Band 28, Heft 11-12

R-P(Se)F 2 - (R = CH 3 , C 2 H 5 , C 3 H 11 , C 6 H 5 , N(CH 3 ) 2 , N(C 2 H 5 ) 2 , NHSi(CH 3 ) 3 ) and R-P(Se)FCl-compounds (R = CH 3 , C 2 H 5 ) can be prepared by reaction of R-P(Se)Cl 2 -derivatives with antimony(III)fluoride under reduced pressure. In some cases the oxidation of fluorophophines with elemental selenium is successful. The isolated compounds are colourless volatile liquids which are sensitive to air and moisture. The chemical properties are described. 1 H-, 19 F-, 31 P-NMR-, IR- and Raman-spectroscopic data are given. Main stretching frequencies are discussed by comparison with similar oxygen- and sulphur-compounds.

The preparation of (CH 3 ) 3 SnSPSFC 2 H 5 , Pb(SPSFCH 3 ) 2 , Pb(SPSFC 2 H 5 ) 2 and CH 3 HgSPSFCH 3 is described. On the basis of NMR the structure was formulated as . All the complexes are colourless and monomeric in solution. The magnetic and reflectance spectra of Cr(S 2 PFCH 3 ) 3 , Mn(S 2 PFC 2 H 5 ) 2 , Co(S 2 PFCH 3 ) 2 , Ni(S 2 PFCH 3 ) 2 and Ni(S 2 PFC 2 H 5 ) 2 are reported and interpreted.

Nonstoichiometric ternary phases (M I ) x [TiS 2 ] with M I = Li, Na, K were prepared by reaction of TiS 2 in salt melts of the corresponding alkali halides under H 2 S/CS 2 atmosphere. The compounds form hexagonal crystal plates with negatively charged [TiS 2 ] x- -layers of the CdJ 2 -type and alkali cations located between the metal sulfide sheets. They react with water to form hydrates, whose layer distances depend on the radius of the alkali cation and on the ambient water vapour pressure. A variety of layer solvate complexes is obtained by partial or total replacement of the water with polar molecules, which are able to solvate the metal sulfide layers and the interlayer cations. The latter may be exchanged with mono- and divalent inorganic and organic cations. Similar reactions were observed with a number of ternary layer chalcogenides (M I ) x⁻ [(M II ) y X z ] with M I = Li, Na. K, Rb, Cs; M II = Zr, Hf, V. Nb, Ta, Cr, Ni, Pd, Pt and X = S, Se.

A new series of nonstoichiometric intercalation compounds has been found with the complex carbide Ta 2 S 2 C as host lattice. Typical compositions of the new compounds arc Ta 2 S 2 C · nY with nY = 0,5 7 N 2 H 4 , 0,2 6 H 3 CHNNHCH 3 , 0,7 8 n-C 8 H 17 NH 2 , 0,5 2 C 6 H 11 NH 2 , 0,2 3 piperidine, 0,2 6 pyrrolidine, 0,2 6 dimethylaniline, 0,4, imidazole, 0,3 9 N-methylimidazole, 0,4 3 pyrazole, 0,3 8 pyridine, 0,3 2 4-methylpyridine, 0,3 7 2-aminopyridine, 0,4 0 3-aminopyridine, 0.3 6 4-aminopyridine, 1,4 5 HCONH 2 , 0,41 HCONHCH 3 , 0,2 5 (HOCH 2 ) 3 PO and 0,2 8 (HOCH 2 ) 3 PO, 0,2 9 HCONHC 2 H 5 ,0,2 6 HCON(CH 3 ) 2 ,0,2 1 HCON(C 2 H 5 ) 2 ,0,7 0 H 2 NCONH 2 , 0,1 9 (H 3 C) 2 NCON(CH 3 ) 2 , 0,4 6 pyridine-N-oxide, 0,7 2 2-methylpyridine-N-oxide, 0,3 9 4-methylpyridine-N-oxide, 0,9 1 (CH 3 ) 2 SO, 0,6 4 (CH 3 ) 3 PO, 0.2 3 hexamethylphosphortriamide. These intercalation compounds resemble those obtained with transition metal dichalcogenides, e.g. TaS 2 ,the basal spacings being about 2,6-2,8 Å higher than in the latter ones. The observed increment of 2,7 Å confirms the proposed structuref or the host lattice with S Ta C Ta S-sandwich layers.

Dielectric measurements have been made on single-crystals of mica-type layer silicates (vermiculites) in the frequency range between 30 Hz and 10 MHz. The migration of K + -and NH 4 + -interlayer cations by free cation sites causes a low-frequency relaxation. It is interpreted by the orientation of large dipoles they form with parent negative layer charges. For both ions the activation enthalpy of diffusion across the lattice is 11.9 4 kcal/mole. Additional N-H · · · O hydrogen bonds are formed by the NH 4 + ions at low temperatures. There results a bond enthalpy of 1.3 kcal/mole and a life-time of 1.2 · 10 -5 sec (at 40°C). A discussion of the different rate process equations yields the applicability of the Bauer equation.

The chemical behaviour of the [py 2 X] + ion in acetonitrile as solvent can be well characterized by its intense charge transfer band. The two pyridine molecules of the ion can be substituted successively by chloride ions, the resulting species being py · XCl and XCl 2 - . In the order of stability of the species [py 2 X] + < py · XCl < XCl 2 - the adduct py · XCl thus is placed near the XCl 2 - ion. Consequently even this ion can act as Cl donor against the [py 2 X] + ion. The XCl and pyridine arising from this reaction on their part form the adduct py · XCl as well. The ionization of the adduct py · JCl giving [py 2 J] + and JCl 2 - , as proposed in the literature, cannot be correct.

Salts of the anions WS 4 2 -, WOS 3 2 - and WO 2 S 2 2 - can be obtained from ethanol by sulfanolysis of tungsten(VI)oxidetetraethoxide, WO(OC 2 H 5 ) 4 , in the presence of bases.

Adducts of bis(triphenylphosphine)platinum with diphenylketen and keten-S,S-acetales are formed by reaction of the ketene derivatives with (Ph 3 P) 2 Pt(C 2 H 4 ).

Two isomeric 10,10-dihydro-endosulfans are isolated, and their configurations are determined by means of infrared and nuclear magnetic resonance spectra. The isomerisation of the sulfurous ester ring of 10,10-dihydro-endosulfan yields a 67/33 ratio for the α/β isomers, while the endosulfan gives a 45/55 ratio. Both the 10,10-dihydro-endosulfans prove to be less easily hydrolised than endosulfan.

Photoelectron spectra, hyperconjugation, methylene derivatives The photoelectron (PE) spectra of dicyano methane and of its dimethyl derivative are tentatively assigned on the basis of a simple MO model. The interactions defined therein between the two cyano groups as well as with the R 2 C-framework can be parametrized using the PE data. Thus the hyperconjugation π CN /π CR₂ is estimated to amount to 1.7 eV in both compounds. Hyperconjugative effects in methane derivatives H 3 CX and H 2 CX 2 with X = Br, Cl and CN are compared.

The reaction between 1,2-dibenzoyl-1,2-dibromoethane and two moles of trimethylphosphite produces 1 -phenacyl-1 -dimethoxyphosphoryl-2-phenyl-vinyl-dimethylphosphate and not a symmetrical bis-Arbuzov - product. 1 H-, 1 H{ 31 Ρ}- and 13 C-FT-spectra were used to derive the molecular structure of C 20 H 24 O 8 P 2 .

Two isomers of hexafluorodiazabiphenylene were obtained via the pyrolysis of 2,3,6-trifluoropyridine-4,5-dicarboxylic acid disilver salt. Their [AMX] 2 fluorine NMR spectra were recorded in Fourier transform technique, partially analyzed and correlated with the molecular symmetry of the isomers. Relative signs of n J FF in 2.3,6-trifluoropyridine-4,5-dicarboxylic acid were determined by nuclear Overhauser experiments.

Some transition metal halides are tested for their suitability as cathode materials in secondary high energy batteries. The solubilities of the silver halides are determined colorimetrically. Furthermore the generation of halide complexes of silver and copper halides in different electrolytes is tested by cyclic voltammetry. It is shown, that with silver and copper halides in different electrolytes, even in a solution of 1 ᴍ LiAlCl 4 in PC halide complexes are formed, which rapidly diffuse from the working electrode. The generated chloro complexes were determined by potentiometric titrations as AgCl 2 , CuCl 2 and CuCl 2- 4 . The use of other transition metal halides is also considered.

The preparation of a series of metal complexes of N-formyl-N-hydroxyl-glycine (Hadacidin) is reported as well as their IR-. UV- and 1 H-XMR spectra. The complex formation is characterized by means of the complex formation constants.

Good yields of 2,2-dialkyltriazanium sulfates were obtained by reaction of hydroxylamido-O-sulfuric acid or its sodium salt with 1,1-dialkylhydrazines. Thus N,N-diaminopiperidinium sulfate and N,N -diamino-α-pipecolinium sulfate could be prepared for the first time. Reaction of these compounds with various barium salts in aqueous solution led to the corresponding triazanium salts due to precipitation of barium sulfate. The structure of these substances were verified by NMR and IR spectroscopic data and elementary analysis. Analogous syntheses of triazanium salts from mono-, 1,2-di-, tri- and tetramethylhydrazine were not successful.

The influence of thermal treatment of photochromic spiropyran films has been investigated. The measurements demonstrate that the decompositions of the photochromic films and the different components are changed noticeable at temperatures of 100°C and above.

It will be shown that the sensitivity of UV-sensitive spiropyran films to visible light is caused by the absorption of the open, coloured form of the spiropyran. The dependence of the fraction of this open to the closed form of the spiropyran from the solvent, HX-donator, polymer-binder, and the structur of the spiropyran molecule has been examined.

Reactions of 1-alkoxy-isoindolenines with electrophilic, nucleophilic and dienophilic reagents have been investigated as a general route for the synthesis of substituted isoindoles and isoindolenines.

UV-photolysis of aqueous solution of 5-iodouracil in presence of cystamine and oxygen leads to isodialuric acid and 5-S-cysteamine-uracil. The yields of these procucts were determined as a function of cystamine concentration. In absence of oxygen but in presence of low concentration of cystamine another competition reaction in addition to the formation of 5-S-cysteamine-uracil is observed which leads to the formation of uracil dimer. UV-photolysis of iodouracil in presence of cysteamine and oxygen leads to isodialuric acid, 5-S-cysteamine-uracil and uracil. The results suggest that cystamine accounts for the formation of 5-S-cysteamine-uracil and cysteamine for the occurence of uracil. Iodouracil and cysteamine react at pH’s between 7 and 12 in a dark reaction to give uracil.

The nature of the radicals produced by UV photolysis of methanolic solutions of o-nitrobenzaldehyde have been investigated. Contrary to an earlier report the radicals are proven to originate intramolecularly. The ESR parameters support the assignment of a nitrogen centred structure.

The structure of two new arginine antagonists, isolated from microorganisms, was determined by mass spectrometry after formation of adequate derivatives and by comparison with derivatives of reference compounds.

The mass spectral fragmentation patterns of trimethylsilyl derivatives of TRH and its constituents are discussed. The utility of these derivatives for the control of the synthesis of peptide hormones by mass spectrometry is obvious.

In order to elucidate the reaction scheme of the oscillatory malonic acid-KBrO 3 system in sulphuric acid the products extracted from the reaction system by ether are analysed by gas chromatography and mass spectrometry. After 2 hours reaction time implying approx. 80 to 100 cycles malonic acid, monobromomalonic acid and dibromoacetic acid are identified in a relative ratio of about 1.0, 0.14 and 0.023.