Derivatives of 2,3‐dihydroimidazo[1,5,4‐ef][1,2,5]‐benzothiadiazepin‐6(4h,7h)‐thione 1,1‐dioxide,a new heterocyclic system related to tibo

The synthesis of derivatives of 2,3‐dihydroimidazo[1,5,4‐ef][1,2,5]benzothiadiazepin‐6(4H,7H)‐thione 1,1‐dioxide is reported starting from N‐substituted ethyl 2‐(5‐chloro‐2‐nitrobenzenesulfonamido)‐2‐alkyl‐acetates. Fundamental steps of the synthetic pathway were: i) intramolecular cyclization of N‐substituted 2‐(2‐amino‐5‐chlorobenzenesulfonamido)‐2‐alkylacetic acids in the presence of N‐(3‐dimethyl‐aminopropyl)‐N′‐ethyl carbodiimide hydrochloride‐N,N‐dimethylaminopyridine complex; ii) building of imidazole ring from 2‐alkyl‐8‐chloro‐2,3‐dihydro‐3‐methyl‐1,2,5‐benzothiadiazepin‐4(5H)‐one 1,1‐dioxide to achieve 2‐alkyl‐9‐chloro‐2,3‐dihydro‐3‐methylimidazo[1,5,4‐ef][1,2,5]benzothiadiazepin‐6(4H,7H)‐one 1,1‐dioxide; iii) preparation of thiocarbonyl derivative by treatment with Lawesson's reagent. Introduction of a 3‐methyl‐2‐butenyl chain at position 2 of above imidazobenzothiadiazepinone required protection at the 7 position with thermally removable tert‐butoxycarbonyl moiety, due to the fact that alkylation of unprotected structure proved to be regioselective for the 7 position.     

Salt Stress Proteins Identified by a Functional Approach in Yeast

We have performed functional genomics of salt stress by overexpression of gene libraries in yeast and selection for salt tolerance. Thirty halotolerance genes were isolated from yeast, Arabidopsis, and sugar beet. The results indicate that Na⁺ transport (uptake, efflux, and compartmentation), sulfate activation, RNA processing, and protein synthesis are crucial for salt tolerance.     

Quantum mechanical study of the conformational behavior of proline and 4R-hydroxyproline dipeptide analogues in vacuum and in aqueous solution

The conformational behavior of the title compounds has been investigated by Hartree-Fock, MP2, and DFT computations on the most significant structures related to variations of the backbone dihedral angles, cis/trans isomerism around the peptide bond, and diastereoisomeric puckering of the pyrrolidine ring. In vacuum the reversed gamma turn (gammal), characterized by an intramolecular hydrogen bridge, corresponds to the absolute energy minimum for both puckerings (up and down) of the pyrrolidine ring. An additional energy minimum is found in the helix region, but only for an up puckering of the pyrrolidine ring. When solvent effects are included by means of the polarizable continuum model the conformer observed experimentally in condensed phases becomes the absolute minimum. The down puckering is always favored over its up counterpart, albeit by different amounts (0.4-0.5 kcal/mol for helical structures and about 2 kcal/mol for gammal structures). In helical structures cis arrangements of the peptide bond are only slightly less stable than their trans counterparts. This is no longer true for gammal structures, because the formation of an intramolecular hydrogen bond is possible only for trans peptide bonds. In most cases, proline and hydroxyproline show the same general trends; however, the electronegative 4(R) substituent of hydroxyproline leads to a strong preference for up puckerings irrespective of the backbone conformation.     

Studies on isocyanides and related compounds. A convenient synthesis of 2,3-disubstituted spiroimidazolones

The four-component condensation between cycloketones 1 , ammonium formate, and isocyanides 2 afforded formamides 3 , which were dehydrated to the corresponding isocyanides 4 . Upon treatment with n-butyllithium, compounds 4 cyclized to spiroimidazolones 6 , via the carbanions 5 . A series of 2,3-disubstituted spiroimidazolones 8 was obtained by reacting 5 with aldehydes 7 .     

Two New Antiferromagnetic Nickel(II) Complexes Bridged by Azido Ligands in the Cis Position. Effect of the Counteranion on the Crystal Structure and Magnetic Properties

Two new nickel(II) end-to-end azido-bridged compounds, cis-catena-[NiL(2)(&mgr;-N(3))](n)()(ClO(4))(n)().nH(2)O (1) and [Ni(2)L(4)(&mgr;-N(3))(2)](PF(6))(2) (2), were synthesized and characterized; L is 2-(aminoethyl)pyridine. The crystal structures of 1 and 2 were solved. Complex 1: monoclinic system, space group P2(1)/a, a = 8.637(2) ?, b = 18.9995(7) ?, c = 12.3093(7) ?, beta = 105.92(2) degrees, Z = 4. Complex 2: triclinic system, space group P&onemacr;, a = 9.139(7) ?, b = 10.124(3) ?, c = 12.024(2) ?, alpha = 70.407(14) degrees, beta = 84.19(2) degrees, gamma = 67.67(4) degrees, Z = 1. In the two complexes the nickel atom is situated in a similarly distorted octahedral environment. The two complexes are different; 1 is a one-dimensional helicoidal complex with the two L ligands and the two end-to-end azido bridges in a cis arrangement while complex 2 is a dinuclear system with two end-to-end azido bridges, indicating the extreme importance of the counteranion present (ClO(4)(-) for 1 and PF(6)(-) for 2). The magnetic properties of the two compounds were studied by susceptibility measurements vs temperature. The chi(M) vs T plot for 1 shows the shape for a weakly antiferromagnetically coupled nickel(II) one-dimensional complex without a maximum until 4 K. In contrast, for complex 2 the shape of the chi(M) vs T curve shows a maximum near 40 K, indicating medium antiferromagnetic coupling. From the spin Hamiltonian -J(ij)()S(i)()S(j)(), J values for 1 and 2 were less than -1 and -29.1 cm(-)(1), respectively. The magnetic behavior for 1 and 2 may be explained in terms of the overlap between magnetic orbitals, taking into account the torsion of the Ni(II) atoms and azido-bridging ligands in the two structures.     

Synthesis and structure of chiral-at-metal complexes with the ligand (S)-2-[(Sp)-2-(diphenylphosphino)ferrocenyl]-4-isopropyloxazoline

Half-sandwich complexes of formula [(ηⁿ-ring)MClL]PF₆ [L = (S)-2-[(S_p)-2-(diphenylphosphino)ferrocenyl]-4-isopropyloxazoline; (ηⁿ-ring)M = (η⁵-C₅Me₅)Rh; (η⁵-C₅Me₅)Ir; (η⁶-p-MeC₆H₄iPr)Ru; (η⁶-p-MeC₆H₄iPr)Os] have been prepared and spectroscopically characterised. The molecular structures of the rhodium and iridium compounds have been determined by X-ray crystallography. The related solvate complexes [(η⁵-C₅Me₅)ML(Me₂CO)]²⁺ (M = Rh, Ir) are active catalysts for the Diels-Alder reaction between methacrolein and cyclopentadiene.     

Comparison of three sequential extraction procedures (original and modified 3 steps BCR procedure) applied to sediments of different origin

The 3 steps sequential extraction procedure proposed by the Standards Measurements and Testing program (SM&T--formerly BCR) of the European Union has been applied for the speciation of metals in sediments. Results obtained by the application of the BCR standardized procedure were compared to those of two four step sequential extraction procedures, which are different from the BCR procedure only for the introduction of an additional step with NaOCl, as 2nd and 3rd step respectively. Five different metals have been taken into consideration: Cd, Cu, Ni, Pb and Zn. The analytical performances of the laboratory have been evaluated using three certified reference materials: the BCR 601 lake sediment for the BCR sequential extraction procedure, PACS-1 and MESS-1 for total metal concentration. Results showed that the efficiency of NaOCl treatment is higher or at least equal to that of H2O2 treatment and that its selectivity is quite satisfying. Moreover the NaOCl treatment doesn't significantly influence the extraction of the easily reducible fraction.     

Synthesis and coordination properties of new macrocyclic ligands: equilibrium studies and crystal structures

The synthesis and characterization of two new macrocyclic ligands, the bis-macrocyclic compound 2,6-bis(1,4,13-triaza-7,10-dioxacyclopentadec-1-ylmethyl)phenol (L) and 38-methoxy-1,4,13,16,19,28-hexaaza-7,10,22,25-tetraoxatricyclo[14.14.7.1(32,36)]octatriconta-32,34,Delta(36,38)-triene (L1) are reported. Equilibrium studies of basicity and coordination properties toward metal ions such as Cu(II), Zn(II), Cd(II) and Pb(II) were performed for ligand by potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, I= 0.15 mol dm(-3)). L behaves as a hexaprotic base (logK(1)= 10.93, logK(2)= 9.70, logK(3)= 8.79, logK(4)= 8.05, logK(5)= 6.83, logK(6)= 2.55). All metal ions form stable mono- and dinuclear complexes: logK(MLH(-1))= 25.61 for Cu(II), 15.37 for Zn(II), 12.58 for Cd(II) and 13.79 for Pb(II); logK(M(2)LH(-1))= 31.61 for Cu(II), 23.38 for Zn(II), 24.49 for Cd(II) and 23.68 for Pb(II). All these dinuclear species show a great tendency to add the OH(-) group: the equilibrium constant for the addition reaction was found to be logK(M(2)LH(-1)OH)= 4.77 for Cu(II), 5.66 for Zn(II), 2.8 for Cd(II) and 3.18 for Pb(II). In the case of Ni(II), kinetic inertness prevents the possibility of solution studies. The dinuclear solid adducts [Ni(2)H(-1)L(N(3))(3)].EtOH and [Cu(2)H(-1)L(N(3))](ClO(4))(2) were characterized by X-ray analysis.     

Triorganostannylation of halo- and dihaloadamantanes and 5-chloro-2-adamantanone in liquid ammonia by the S(RN)1 mechanism. Relative reactivity of nucleophiles and bridgehead halides

The reactions of 1-bromo-, 1-iodo-, 2-bromo-, 1,3-dibromo-, and 1,4-dibromoadamantane with Me(3)Sn(-) ions were studied in liquid ammonia. The photostimulated reaction of 1-haloadamantane (1-XAd, X = Br, I) or 2-BrAd with Me(3)Sn(-) ions gave in a few minutes excellent yields of the substitution products. The 1,3-dibromo- and 1,4-dibromoadamantane with Me(3)Sn(-) ions also reacted very fast under irradiation to give the disubstitution product in good yields. In competition experiments, 1-ClAd is 5.3 times more reactive than 5-chloro-2-adamantanone (9) toward Me(3)Sn(-) ions in liquid ammonia. When the nucleophile is the Ph(2)P(-) ion, 1-ClAd reacts 2.4 times faster than 9. This is the first time that no redox catalysis was observed when the bridgehead compound bears a carbonyl group as a pi acceptor. On the other hand, the nucleophile Me(3)Sn(-) ion was ca. >1000 times more reactive than Ph(3)Sn(-) ions toward 1-adamantyl radicals, in contrast to the behavior of aryl radicals, where both nucleophiles have the same reactivity.