Simple and condensed β-lactams-I : The application of diketene in β-lactam synthesis. The synthesis and functional group manipulations of diethyl 3-acetyl-4-oxoazetidine-2,2-dicarboxylates

Acylation of the N-substituted diethyl aminomalonates 3a–3d with diketene furnished the ring tautomers 6a–6d of the expected acetoacetyl derivatives 5. By treatment with iodine and sodium ethoxide compounds 6a–6d are smoothly converted into the β-lactam derivatives 2a–2d. Deethoxycarbonylation of the ethylene ketals 7a–7d of the latter furnishes mixtures of the corresponding diastereomeric monoesters 8 and10. The ethoxycarbonyl groups of the trans esters 8 are more reactive than those of the cis isomers 10. This permits, under appropriate conditions, selective alkaline hydrolysis and NaBH₄ reduction of the trans esters 8 in the presence of the cis esters 10. Reduction of the cis ester 10c under more forceful conditions furnishes the trans hydroxymethyl derivative 11c.     

Determination of trace metals in industrial boron carbide by solid sampling optical emission spectrometry. Optimization of DC arc excitation (current, atmosphere and chemical modifier)

Graphite arc emission spectrometry has become possible as a result of the invention of novel types of optical spectrometers with Echelle-optics and semiconductor array detectors, and by the application of electronically controlled, high current arc generators. An optimization of the excitation parameters to boron carbide analysis is reported here, measuring background corrected line intensities that were integrated for the time of total evaporation of 5 mg boron carbide sample with or without added chemical modifiers. The following set of experimental conditions were compared with respect of analytical sensitivity and precision: (A) no modifier, Ar + O₂ (20%), 16 A; (B) sample + graphite powder (1 + 1), Ar + O₂ (20%), 16 A; (C) sample + CaF₂ (1 + 1), Ar, 25 A; (D) sample + CaF₂ + graphite powder (1 + 1 + 1), Ar, 25 A. The graphite powder modifier resulted in improved precision in general, and the CaF₂ was effective as a plasma ionization buffer and fluorinating agent. The best compromise was found under conditions B, when oxygen was present in the discharge atmosphere. This is likely due to the stepwise conversion of the boron carbide matrix to the more volatile boron oxide. Under conditions B, detection limits in the ranges of 0.3–9 μg g⁻¹ for Al, Ca, Cr, Cu, Fe, Mg, Mn and Si and that of 18–38 μg g⁻¹ for Ti, W, and Zr were attained. Average RSDs of 10.2 and 9.7% were found, respectively, without and with internal referencing to boron.     

“Integer-making” theorems

Let X = {x₁, x₂,…} be a finite set and associate to every x_i a real number α_i. Let f(n) [g (n)] be the least value such that given any family $\text{F}$ of subsets of X having maximum degree n [cardinality n], one can find integers α_i, i=1,2,… so that α_i ? α_i|<1 and

$\text{∑}\text{x}{}_{\mathrm{i\; ?\; E}}\text{a}{}_{\mathrm{i}}\text{?}\text{∑}\text{x}{}_{\mathrm{i\; ?\; E}}\text{α}{}_{\mathrm{i}}\text{≤?(n)}\text{∑}\text{x}{}_{\mathrm{i\; ?\; E}}\text{a}{}_{\mathrm{i}}\text{?}\text{∑}\text{x}{}_{\mathrm{i\; ?\; E}}\text{α}{}_{\mathrm{i}}\text{≤}\text{g(n)}$

for all $\text{E ?}\text{F}$. We prove

$\text{f(n)≤n ? 1 and g(n)≤c(n}\text{log}\text{n)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$

.     

Living Carbocationic Polymerization. LVII. Kinetic Treatment of Living Carbocationic Polymerization Mediated by the Common Ion Effect

Abstract

The effect of anion concentration on the apparent rate constant of polymerization k^A _p of isobutylene (IB) induced by the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl₄ initiating system using the CH₂Cl₂/nC₆H₁₄ (60/40 v/v) solvent system at ?40 and ?80°C was studied by the use of nBu₄NCl. Computer simulation has shown that k^A _p decreases several orders of magnitude upon the addition of even a very small amount of common anion TiCl^?- ₅ to the charge. The rate of change is reduced in the concentration range of experimental interest. It was concluded that the decrease of k^A _p with increasing TiCl ^?- ₅ concentration is mainly due to the decreasing contribution of propagation by free ions. The contribution (%) of propagation by free ions to the apparent rate of propagation was calculated.     

Expedient and Diastereodivergent Assembly of Terpenoid Decalin Subunits having Quaternary Stereocenters through Organocatalytic Robinson Annulation of Nazarov Reagent

We report an expedient approach to highly functionalized cis‐ and trans‐decalines that could function as key structural subunits toward the synthesis of various classes of terpenoids. Key to the strategy is an organocatalyzed Robinson annulation reaction of the Nazarov reagent that affords chiral enone building blocks with high enantioselectivities. The quaternary carbon stereogenic center can direct the subsequent reactions and allow the rapid and diastereoconvergent assembly of complex decalines with contiguous stereocenters.     

Synthesis and characterization of iPP‐sPP stereoblock produced by a binary metallocene system

Stereoblock polypropylenes comprising of iPP and sPP segments are synthesized by polymerization of the following binary system of metallocenes: the C_s‐symmetric [2,7‐t‐Bu₂(Flu)₂Ph₂C(Cp)ZrCl₂] and the C₂‐symmetric rac‐Me₂Si(2‐Me‐4‐Ph‐Ind)₂ZrCl₂. Blends of samples made either by each catalyst individually (solution blend) with materials obtained with the mixed catalyst system (reactor blend) are compared. The simultaneous presence of MAO and DEZ, enhancing fast and reversible transfer of the growing chains between the two active centers, leads to the formation of a stereoblock microstructure. In this case, low molecular weight polymers are obtained. The junction between the blocks is qualitatively observed in ¹³C NMR. When made in toluene, the stereoblock material consists of a majority of syndiotactic sequences, whereas the ratio is more equilibrated when the polymerization was conducted in the more polar chlorobenzene. This is confirmed by the results obtained with ¹³C NMR, CRYSTAF, HT HPLC, DSC, SSA, WAXD, and optical microscopy. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1422–1434