bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesen von Heterocyclen, CCIV1 Reaktionen mit cyclischen Oxalylverbindungen, XIX2 Eine einfache Synthese von 5-Benzoyl-6-phenyl-1.3-dioxin-4-onen / Syntheses of Heterocycles, CCIV1 Reactions of Cyclic Oxalyl Compounds, XIX 2 A Simple Synthesis of 5 Benzoyl-6-phenyl-1,3-dioxin-4-ones
Authors: Kollenz Gert , Ziegler Erich , Ott Walter , Kriwetz Gert
Published: March 2015

4-Benzoyl-5-phenyl-2,3-dihydrofuran-2,3-dione (1) reacts with aldehydes or ketones via the acylketene-intermediate (2) yielding the 1,3-dioxin-4-ones (3). The aldehyde derivatives (3 a-e) can be converted into the anilino-chalcone (5) or the anilino acrylic acid (6) by treating with aniline at 20 °C. 6 and diazomethane combine to the acrylic acid methyl ester (7), which by heating (200 °C) is cyclisized to the quinolin-4-ole (8). On the other hand, the keto derivatives 3f-h and aniline give the dibenzoyl acetic acid anilide (9).
Anionenaktivierung, V / Anion Activation, V
Authors: Dorn W. L. , Knöchel A. , Oehler J. , Rudolph G.
Published: March 2015

The rate constants of the reaction between benzyl chloride and acetate ion, generated from several alkali acetates and a series of macrocyclic polyethers, were measured under equal conditions. It appears that aminopolyethers are superior to crown ethers in rate acceleration. This behaviour is correlated to the amount of ion-pair separation by certain macrocyclic polyethers, as detected by 1H NMR spectroscopy, which is a simple method to evaluate the anion activation of every ligand/cation-combination.
Formose-Reaktion, I Kinetik und Mechanismus der Sekundärreaktionen bei Anwesenheit von Formaldehyd / Formose Reaction, I Kinetics and Mechanism of the Secondary Reaction Step in the Presence of Formaldehyde
Authors: Harsch Günther , Voelter Wolfgang , Bauer Hermann
Published: March 2015

Quantitative kinetic results of the intermediates and end products of the formose reaction are obtained for the first time by the application of high pressure liquid chromatography. A mechanism for the secondary reaction step of the formose reaction in the presence of excess formaldehyde is derived from these results : Formaldehyde adds successively to intermediates and the formation of xylose is highly favoured. All results are characteristic for typical aldol-type reactions. Almost no cleavage of the intermediate and end products is observed.
Kombinierte 3.3- und 3.4-Addition an ein 1.2.4.3λ3-Triazaphosphol zu Tricyclophosphoranen / Combined 3,3- and 3,4-Addition to a 1,2,4,3λ3-Triazaphosphole Yielding Tricyclic Phosphoranes
Authors: Schmidpeter Alfred , Junius Martina , Weinmaier Josef Helmut , Barrans Jean , Charbonnel Yves
Published: March 2015

2-Methyl-5-phenyl-2H-1,2,4,3λ3-triazaphosphole, which does not lend itself to oxidative additions alone, reacts smoothly with o-heterodienyl-phenols yielding tricyclic phosphoranes. The reaction involves an initial addition of the phenolic end to the P=N bond and a subsequent fast intramolecular addition of the heterodiene moiety to the phosphorus.

The structure of the resulting phosphoranes is proposed to have all three fivemembered rings attached to the central trigonal bipyramidal phosphorus by one axial and one equatorial bond with the bond in common to the two condensed rings in axial position. NMR data back this proposal.
Aminyle, VIIΙ ESR des Bis(9-fluorenylidenmethyl)aminyls / Aminyls, VIII ESR of Bis(9-fluorenylidenmethyl)aminyl
Authors: Neugebauer F. A. , Fischer H.
Published: March 2015

The specifically substituted derivatives 3b, 3c of the aminyl 3a and the corresponding carbon centered radicals 6b, 6c yield resolved analyzable ESR spectra. In these systems the unpaired electron is highly delocalized. The aminyl radicals 3a-3c form C—C dimers.
Synthesis of New 4–Arylhydrazono-3-methyl-2-pyrazolin-5-one Derivatives and their Reactivity towards Active Methylene Components and Grignard Reagents
Authors: Amer Fathy A. , Haraash Abd El-Hamid , Metwally Mohamed Abbas
Published: March 2015

Treatment of 4-arylhydrazono-3-methyl-2-pyrazolin-5-ones (1 a-e) with dimethylsulphate afforded the N-methyl derivatives (2a-e) which on treatment with phenylmagnesium bromide gave the carbinol (8). The hydroxy pyrazolones (4a-e) were reacted with ethyl acetoacetate and diethyl malonate to give the a-N-methyl derivatives (5 and 6 a-e). The hitherto unknown 4-arylhydrazono-3-methyl-l-benzenesulphonyl-2-pyrazolin-5-ones (7 a, e-e) were now obtained and upon treatment with Grignard reagent gave 4-arylhydrazono-3-methyl-3,5,5-triphenylpyrazolines (7 a, c and d).
Notizen: Oxide der 1.2.3-Thiadiazole 13C–NMR-Untersuchungen zur Photolyse der 1.2.3-Thiadiazol-1.1.2-trioxide / Oxides of 1,2,3-Thiadiazoles 13C NMR Studies on Photolysis of 1,2,3-Thiadiazole-1,1,2-trioxides
Authors: Trickes Georg , Plücken Udo , Meier Herbert
Published: March 2015

By the use of 13C NMR spectroscopy the photolytical fragmentation of 1,2,3-thiadiazole-1,1,2-trioxides is demonstrated.
N-Chlorsilyl-triorganophosphinimine, Darstellung und Eigenschaften / N-Chlorosilyl Triorganophosphine Imines, Preparation and Properties
Authors: Wolfsberger Werner
Published: March 2015

A series of N-chlorosilyl triorganophosphine imines have been prepared by transsilylation reactions of the corresponding N-trimethylsilyl triorganophosphine imines with halosilanes. The new compounds were characterized by elemental analyses, molecular weight determinations, IR and 1H and 31P NMR spectra.
Tetraquecksilbermethane. Tetrakis(methylthioquecksilber)-methan C(HgSCH3)4 und µ-Dithiotetraquecksilbermethan CHg4S2; Synthesen und Schwingungsspektren / Tetramercurimethanes. Tetrakis(methylthiomercuri)methane C(HgSCH3)4 and µ-Dithiotetramercurimethane CHg4S2; Syntheses and Vibrational Spectra
Authors: Breitinger Dietrich , Morell Wilfred
Published: March 2015

Reactions of tetrakis(acetoxymercuri)methanes C(HgOOCCR3)4 (R = H, or F) in aqueous solutions with methylsulfane CH3SH, or sulfane H2S, yield tetrakis(methylthiomercuri)methane C(HgSCH3)4, and μ-dithiotetramercurimethane CHg4S2, respectively, both insoluble in common solvents and thermally remarkably stable. The central CHg4 groups of the starting materials have been preserved under the reaction conditions, thus tetrahedral entities C(HgS–)4 are common to both compounds. In the polymeric, amorphous CHg4S2 the CHg4 units are linked by sulfur bridges in a highly disordered manner, as is suggested by vibrational spectra. In other respects close similarities in the vibrational behaviour of these CHg4 fragments and of the isosteric NHg4 tetrahedra in tetramercurioammonium complexes have been observed.
Wideline 1H NMR Study on Hydrated Layered Sulfides K0.5(H2O)y[NbS2] and Na0.5(H2O)y[NbS2]
Authors: Lerf Anton , Burkert Paul , Besenhard Jürgen O. , Schöllhorn Robert
Published: March 2015

H NMR spectra of different hydration stages show that the water molecules in hydrated layered niobium sulfides A0.5(H2O)y[NbS2] are rather mobile at room temperature. A structural scheme of water arrangement in the interlayer space is proposed with the C2-axis of the H2O molecules parallel to the basal planes of the NbS2 layer units.
Transphosphorylative Spin-Labeling Utilizing Diimidazolides of Pentavalent Phosphorus
Authors: Sosnovsky George , Konieczny Maria
Published: March 2015

The reaction of the spin-labeled diimidazolide 1 with hydroxy and amino compounds was studied. Diimidazolide 1 was superior to the dichloridate 6 for the preparation of spinlabeled phosphates 3 and phosphorodiamidates 2. The spin-labeled phosphate 15 was synthesized through hydrolysis of 6. Spin-labeled cyclophosphoramidates (10-13), analogs of the cytotoxic Endoxan, were prepared by the reaction of 1 and 6 with the appropriate difunctional nucleophile. Inductive effects of substituents in the imidazolyl moiety on the transphosphorylation reaction were also studied.

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Reactions of Benzofuran Oxidation, Nitration and Bromination of 7-Hydroxy' and 7-Metboxy-benzofuran Derivatives
Authors: Abdel Rahmanand A.H. , Basha R.M.
Published: March 2015

Condensation of benzoin and pyrocatchol gave 7-hydroxy-2,3-diphenylbenzofuran (1a), which on oxidation yielded the quinone 3a whereas, its methyl ether 1b gave the benzophenone 2a on oxidation. Nitration of 1a and 1b led to the formation 4,6-dinitro- (1c) and 4-nitro (1h) derivatives,respectively, also bromination of 1a and 1b gave 4,6-dibromo- (1f) and 6 -bromo- (1j), respectively
Notizen: The Preparation and Structure of Lithium (R, S)-Ethylenediamine-N,N′-disuccinatocobaltate(III) Trihydrate
Authors: Pavelcík F. , Majer J.
Published: March 2015

Crystals of LiCo[(R,S)-EDDS] • 3 H2O have been synthetized and its structure was determined by X-ray analysis. Monoclinic, α = 9.624, b = 12.788, c = 12.049 Å, β = 94.85°, space group P21/c. The crystal consists of binuclear units Co2[(R,S)-EDDS]2
2-. The central ethylenediamine chelate ring has an envelope conformation.
Notizen: Ternäre Fluoride vom Typ AgLnF4 (Ln = Nd, Sm-Lu, Y) / Ternary Fluorides of the AgLnF4-Type (Ln = Nd, Sm-Lu, Y)
Authors: Lösch Roland , Hebecker Christoph
Published: March 2015

Single crystals of AgGdF4 have been investigated by X-ray methods. AgGdF4 is hexagonal (isostructural to NaNdF4) with a = 6.233, c = 3.599 Å, Z, = 3/2. Guinierphotographs give the same structure for AgLnF4-compounds with Ln = Nd, Sm-Ho. The other five (Ln = Er-Lu, Y) crystallize trigonal (isostructural to KErF4) in a superstructure variant of the CaF2-type (Z = 18).
Über die Reaktionen von K2 [Fe2(CO)8] mit Ph3SnCl und Ph2SnCl2 / On the Reactions of K2[Fe2(CO)8] with Ph3SnCl and Ph2SnCl2
Authors: Behrens Helmut , Moll Matthias , Sixtus Eduard , Sepp Erich
Published: March 2015

Ph3Sn(OC)4Fe-Fe(CO)4SnPh3 and ClPh2Sn(OC)4Fe-Fe(CO)4SnPh2Cl are formed by the reactions of dipotassium octacarbonyl diferrate(-I) with Ph3SnCl and Ph2SnCl2:

K2[(OC)4Fe-Fe(CO)4] + 2 Ph3SnCl → Ph3Sn(OC)4Fe-Fe(CO)4SnPh3 + 2 KCl K2[(OC)4Fe-Fe(CO)4] + 2 Ph2SnCl2 → ClPh2Sn(OC)4Fe-Fe(CO)4SnPh2Cl + 2 KCl.
Phasendiagramm des V1-xFexO2-xFx-Systems für o < x ≦ 0,04 / Study of Phase-Diagram in V1-xFexO2-xFx with ο < x ≦ 0.04
Authors: Pebler Jürgen , Schmidt Klaus
Published: March 2015

V1-xFexO2-xFx samples (0 ≤ x ≦ 0.20) have been prepared by solid state reaction in sealed platinum tubes. The temperature-composition phase diagram with 0 < x ≦ 0.04 is found to contain four phases which were determined by X-ray diffraction and 57Fe-Mössbauer measurements. At small (Fe3+, F-) concentrations (x < 0.005) only one Fe-site is seen in the low-temperature M1 phase and one transition from the insulator to metallic phase. For 0.005 ≦ x ≦ 0.008 at temperatures just below the metal-insulator transition a second monoclinic phase M2 is stable in which two Fe-sites are resolved by their electric field gradients and their isomer shifts. These two sites are identified as the Fe atoms on the paired V-V chains and the equispaced V-V chains in the C2/m structure of MAREZIO et al. At higher Fe3+, F- concentrations (x > 0.008) the existence of the intermediate phases M2 and M3, between M1 and the rutile phase, has been confirmed.
Photochemische Umsetzungen von η5-Indenyl-tricarbonyl-methyl-molybdän und -wolfram, C9H7M(CO)3CH3 (M = Mo, W), mit Acetylenen / Photochemical Reactions of Indenyl-tricarbonyl-methyl-molybdenum and -tungsten, C9H7M(CO)3CH3 (M = Mo, W), with Acetylenes
Authors: Alt H. G.
Published: March 2015

The photoreaction of the indenyl complexes C9H7M(CO)3CH3 (M = Mo, W) with alkynes (L) in solution leads to 1:1 adducts, which are found to be metallocyclic alkenylketone compounds C9H7M(CO)2(L-COCH3). UV irradiation of C9H7W(CO)3CH3 in the presence of either acetylene or methylacetylene also gives substituted derivatives C9H7W(CO)(L)CH3 in low yields. For these compounds, the intramolecular mobility of the π-bonded alkyne ligand can be demonstrated by temperature-dependent 1H NMR spectroscopy.
Mass Spectral Fragmentation Pattern of Ν,N′ -Diphenylformamidines
Authors: Keats Neil G. , Rockley Jean E. , Summers Lindsay A.
Published: March 2015

The base peaks in the mass spectra of Ν,N′-diphenylformamidine, N,N′-di-(4-chlorophenyl)formamidine and N,N′-di-(3-chlorophenyl)formamidine are due to the molecular ions of aniline, 4-chloroaniline and 3-chloroaniline respectively. The species responsible for the base peaks are thought to be formed by rupture of the CH-NH bond with concomitant hydrogen migration.
Inductive Effects on Molecular Ionization Potentials, XVIII Alkylpyridines and Alkylthiophenes. Molecular Orbital Calculations on Alkylbenzenes and Alkylpyridines
Authors: Párkányi Cyril , Levitt Leonard S.
Published: March 2015

Models of alkylbenzenes were treated by the HMO and SCF—MO methods and excellent linear correlations were found between the experimental ionization potentials, EI, and the energies of the highest occupied π-molecular orbitals calculated by the above-mentioned methods. A similar linear correlation was obtained for a group of methylpyridines. Also, the experimental ionization potentials of methylpyridines and alkylthiophenes have been linearly correlated with the sum of TAFT'S inductive substituent constants, ΣσI of the alkyl groups.
Zur kinetisch kontrollierten Racematspaltung phosphororganischer Verbindungen / The Kinetically Controlled Racemate Separation of Organophosphorus Compounds
Authors: Luckenbach Reiner , Kern Manfred
Published: March 2015

The kinetically controlled racemate separation of unsymmetrically substituted organophosphorus compounds is described. Treatment of racemic methyl-tbutyl-phenyl-phosphine (1) with a half molar quantity of R-(+)-methyl-phenyl-sulfoxide (8) results in formation of S-(—)-methyl-tbutyl-phenyl-phosphine oxide (4) and – after quaternization with allyl bromide - of R-(+)-methyl-tbutyl-phenyl-allylphosphonium bromide (5) of ca. 1% optical purity.
Organische Schwefelverbindungen, XXV Freie 9-Fluorenyl-Radikale als Zwischenstufe bei Photolyse eines Fluorenon-Dithioketals / Organic Sulfur Compounds, XXV Free 9-Fluorenyl Radicals as Intermediates in Photolysis of a Fluorenone Dithioketal
Authors: Praefcke Klaus , Simon Helmut
Published: March 2015

Fluorenone diaryldithioketal (4) decomposes photochemically into free 9-arylthio fluorenyl radicals which dimerize under formation of 9.9′-bifluorenyl (6). The reaction behavior of both 4 and 6 under UV irradiation as well as under electron impact conditions can be compared.
Struktur und Reaktivität von 4-Hydroxy-5-oximino-7-methyl-5H-pyrano-[2.3-b]-pyridin-8-oxid / Structure and Reactivity of 4-Hydroxy-5-oximino-7-methyl-5H-pyrano-[2,3-b]-pyridine-8-oxide
Authors: Roth K. , Löwe W.
Published: March 2015

For the reaction product of 1 with dimethylformamidedimethylacetal in the presence of hydroxylamine there might exist five possible tautomeric forms 2 a-e. The structure of the title compound was determined to be 2 d by applying carbon-13 NMR spectroscopy to 2 a-e and some derivatives 8-5 in DMSO-d6 resp. DMSO-d6/NaOD.
A Novel Approach to the Transformation of Aldoximes to Nitriles Utilizing Spin-Labeled Phosphoryl Imidazolides
Authors: Sosnovsky George , Konieczny Maria
Published: March 2015

The spin-labeled imidazolides of phosphorus 1 and 3 were utilized for the conversion of

[xxx]

aldoximes to nitriles in high yield. It is hypothesized that this transformation under mild, neutral conditions might serve as a model reaction, mimicking the detoxification of phosphorus-inhibited acetyl cholinesterases.
Isolierung, Auftrennung und Strukturaufklärung des blauen Bakterienpigments „Amylocyanin" aus Streptomyces coelicolor Müller / Isolation, Separation and Structure of the Blue Pigment „Amylocyanin“ from Streptomyces coelicolor Müller
Authors: Habermehl Gerhard , Christ Bernhard G. , Kutzner Hans J.
Published: March 2015

The isolation and chromatographic separation of “Amylocyanin”, the blue pigment mixture of Streptomyces coelicolor is described. The main component is 5-(hydroxy-3-β-D-ribopyranosyl-pyrid-2-on-5-yl)-imino-3-β-D-ribopyranosyl-2,6-pyridindione (1), as is prooved by degradation reactions, model compounds and spectroscopic data. The nine minor components are α- and β-D-ribopyranosyl- and α- and β-ribofuranosyl derivatives of 1. Degradation with acetic acid/phenylhydrazine yields the isomere 3-α- and 3-β-D-ribopyranosyl- and 3-α- and 3-β-D-ribofuranosyl-5-phenylhydrazono-2,6-pyridindiones 2, 8, 9 and 10; ozonolysis of 1 liberates D-ribose.
Notizen: Si-N-Rotationshinderung in Fluor-Silyl-Hydrazinen / Si-N-Rotational Barrier in Fluoro-Silyl-Hydrazines
Authors: Klingebiel Uwe
Published: March 2015

Fluorosilanes react with lithium salts of hydrazines to give fluorosilylhydrazines. The 19F NMR spectra of N,N′-bis(difluoromethylsilyl)-N,N′-diphenylhydrazine and N,N′-bis-(difluoroorganylsilyl) - N, N′ - bis (trimethylsilyl)-hydrazines show an AB system for the fluorineatoms at room temperature, which results from hindered rotation about the Si–N bonds. The coalescence temperature of N,N′bis(difluoromethylsilyl)-N,N′-diphenylhydrazine was observed at + 170 °C ± 10 °C.
Notizen: Notiz über die Umsetzung von Isatosäureanhydrid mit β-Aminocrotonsäureester und Acetylacetonimin / Note on the Reaction of Isatoic Anhydride with Ethyl β-Aminocrotonate and Acetylacetone-imine
Authors: Mayer Cölestin , Kappe Thomas
Published: March 2015

Isatoic anhydride (1) reacts with ethyl ß-aminocrotonate (2 a) or acetylacetoneimine (2 b) to give 2-methyl-4-quinazolone (6). The formation of 6 can be rationalized as proceeding through the loss of ethyl acetate or acetone from the intermediate 1,2-dihydroquinazolone 5 by a retro-Claisen or retro-Aldol type elimination, respectively.
Notizen: Kristall- und Molekülstruktur eines koordinationspolymeren 2-Organo-1.3.2-dioxastibols / Crystal and Molecular Structure of a Coordination-Polymeric 2-Organo-1,3,2-dioxastibole
Authors: Wieber Markus , Baumann Norbert , Burschka Christian
Published: March 2015

2-Methoxi-1,3,2-benzodioxastibole is prepared by transesterification of (CH3O)3Sb with catechol. Recrystallization from m ethanol yields colourless crystals, the structure of which was solved and refined to a conventional R-value of 0.04 with 915 reflections observed. The space group is P 21/n with 4 molecules in the unit cell. Interaction with oxygen atoms of two neighbouring molecules enlarges the coordination number on the antimony to five, thus forming a structure with infinite chains along the α-axis.
Photoelektronenspektren von einigen Trihalogensilylphosphanen und -arsanen X3SiER2 (X =F, Cl; E = N, P, As; R = H, CH3) / Photoelectron Spectra of Some Trihalogensilyl Phosphines and Arsines X3SiER2 (X = F, Cl; E = N, P, As; R = H, CH3)
Authors: Demuth Reinhard
Published: March 2015

The He (I) photoelectron spectra of the title compounds are described. The PE assignments are based on the comparison with the spectra of related compounds and on simple MO considerations (composite molecule–approach). The correlation between PE ionisation energies and molecular properties (e.g. SiP-(p→d)π-bonding) is discussed.
Photoelectron Spectroscopy of Substituted N-Benzylideneanilines
Authors: Klasinc L. , Ruščić B. , Heinrich G. , Güsten H.
Published: March 2015

The electronic structure and conformation in the gas phase of N-benzylideneaniline, its para-nitro and -methoxy as well as the ring perfluorinated derivatives were investigated by photoelectron (PE) spectroscopy and semiempirical molecular orbital (HMO) calculations. The π-ionizations were assigned and it is shown that these compounds in the gas phase are in a nonplanar conformation.
Notizen: Kristall- und Molekülstruktur von Bis (trimethylsilyl)amino-trimethylsilyliminophosphin bei —130 °C / Crystal and Molecular Structure of Bis (trimethylsilyl)amino-trimethylsilyliminophosphine at —130 °C
Authors: Pohl Siegfried
Published: March 2015

The crystal structure of R2N–P=NR (R = Si(CH3)3) was determined by single crystal X-ray data collected at —130 °C and refined to a conventional R-value of 0.029. The structure exhibits a two-connected phosphorus atom. The short P = N multiple bond (154.5 pm) indicates a 3pπ(P)—2pπ(Ν) interaction. The N–P–N angle was found to be 108.4°.
Notizen: Hydrogen Bonding in MoO2Cl2 · H2O Determined by Electrostatic Energy Calculations
Authors: Baur Werner H.
Published: March 2015

The configuration of least electrostatic energy for the hydrogen atoms in both polytypes of MoO2Cl2 · H2O was obtained by systematic variation of the orientations of the water molecules. The internal geometry of the H2O group was kept constant throughout the variation. The hydrogen bonds are of the bifurcated type: [xxx]
Notizen: Nitridochlorokomplexe [MNCl4]-von Molybdän(VI) und Wolfram(VI) / Nitrido-chloro Complexes [MNCl4]-of Molybdenum(VI) and Tungsten(VI)
Authors: Dehnicke Kurt , Kolitsch Werner
Published: March 2015

The nitrido-chloro complexes X[MNCl4] (M = Mo, W; X = NMe4, AsPh4) were prepared by the reaction of NMe4Cl and AsPh4Cl with MoNCl3 and WNCl3, respectively. The complexes were characterised by their IR spectra; they contain M=N-triple bonds.
Notizen: Rhenium(VI)-Nitridchlorid, ReNCl3 / Rhenium(VI) Nitridochloride, ReNCl3
Authors: Dehnicke Kurt , Liese Werner , Köhler Peter
Published: March 2015

Rhenium(VI) nitridochloride, ReNCl3, is prepared by the reaction of ReCl5 with chlorine azide. It forms a black powder with a rhenium-nitrogen triplebond (vReN 1080 cm-1) and a magnetic moment of 1,75 B.M.
Notizen: Solvent Deuterium Isotope Effect on Hydrolysis of Nd3+ Ion
Authors: Maeda Masunobu , Amaya Toshihiko , Kaeihana Hidetake
Published: March 2015

The hydrolysis equilibria of Nd3+ ion in light- and heavy-water solutions containing 3 mol dm-3 (Li)ClO4 as an ionic medium were studied at 25 °C by measuring the lyoniumion concentration with a glass electrode. Analysis of the emf data indicated the formation of only the mononuclear complex Nd(OL)2
+ in both light and heavy water. The formation constant *β2,1 was smaller in D2O (log *β2,1 = —16.54 ± 0.04) than in H2O (log *β2,1 = —15.90 ± 0.06). The formation constant K2,1 for the heavy-water system (log K2,1 = 12.28) had a larger value than that for the light-water system (log K2,1 = 11.86).
Die Oxidation von Phthalocyaninen: Darstellung und Charakterisierung von Lithiumphthalocyanin(1-) / The Oxidation of Phthalocyanines: Preparation and Characterisation of Lithiumphthalocyanine(1-)
Authors: Homborg Heinrich , Kalz Winfried
Published: March 2015

Lithiumphthalocyanine(1-), to date the most simple representative of radical phthalocyanine species, is prepared in nonpolar aprotic solvents by the chemical, electrochemical and photochemical oxidation of quarternary ammonium phthalocyanines(2-). The compound is characterized by its electronic and vibrational spectra.
The Mechanism of the Sorption of Monovalent Cations on Cobalt(II)-hexacyanoferrate(II)
Authors: Ćeranić T. , Trifunović D. , Adamović R.
Published: March 2015

Cobalt(II)-M-hexacyanoferrate(II), M = K, NH4, Cs, as synthetic sorbents have ion exchange properties selective for monovalent cations. They show a higher selectivity for the ions with larger crystal radius if the sorption takes place in dilute solutions, whereas in concentrated sulutions the selectivity sequence is reversed. The phenomenon is attributed to the differences in physico-chemical properties of the given pair of competing ions in the solution phase and to steric limitations in the phase of ion exchanger.
Darstellung von Cyclopentadienylvanadylidyntrikobaltenneacarbonyl / Preparation of Cyclopentadienyl-vanadyhdyne-tricobaltenneacarbonyl
Authors: Haustein Hans , Schwarzhans Karl
Published: March 2015

A new vanadium-cobaltcarbonyl-cluster, cyclopentadienyl-vanadylidyne-tricobaltennea-carbonyl, has been prepared and identified by IR and masspectrometric measurements.
Hydrolyse von Per(fluorchlor)methylsulfenylchloriden: Isolierung und Charakterisierung stabiler Zwischenstufen / Hydrolysis of Per(fluorochloro)methylsulfenylchlorides: Isolation and Characterization of Stable Intermediates
Authors: Haas Alois , Wanzke Wolfgang , Welcman Nathan
Published: March 2015

Hydrolysis of CF3-nClnSCl with water yields the thiosulfinates CF3-nClnSS(O)CF3-nCln and thiosulfonates CF3-nClnSSO2CF3-nCln as stable intermediates. They were synthesized on a preparative scale by special reactions and characterized. A new mechanism, based upon additional reactions of the isolated products, is discussed and extended to the reaction of chlorine with water
Synthesis of 3,4-Benzo-1-oxacephem / Synthesis of 3,4-Benzo-1-oxacephem
Authors: Ongania Karl-Hans
Published: March 2015

The thioformimidate 4, which may be obtained by S-methylation of 5 reacts with chloroacetyl chloride/triethylamine to yield the trans-2-azetidinone 7. 7 is dehalogenated to 8. Removal of the protective group leads to 9, which undergoes ring closure by the action with mercuric chloride/ mercuric oxide. Chlorolysis of 8 and the subsequent reaction with hydrofluoric acid/acetonitrile yields 12. The treatment of 12 with silver tetrafluoroborate/silver oxide gives also the title compound 10
A Novel Synthesis of Heterocyclic β-Enaminoamides: The Reaction of Halomethyl Acet-p-toluidide with Isothiocyanates and with Isocyanates
Authors: Ibrahim Nadia Sobhy , Sadek Kamal Usef , Aziz Suzan Ibrahim , Elnagdi Mohamed Hilmy
Published: March 2015

A novel synthesis of thiophene and furan β-enaminoamides via the reaction of halomethyl acet-p-toluidide with isothiocyanates and isocyanates were reported
Organoboron-Monosaccharides, XIV Routes to α-and β-D-Mannofuranosyl β-D-Mannofuranosides
Authors: Dahlhoff Wilhelm Volker , Geisheimer Angelika
Published: March 2015

Stereoselective glycosylations of 2,3:5,6-di-O-ethylboranediyl-α-D-mannofuranosyl bromide (1) by two independent routes involving 1-O-tri-n-butyl-stannyl and 1-O-triethylborate α-D-mannofuranosyl derivatives give α-D-mannofuranosyl /β-D-mannofuranoside (8a) after deprotection. β-D-Mannofuranosyl β-D-mannofuranosides can be prepared by reaction of 1 with the sodium triethylborate derivative of 2,3:5,6-di-O-isopropylidene-β-D-mannofuranose (11) and by reacting 1 with hexabutyldistannoxane. The latter approach allows the synthesis of β-D-mannofuranosyl β-D-mannofuranoside (8b) after total deprotection.
(2,3-Bis(methylen)bicycIo[2.2.2]octan)zirconocen: Synthese, Struktur und elektrochemische Reduktion/(2,3-Bis(methylene)bicyclo[2.2.2]octane)zirconocene: Synthesis, Structure, and Electrochemical Reduction
Authors: Erker Gerhard , Engel Klaus , Krüger Carl , Tsay Yi-Hung , Samuel Edmond , Vogel Pierre
Published: March 2015

Photolysis of diphenylzirconocene and 2,3-bis(methylene)bicyclo[2.2.2]octane in toluene at -25 °C yields biphenyl and (2,3-bis(methylene)bicyclo[2.2.2]octane)zirconocene (lg) (67.5% isolated yield).1g exhibits dynamic NMR spectra indicating rapid alternation of diene faces coordinated to zirconium (ring-flip mechanism). This degenerate intramolecular rearrangement is characterized by an extremely low activation barrier (⊿G≠
-131°C = 7.1 ± 0.3 kcal/mol). 1g crystallizes in space group P1̄with a = 7.215(1) Å, b = 9.654(1) Å, c = 11.831(1) Å, α = 94.97(1)°, β = 91.81(1)°, and γ = 103.22(1)°. The X-ray structure determination reveals a pronounced metal alkyl character of the (diene)ZrCp2 moiety. Accordingly, 1g is easily reduced electrochemically to give a Zr(III) radical anion (7) observed by esr (g = 1.990; a(H) = 2.976 G; a(Zr) = 18.36 G).
Ein-und zweikernige Phosphorinylnickel-Komplexe/Mono-and Binuclear Phosphorinylnickel Complexes
Authors: Lehmkuhl Herbert , Elsäßer Johannes , Benn Reinhard , Gabor Barbara , Rufińska Anna , Goddard Richard , Krüger Carl
Published: March 2015

The ethylene molecule in the binuclear complex [bis(2-4η-phosphorinyl)nickel](η2 -ethylene)-P,P′-nickel (1) is displaced by 1-alkenes in an equilibration reaction to give the corresponding (η2 -1-alkene)nickel complexes 2-5. The NMR spectra of the octene complex 3 and the propene complex 6 are temperature dependent because of valence isomerization in the phosphorinyl group and rotation of the olefin. The binuclear structure is not maintained upon displacement of the ethylene by butadiene or isoprene. One nickel atom is displaced as the dodecatrienediylnickel complex 9 and the remaining bis(phosphorinyl)nickel fragment B reacts with insertion of the diene into one allyl-Ni bond to give 7 resp. 8. The molecular structure of 7 was determined by X-ray crystallography.
Neue Bis(phosphan)-nickel(0)-alkin-Komplexe /New Bis(phosphane)-nickel(0)-alkyne Complexes
Authors: Pörschke Klaus R. , Mynott Richard , Angermund Klaus , Krüger Carl
Published: March 2015

(Me3P)2Ni(C2H4) (5) and (dmpe) 2Ni2(C2H4)3 (6) react with various alkynes including ethyne (acetylene) and 1-alkynes to form the crystalline compounds (Me3P)2Ni(C2RR′), (dmpe)Ni(C2RR′), and (dmpe)2Ni2(C2R2)2 (R.R′ = H, Me, Ph). Structural assignments were made on the basis of 1H, 13C, and 31P NMR data. The crystal and molecular structure of (dmpe)Ni(C2Ph2) (17) has been determined by X-ray crystallography.
Darstellung und Kristallstruktur von Tl2TiS4 : Ein Perthiotitanat(IV) mit ∞
1-[TiS4
2-]-Ketten Preparation and Crystal Structure of Tl2TiS4 : A Perthiotitanate(IV) with ∞
1-[TiS4
2-]-Chains
Authors: Klepp Kurt O.
Published: March 2015

Tl2TiS4 is orthorhombic, space group Pbca, with a = 22.176(7), b = 9.484(4), c = 6.3977(9) Å, Z = 8. The crystal structure was solved by direct methods and refined to a conventional R of0.058 for 704 reflections with I ≥3σ(I). The crystal structure is characterized by infinite perthioanions, ∞
1-[TiS 4/2 (S2)2- ], which are separated by Tl+ -cations. The anion chains are built up by distorted octahedra which share two skew edges to form infinite cis-chains running along [001], The two unshared S-atoms of each octahedron are connected via a S -S-single bond of 2.10 Å length. The crystal structure is described as a mixed packing of TI-and S-atoms, composed of puckered TlS2 -layers, in which the Ti-atoms occupy the octahedral interstices. The relationship of the ∞
1-[TiS4
2- -]-chains to the anionic groups of Cs2TiS3 is discussed.
Zur Kenntnis der Selenidosilikate und -germanate Na4Si4Se10, Na2GeSe3 und Na8Ge4Se10 / On the Selenidosilicates and Germanates Na4Si4Se10, Na2GeSe3 and Na8Ge4Se10
Authors: Eisenmann Brigitte , Hansa Jendy , Schafer Herbert
Published: March 2015

The following new compounds have been prepared and structurally characterized: Na4Si4Se10: orthorhombic, space group Cmcm (No. 63). a = 1340.9(5) pm, b = 1318.4(5) pm, c = 1086.5(4) pm, Z = 4. ρx = 3.44 g/cm3, ρexp = 3.47 g/cm3. The compound crystallizes in the Na4Si4S10 type with adamantane analogous Si4Se10
4- anions.

Na2GeSe3: Monoclinic, space group P21/c (No. 14). a = 709.7(2) pm, b = 1606.8(5) pm, c = 607.3(2) pm, β = 113.69(8)°, Z = 4, ρx = 3.72 g/cm3, ρexp = 3.76 g/cm3. The compound is isotypic with Na2GeS3. GeSe4-tetrahedra are connected by common corners to infinite “Zweiereinfach” chains.

Na8Ge4Se10: monoclinic, space group P21/c (No. 14). a = 1310.4(5) pm, b = 1205.7(5) pm, c = 1410.1(5) pm, β = 92.9(1)°, Z = 4, ρx = 3.77 g/cm3, ρexp = 3.75 g/cm3. Analogous to Na8Ge4Te10 (mod. I), two octahedral Ge2Se6 - units are connected by a common edge to a Ge4Se10
8-“ - anion.
Über Inhaltsstoffe von Euphorbiaceae, 8. Mitt. [1]. Triterpenester und Triterpenalkohole aus Euphorbia biglandulosa Desf. / Constituents of Euphorbiaceae, 8. Comm. [1]. Triterpen Esters and Triterpen Alcohols from Euphorbia biglandulosa Desf.
Authors: Falsone Gioacchino , Schneider Claudia
Published: March 2015

Fatty acids and acetic acid esters of lanosterol and cycloartenol and triterpens alcohols were isolated from the latex of Euphorbia biglandulosa Desf. The triterpenesters were identified as (E,Z)-2,4-decadienoyllanosterol (1a), (E,Z)-2,4-octadienoyllanosterol (1b), (E,Z)-2,4-oc- tadienoylcycloartenol (2a), (2E,4Z)-2,4,6-decatrienoyllanosterol (1c), (2E,4Z)-2,4,6-deca- trienoylcycloartenol (2b), lanosterylacetat (1d) and cycloartenylacetat (2c) by IR-, 1H-NMR- and MS-spectroscopy and hydrolysis. The triterpens alcohols were identified as butyrospermol, cyclo­artenol, 24-methylencycloartanol and obtusifoliol.
Preparation of Precocene 2 and 3,4-Epoxyprecocene 2 Deuterated Analogues at C-3, C-4 and C-3, C-4
Authors: Camps F. , Conchillo A. , Messeguer A.
Published: March 2015

A convenient route for the preparation of title compounds from benzopyran-4-one (1) and its corresponding 3,3-2H2 deuterated analogue (2) is reported. Treatment of 1 or 2 with lithium aluminum deuteride followed by dehydration afforded, respectively, 4-2H precocene (3c) or 3,4-2H2 precocene (3b). Likewise, reduction of 2 with lithium aluminum hydride and subsequent dehydration led to the formation of 3-2H precocene (3d). Finally, the corresponding 3,4-epoxy derivatives of all these compounds were prepared in good yields by conventional procedures.
Darstellung und Struktur von Cs2As8S13 / Preparation and Structure of Cs2As8S13
Authors: Sheldrick W. S. , Kaub J.
Published: March 2015

The thioarsenate(III) Cs2As8S13 has been prepared by the reaction of Cs2CO3 with As2S3 in aqueous solution under pressure at 180 °C. Its structure has been established by X-ray structural analysis. The polymeric anion (As8S13
2-)n is composed of individual As4S4 -rings, which are each connected to three further eight-membered rings via As-S-As bridges, so giving rise to an infinite layer structure.
Über die Reaktion von Hydroxylamin mit Acrylsäure / On the Reaction between Hydroxylamine and Acrylic Acid
Authors: Brachtel G. , Jansen M.
Published: March 2015

Hydroxylamine reacts with acrylic acid via a triple Michael-addition forming the 3,3-bis-[2-carboxyethyl]-3-hydroxyaminopropionic acid betain (C9H15NO7). The crystal and molecular structures have been determined by X-Ray methods (P21/n; a = 8.097(2), b = 9.343(3), c = 14,647(4) Å, β= 91.35(3)°, Z = 4).
Synthese und Bindungsverhältnisse von 1-Dimethylaminothiabenzol-1-oxiden / Synthesis and Bonding Properties of 1-Dimethylaminothiabenzene-1-oxides
Authors: Weber Lothar
Published: March 2015

The 1-dimethylaminothiabenzene-l-oxides 5a-d are obtained by the reaction of the 2-propy-nones 2a-d with methyl-dimethylamino-oxosulfonio methanide 3 and subsequent treatment of the mixture with t-BuOK. The bonding properties of 5a-d are discussed by comparison of their IR, 1H and 13C NMR data with those of the already known 1-methylthiabenzene-1-oxides 6a-d.
A Convenient Synthesis of the 2-Dimethyl-2H-Chroinene-System
Authors: Reisch Johannes , Dharmaratne H. Ranjith W.
Published: March 2015

2,2-Dimethyl-5H-pyrano(3,2-c)-l-benzopyrano-5-one(2) and 4H-2,3-dihydro-3-methyl-2-methylene-furan-1-benzopyran-4-one (3), two new coumarin derivatives were synthesised from 4-hydroxycoumarin by treating with 3-chloro-3-methylbut-1-yne and 3-chlorobut-1-yne respectively, both reactions progressing via the phase-transfer catalysis.
Activated Nitriles in Heterocyclic Synthesis: A Novel Synthesis of Pyridazine, Pyrimidine, Pyridine and Pyrano[4,3-b]pyridine Derivatives
Authors: Mohareb R. M. , Fahmy S. M.
Published: March 2015

Diethyl-3-amino-2-cyano-2-pentendioate (1) reacts with aromatic amines and aminohetero-cyclic compounds to yield amide derivatives (2 c-h). The latter derivatives were utilised in synthesis of pyridazines (4a, b), pyrimidine (6), pyridone (9) and pyrano[4,3-b]pyridine (16a, b) derivatives via reaction with aryldiazonium chloride, trichloroacetonitrile, sodiummethoxide and cinnamonitrile derivatives, respectively.
Dynamik und Struktur Phosphit-substituierter Olefinwolfram-Komplexe / Dynamics and Structure of Phosphite Substituted Olefintungsten Complexes
Authors: Berke Heinz , Huttner Gottfried , Sontag Christoph , Zsolnai Laszlo
Published: March 2015

The barriers of rotation of olefin ligands in (OC)3 LL′W(olefin) complexes, L - P(OMe)3 , L′ = P(OMe)3 or P(OEt)3 , olefin = ethylene, methylmaleate, methylfumarate, methylacrylate (1-4) have been determined from D-NMR measurements. The preferred olefin orientation has been deduced from an X-ray analysis of the tricarbonyl-triethylphosphite-trimethylphosphite-methyl-maleatetungsten compound 2. The influence of steric and electronic factors on the rotational process has been discussed by use of EHT-calculations.
Studien zum Vorgang der Wasserstoffübertragung, 74 [1]. Elektroreduktive Hydrierungen an Raney-Nickel-Pulver als Kathode / Studies on the Occurrence of Hydrogen Transfer, 74 [1]. Electroreductive Hydrogenation Using Raney-Nickel-Powder as a Cathode
Authors: Horner L. , Franz Ch.
Published: March 2015

Cathodically pretreated Raney-nickel-powder with a potential of -900 to -1000 mV (vs SCE) shows a positive potential shift of 200 to 300 mV in the presence of a hydrogen acceptor (coumarine or 1-ethinylcyclohexanol (1)). Pyridine and quinoline do not have any strong influence on the potential but retard the hydrogenation of coumarine. Acetylene derivatives as 1-ethinylcyclohexanol are hydrogenated in two steps applying a potential down to -1050 mV. At -1150 mV the selectivity is lost. With Raney-nickel-powder pre-treated with pyridine or hydrogensulfide the two-step selectivity of the hydrogenation of 1 is preserved applying also a potential of -1200 mV.
Ein Beitrag zur Photochemie des singulett-angeregten 5-MethyIencyclohexa-1,3-dien-Systems / A Contribution to the Photochemistry of the Singlet Excited 5-Methylenecyclohexa-1,3-diene System
Authors: Brune Hans Albert , Günther Uwe , Lach Peter , Sihler Rolf
Published: March 2015

5-Methylenecyclohexa-13-diene System, S, Excitation, Isomerizations 1,2,3,4,6-Pentamethyl-5-methylenecyclohexa-1,3-diene and 1,2,3,4,6,6-Hexamethyl-5-methy-lenecyclohexa-1,3-diene have been synthesized. The isomerizations following singlet excitation have been studied.
Darstellung von Pyrrolochinolinen aus N-(3-Chinolincarbonyl)aminosäure-Derivaten / Preparation of Pyrrolo-quinolines from Derivatives of N-(3-Quinolinecarbonyl)-amino Acids
Authors: Gündel Wolf-H. , Bohnert Sabine
Published: March 2015

Ester and amides of N-(3-quinolinecarbonyl)-N-methyl-phenylglycine (4) cyclise under the influence of base to derivatives of pyrrolo-quinolines (6-9, 11). Tetracyclic products (10) are formed in the reaction of 4 with ammonia.
Synthesen und Strukturen von Distibankomplexen / Syntheses and Structures of Distibane Complexes
Authors: Weber Ute , Zsolnai Laszlo , Hüttner Gottfried
Published: March 2015

Stibanes RSbHal2 are reductivly coupled by interaction with Na2M2(CO)10 (M = Cr, W) or Cp(CO)2MnTHF. The resulting distibanes RS̲b̲(Hal)-(Hal)S̲b̲R are coordinated to sixteen elec­tron LnM-fragments (LnM=M(CO)5, Cp(CO)2Mn). Both the meso and d/l stereoisomeres are structurally characterised by X-ray analyses.
Oligophosphan-Liganden, X II [1] Pseudohalogeno- und Halogenohydridoeisen(II)-Komplexe des tripodal-tetratertiären Phosphanliganden P(CH2CH2CH2PMe2)3 / Oligophosphine Ligands, X II [1] Pseudohalo and Halohydro Complexes of Iron (II) Containing the Tripod Tetratertiary Phosphine Ligand P(CH2CH2CH2PMe2)3
Authors: Antberg Martin , Dahlenburg Lutz
Published: March 2015

The iron(II) complexes FeX2[P(CH2CH2CH2PMe2)3] with X = CN (4), N3 (5). and NCS (6) have been prepared by metathetical reaction of FeCl2[P(CH2CH2CH2PMe2)3] (1) with the corresponding sodium pseudohalide. Treatment of the dihalo compounds FeX2[P(CH2CH2CH2PMe2)3] (X2 = Cl2 (1). Br2 (2), I2 (3)) with LiAlH4 gave the halohydro derivatives FeHX[P(CH2CH2CH2PMe2)3], where HX = HCl (7). HBr (8). and HI (9). Consistent with a cis-octahedral coordination geometry, the 31P NMR spectra of 1−9 exhibit AMX2 type splitting. The halohydro complexes 7−9 have also been studied by IR and 1H NMR spectroscopy. 57Fe Möβbauer data have been collected for compounds 1, 4, and 5.
Unusual Quadrupole Splitting in D i- and Trialkylamine Substituted Pentacyanoferrate(II) Complexes
Authors: Parwate D. V. , Garg A. N.
Published: March 2015

A series of pentacyanoferrate complexes, Na3[Fe(CN)5L] ·nH2O, where L = (CH3)2NH, (C2H5)2NH, (C2H5)3N, (C3H7)2NH, (C4H9)2NH, (C4H9)3N and (C6H5)2NH were studied by Mössbauer and infrared spectroscopy. All the complexes exhibited two line spectra with ⊿ EQ = 0.73-1.92 mms-1 and δ = −0.04−0.49 mms-1 (w.r.t. SNP) and can be divided into two groups with well defined parameters. Partial isomer shift and partial quadrupole splitting values were correlated with bonding characteristics.
Übergangsmetallketen-Verbindungen, XXYI[1] Darstellung und Struktur eines Dekaboran(14)oxyalkin-Komplexes / Compounds of Transition Metal Ketenes, XXVI[1] Synthesis and Structure of a Decaboran(14)oxyalkyne Complex
Authors: Sieber Werner J. , Neugebauer Dietmar , Kreißl Fritz R.
Published: March 2015

Carbonyl(η5-cyclopentadienyl)(η2-4-methylphenylketenyl)trimethylphosphinetungsten reacts with decaborane(14) under conversion of the η2-ketenyl into a η2-alkyne complex. Reaction conditions, spectroscopic data and the X-ray structure of the new compound are reported.
Strukturvergleich bei 9,10-Dihydro-9,10-anthrylen-Verbindungen des Magnesiums und des Alkylaluminiums / Comparison between the Structures of 9,10-Dihydro-9,10-anthrylene Compounds of Magnesium and Alkylaluminium
Authors: Lehmkuhl Herbert , Shakoor Abdul , Mehler Klaus , Krüger Carl , Tsay Yi-Hung
Published: March 2015

In magnesium as well as in aluminium derivatives of anthracene (1−4, 8) and its trimethylsilyl derivatives (5, 6 and 11), the metals occupy the axial positions at C9 and CIO, to form five-, seven- or ten-membered metallacycles, respectively, in 1−3, 5, 6 and 11. It appears that the metalla-ring size, and thus the coordination geometry of the bridging metal is of influence upon the chemical behaviour.
Isolation and Characterization of the Radiation-Induced Degradation Products of 2′-Deoxyguanosine in Oxygen-Free Aqueous Solutions
Authors: Berger Maurice , Cadet Jean
Published: March 2015

The bulk of the radiation-induced degradation products of 2′-deoxyguanosine in oxygen-free aqueous solution have been separated by high performance liquid chromatography and charac­terized by various spectroscopic techniques including fast atom bombardment mass spectrometry, 1H NMR and circular dichroism. The two main decomposition products result from the opening of the imidazole ring and further rearrangement of the sugar moiety. In addition, the formation of six other nucleosides was shown to involve sugar radicals with subsequent epimerization, re­arrangement or cyclization reactions.
Chiral Rotamers of N-(1-Indanyl)-pyridinium Salts and their Restricted Rotation Around the C(sp3)—N+(sp2) Single Bond
Authors: Balaban Teodor-Silviu , Gheorghiu Mircea D. , Roussel Christian , Balaban Alexandru T.
Published: March 2015

Various alkyl- or aryl-substituted N-(1-indanyl)-pyridinium perchlorates present evidence for restricted rotation around the C(sp3)-N + (sp2) single bond giving rise to chiral rotamers as shown by their 1H NMR spectra.
Ein monocyclisches Phosphoran mit axial gebundenem Wasserstoff: Darstellung und Molekülstruktur / A Monocyclic Phosphorane with Hydrogen in Axial Position: Preparation and Molecular Structure
Authors: Röschenthaler Gerd-Volker , Bohlen Rainer , Schomburg Dietmar
Published: March 2015

Chlorodiphenylphosphane and triethylammonium perfluoropinacolate yield the monocyclic hydrophosphorane 3. The X-ray structure analysis reveals that hydrogen is bonded in the axial position of a trigonal bipyramide. With dimethyl sulfoxide 3 undergoes a ring opening reaction to give phosphinate 5.
Preparation, Structure and Investigations of BEDT-TTF Trihalides
Authors: Endres H. , Hiller M. , Keller H. J.
Published: March 2015

Crystals of the β-phases of (BEDT-TTF)2Br-I-Br (1) and (BEDT-TTF)2I-I - Br (2) have been isolated by electrocrystallization. The solids can be obtained using different tetrabutylammonium trihalides containing iodine and bromine as supporting electrolytes. Cyclovoltam metric results show clearly that the trihalide anions are involved in the oxidation reactions near the anode which finally lead to the crystals.

1 C20H16Br2IS16, Mr = 1056.01, and 2 C20H16BrI2S16, Mt = 1103.01 are isom orphous, crystallizing in the triclinic space group P1̄, with Z = 1. Unit cell parameters for 1: a = 6.5979(6) A , b = 8.998(1) Å, c = 15.138(3) Å , a = 94.03(1)°, β = 95.13(1), γ = 110.28(1), V = 834.7 Å and for 2: α = 6.606(2) Å , b = 9.047(6) A , c = 15.229(6) Å, α = 94.28(2)°, β = 95.34(2), v = 109.92(2), V = 846.5 Å3.

The different sizes of the Br2I- and Brl2
- counterions lead to different intra- and interstack S -S contacts in the solids thus influencing the physical properties. An additional Br2I- phase with a modulation of the above-described structure could be found. Some relevant physical properties of 1 and 2 are reported
Bildungsmechanismus und Folgereaktionen von 1.2.5.6-Tetraphospha-3.4—7.8-dibenzo-2.6-diiodo-bicycIo[3.3.0]octan Elektrochemische Darstellung von 1.2.5.6-Tetraphospha-3.4—7.8-dibenzo-2.6-dichloro-bicyclo[3.3.0]octan / Formation and Reaction Products of 1.2.5.6-Tetraphospha-3.4—7.8-dibenzo-2.6-diiodo-bicyclo[3.3.0]octane Electrochemical Synthesis of 1.2.5.6-Tetraphospha-3.4—7.8-dibenzo-2.6-diiodo-bicyclo[3.3.0]octane
Authors: Stritt H.-P. , Wörz H.-J. , Latscha H. P.
Published: March 2015

The reaction of o-phenylene-bis(dichlorophosphane) (1) [2] with anhydrous Lil in benzene gives o-phenylene-bis(diiodophosphane) (2). In the presence of water the reaction leads to the bicyclus 3 [1], Electrolysis of 1 with a mercury-pool at a potential of -800 mV in a 1.2-dichloroethane/ 0.1 Mtetrabutylammonium tetrafluoroborate solution gives 1.2.5.6-tetraphospha- 3.4-7.8-dibenzo-2.6-dichloro-bicyclo[3.3.0]octane (4). The reduction of 3, either by magnesium in THF or by electrolysis in 1.2-DCE/0.1 M TBATFB solution at a potential of -1 V yields the oligomer (o-C6H4P2)5
A Pulse Radiolysis Study of Some Dicarboxylic Acids of the Citric Acid Cycle. The Kinetics and Spectral Properties of the Free Radicals Formed by Reaction with the OH Radical
Authors: Cabelli Diane E. , Bielski Benon H. J.
Published: March 2015

The reactions between the OH radical and fumaric acid, maleic acid, malic acid and succinic acid were studied using pulse radiolysis techniques. The rates of reaction, the absorption spectra of the resultant free radicals and the rates of disappearance of those radicals were determined as a function of pH over virtually the entire pH range (pH 2-14)
Mono- and Binuclear Gold(I) Compounds Containing Deprotonated Purines and Pyrimidines
Authors: Bonati Flavio , Burini Alfredo , Pietroni Bianca Rosa
Published: March 2015

In the presence of alkali and LAuCl one or two -NH - groups of a purine or pyrimidine base can be transformed into - N(AuL)- groups giving stable and soluble compounds containing one or two two-coordinated gold(I) nuclei; mononuclear LAu - Q' or binuclear LAu - Q - AuL with a monodentate Q'- or an exobidentate O-- ligand, resp. (Q'H = adenine, guanine, theobromine, theophylline, azaguanine or cytosine; QH2 - thymine or uracyl; L = triphenylphosphine)