Phosphorus-nitrogen compounds. 14. Synthesis, stereogenism, and structural investigations of novel n/o spirocyclic phosphazene derivatives

The reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6, with N/O donor-type N-alkyl-o-hydroxybenzyl- and o-hydroxynaphthylamines result in novel mono- (3a, 4a and 4b), di- (5a and 5b), and tri- (3b, 6a, and 6b) spirocyclic phosphazene derivatives. The tetrakis-pyrrolidinophosphazene, 3b, has been obtained from the reaction of partly substituted compound 3a with the excess pyrrolidine in tetrahydrofuran. The relationship between the endocyclic NPN (alpha) and exocyclic NPO (alpha') bond angles of the analogous spirocyclic phosphazenes with the deltaP shifts of NPO phosphorus atoms have been presented. It was observed that there is a linearity between alpha angles and deltaP shifts, while no linear relationship has been observed for alpha' angles. In addition, we have found the correlation between Delta(P-N) and deltaNPO shifts, which implies a linear relationship. Delta(P-N)=(a-b), where a and b are the average lengths of two adjacent P-N bonds. The structural investigations of all of the compounds have been made by elemental analyses; mass spectrometry; Fourier transform infrared spectroscopy; one-dimensional 1H, 13C, and 31P NMR; distortionless enhancement by polarization transfer; and two-dimensional correlation spectroscopy, heteronuclear shift correlation, and heteronuclear multiple-bond correlation homo- and heteronuclear correlation techniques. The solid-state structures of 3a, 4a, 4b, and 5a have been determined by X-ray crystallographic techniques. The asymmetric units of compounds 3a and 4a contain two independent molecules, and 3a has strong intermolecular N-H...N hydrogen bonds linking three phosphazene rings. The molecular structure of 6a looks like a propeller where the chemical environment of P1 is different from that of P2 and P3. On the other hand, compounds 5a and 5b are expected to exist as cis- or trans-geometric isomers and to be in cis (meso) or trans (racemic) configurations. The crystallographic and preliminary chiral solvating agents results show that both of them are trans (racemic). In addition, 6a and 6b are also expected to exist as cis-trans-trans- and cis-cis-cis-geometric isomers; both of them are found to be in cis-trans-trans geometries. According to the two-dimensional spectroscopic data, the possible conformations of 3a and 4a in CDCl3 are the same with the solid-state structures.     

Phosphorus–nitrogen compounds: part 16. Synthesis, stereogenism, anisochronism and the relationship between 31P NMR spectral and crystallographic data of monotopic spiro-crypta phosphazene derivatives

The condensation reactions of N₂O₃-donor type coronands (1–3) with hexachlorocyclotriphosphazatriene, N₃P₃Cl₆, resulted in the formation of spiro-crypta phosphazene derivatives (4–6). These compounds with excess morpholine and 1,4-dioxa-8-azaspiro[4,5]decane (DASD) afford fully substituted morpholino (7 and 10) and 1,4-dioxa-8-azaspiro[4,5]deca (8)-substituted phosphazene derivatives, respectively. Whilst, in the same conditions, the reactions of 4, 5 and 6 with pyrrolidine, morpholine and DASD also produce partially pyrrolidino-substituted geminal (9 and 11), mono-substituted pyrrolidino (12), morpholino (13) and 1,4-dioxa-8-azaspiro[4,5]deca (14) phosphazenes. It has been clearly observed that the chloride replacement reactions of 4, 5 and 6 with pyrrolidine lead to the geminal products. Compounds 7, 8 and 10 are the first examples of anisochronic tetrakis (amino) phosphazenes according to ³¹P NMR data. The structures of 7, 8 and 10–14 have been determined by FTIR, MS, ¹H, ¹³C and ³¹P NMR, DEPT, and HETCOR spectral data. The solid-state structures of 9, 13 and 14 have been examined by X-ray diffraction techniques. The sums of the bond angles around the spiro cyclic nitrogen atoms [344.8(4)° and 347.6(4)°] of 9, indicate that the nitrogen atoms have pyramidal geometries. Thus, the N atoms seem to have stereogenic configurations. Compounds 12–14 also have two stereogenic P-atoms, and they are expected to be in the mixture of enantiomers. The relationships between NPN (α and α′) bond angles and δP_spiro values and the correlation of Δ(P–N) with δP_spiro and Δ(δP) values are presented.     

Solid phase extraction and determination of nickel in water samples by using novel thiol-containing sulfonamide polymeric resin and atomic absorption spectrophotometer

Interest in preconcentration techniques for the determination of metals at ultratrace levels still continues increasingly because of some disadvantages of flameless atomic absorption spectrometry as well as the high costs of other sensitive methods in compared to flame atomic absorption spectrometry.In this study,thiol-containing sulfonamide resin was synthesized,characterized and applied as a new sorption material for solid phase extraction of nickel in drinking water samples.After preconcentration procedure,flame atomic absorption spectrometry was used for determinations.Optimum parameters were found to be pH=3.2,contact time =20 min and eluate volume=3 mL.The limit of detection was found to be 0.75 ng · mL-1.The synthesized resin exhibits the superiority in compared to the other adsorption reagents because of the fact that there is no necessity of any complexing reagent,high sorption capacity as well as the relatively fast extraction rate.The Ni concentrations in the studied 21 kind of water samples were found to be in the range of BDL-4.0 ng ·mL-1.     

Managing transshipments in a multi-retailer system with approximate policies

Using the right transshipment policy is important when transshipments are exercised under demand uncertainty. Optimal transshipment policy can be quite complex in a multi-firm system as optimal actions depend on all system variables. Moreover, both how to select requested retailer and how to respond to requests are in question. We introduce simple, close-to-optimal heuristic transshipment policies for multiple retailers. We first show that heuristic policies may perform even better than self-optimal policy, which is explained by Braess’s paradox. Then we test the performances of various heuristics with respect to centrally optimal policy. When retailers can observe others’ inventory levels, more effective transshipments can be made. Otherwise, a random selection performs quite well. We also observe that although always-accept respond policy is quite close to centrally optimal in small systems, the performance of pairwise-optimal holdback levels to respond requests is more clear and consistent for larger systems.     

Synthesis,Configuration, and Antimicrobial Properties of Novel Substituted and Cyclized ‘2′,3″‐Thiazachalcones’

Nine new thiazachalcone‐based drugs, compounds 1 – 9 , were prepared and fully characterized. The configurations of the photochemical‐dimerization products 7 – 9 were rationalized by semi‐empirical calculations. Both the experimental data and the theoretical calculations showed that the δ‐truxinic acid type dimer is the most stable isomer of all. All compounds were tested for their antibacterial and antifungal activities. The N‐alkylated congeners 4 – 6 showed strong antimicrobial activities against various bacteria and a yeast‐like fungus. The MIC and MBC values were as low as 0.1 μg/ml. All the compounds were active against the Gram‐positive bacterium Staphylococcus aureus.     

On the Cartan Curvatures of a Null Curve in Minkowski Spacetime

We reconstruct the Cartan frame of a null curve in Minkowski spacetime for an arbitrary parameter, and we characterize pseudo-spherical null curves and Bertrand null curves.Mathematics Subject Classification(2000). 53B30, 53A04.     

DNA Hydrolysis by Homo- and Heteronuclear Cu(II)–Ni(II) Complexes of Two Diester-type Ligands

Summary. Nucleolytic activities of novel mononuclear Cu(II), homo- and heterodinuclear Cu(II)–Ni(II) complexes with two diester-type ligands were investigated on pCYTEXP by neutral agarose gel electrophoresis. The analyses of the cleavage products obtained electrophoretically indicate that the examined complexes induce very similar conformational changes on supercoiled DNA by converting supercoiled form to nicked form. At concentrations greater than 100M, the complexes possessed effective nucleolytic activities for 10min of incubation time. However, their nucleolytic activities did not increase significantly with longer periods of incubation. The pH-nucleolytic activity profiles of the complexes differed significantly. Metal complex induced DNA cleavage was also tested for inhibition by various radical scavengers. It could be proposed from the data that diffusible intermediate oxidants are not involved in these reactions or they are not necessary for DNA cleavage since none of antioxidants inhibited DNA cleaving activities of the complexes.     

Chemosensor properties of 7-hydroxycoumarin substituted cyclotriphosphazenes

The newly synthesized cyclotriphosphazene cored coumarin chemosensors 5, 6, and 7 were successfully characterized by ¹ H NMR, ³¹ P NMR, and MALDI-TOF mass spectrometry. Additionally, the photophysical and metal sensing properties of the targeted compounds were determined by fluorescence spectroscopy in the presence of various metals (Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Cr ³⁺ , Mn ²⁺ , Fe ³⁺ , Co ²⁺ , Al ³⁺ , Hg ⁺ , Cu ²⁺ , Zn ²⁺ , Ag ⁺ , and Cd ²⁺ ) . The fluorescence titration results showed that compounds 5, 6, and 7 could be employed as fluorescent chemosensors for Fe ³⁺ ions with high sensitivity. The complex stoichiometry between final cyclotriphosphazene chemosensors and Fe ³⁺ ions was also determined by Job’s plots.     

Microwave‐assisted synthesis of 1,3′‐diaza‐flavanone/flavone and their alkyl derivatives with antimicrobial activity

A simple environmentally friendly solid‐phase microwave‐assisted method was used to synthesis of the 1,3′‐diazaflavanone ( 2 ) and 1,3′‐diazaflavone ( 3 ) from the cyclization of 2′‐amino (E)‐3″‐azachalcone ( 1 ). Ten new N‐alkyl (C_5–12,14,15)‐substituted 1,3′‐diazaflavanonium bromides ( 2a–j ) were prepared from compound 2 with corresponding alkyl halides in acetonitrile under reflux. In addition, nine new N,N′‐dialkyl (C_5–12,14)‐substituted 1,3′‐diazaflavonium bromides ( 3a–i ) were also synthesized from compound 3 with corresponding alkyl halides using basic silica in acetonitrile. The antimicrobial activities of compounds 1–3 , 2a–j , and 3a–i were tested against Gram‐positive (G+) (Bacillus subtilis, Staphylococcus epidermidis, Staphylococcus aureus, and Enterococcus faecalis) and Gram‐negative (G?) (Escherichia coli, Klebsiella pneumonia, Pseudomonas aeruginosa, Proteus vulgaris, Salmonella typhimirium, Yersinia pseudotuberculosis, and Enterobacter cloaceae) microorganisms. They showed good antimicrobial activity against the Gram‐positive bacteria tested with the minimal inhibitory concentration values less than 7.8 μg/mL in most cases. The optimum length of the alkyl chain for better and broader activity is situated in the range of 9–12 carbon atoms in the series of compounds 2a–j and five to six carbon atoms in the series of compounds 3a–i . The nonalkylated compounds 1–3 were not effective, as were the ones alkylated with five or six C alkyl groups ( 2a and 2b ) and 8–13 C alkyl groups for N,N′‐dialkyl compounds ( 3c–3i ). The antimicrobial activity increased as the length of the alkyl substitution increased from 8 to 12 carbons in compounds 2a–j . However, antimicrobial activity decreased as the length of the alkyl substitution increased from 7 to 13 carbons in compounds 3c–i . J. Heterocyclic Chem., (2012)