Etude de la Fragmentation de Derives Substitues Polycycliques du Benzodioxinne-1,4

The mass spectra of five polycyclic 1,4 benzodioxin derivatives have been studied. The breakdown patterns of the more important ions have been suggested by comparison with three compounds in a deuterated specific position. Some rearrangements are produced by specific hydrogen migration and a few others after scrambling.     

Conformations of luteoskyrin and rugulosin in solution

The pigments Luteoskyrin (Ls) and Rugulosin (Rg) might adopt a priori two extreme conformations, a planar and an angular one. To determine the predominant conformation in solution, the nature of the lowest energy transition of the chromophores and the presence of intramolecular H-bonding have been investigated. The solvent effects on electronic absorption and CD spectra indicated the π-π* nature of the lowest energy transition. Treatments of the electronic absorption results according to McRae and Kosower relations, IR absorption and PMR spectra suggested the presence of strong intra-molecular H-bonds. From these results it was concluded that Ls and Rg adopted in a variety of solvents the most planar conformation.     

Synthetic analogues of wedelolactone

The syntheses of 7′-methoxy- and 5′,7′,6-trimethoxy-coumarino(3′,4′:3,2)coumarones (IIa and IIb) are described.     

A complexometric titration of inorganic sulphate in synthetic detergents

An accurate method for the determination of inorganic sulphate in synthetic detergents has been developed. After addition of a cationic surface-active agent (cetyl pyridinium chloride) to an anionic detergent, sulphate can be determined by means of indirect titration with EDTA, using a mixture of Metalphthalein and Naphthol Green B as indicator.     

Spectral study of the conversion of porphyrins during interaction with molecular negative ions

In the interaction of ethioporphyrin and of several of its metal derivatives with negative ions of pyridine and anthracene in tetrahydrofuran solutions, an electron transfer takes place which results in the conversion of the pyridine and anthracene ions into neutral molecules, whereas the molecules of the pigment are first transformed into monovalent anions and subsequently into the di-, tri-, tetra-, and sometimes even into the hexavalent anions. In the first stage of this interaction, ferriethioporphyrin is reduced to ferro-ethioporphyrin, whereas the unmetallized pigment and its copper complex are transformed into the disodium derivative of ethioporphyrin. When the temperature is lowered, the rate of the electron transfer from pyridine ions to zinc-ethioporphyrin is decreased, and illumination leads to a substantial rate increase. The photochemical sensitivity of this system is possibly linked to the formation of stable complexes between pigment molecules and pyridine ions.     

Metal coordination polymers. II. Molecular weight studies of beryllium phosphinate polymers in toluene

The number-average molecular weights of beryllium 4-biphenyl(phenyl)phosphinate, di-n-pentylphosphinate, di-n-heptylphosphinate, and trifluoromethyl(phenyl)phosphinate are degraded by the presence of water in toluene. It is proposed that easily hydrolyzable P? O? P bonds contribute, in part, to the bonding of these polymers.     

Magnetic properties of copper(II) complexes with some hydrazones of substituted salicylaldehydes

A series of novel mono-and binuclear copper(II) complexes with substituted salicylaldehyde acylhydrazones H₂L of the formula CuL · xH2O (x = 0 and 1) and [Cu(HL)](ClO₄)(CH₃OH) were synthesized. The isolated dimeric complexes of copper acetate were found to exist as isomers with different bridging atoms. In dimers showing a superexchange between the paramagnetic centers through bridging phenoxide O atoms, the antiferromagnetic exchange couplings were much stronger than those in complexes with bridging O atoms of the a-oxyazine fragment.     

Syntheses of anomerically phosphodiester-linked oligomers of the repeating units of the Haemophilus influenzae types c and f capsular polysaccharides

Spacer-equipped dimers and trimers of the repeating units of the capsular polysaccharide of Haemophilus influenzae type c, -4)-3-O-Ac-beta-D-GlcpNAc-(1-->3)-alpha-D-Galp-(1-OPO(3-)-, and type f, -3)-beta-D-GalpNAc-(1-->4)-3-O-Ac-alpha-D-GalpNAc-(1-OPO(3-)-, have been synthesized for use in immunological studies. H-Phosphonate chemistry was used for the formation of the interglycosidic phosphate diester linkages. Two types of building blocks, a spacer glycoside disaccharide starting monomer (15 and 22) and an anomeric monoester alpha-H-phosphonate disaccharide elongating monomer (12 and 27), were built up for each serotype structure from properly protected monosaccharide precursors using mainly thioglycosides as glycosyl donors. Stereospecificity in the formation of the alpha-linked monoester H-phosphonate was possible in type c through crystallization of the pure alpha-anomer of the precursor hemiacetal from an alpha/beta-mixture, whereas in type f, the hemiacetal was isolated directly as exclusively the alpha-anomer. Subsequent phosphonylation using triimidazolylphosphine was performed without anomerization. Formation of the anomeric phosphate diester linkages was performed using pivaloyl chloride as coupling reagent followed by I(2)/H(2)O oxidation of the formed diester H-phosphonates. Original experiments afforded no diester product at all, but optimization of the oxidation conditions (lowering the temperature and dilution with pyridine prior to I(2) addition) gave the dimers in good yields (71% and 81%) and, subsequently, after removal of a temporary silyl protecting group in the dimers, the trimers in fair yields (36% and 37%), accompanied by hydrolysis of the dimer phosphate linkage. One-step deprotection through catalytic hydrogenolysis efficiently afforded the target dimer (30 and 36) and trimer structures (32 and 39). The synthetic scheme allows for further elongation to give higher oligomers.     

New Method of Analysis of Intermolecular Contacts in the Crystal Structure: π-Complexes

A new method for analysis of intermolecular contacts in the crystal structure based on characteristics of the Voronoi-Dirichlet polyhedra (VDP) is considered using metal π-complexes as examples. The crystal data of the compounds were used to determine the surface area of the VDP faces corresponding to all intermolecular contacts in one π-complex, the total volume of the pyramids with VDP faces as bases and the nuclei of atoms involved in the intermolecular contacts at the vertices, and the total solid angle at which the “intermolecular” VDP faces are seen from the corresponding nuclei of the molecule. A common linear correlation between the enthalpy of sublimation of π-complexes and saturated or unsaturated hydrocarbons and the molecular VDP characteristics was elucidated. On the basis of the results, the enthalpies of sublimation were calculated for some iron π-complexes (for which data on the crystal structure were available) and C₆₀ and C₇₀ fullerenes.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 7, 2005, pp. 495–505.Original Russian Text Copyright © 2005 by Serezhkin, Shevchenko, Serezhkina.     

Synthesis and reactivity of dimeric Ar'TlTlAr' and trimeric (Ar"T1)3 (Ar', Ar" = bulky terphenyl group) thallium(I) derivatives: Tl(I)-Tl(I) bonding in species ligated by monodentate ligands

The synthesis and characterization of three new organothallium(I) compounds are reported. Reaction of (Ar'Li)(2) (Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)) and Ar"Li (Ar" = C(6)H(3)-2,6-(C(6)H(3)-2,6-Me(2))(2)) with TlCl in Et(2)O afforded (Ar'Tl)(2) (1) and (Ar' 'Tl)(3) (2). The "dithallene" 1 is the heaviest group 13 dimetallene and features a planar, trans-bent structure with Ar'Tl-Tl = 119.74(14) degrees and Tl-Tl = 3.0936(8) A. Compound 2 is the first structurally characterized neutral, three-membered ring species of formula c-(MR)(3) (M = Al-Tl; R = organo group). The Tl(3) ring has Tl-Tl distances in the range ca. 3.21-3.37 A as well as pyramidal Tl geometries. The Tl-Tl bonds in 1 and 2 are outside the range (2.88-2.97 A) of Tl-Tl single bonds in R(2)TlTlR(2) compounds. The weak Tl-Tl bonding in 1 and 2 leads to their dissociation into Ar'Tl and Ar' 'Tl monomers in hexane. The Ar'Tl monomer behaves as a Lewis base and readily forms a 1:1 donor-acceptor complex with B(C(6)F(5))(3) to give Ar'TlB(C(6)F(5))(3), 3. Adduct 3 features an almost linear thallium C(ipso)-Tl-B angle of 174.358(7) degrees and a Tl-B distance of 2.311(2) A, which indicates strong association. Treatment of 1 with a variety of reagents resulted in no reactions. The lower reactivity of 1 is in accord with the reluctance of Tl(I) to undergo oxidation to Tl(III) due to the unreactive character of the 6s(2) electrons.