Computations for the familial analysis of binary traits

For familial aggregation of a binary trait, one method that has been used is the GEE2 (generalized estimating equation) method corresponding to a multivariate logit model. We solve the complex estimating equations for the GEE2 method using an automatic differentiation software which computes the derivatives of a function numerically using the chain rule of the calculus repeatedly on the elementary operations of the function. Based on this, we are able to show in a simulation study that the GEE2 estimates are quite close to the maximum likelihood estimates assuming a multivariate logit model, and that the GEE2 method is computationally faster when the dimension or family size is larger than four.     

Novel chalcones derived from 2‐chloro‐3‐formyl‐6‐methylquinoline

Molecules of (E)‐3‐(2‐chloro‐6‐methylquinolin‐3‐yl)‐1‐(5‐iodo‐2‐thienyl)prop‐2‐en‐1‐one, C₁₇H₁₁ClINOS, (I), and (E)‐3‐(2‐chloro‐6‐methylquinolin‐3‐yl)‐1‐(5‐methyl‐2‐furyl)prop‐2‐en‐1‐one, C₁₈H₁₄ClNO₂, (II), adopt conformations slightly twisted from coplanarity. Both structures are devoid of classical hydrogen bonds. However, nonclassical C—H...O/N interactions [with C...O = 3.146 (5) Å and C...N = 3.487 (3) Å] link the molecules into chains extended along the b axis in (I) and form dimers with an R₂²(8) motif in (II). The structural analysis of these compounds provides an insight into the correlation between molecular structures and intermolecular interactions in compounds for drug development.     

Carbonyl and thiocarbonyl compounds. XI. Synthesis of halogenated benzodioxoles by the action of tetrahalo-o-benzoquinones on benzophenone hydrazones and their cleavage by nucleophilic reagents

p,p′-Dichloro-, p,p′-dimethyl- and p,p′-dimethoxybenzophenone hydrazones react with tetrachloro- and tetrabromo-o-benzoquinone to give directly the halogenated benzodioxoles (IIIa-IIIf), respectively, together with the corresponding tetrahalocatechol. Cleavage of the dioxole ring by nucleophilic reagents depends markedly on the nature of the substituents. The dimethoxyderivatives (IIIc) and (IIIf) proved to be unusually reactive toward cleavage by dilute mineral acids, lithium aluminum hydride, hydrazines and malonitrile, whereas the dichloro analog behaves normally and is not cleaved under the same conditions.     

Oxazolidinone polycyclitols. Stereospecific synthesis of novel aminocarbasugars with oxazolidinone ring

Two new oxazolidinone polycyclitols, 4,5,7,8,9-pentahydroxy-3-tosyldecahydronaphtho [2,1-d]oxazol-2(9bH)-one and 4,5,6,7,8-pentahydroxy-3-tosyldecahydronaphtho [2,1-d]oxazol-2(9bH)-one were synthesized starting from p-benzoquinone. An endo selective Diels–Alder cycloaddition between p-benzoquinone and 1-acetoxybutadiene followed by stereoselective reduction with NaBH₄–CeCl₃·7H₂O led to the formation of an allylic cis-diol. The obtained diols were protected with p-TsNCO to yield bis-carbamates and then a palladium-catalyzed ionization/cyclization reaction produced two oxazolidinone derivatives. Oxidation of the two double bonds in either oxazolidinones with OsO₄ followed by acetylation produced oxazolidinone-pentaacetates whose exact configurations were determined by X-ray diffraction analysis. Controlled removal of the acetate groups furnished the desired two new oxazolidinone polycyclitols.     

12-Tungstophosphoric acid niched in Zr-based metal-organic framework: a stable and efficient catalyst for Friedel-Crafts acylation

Heteropoly acids(HPA) are well known for their versatile solid acid catalysis in diverse chemical reactions, however they suffer from low surface area(10 m~2/g) and leaching into the reactions media, which reduce their prospects as industrial catalyst.Herein, a novel hybrid material HPW@Zr-BTC,composed of 12-tungstophoric acid(HPW) and Zr~(Ⅳ)-benzene tri-carboxylate(Zr-BTC) metal-organic framework(MOF), was prepared via one-pot solvothermal method. Excellent HPW loading up to 32.3 wt% was achieved, and HPW@Zr-BTC composite proved to be highly stable, besides the crystalline morphology of Zr-BTC was intact. The catalytic activity of the hybrid composite was explored via Friedel-Crafts acylation of anisole with benzoyl chloride.The 28.2 wt% HPW@Zr-BTC showed excellent catalytic performance, with 99.4% anisole conversion and 97.6% yield(pmethoxybenzophenone) under solvent free conditions. Excellent retention of catalytic activity was achieved after at least five consecutive runs due to non-observable HPW leaching. The promising activity and stability of the catalyst forecasted its potential industrial applications.     

Reactions of 2-Cyano-2-nitrosomethylbenzthiazole: One-Pot Synthesis of New Polyfunctional Pyrazine Derivatives

2-Cyano-2-nitrosomethylbenzthiazole reacts with some active methylene and nucleophile derivatives to yield new fused and isolated polyfunctional pyrazine, -[1,2,4]triazine, -[1,4,5]benzoxadiazepin, -[1,4,5]benzothiadiazepine, [1,4,5]benzotriazepine, -triazole and -triazolo[3,2-c]triazine derivatives in one-pot reaction. The structures were based on IR, MS, and 1 H NMR spectra and elemental data.     

An Efficient and Facile Synthesis of Novel Benzimid-(Thi) Azole Dicarboxaldehydes as a Versatile Precursors for new Ox-, Thi-and Diazepine Derivatives

Abstract

Novel 2-cyanomethylbenzimid-(thi)-azole-2,2-dicarboxaldehydes were prepared in quantitative yields and reacted easily with o-aminophenol derivatives to yield new multi-functionallized ox-, thi- and diazepine derivatives in one-pot reaction.