Hetero‐π‐systems from 2 + 2 cycloreversion,part 2.1Ab initio thermochemical study of heterocyclobutanes 2 + 2 cycloreversion to form heteroethenes H2C=X (X=NH,O, SiH2, PH,S)

Ab initio and DFT thermochemical study of diradical mechanism of 2 + 2 cycloreversion of parent heterocyclobutanes and 1,3‐diheterocyclobutanes, cyclo‐(CH₂CH₂CH₂X), and cyclo‐(CH₂XCH₂X), where X = NH, O, SiH₂, PH, S, was undertaken by calculating closed‐shell singlet molecules at three levels of theory: MP4/6‐311G(d)//MP2/6‐31G(d)+ZPE, MP4/6‐311G(d,p)//MP2/6‐31G (d,p)+ZPE, and B3LYP/6‐311+G(d,p)+ZPE. The enthalpies of 2 + 2 cycloreversion decrease on going from group 14 to group 16 elements, being substantially higher for the second row elements. Normally endothermic 2 + 2 cycloreversion is predicted to be exothermic for 1,3‐diazetidine and 1,3‐dioxtane. Strain energies of the four‐membered rings were calculated via the appropriate homodesmic reactions. The enthalpies of ring opening via the every possible one‐bond homolysis that results in the formation of the corresponding 1,4‐diradical were found by subtracting the strain energies from the central bond dissociation energies of the heterobutanes CH₃CH₂—CH₂XH, CH₃CH₂—XCH₃, and HXCH₂—XCH₃. The latter energies were determined via the enthalpies of the appropriate dehydrocondensation reactions, using C—H and X—H bond energies in CH₃XH calculated at G2 level of theory. Except 1,3‐disiletane, in which ring‐opening enthalpy attains 69.7 kcal/mol, the enthalpies of the most economical ring openings do not exceed 60.7 kcal/mol. The 1,4‐diradical decomposition enthalpies found as differences between 2 + 2 cycloreversion and ring‐opening enthalpies were negative, the least exothermicity was calculated for ⋅ CH₂SiH₂CH₂CH₂. The only exception was 1,3‐disiletane, which being diradical, CH₂SiH₂CH₂SiH₂, decomposed endothermically. Since decomposition of the diradical containing two silicon atoms required extra energy, raising the enthalpy of the overall reaction to 78.9 kcal/mol, 1,3‐disiletane was predicted to be highly resisting to 2 + 2 cycloreversion. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:704–720, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20377     

Manner for Instantenious Determination of Base Impurity and Dissociation Constant of Carboxylic Acid

It is known that the commercial solvents are polluted of basic impurities as usual.     

Penta‐ and hexa‐m‐phenylcyclophosphites and their derivatives

New representatives of an original class of crown ethers—cyclopenta‐ and cyclohexaresorcinolamidophosphites—were synthesized using the molecular assemblage technique. Their thio and oxo derivatives were obtained, as well as the rhodium (I) complexes. A macrocycle containing both tri‐ and pentavalent phosphorus atoms was synthesized. ¹H and ³¹P NMR spectroscopy data suggested the higher conformational flexibility of phosphite macrocycles as compared to phosphate ones. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:129–137, 2000     

Exact Recursive Calculation of Circulant Permanents: A Band of Different Diagonals inside a Uniform Matrix

We present a finite-order system of recurrence relations for the permanent of circulant matrices containing a band of k any-value diagonals on top of a uniform matrix (for k=1,2 and 3) and the method for deriving such recurrence relations, which is based on the permanents of the matrices with defects. The proposed system of linear recurrence equations with variable coefficients provides a powerful tool for the analysis of the circulant permanents, their fast, linear-time computing; and finding their asymptotics in a large-matrix-size limit. The latter problem is an open fundamental problem. Its solution would be tremendously important for a unified analysis of a wide range of the nature’s ♯P-hard problems, including problems in the physics of many-body systems, critical phenomena, quantum computing, quantum field theory, theory of chaos, fractals, theory of graphs, number theory, combinatorics, cryptography, etc.     

Scheduling Three-Operation Jobs in a Two-Machine Flow Shop to Minimize Makespan

This paper considers a variant of the classical problem of minimizing makespan in a two-machine flow shop. In this variant, each job has three operations, where the first operation must be performed on the first machine, the second operation can be performed on either machine but cannot be preempted, and the third operation must be performed on the second machine. The NP-hard nature of the problem motivates the design and analysis of approximation algorithms. It is shown that a schedule in which the operations are sequenced arbitrarily, but without inserted machine idle time, has a worst-case performance ratio of 2. Also, an algorithm that constructs four schedules and selects the best is shown to have a worst-case performance ratio of 3/2. A polynomial time approximation scheme (PTAS) is also presented.     

Multiplicative structures in additively large sets

Previous research extending over a few decades has established that multiplicatively large sets (in any of several interpretations) must have substantial additive structure. We investigate here the question of how much multiplicative structure can be found in additively large sets. For example, we show that any translate of a set of finite sums from an infinite sequence must contain all of the initial products from another infinite sequence. And, as a corollary of a result of Renling Jin, we show that if A and B have positive upper Banach density, then A+B contains all of the initial products from an infinite sequence. We also show that if a set has a complement which is not additively piecewise syndetic, then any translate of that set is both additively and multiplicatively large in several senses.We investigate whether a subset of N with bounded gaps—a syndetic set—must contain arbitrarily long geometric progressions. We believe that we establish that this is a significant open question.     

Approximation algorithms for two-machine flow shop scheduling with batch setup times

In many practical situations, batching of similar jobs to avoid setups is performed while constructing a schedule. This paper addresses the problem of non-preemptively scheduling independent jobs in a two-machine flow shop with the objective of minimizing the makespan. Jobs are grouped into batches. A sequence independent batch setup time on each machine is required before the first job is processed, and when a machine switches from processing a job in some batch to a job of another batch. Besides its practical interest, this problem is a direct generalization of the classical two-machine flow shop problem with no grouping of jobs, which can be solved optimally by Johnson's well-known algorithm. The problem under investigation is known to be NP-hard. We propose two O(n logn) time heuristic algorithms. The first heuristic, which creates a schedule with minimum total setup time by forcing all jobs in the same batch to be sequenced in adjacent positions, has a worst-case performance ratio of 3/2. By allowing each batch to be split into at most two sub-batches, a second heuristic is developed which has an improved worst-case performance ratio of 4/3. © 1998 The Mathematical Programming Society, Inc. Published by Elsevier Science B.V.     

Alkylation of narrow rim calix[4]arenes in a DMSO-NaOH medium

An effective method of 5,11,17,23-tetra-tert-butyl-25,26-dialkoxy-27,28-dihydroxy-calix[4]arenes and 25,26,27,28-tetraalkoxycalix[4]arenes synthesis by alkylation of tetrahydroxycalix[4]arenes in a DMSO-NaOH medium was developed.     

On fibers of the toric resolution of the extended Prym map

We study the minimal toric resolution of the extended Prym map. We describe the blowup at certain singular points of the indeterminacy locus of the extended Prym map.