directly from an infeasible “warm start”

This paper develops an algorithm for solving a standard-form linear program directly from an infeasible “warm start”, i.e., directly from a given infeasible solution \(\hat x\) that satisfies \(A\hat x = b\) but \(\hat x \ngeqslant 0\) . The algorithm is a potential function reduction algorithm, but the potential function is somewhat different than other interior-point method potential functions, and is given by $$F(x,B) = q\ln (c^T x - B) - \sum\limits_{j = 1}^n {\ln (x_j + h_j (c^T x - B))}$$ where \(q = n + \sqrt n\) is a given constant,h is a given strictly positive shift vector used to shift the nonnegativity constaints, andB is a lower bound on the optimal value of the linear program. The duality gapc ^T x ? B is used both in the leading term as well as in the barrier term to help shift the nonnegativity constraints. The algorithm is shown under suitable conditions to achieve a constant decrease in the potential function and so achieves a constant decrease in the duality gap (and hence also in the infeasibility) in O(n) iterations. Under more restrictive assumptions regarding the dual feasible region, this algorithm is modified by the addition of a dual barrier term, and will achieve a constant decrease in the duality gap (and in the infeasibility) in \(O(\sqrt n )\) iterations.     

Polynomial-time algorithms for linear programming based only on primal scaling and projected gradients of a potential function

This paper presents extensions and further analytical properties of algorithms for linear programming based only on primal scaling and projected gradients of a potential function. The paper contains extensions and analysis of two polynomial-time algorithms for linear programming. We first present an extension of Gonzaga's O(nL) iteration algorithm, that computes dual variables and does not assume a known optimal objective function value. This algorithm uses only affine scaling, and is based on computing the projected gradient of the potential function $$q\ln (x^T s) - \sum\limits_{j = 1}^n {\ln (x_j )} $$ wherex is the vector of primal variables ands is the vector of dual slack variables, and q = n + \(\sqrt n \) . The algorithm takes either a primal step or recomputes dual variables at each iteration. We next present an alternate form of Ye's O( \(\sqrt n \) L) iteration algorithm, that is an extension of the first algorithm of the paper, but uses the potential function $$q\ln (x^T s) - \sum\limits_{j = 1}^n {\ln (x_j ) - \sum\limits_{j - 1}^n {\ln (s_j )} } $$ where q = n + \(\sqrt n \) . We use this alternate form of Ye's algorithm to show that Ye's algorithm is optimal with respect to the choice of the parameterq in the following sense. Suppose thatq = n + n ^t wheret?0. Then the algorithm will solve the linear program in O(n ^r L) iterations, wherer = max{t, 1 ? t}. Thus the value oft that minimizes the complexity bound ist = 1/2, yielding Ye's O( \(\sqrt n \) L) iteration bound.     

Elementary abelian p-subgroups of algebraic groups

Let be an algebraically closed field and let G be a finite-dimensional algebraic group over which is nearly simple, i.e. the connected component of the identity G ⁰ is perfect, C _G(G ⁰)=Z(G ⁰) and G ⁰/Z(G ⁰) is simple. We classify maximal elementary abelian p-subgroups of G which consist of semisimple elements, i.e. for all primes p char .Call a group quasisimple if it is perfect and is simple modulo the center. Call a subset of an algebraic group toral if it is in a torus; otherwise nontoral. For several quasisimple algebraic groups and p=2, we define complexity, and give local criteria for whether an elementary abelian 2-subgroup of G is toral.For all primes, we analyze the nontoral examples, include a classification of all the maximal elementary abelian p-groups, many of the nonmaximal ones, discuss their normalizers and fusion (i.e. how conjugacy classes of the ambient algebraic group meet the subgroup). For some cases, we give a very detailed discussion, e.g. p=3 and G of type E ₆, E ₇ and E ₈. We explain how the presence of spin up and spin down elements influences the structure of projectively elementary abelian 2-groups in Spin(2n, ). Examples of an elementary abelian group which is nontoral in one algebraic group but toral in a larger one are noted.Two subsets of a maximal torus are conjugate in G iff they are conjugate in the normalizer of the torus; this observation, with our discussion of the nontoral cases, gives a detailed guide to the possibilities for the embedding of an elementary abelian p-group in G. To give an application of our methods, we study extraspecial p-groups in E ₈( ).Dedicated to Jacques Tits for his sixtieth birthday