Volume 27, Issue 7

In the K 2 S/Sb 2 S 3 -System the compound K 2 Sb 4 S 7 has been prepared and its structure determined. In this structure there are two differently coordinated Sb-atoms: the Sb I -atoms in the vertices of flat SbS 3 -pyramides have the CN 3 to sulfur, the Sb II -atoms are ψ-trigonal-bipyramidal coordinated with one free position in the equatorial plane. These polyhedra are connected to each other by common corners and edges to a three-dimensional net, which has channels parallel the b-axis, in which the K + -ions are located.

For the first time single crystals of Ba 3 (CrO 4 ) 2 have been examined by X-ray diffraction. The already well known isotypy with Ba 3 (PO 4 ) 2 has been completed by exact parameters. There are isolated tetrahedrons of O 2- surrounding Cr 5+ and octahedrons surrounding Ba I . The complicated coordination of Ba II is discussed.

Cycloaddition reactions of (R 3 P) 2 M(N 3 ) 2 (M = Pd, Pt) with organic nitriles, thiocyanates, isothiocyanates, dimethylacetylenedicarboxylate and carbon disulphide are described; an X-ray analysis of the crystal structure of bis (5-phenyltetrazolato) -bis (triphenylphosphine) palladium (II) is summarised and related to isomerism of the complex in solution.

The preparation of surface active MgF 2 , CaF 2 , AlF 3 and BiF 3 in the shape of pellets is described. The testing of the adsorptive capacity of these pellets as well as of NaF pellets of the commercial qualities at temperatures in the range from 60°C to 400°C showed that sodium fluoride seems to be the most efficient adsorbent for the purification of UF 6 containing gas streams from small quantities of VOF 3 and VF 5 at 250-300°C - a problem occurring at the conversion of uranium. For short-time separations of UF e /VOF 3 /VF 5 or of UF 6 /VOF 3 the use of MgF 2 at about 300°C, respectively AlF 3 at 100-200°C, may be taken into consideration.

BF 3 reacts at 0° with tertiary phosphites, P(OR) 3 , stepwise to give mono- and difluorophosphites, FP(OR)s and F 2 P(OR), by ligand exchange. A new method for the preparation of monoand difluorophosphites is described. 31 P and 11 B N.M.R. spectra are reported.

A number of new solvates and adducts containing bisphenyldimethylaminophosphine oxide is reported. The solvates have the general formula M[(C 6 H 5 ) 2 P(O)N(CH 3 ) 2 ] 4 2+ (anion - ) 2 , in which M = Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn and Cd, and the anions are ClO 4 - and BF 4 - . The adducts have the general formula M[(C 6 H 5 ) 2 P(O)N(CH 3 )2] 2 Cl 2 , where M stands for the same series of metals. The compounds are characterized and identified by chemical analyses and physical measurements. Ligand-field and vibrational spectra have been investigated; values for the ligand-field parameters are reported. It is concluded that coordination takes place via the oxygen atom of the ligand. X-ray powder patterns were used in combination with ligand-field spectra to deduce the coordination around the metal ions. The interesting behaviour of the nickel (II) chloride adduct upon heating is discussed and it is shown that both a square pyramidal and a tetrahedral modification exists.

The n.m.r. signal of white phosphorus in some substituted benzenes and halogen-free solvents was measured. In both types of solvents the chemical shifts were caused mainly by van der Waals interactions. An average anisotropy term of +2.4 ppm was obtained for phosphorus dissolved in benzene derivatives. A possible use for the large solvent effects of white phosphorus is given.

According to eq. (1) the hitherto unknown (C 2 H 5 ) 2 PSS - -bridged [ (C 2 H 5 ) 2 PSSRe (CO) 3 NH 3 ] 2 (1) is obtained by reaction of [(C 2 H 5 ) 2 PSSRe(CO) 2 ] 2 with liquid ammonia between -70° and -30°. The complex can be transformed into the monomeric (C 2 H 5 ) 2 PSSRe (CO) 3 NH 3 according to eq. (2) at room temperature in THF. The 1 H NMR and IR spectra of the newly prepared compounds are discussed.

P,P-Dimethyl-C-alkoxy-methylenamino-phosphines 7 react with electrophilic olefines 8 such as acrylic, crotonic, cinnamic acid derivatives and α,β-unsaturated ketones in a 1,3-dipolar cycloaddition and immediate elimination of alcohol to give the title compounds 10. 1 H- and 31 P-NMR data prove their structure and show the electronic interaction of the P=N and C=C ring fragments. Contrasting to pyrrole, where the cyclic π-system stabilises the enamine form, the prototropic equilibrium of its phospha analogues 10 is completely on the side of the imine form.

The kinetics of the oxidation of aceltaldehyde by acid permanganate has been studied. The reaction is of first order with respect to the aldehyde, the oxidant and hydrogen ion individually. The oxidation does not induce polymerisation of acrylonitrile and show a kinetic isotope effect (k H /k D = 6.1). The activation parameters for the oxidation and enolisation reactions have been evaluated. The rate of enolisation, under similar conditions, is less than that of oxidation. A mechanism involving the transfer of a hydride ion from the aldehyde hydrate to the oxidant has been suggested.

One unsymmetricly p,p′-disubstituted trans-stilben and more than 60 new phenylbenzoates are described (Tab. 1). These compounds show partly enantiotropic, partly monotropic nematic behaviour. Some low melting substances and especially eutectic mixtures of this class of compounds are useful as room-temperature nematic, colourless liquids for electro-optical applications.

The structure of tripalmitin multilayers prepared by the Langmuir-Blodgett technique has been investigated within room temperature and 62°C using infrared internal reflection spectroscopy (ATR). It was found that the bilayer structure exhibits crystalline features with pseudo hexagonal structure. The methylene groups of the hydrocarbon chains are in the all-trans-zig-zag conformation, oriented perpendicularly to the germanium internal reflection plate. Increasing temperature produces at first a continuous conformational change in the glycerol part of the molecule. This process is extended over nearly 10° and followed by sudden melting (disordering) of the hydrocarbon chains within 1°. In comparison microcrystalline tripalmitin shows an identical infrared spectrum and analogous behaviour at increased temperatures. This indicates that the bilayer structure (head-head, tail-tail) also exicts in the crystal.

Glyoxylanilide 2-oximes (I a—c) condense with formaldehyde and secondary amines to give the corresponding Mannich bases (II a—1). The assigned structure II finds support from chemical and spectral evidences. Representative examples of the Mannich bases are tested as inhibitors for the Hill reaction and the result of the biological assay are discussed.

From the seeds of Evonymus europaea L. have been isolated evonine, neo-evonine and a new alkaloid whose structure was determined to be 4-desoxyevonine.

Rutacridone, 1-hydroxy-N-methylacridone, and 1-hydroxy-3-methoxy-N-methylacridone have been isolated for the first time from callus cultures, which had been obtained from meristematic stem cells of Ruta graveolens L. The alkaloids were identified by co-chromatography with authentic compounds, by IR spectra, and by electronic spectra before and after addition of AlCl 3 . The use of the bathochromic shift by the AlCl 3 -complex in the analysis of acridine-alkaloids has been demonstrated for the first time.

Linoside from Linum maritimum L. to which the structure 3′,4′-Dimethyl-luteolin-7-0-rhamnoside was assigned by VOLK and SINN turned out not to be identical with the synthesized glycoside. On reinvestigation Linoside could be separated into two components (Linoside A and B) and structurally elucidated as the new flavone-C-glycosides 5-hydroxy-7,3′,4′-trimethoxy-flavone-6-C- [6-or 2-O α-L- (O-acetyl-rhamno) -β-ᴅ-glucopyranoside and its desacetylderivative respectively.

The Authors have studied the biosynthesis of some furocoumarins contained in Ruta graveolens. Labeled 5,7- and 7,8-dihydroxycoumarins have been administered to the herb, however practically no incorporation of radioactivity was observed in the isolated furocoumarins. Moreover, with the aim to study in a more detailed way the role of rutaretin and marmesin, trapping experiments have been performed administering to the herb labeled umbelliferone together with unlabeled rutaretin and marmesin respectively. A very effective incorporation was observed into marmesin, in lesser extent into rutaretin. In trapping experiments carried out using labeled rutaretin together with unlabeled marmesin and “vice versa”, the results obtained clearly show that while marmesin was converted into rutaretin in a very effective way, rutaretin was transformed into marmesin only in a smaller extent. The Authors suggest the biogenetic origin of rutaretin and moreover formulate a new and more detailed aspect of the scheme for the biosynthetic pathway of furocoumarins in Ruta graveolens.

The antibacterial activity of 2-thiouracil, 2-methylthiouracil, 2-hydrazinouracil, 2,4-dithiouracil, 2-thio-4-hydrazinouracil, 2-thio-6-azathymine, 2-hydrazino-6-azathymine, 2,4-dithio-6-azathymine, 2-thio-4-hydrazino-6-azathymine, 2,4-dimethylthio-6-azathymine, 2-methylthio-4-hydrazino-6-azathymine, 4-thio-6-azauracil and 4-hydrazino-6-azauracil has been studied on the growth of: Staphylococcus aureus 209, Streptococcus faecalis 775, Escherichiia coli 387, Pseudomonas aeruginosa, Bacillus subtilis, Candida tropicalis and Neurospora crassa 9863. The highest inhibitory effect was observed with 4-hydrazino-derivatives of 2-thiouracil, 6-azauracil and 2-thio-6-azathymine.

Immunoglobulins to monogalactosyl diglyceride have been found in antisera to different chloroplast preparations. A specific antiserum to this lipid has been obtained by injection of monogalactosyl diglyceride which was adsorbed onto methylated bovine serum albumin. Inhibition tests with mono- and oligosaccharides, as well as with mono- and digalactosyl glycerol, showed that the immunoglobulin was directed to the β-galactosyl-(1 → 1) -glycerol configuration. Digalactosyl diglyceride and sulphoquinovosyl diglyceride did not react with the antiserum. The immunoglobulin is of the Ig M-type. The antiserum to monogalactosyl diglyceride agglutinates stroma-freed chloroplasts. Fragments of the thylakoid membrane, obtained by ultrasonication and fractioning centrifugation, thylakoids and thylakoid stacks are all precipitated. In a preparation of stroma-containing chloroplasts agglutination takes place but after rupture of the chloroplast membrane and loss of the stroma. The ultrasonicated lamellar system binds a larger amount of the monogalactosyl diglyceride immunoglobulins than does stroma-freed chloroplasts. It is concluded from these experiments that some of the chloroplasts monogalactosyl diglyceride is located at the surface of the thylakoids.

Diaphorase and transhydrogenase activities (system NADPH; dichlorophenolindophenol and NADPH;NAD, respectively) of ferredoxin-NADP reductase are increased by ferredoxin. Reduced thionicotinamide-NADP (TN-NADPH) only slightly inhibits these activities with no ferredoxin present in the assay, but the activity increments in the presence of ferredoxin are strongly decreased. Photosynthetic pyridine nucleotide reduction is also inhibited by the reduced analog, the extent of inhibition being approx. in the same order with all three activities. The ferredoxin stimulated activities therefore appear to be due to the same interaction between reductase and ferredoxin in all three cases. The inhibition by TN-NADPH resembles that with Na-pyrophosphate (or NaCl), although in contrast to salt inhibition it is a.) not alleviated by higher ferredoxin concentrations, and b.) it still allows reductase/ferredoxin binding. The binding of the reduced pyridine nucleotide analog to the reductase seems to interfere rather specifically with the stimulation which ferredoxin can exert on the enzymic activities of the reductase.

The production of BU-phages with a relative high amount of hybrid DNA is described. Transforming experiments with the irradiated phage BU-DNA and the investigation of the photodecomposition of the single strands of hybrid DNA demonstrate clearly intramolecular energy transfer. From the breakage rates of the single strands of hybrid DNA a calculation for the relative amount of intramolecular energy transfer in hybrid BU-phage DNA is given.

The cellular activity of ouabain-sensitive sodium-potassium-activated adenosine triphosphatase (Na + -K + -ATPase) and ouabain-insensitive Mg ++ -ATPase was analysed in sublines of Ehrlich ascites tumor cells serially cultivated either in isotonic media or in media with progressively increased NaCl concentration (up to 0.40 ᴍ). Progressive elevation in the NaCl content of the medium resulted in a progressive increase of cellular ATPase activity, Na + -K + -ATPase thereby being more affected than Mg ++ -ATPase. These alterations in ATPase activities are interpreted as “adaptive” changes in response to the elevated ionic environment, since “readaptation” of these “high-salt”-tolerant cells to growth in isotonic media resulted in a reversion of the enzyme activities to the level characteristic of the original parent cells.

Ehrlich ascites tumor cells adapted to serial cultivation in vitro in media with increased NaCl content (“high-salt”-tolerant cells) exhibit — in comparison with cells cultivated either in isotonic media or intraperitoneally in mice (in vivo) — an increased rate of cellular oxygen consumption. It is suggested that this increased respiratory rate of “high-salt”-tolerant cells reflects enhanced energy requirements associated with processes of active ion transport; and that the elevated environmental NaCl concentration may have “induced” a “step up” of the respiratory metabolism of these tumor cells.

During the growth of Morris- hepatoma No. 3924 in rats changes in the level of trace elements were observed using neutron activation analysis. The increase of copper concentration in the plasma correlated with the incorporation of 3 H-thymidine in the tumor. In contrast to our investigations on Yoshida-sarcoma, the decrease of manganese in the liver did not correlate with the incorporation of tritiated thymidine in the hepatomas.

The differences in the properties of electronic structure between 3,4-Benzpyrene and 1,2-Beuzpyrene are used to construct a possible model of the mechanism of chemical carcinogenesis. This model proposes an alternative hypothesis to Masons theory and describes the primary step *n carcinogenesis as a resonance-phenomenon between the carcinogenic hydrocarbon and the bioreceptor which is likely to be a base of DNA or RNA.

Structural chemistry of intermetallic AB 2 X 2 -Compounds