Synthesis of 4,4′-biquinazoline alcohols as chiral catalysts in enantioselective alkynylation of aldehydes with phenyl acetylene

Optically active propargylic alcohols are important chiral-building blocks in asymmetric synthesis, while the asymmetric addition of a terminal alkyne to an aldehyde is one of the most important procedures to prepare these chiral-building blocks. In this work, a family of chiral 4,4′-biquinazoline alcohols has been conveniently prepared from the easily accessible (S)-2-acetoxycarboxylic acid chlorides by reaction sequences beginning with condensation and followed by key synthetic steps including chlorination, nickel(0)-mediated homocoupling, and deprotection in addition to being examined as potential ligands in the enantioselective addition of phenylacetylene to aldehydes. These chiral ligands can be combined with Ti(OiPr)₄ and then used to catalyze the asymmetric addition of zinc acetylide, produced in situ by the reaction of phenylacetylene with diethylzinc, to aldehydes. The best enantiomeric excess obtained in this study was 75%.     

A bicriteria flowshop scheduling with a learning effect

In many situations, a worker’s ability improves as a result of repeating the same or similar tasks; this phenomenon is known as the learning effect. In this paper the learning effect is considered in a two-machine flowshop. The objective is to find a sequence that minimizes a weighted sum of total completion time and makespan. Total completion time and makespan are widely used performance measures in scheduling literature. To solve this scheduling problem, an integer programming model with n² + 6n variables and 7n constraints where n is the number of jobs is formulated. Because of the lengthy computing time and high computing complexity of the integer programming model, the problem with up to 30 jobs can be solved. A heuristic algorithm and a tabu search based heuristic algorithm are presented to solve large size problems. Experimental results show that the proposed heuristic methods can solve this problem with up to 300 jobs rapidly. According to the best of our knowledge, no work exists on the bicriteria flowshop with a learning effect.     

Cycloaddition Reaction of 1,4‐Dihydronaphthalene 1,4‐Epoxide with Cyclooctatetraene: Cope Rearrangement in an Adduct

The reaction of 1,4‐dihydro‐1,4‐epoxynaphthalene with cyclooctatetraene at 130±5° for 14 days gave the four products 2a,3,3a,4,9,9a,10,10a‐octahydro‐4,9‐epoxy‐3,10‐ethenocyclobuta[b]anthracene ( 13 ), 25‐oxanonacyclo[10.10.2.2^5,9.1^14,21.0^2,11.0^3,10.0^4,6.0^13,22.0^15,20]heptacosa‐7,15,17,19,23,26‐hexaene ( 14 ), 5,5a,6,6a,6b,6c,12a,12b,12c,13,13a,14‐dodecahydro‐5,14‐epoxy‐6,13‐ethenocycloocta[3′,4′]cyclobuta[1′,2′:3,4]cyclobuta[1,2‐b]anthracene ( 15 ) and bis‐adduct 16 . The structures of the products were determined by spectroscopic methods. It was observed that adduct 14 undergoes a Cope rearrangement. The Cope rearrangement of this adduct was investigated in the temperature range of ?85° to 100° by NMR spectroscopy.     

The synthesis of unusual isocoumarin derivatives: the chemistry of homophthalic acid

Homophthalic acid was reacted with thionyl chloride/DMF and ethyl chloroformate/NEt₃ in the presence and absence of NaN₃. In all cases completely different isocoumarin derivatives were obtained. These unusual isocoumarin derivatives were characterized and their mechanism of formation is discussed.     

4-Methyl morpholinium bis-(thio)barbiturates: Synthesis,structure, anticancer evaluation,and CoMFA study

The reaction of symmetrical (thio)barbituric acids with aldehydes in the presence of 4-methyl morpholine yielded a new form of 4-methyl morpholinium bis-(thio)barbiturate containing charge-separated intermolecular and eight-membered intramolecular H-bonds. X-ray Crystallography, FT-IR, and ¹H and ¹³C-NMR spectroscopy techniques were used for structure characterizations. Some of these compounds showed potent anticancer activities. Cytotoxicity of the synthetic compounds against HeLa and MCF-7 cell lines were performed by MTT assay. In addition, a comparative molecular field analysis was carried out, and the effects of substituents on the biological activities of these compounds were explained.     

Synthesis, characterization and spectroscopic properties of some new phenylazo-6-aminouracil

In this study, a series of new 5-phenylazo-6-aminouracil dyes were prepared by linking m-,p-nitroaniline, m-,p-chloroaniline, m-,p-anisidine, m-,p-toluidine, m-,p-cyanoaniline, p-ethoxyaniline, p-phenoxyaniline, p-ethylaniline, p-acetamidoaniline, p-acetylaniline, p-carboxyaniline and aniline to 6-aminouracil. The prepared dyes were characterized by UV-vis, FT-IR, ¹H NMR spectroscopic techniques and elemental analysis. The effect of acid and base upon the UV-vis spectra of these dyes were investigated. In addition, the solvatochromic behaviors and substituent effects in various solvents were evaluated.      

Synthesis and spectral properties of new hetarylazo indole dyes

A series of new hetarylazo indole dyes were synthesized by azo coupling of 2-phenyl-, 2-methyl-, and 1-methyl-1-phenyl-1H-indole with diazonium salts derived from 5-methylsulfanyl-1H-1,2,4-triazol-3-amine, 1H-1,2,4-triazol-3-amine, 5-methylisoxazol-3-amine, and 5-amino-1,3,4-thiadiazole-2-thiol. The dyes were characterized by the IR spectra, electronic absorption spectra in the UV and visible regions, and ¹H NMR and mass spectra. The effects of solvent nature, acidity of the medium, temperature, and concentration on the electronic absorption spectra in the visible region and the dependence of the color of the dyes on the nature of heterocyclic fragment were examined. Published in Russian in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 7, pp. 1041–1047. The text was submitted by the authors in English.     

Stereoselective synthesis of deoxycarbaheptopyranose derivatives: 5a-carba-6-deoxy-α-dl-galacto-heptopyranose and 5a-carba-6-deoxy-α-dl-gulo-heptopyranose

Two new deoxycarbaheptopyranoses, 5a-carba-6-deoxy-α-dl-galacto-heptopyranose and 5a-carba-6-deoxy-α-dl-gulo-heptopyranose were prepared starting from cyclohexa-1,4-diene. The addition of dichloroketene to cyclohexa-1,4-diene followed by the subsequent reductive elimination and Baeyer-Villiger oxidation in turn led to the formation of a bicyclic lactone. Reduction of the lactone moiety followed by acetylation gave a diacetate with cis-configuration. The introduction of additional acetate functionality into the molecule was achieved by singlet oxygen ene-reaction. The formed hydroperoxide was reduced and then acetylated. The triacetate was further functionalized either by direct cis-hydroxylation using OsO₄ or by epoxidation followed by a ring-opening reaction to give the title heptopyranose derivatives. One of the synthesized molecules, galacto-heptopyranose exhibited enzyme specific inhibition against α-glycosidase. On the other hand, they did not show any inhibition for α-amylase. However, both compounds, gulo-heptopyranose and galacto-heptopyranose increased the activity of α-amylase.