bluuebunny/crossref_metadata_2025 huggingface dataset:
Beiträge zum thermischen Verhalten von Sulfaten, IV* Neues zum Verhalten von PbSO4 bei höherer Temperatur / Contributions to the Thermal Behaviour of Sulfates, IV* New Facts About the Behaviour of PbSO4 at Higher Temperature
Authors: Spieß Manfred , Gruehn Reginald
Published: February 2015

Thermal Behaviour, Crystal Structures, Modifications Using the high temperature Guinier technique the transformation of the room temperature form N-PbSO4 to the cubic high-temperature form H-PbSO4 was observed. The nonquenchable H-PbSO4 modification crystallizes in the α-NaClO4-type with a(900°) = 7,23 Å, Z = 4 and dX-ray (900 °C) = 5,33 g/cm3 . The thermal dilatation of N-and H-PbSO4 was measured.
Crystal Structure of (NH4)2[Mo3S(S2)6] Containing the Novel Isolated Cluster [MO3S13]2-
Authors: Müller A. , Pohl S. , Dartmann M. , Cohen J. P. , Bennett J. M. , Kirchner R. M.
Published: February 2015

The novel tri-nuclear metal-sulfur cluster [Mo3S(S2)6]2- can be obtained as its ammonium salt by the reaction of a Moiv containing aqueous solutions with polysulfide. Its crystal and molecular structure has been determined by a single crystal X-ray study. The crystals are monoclinic (space group Cm, with a = 11.577(6) Å, b = 16.448(7) Å, c = 5.716(2) Å, β = 117.30(3)°, V = 967.2 Å3 , Z = 2, dexptl. = 2.54(2) g/cm3 , dcal = 2.54 g/cm3). The structure consists of isolated [Mo3S(S2)6]2- units, with three Mo atoms at the vertices of a triangle. There are bridging as well as terminal S2
2--ligands lying above and below the Mo3-plane (bond distances: Mo-Mo = 2.722 Å, Mo-S(terminal) = 2.435, Mo-S(bridging) = 2.452, Mo3-S = 2.353(4) Å and S-S = 2.04 Å (mean values)).
Catalytic Oxygenation of 3-Methylindole by Co(II)-Schiff Base Planar Complexes
Authors: Nomiya Kenji , Wako Nahoko , Komiyama Tomoko , Miwa Makoto
Published: February 2015

N,N′-Ethylenebis(acetylacetoniminato)Co(II),Co(acacen),and N,N′-ethylenebis(benzoyl acetoniminato)Co(II), Co(bzacen), catalyze the oxygen incorporation into 3-methylindole to give o-formylaminoacetophenone selectively. The adducts formation process of three components, that is, substrate, planar cobalt complex and molecular oxygen, and the following catalytic oxygen incorporation process were confirmed by manometric measurements of oxygen uptake, gas-chromatographic analyses of products and electronic spectra of intermediate oxygen adducts. The mechanism was further justified by the study of 1H NMR spectra on overall reactions.
Elementorganische Verbindungen mit o-Phenylenresten, IV [1]Synthese von 2.3.7.8.12.13-Hexamethoxytribenzo[b.e.h] [1.4.7]- trithiacyclononatrien / Organometalloidal Compounds with o-Phenylene Substituents, IV [1]Synthesis of 2,3,7,8,12,13 - Hexamethoxytribenzo [b,e,h] [1,4,7] trithiaonin
Authors: Weiss Tilman , Klar Günter
Published: February 2015

The synthesis of the title compund, starting from 1,2-dimethoxybenzene, is described.
Zur elektrocyclischen Ringöffnung von Cyclopropylhalogeniden bei der Reaktion mit Natriumiodid in Aceton / Electrocyclic Ring Opening of Cyclopropyl Halides in the Course of their Reaction with Sodium Iodide in Acetone
Authors: Luckenbach Reiner , Müller Nikolaus
Published: February 2015

Reaction of cyclopropyl halides with sodium iodide in acetone (i.e. under typical SN2-conditions), proceeds via ring opening to allylic systems finally yielding 1,5-hexadienes upon dimerisation; ring-retained products were not detected. Application of the Wood-ward-Hoffmann rules lends strong support to a cationic synchronous mechanism. This is also confirmed by kinetic measurements proving this reaction to be first order over all. The kinetic data are shown to fit the Hammett equation using σ-values for cyclopropyl bromides and σ+-values for geminal cyclopropyl dichlorides, respectively. The validity of the Woodward-Hoffmann-De Puyrule (according to which in synchronous reactions leaving groups situated endo are strongly favored over those situated exo) is tested in corresponding experiments involving condensed ring systems.
Transalkylierung und protonenkatalysierte C-C-Spaltung bei n-Butyl-und n-Pentylbenzol in der Gasphase / Transalkylation and Proton Catalyzed C-C-Cleavage of Gaseous n-Butyl and w-Pentyl Benzenes
Authors: Wesdemiotis C. , Schwarz H. , Sande C. C. Van de , Van Gaever F.
Published: February 2015

The investigation of several 13carbon and deuterium labelled n-butyl and n-pentyl benzenes demonstrate that chemical ionization (reagent gas: methane) induces specific carbon-carbon bond cleavages of the alkyl group. The extent of competing reaction channels as for instance direct alkene elimination versus dealkylation/reprotonation is analyzed. Partial hydrogen exchange processes between reagent ions and substrate molecules are restricted to the phenyl ring. Intramolecular exchange reactions between the side chain and the aromatic ring which are typical for the open shell molecular ions of alkyl benzenes are not observed for analogous closed shell cations.
Synthesis of 2-Cinnamoyl-1,3-indandione Derivatives and their Reactions with Hydrazine, Hydroxylamine Hydrochloride, Thiourea, Secondary Amines and Diethyl Oxalate
Authors: Afsah El - Sayed , Amer Fathy Abdel Kader , Etman Hassan
Published: February 2015

A series of 2-cinnamoyl-1,3-indandiones (2a-e) were obtained by condensing 1 with aldehydes. Treatment of 2 a with hydrazine or hydroxylamine hydrochloride gave 2-(5-phenyl-2-pyrazolinyl or -isoxazolinyl)-1,3-indandione (3 and 5) respectively, and when treated with thiourea gave 2-(6-phenyl-2-thioxo-4-pyrimidinyl)-1,3-indandione (6).

The formation of 2-(β-piperidino-, -morpholino- and -arylmercaptohydrocinnamoyl)- 1,3-indandiones (7a-b and 8a-b) from 2 a was investigated. Compound 7b when treated with hydrazine gave 9. The 2-(α, β-dimorpholinohydrocinnamoyl) derivative (11) was obtained by the action of morpholine on the dibromo derivative (10). The Michael condensation of 2a with ethyl acetoacetate or acetyl acetone was investigated. Treatment of 1 with benzaldehyde in (3:1) molar ratio gave 14, which reacted with diethyl oxalate to give 15. Cyclization of 15 with polyphosphoric acid lead to the formation of 16.
Arylhydrazonothiazolidinones: Ring Cleavage and Alkylation of the 5-Arylhydrazono Derivatives of Rhodanine and Isorhodanine
Authors: Kassab Nazmi A. , Allah Sanaa O. Abd , Elbahaii Said A.
Published: February 2015

The 5-arylhydrazono derivatives of rhodanine and isorhodanine were subjected to the action of hydrazine hydrate to afford the arylhydrazonomercaptomethyl-triazolinones (3) and -triazolinthiones (3) respectively. Treatment of 1 with benzylamine afforded thioxalic acid dibenzylamide (5). On the other hand treatment of 2 with the same reagent afforded the corresponding benzylimino derivatives (6).

Alkylation of 1 and 2 with ethyl bromoacetate and chloroacetamide yielded the corresponding S-alkyl derivatives (7) and (8), respectively.
The Utilization of Sulfur, Sulfenyl, Selenenyl, and Seleninyl Chlorides in the Conversion of Aldoximes to Nitriles
Authors: Sosnovsky George , Krogh James A.
Published: February 2015

The comparative usefulness of six sulfur, sulfenyl, selenenyl, and seleninyl chlorides towards aldoximes in the presence of a base were examined under similar reaction condi-tions. The reactions of aromatic aldoximes with either sulfur dichloride (1), sulfur mono-chloride (2), or trichloromethane sulfenyl chloride (3) in either ether or chloroform at 23-35 °C after one hour resulted in 60-84% yields of nitriles. Under the same conditions, the reactions of aliphatic aldoximes with either 1, 2, or 3 gave mixtures of products, while at -40 to -30 °C, 15-22% yields of aliphatic nitriles were obtained. The reactions of aliphatic and aromatic oximes with either benzenesulfenyl chloride (4), benzene-selenenyl chloride (5), or benzeneseleninyl chloride (6) produced after fifteen minutes to three hours the corresponding nitriles in 71-96% yields at 23-35 °C.
13C, 1H-Spin-Spin Kopplungskonstanten, Teil IVAdamantan / 13C, 1H Spin-Spin Coupling Constants, Part IVAdamantane
Authors: Aydin Rafet , Günther Harald
Published: February 2015

One-bond, geminal, and vicinal 13C, 1H coupling constants have been determined for adamantane using α-and β-[D]adamantane and the relation nJp(13C, 1H) = 6,5144 nJ(13C, 2H) for the conversion of the measured nJ(13C, 2H) values. It is shown that the magnitude of 3Jtrans is strongly influenced by the substitution pattern. Relative H,D isotope effects for 13C chemical shifts are given.
15N—NMR-Spektroskopische Untersuchung von Dimethylaluminiumazid, Dimethylgalliumazid und Dimethylarsenazid /15N NMR Spectra of the Azides of Dimethylaluminium, Dimethylgallium, and Dimethylarsenic
Authors: Müller Joachim
Published: February 2015

By new preparative methods [(CH3)2AlN3]3, [(CH3)2GaN3]3, and (CH3)2AsN3 were 15N-labelled. The compounds show a temperature-dependent exchange of the azido groups on the NMR time scale. For the last two compounds the vibrational spectra were recorded and discussed.
Synthese und Struktur der Phasen K2CdSn und K2CdPb / Synthesis and Structure of the Phase K2CdSn and K2CdPb
Authors: Matthes Reinhard , Schuster Hans-Uwe
Published: February 2015

K2CdPb crystallizes orthorhombically, with space group Ama2 = Cmc2, a = 645.8 pm, b = 860.2 pm, c - 1095.5 pm. The structure is built of a potassium-3D-net forming eight-edged channels parallel to the a-axis; these channels are penetrated by infinite Cd-Pb-zigzag-chains. The powder-diagram shows the homologous phase K2CdSn (a = 643.2 pm, b = 854.3 pm, c = 1087.7 pm) to be isotypic to K2CdPb.
Bildung von Alkylcarbenium-Ionen im System Aluminium-(Gallium-)halogenid/Halogenwasserstoff / Formation of Alkylcarbenium Ions in the System Aluminium (Gallium) Halide/ Hydrogen Halide
Authors: Kalchsclimid Franz , Mayer Erwin
Published: February 2015

The tert-butyl cation is formed in the reaction of tert-BuCl with AlCl3 or GaCl3 in anhydrous liquid HCl as a solvent, or of tert-BuBr with AlBr3 in HBr. At - 30 °C solutions of [C(CH3)3
+] are stable. At room temperature very slow decomposition occurs over months. In the systems BCI3/HCl, InCl3/HCl and BBr3/HBr no formation of [C(CH3)3+] from the corresponding tert-butyl halide was observed. The tert-amyl cation can be stabilized only in AlBr3/HBr. The iso-propyl cation is not stable in any of the systems investigated. The ability of the Lewis acids employed to form carbenium ions corresponds with their catalytic activity in Friedel-Crafts alkylations.
Untersuchungen zur Existenz der Radikale Cp(CO)3M (M = Cr, Mo, W) / Investigations on the Existence of the Radicals Cp(CO)3M (M = Cr, Mo, W)
Authors: Madach Thomas , Vahrenkamp Heinrich
Published: February 2015

The mutual interconversions of the species Cp(CO)3M- (2), Cp(CO)3M-M′(CO)3Cp (1), and Cp(CO)3M (3), (M,M′ = Cr, Mo, W) were investigated. Of the mixed dinuclear complexes 1, the Cr-Mo and Cr-W compounds were prepared for the first time, and the Mo-W compound was shown not to exist in a pure state. The Mo and W radicals 3, in contrast to the corresponding Cr radical, are not stable in measurable quantities in solution. Electrochemical measurements as well as simple redox and redistribution reactions, however, prove their ready formation and existence under normal conditions. There is a good correlation between the energies of the σ-σ* transitions of the metal-metal bonded dimers (1) and the electrochemical potentials for their reductive cleavage.
η3- Allymetall-Schwefel-Cluster des Nickels, Palladiums und Platins / η3-Allyl Metal Sulfur Cluster Compounds of Nickel, Palladium, and Platinum
Authors: Bogdanović Borislav , Goddard Richard , Göttsch Peter , Krüger Carl , Schlichte Klaus , Tsay Yi-Hung
Published: February 2015

Novel cluster compounds of the composition [(η3-C3H5)2M2S]x, wherein M represents nickel, palladium or platinum are obtained by reaction of 2,5-disubstituted-1,6,6a-trithiopentalenes or H2S with (η3-C3H5)2M in THF solution. The molecular structure of one of these new cluster types [(η3-C3H5Ni)2S]3 has been established by X-ray methods. It is best described as being a fraction of a NiS-framework in which peripheral coordination sites are occupied by partial disordered η3-allyl groups. Molecular data (cell data: a = 19.868(4), b = 8.988(2), c = 14.501(3) Å, β = 115.30(2)°, space group C2/c, Z = 4, R = 0.106) are compared with the parent Bs-NiS lattice. Spectroscopic evidence for the structural similarity of the related Pd- and Pt-compounds is given.
Die Einzelkomponenten der Bacteriophäophorbidmethylester von Bacteriochlorophyll c und d / The Individual Components of Bacteriophaeophorbide Methyl Esters from Bacteriochlorophyll c and d
Authors: Kemmer Thorsten , Brockmann Hans , Risch Nikolaus
Published: February 2015

The preparative column chromatographic separation on small grained silica gel of the bacteriophaeophorbide-c- and -d-methyl esters into their homologous and isomeric components is described. The influence of particular regions of the molecule, which carry different alkyl-substituents, on the chromatographic separability is selectively enhanced through the variation of the eluent. Mass and 1H NMR spectra of the pure components are discussed.
Die Kristallstrukturen von Li3In2, Li5Tl2 und Li3Tl / The Crystal Structures of Li3In2, Li5Tl2 and Li3Tl
Authors: Stöhr Joachim , Schäfer Herbert
Published: February 2015

The crystal structures of Li3In2, Li5Tl2 and Li3Tl have been determined by single crystal methods. Li3In2 crystallizes trigonalrhombohedrally, space group R3̅m-D5
3d, a = 475.3(1) pm and c = 1478(1) pm. It is isotypic with Li3Al2 and Li3Ga2. Li5Tl2 is isotypic with Li5Sn2, space group R3̅m-D5
3d with a = 471.6(1) pm and c = 2039(5) pm. Li3Tl crystallizes cubicly, Fm3m-O5
h, a = 667.1(3) pm in a structure formerly described as „BiF3-type’’ structure.
Zur Darstellung und Kristallstruktur von CaAl6Te10 und CaGa6Te10 / On the Preparation and Crystal Structure of CaAl6Te10 and CaGa6Te10
Authors: Klee Wilfried , Schäfer Herbert
Published: February 2015

The new compounds CaAleTeio and CaGaeTeio crystallize with the following lattice constants

There are dense packings of the Te atoms which are very similar to each other. Different in both structures are the distributions of the element(III) atoms at the distorted tetrahedral sites and of the Ca atoms at the distorted octahedral sites.
Vinyldifluorphosphorane: Synthese durch Direktfluorierung und Additionsverhalten [1]. / Vinyldifluorophosphoranes: Synthesis by Direct Fluorination and Addition Behaviour [1].
Authors: Ruppert Ingo
Published: February 2015

The vinyldifluorophosphoranes PhnPF2(CH = CH2)3-n (2a: n = 1, 2b: n = 2) or Ph2PF2(C6H4-CH = CH2) 4 were obtained in good yield by direct fluorination of the corresponding phosphines. Catalytic addition of Ph2PH or PhPH2 to 2b gives phosphino-ethyl-substituted fluorophosphoranes which have not yet been obtained by partial fluorination. The structures have been established by NMR (19F, 31P) and in addition by sulfurisation. Whereas 2b does not polymerize, homopolymerisation of the styrene derivative 4 gives polymer fixed difluorophosphorane.
Darstellung, Eigenschaften und Kristallstruktur von Rhenium(VII)-Nitridchlorid, ReNCl4 / Preparation, Properties and Crystal Structure of Rhenium(VII) Nitride Chloride, ReNCl4
Authors: Liese Werner , Dehnicke Kurt , Walker Ingeborg , Strähle Joachim
Published: February 2015

Rhenium(VII) nitride chloride, ReNCl4, is prepared by the reaction of ReCl5 with nitrogen trichloride. It forms metallic glazing, hygroscopic needles with an effective magnetic moment of 0.23 B.M. In the mass spectrum only the molecular ion ReNCl4
⊕ is present, followed by ReNCl3
⊕. The crystal structure was determined by X-ray diffraction methods (space group Il, 265 independent reflexions, R = 0.071). The structure consists of ReNCl4 units, which are linked by strongly alternated Re ≡ N-Re chains with different bond lengths of r Re ≡ N = 158 pm and r Re-N = 248 pm. The structure is very similar to that of WOCl4.
Topotactic Electron/Ion Transfer Reactions of Niobium Chalcogenides Nb3X4 with Tunnel Structure
Authors: Schöllhorn Robert , Schramm Wolfgang
Published: February 2015

Cathodic reduction of Nb3S4 and Nb3Se4 electrodes in electrolytes containing cations of appropriate size results in the formation of ternary phases An+
x/n[Nb3X4]x-. The cations An+ are taken up into empty channels of the rigid lattice framework and exhibit high ionic mobility at room temperature.
Die Strukturen der essentiellen ungesättigten Fettsäuren, Kristallstruktur der Linolsäure sowie Hinweise auf die Kristallstrukturen der α-Linolensäure und der Arachidonsäure / The Structures of the Essential Unsaturated Fatty Acids. Crystal Structure of Linoleic Acid and Evidence for the Crystal Structures of α-Linolenic Acid and Arachidonic Acid
Authors: Ernst Josef , Sheldrick William S. , Fuhrhop Jürgen-Hinrich
Published: February 2015

The essential fatty acids linoleic, α-linolenic and arachidonic acid have been crystallized for the first time. The crystal and molecular structures have been elucidated by X-ray analysis. Linoleic acid crystallizes monoclinic P21/c with a = 4298(3), b = 463.2(3), c = 937.7(6) pm, β = 109.38(8)°, Z = 4. The closely packed molecules are stretched with a tttttts̄CssCs̄tt conformationa. By comparison of the unit-cell constants and calculated densities of the unsaturated fatty acids it may be shown that both α-linolenic acid and arachidonic acid also possess stretched structures in the crystal lattice, α-linolenic acid must display a tttttts̄CssCs̄s̄Cs and arachidonic acid a tts̄CssCs̄s̄CssCs̄ttt conformation.
Nachbargruppeneffekte bei der Aminolyse von Estern, III. Der verlangsamende Einfluß von Triethylamin bei der Aminolyse von 2-(2-Hydroxybenzyl )phenylacetaten / Neighboring Group Effects in the Aminolysis of Esters, III. The Rate Diminishing Influence of Triethylamine in the Aminolysis of 2-(2-Hydroxybenzyl)phenylacetates
Authors: Böhmer Volker , Wörsdörfer Klaus
Published: February 2015

The rate of the aminolysis of 2-(2-hydroxybenzyl)phenylacetates with n-butylamine in dioxane is diminished by the addition of triethylamine. This can be quantitatively described by the competitive formation of complexes between monoacetate and n-butylamine or triethylamine, if the assumption is made, that the complex with triethylamine is aminolysed slowly or not at all. The neighboring group effect in aminolysis cannot be explained therefore by a base catalysed decomposition of the tetrahedral intermediate.
Notizen: Bildung von Wasser-Intercalationskomplexen nach mechanischer Beanspruchung von Kaolinit / Formation of Intercalation Complexes with Water after Mechanical Treatment of Kaolinite
Authors: Bartz Paul , Range Klaus-Jürgen
Published: February 2015

Hydrate formation was observed after mechanical treatment of a type I kaolinite and sub-sequent leaching of the hydrazine-intercalation complex with water. Of the different methods investigated (high-pressure treatment, grinding in a ball mill, ultrasonics), a wet grinding of a hydrazine-kaolinite suspension proved to be most effective.
Zur Kenntnis einer neuen ternären Phase Cu0,5Nbl1,5O3,7 / About a New Phase Cu0,5Nbl1,5O3,7
Authors: Schweizer M. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Cu0,5Nb1,5O3,7 were prepared and investigated by X-ray methods (a = 376.7, b = 507.3, c = 374,9 pm; β = 101.5°; space group: P21-C2
2). The statistically occupied metal positions (Nb/Cu) have a trigonal prismatic O2- surrounding.
Darstellung und spektroskopische Untersuchung von Trimethoxysilylpropylsulfanen / Synthesis and Spectroscopy of Silylsulfanes
Authors: Buder Wolfgang
Published: February 2015

The preparation of the sulfanes [(CH3O)3Si-(CH2)2-]2Sn (n=1-4) 2-5 and the corresponding mercaptane 1 is communicated. The 1H and 13C NMR spectra of 1-5 are reported and discussed. The infrared and Raman spectra are discussed in view of C-S-and S-S-bonding.
Protonenkatalysierte Synthese von Fluorochloro- und Fluorobromophosphiten / Synthesis of Fluorochloro- and Fluorobromophosphites by Proton Catalysis
Authors: Binder Herbert , Fischer Rudi
Published: February 2015

Dialkylmonofluorophosphites react with PCI3 or PBr3 to yield the title compounds 6 and 7. These reactions take place only in the presence of protic catalysts. As a working hypothesis, it is assumed that phosphorus is quinquevalent in the transition state. The 31P and 11F NMR data are tabulated.
Vanadocen-dichlorid - ein weiteres Antitumor-Agens aus der Metallocenreihe / Vanadocene Dichloride - Another Antitumor Agent from the Metallocene Series
Authors: Köpf-Maier Petra , Köpf Hartmut
Published: February 2015

The antitumor activity of vanadocene dichloride is investigated against Ehrlich ascites tumor in CFi mice. The application of 80 or 90 mg/kg 24 h after transplantation achieves 100% tumor inhibition until day 30. On treatment with higher doses death of an increasing number of animals is caused by substance toxicity.

The results of this study indicate that vanadocene dichloride exhibits antineoplastic properties similar to those found for titanocene dichloride and cis-dichlorodiammine-platinum(II).
Effect of Solvent, Leaving and Entering Ligand on Substitution Rates of Square Planar Complexes of Palladium(II) with 1 -(2-Hydroxyphenyl) -3,5-diphenylformazan
Authors: Balt S. , Meuldijk J.
Published: February 2015

Nucleophilic Substitution, Palladium(II), Formazan, 1-(2-hydroxyphenyl)-3,5-diphenylformazan, Solvent Effects, Substitution Reactions Nucleophilic substitution in different non-aqueous solvents at square planar complexes of palladium(II) with 1-(2-hydroxyphenyl)-3,5-diphenylformazan (H2Fo) according to FoPdX + Y → FoPdY + X, with X = ammonia and pyridine and Y = triphenylphos-phine, thiourea and the thiocyanate ion, obeys the rate law: rate = k1[FoPdX] + k2[FoPdX][Y]. Values of k1 and k2 were obtained at 25.0 °C. From measured solubilities and literature values of transfer functions the transfer chemical potentials for initial and transition state were calculated. A comparison of these quantities in different solvents leads to the conclusion that non-specific solvation effects are dominant in these compounds. The mutual dependence of the effects of leaving and entering ligands and solvent on the substitution rate indicates a level of synchronicity of bond-breaking and bond-making that is unusually high for palladium(II) complexes.
Condensation of 2-Acetyl-1,3-indandione with Amines and Diazonium Salts
Authors: Amer Fathy Abdel Kader , Afsah El-Sayed , Etman Hassan
Published: February 2015

2-Acetyl-1,3-indandione Derivatives, Amines, Diazonium Salts 2-Acetyl-1,3-indandione (1) undergoes the Mannich reaction with piperidine or diethyl-amine hydrochloride to give compounds 2 and 3, respectively. On treatment 1 with ethylenediamine hydrochloride and formaldehyde, 2,2′-[ethylene bis[imino(1-oxotri-methylene)]]di-1,3-indandione (4) was obtained.

With primary aromatic amines it yielded 2-[N-(substituted phenyl)acetimidoyl]-1,3-indandione (5a-i). The condensation of 1 with o-aminophenol yielded a mixture of 5c and the oxazepinone (6), while condensation with 2,3-diaminopyridine gave the diazepinone (7). Mannich reaction of 5a and g with piperidine hydrochloride and formaldehyde gave 8a, b. The coupling of 1 with diazonium salts was investigated.
Darstellung, IR-Spektrum und Kristallstruktur von [WNCI3 P0Cl3]4 2 POCI3 / Preparation, IR Spectra and Crystal Structure of [WNCl3 • P0Cl3]4 • 2 P0Cl3
Authors: Musterle Wilfried , Strähle Joachim , Liebelt Wolfgang , Dehnicke Kurt
Published: February 2015

Tungsten nitride chloride-POCl3 solvate, [WNCl3 • POCl3]4 • 2 POCl3 is prepared by the reaction of WNCI3 with excess POCI3. With equimolar amounts of POCI3 in dichloromethane suspension the complex [WNCI3 • POCl3]4 • 2 CH2CI2 is formed, which is easily decomposed leaving pure [WNCI3 • POCl3]4. The IR spectra of these complexes were recorded and assigned. A new preparative route to WNCI3 from tungsten hexachloride and iodine azide is described. [WNCI3 • POCl3]4 • 2 POCl3 crystallizes in the triclinic space group P1̅ with two tetrameric units per unit cell. The crystal structure was solved by X-ray diffraction methods (Å = 0,087; 3085 observed reflexions). The structure consists of planar and almost square W4N4-eight-membered rings with alternating W-N bond lengths. The distorted octahedral environment of the tungsten atoms is completed by three terminal Cl-ligands and by the oxygen atom of a POCI3 molecule, which is coordinated trans to the W = N triple bond. The two additional POCI3 molecules are weakly linked to two of the four POCI3 solvate molecules, giving rise to an increase of the W-O bond lengths to these donor groups
Synthesis and Characterisation of Bis(η5-methylcyclopentadienyl) N-Aryl-dithiocarbamato Chloro Titanium(IV) Compounds
Authors: Kaushik N. K. , Bhushan B. , Chhatwal G. R.
Published: February 2015

Some bis(η5-methylcyclopentadienyl) N-aryl-dithiocarbamato chloro titanium(IV) compounds of the general formula η5-(Mecp)2Ti(S2CNRH)Cl (R = phenyl; o-, m- and p-tolyl; p-methoxy phenyl; o- and p-ethoxy phenyl; o-, m- and p-chlorophenyl; p-bromophenyl and p-iodophenyl groups) have been prepared by the reaction of bis(η5-methylcyclopentadienyl) titanium(IV) dichloride with ammonium N-aryl-dithiocarbamates. A study of the molecular weight, conductance, infrared and electronic spectra, and magnetic susceptibility in addition to elemental analysis has been carried out to throw some light on the probable structure of these derivatives
Chemie polyfunktioneller Liganden, 53 [1] Über methyl-substituierte Triarsa-trioxa-, Triarsa-trithiaund Triarsa-triaza-adamantane und über den stark aufgeweiteten Adamantan-Käfig im Schwefel-Derivat / Chemistry of Polyfunctional Ligands, 53 [1] About Methyl-substituted Triarsa-trioxa-, Triarsa-trithia- and Triarsa-triaza-adamantanes and about the Strongly Spread Adamantane Cage in the Sulfur Derivative
Authors: Ellermann Jochen , Lietz Martin , Merbach Peter , Thiele Gerhard , Zoubek Gerd
Published: February 2015

The reaction of l,l,l-tris(diiodarsinomethyl)ethane, CH3C(CH2Asl2)3 (1), with H2O, H2S and CH3NH2 in THF gives the adamantane cage compounds CH3C(CH2ASO)3 (4), CH3C(CH2ASS)3 (5) and CH3C(CH2ASNCH3)3 (6) in high yields. The crystal structure of 5 has been determinated by X-ray diffraction. The unit cell (space group P2i/w) contains 4 isolated molecules in a cubic closest packing. The heteroadamantane 5 has an enlarged cage structure with extremely spread C-C(H2)-As bond angles of 124° at the methylene carbon atoms. Some pharmacological properties of the adamantane derivatives 4 and 5 have been studied. All compounds have been characterized by mass spectrometry and infrared, Raman and X H NMR spectroscopy.
Synthesis of Isoponcimarin
Authors: Rodighiero P. , Guiotto A. , Manzini P.
Published: February 2015

Synthesis of isoponcimarin, 7-(3'-methyl-2',3'-epoxy-butiloxy)-8-(3"-methyl-2"-oxobutyl) coumarin, a natural coumarin isolated from Poncirus trifoliata L., was obtained starting from acetyl osthenol. From the intermediate 7-acetoxy-8-(3'-methyl-2'-oxobutyl) coumarin, the coumarin derivatives isomeranzin and dihydrooroselone were also prepared
ESR and Optical Studies on the Interaction between cis-Dichlorodiammine Platinum(II) and Tryptophan
Authors: Neubacher Harald , Zaplatynski Peter , Haase Axel , Lohmann Wolfgang
Published: February 2015

cts-Dichlorodiammine platinum(II), which is known to be an active anticancer compound, and tryptophan form paramagnetic complexes in aqueous solution. These can be detected by means of electron spin resonance spectroscopy (ESR) after a reaction time of several hours. The ESR spectra are interpreted to be due to Pt(III) in a low spin d7 configuration. The optical results obtained are in accordance with the assumption of columnar structures of the paramagnetic complexes
Zur Darstellung und Kristallstruktur von BaSb2Se4 / On the Preparation and Crystal Structure of BaSb2Se4
Authors: Cordier Gerhard , Schäfer Herbert
Published: February 2015

BaSb2Se4 crystallizes in the monoclinic system, space group P21/n, with a = 923.7 ± 0.8 pm, b = 2076 ± 3 pm, c = 855.1 ± 0.8 pm, β = 91.2 ± 0.1°. One half of the Sb atoms form ψ-tetrahedra with three neighbouring selenium atoms, the other half forms ψ-trigonal bipyramids with four selenium atoms. These polyhedra are connected by common corners and edges to twisted chains which are ordered to sheets with Ba ions between them
Darstellung und Struktur ternärer Silizide und Germanide des Lithiums mit den Seltenen Erden Y und Gd im Fe2P-Typ / Preparation and Crystal Structure of Ternary Silicides and Germanides of Lithium with the Rare-Earth-Metals Y and Gd in the Fe2P-Type Structure
Authors: Czybulka Axel , Steinberg Günter , Schuster Hans-Uwe
Published: February 2015

In the systems Li-M-X = (M = Y, Gd; X = Si, Ge) the compounds LiYSi, LiYGe and LiGdGe were prepared. Their crystal structures were determined by X-ray investigations. They crystallize hexagonally (space group P 6̄2m), and a C22-(Fe2P-type) lattice was found
Photolysereaktionen mit Komplexen des Typs CpFe(CO)2R (R = Me, Et, Ph)+ / Photolytic Reactions with Complexes of the Type CpFe(CO)2R (R = Me, Et, Ph)+
Authors: Alt H. G. , Herberhold M. , Edwards B. H.
Published: February 2015

Photolysis of CpFe(CO)2R complexes [R = Me (1a), Et (1b), Ph (1c)] in hydrocarbon solvents results in loss of the group R and formation of the binuclear compound [CpFe(CO)2]2 (2). In the case of 1a, the photogenerated methyl group reacts to give methane by intramolecular hydrogen abstraction from the Cp ring, or by intermolecular hydrogen abstraction either from the solvent or another methyl group. The photoinduced dealkylation of the ethyl compound 1b is explained by β-elimination (to give ethylene) and subsequent reaction of the hydrido intermediates thus formed with unchanged 1b (to give ethane). The photolysis of 1c leads to phenyl groups which abstract hydrogen from the solvent to give benzene; a noticeable amount of diphenyl is also observed if benzene is used as a solvent.

In the presence of potential two-electron ligands L [L = PMe3, P(OMe)3], only the carbonyl groups of CpFe(CO)2Me (1a) are photolabile, and substituted derivatives of the type CpFe(CO)(L)Me [L = PMe3 (3a), P(OMe)3 (4a)] and CpFe(L)2Me [L = P(OMe)3 (5a)] are formed.

The photoinduced reaction of CpFe(CO)2Me (1a) and diphenylacetylene in solution gives metallocyclic derivatives containing either one or two diphenylacetylene units. On the basis of the IR, the 1H and 13C NMR, and the mass spectra, the complex CpFe(CO)(Ph2C2-COMe) (6a) is assigned a structure containing a vinyl-ketone unit in a five-membered metallocycle, while in CpFe(Ph4C4-COMe) (7a) a tetraphenylbutadienyl group appears to be incorporated into a seven-membered metallocycle
Rapid Betaine Collapse in the Reactions of Six-Membered Ring Cyclic Phosphines with Styrene Oxide, and Rates of Alkaline Hydrolysis of Related Cyclic Phosphonium Salts
Authors: Allen David W . , Hutley Barrie G. , Oades A. Christopher
Published: February 2015

The reactions of a series of six-membered ring cyclic phosphines (10-phenylphenoxaphosphine, 10-phenylphenothiaphosphine, and the related sulphone) with styrene oxide in ethanol result in the formation of styrene and the corresponding cyclic phosphine oxide, indicating that betaine collapse is rapid compared to alternative routes involving the formation of vinylphosphonium salts. This conclusion is supported by studies of the rates of alkaline hydrolysis of the related methylphosphonium salts which give rise to ringopened products. These salts undergo hydrolysis significantly faster than the acyclic salt methyltriphenylphosphonium iodide, due to the electron-withdrawing effect of the oxygen, sulphur or sulphone grouping in the six-membered ring
Ein Beitrag zum Mechanismus der Singulett-Photoisomerisierung des Homofulven-Systems / On the Mechanism of the Singlet Excited Photoisomerizations of the Homofulvene System
Authors: Jobst Helmuth , Brune Hans Albert
Published: February 2015

The isomerizations following the singlet excitation of 1,2,3,5-exo-6-pentamethyl-4- methylene-bicyclo[3,1,0]hex-2-ene (exo-1) and 1,2,3,5-endo-6-pentamethyl-4-methylenebicyclo[3,1,0]hex-2-ene (endo-1) are studied quantitatively. Besides an reversible endo-exo - isomerization exo-1 and endo-1 form hexamethylbenzene via 1,2,3,4,6-pentamethyl-5- methylene-cyclohexa-l,3-diene as an isolable intermediate
Sr2Sb3, eine Zintl-Phase mit Sb6-Kettenanion / Sr2Sb3, a Zintl-Phase with a Sb6-Chain Anion
Authors: Eisenmann Brigitte
Published: February 2015

The new compound Sr2Sb3 crystallizes in the monoclinic system with a = 667.0(5) pm, 6 = 1297.3(5) pm, c = 1520.8(5) pm, β = 90.09(3)°, space group P21/c. The structure is characterized by Sbe-chains, the compound be­longs to the Zintl-phases
CeLi2As2, eine ternäre Verbindung im CaAl2Si2-Typ / CeLi2As2, a Ternary Compound in the CaAl2Si2-Type
Authors: Schuster Hans-Uwe , Fischer Herrad-Odilia
Published: February 2015

X-ray investigations on the ternary compound CeLi2As2 showed it to crystallize in the trigonal CaAl2Si-2-structure, space group P3̄m1-D3
3d- The cell parameters are: a = 431,1 pm, c = 698,4 pm, c/a = 1,62
Funktionelle Trimethylphosphinderivate, XII Stabilisierte Carbanionen: Phosphinomethanide und ihre Reaktion mit Methyliodid /Functional Derivates of Trimethylphosphine, XII Stabilized Carbanions: Phosphinomethanides and their Reaction with Methyl Iodide
Authors: Karsch Hans Heinz
Published: February 2015

Phosphinomethanides {[(CH3)2P]nCH3-n}Li (n = 1, 2, 3) are obtained from the parent phosphines by reaction with organolithium reagents. The metalation is facilitated with increasing n. With methyl iodide reaction takes place at the phosphorus atom exclusively, yielding stabilized ylids for n = 2, 3.
Darstellung und Kristallstruktur des Niob-(triphenylphosphinimino)tetrachlorids, Nb [NP (C6 H5 )3] Cl4, einer Verbindung mit einer Niob-Stickstoff-Mehrfachbindung /Preparation and Crystal Structure of Niobium(triphenyl-phosphineimino)tetrachloride, Nb[NP(C6H5)3]Cl4, a Compound with a Niobium Nitrogen Multiple Bond
Authors: Bezier Hans , Strahle Joachim
Published: February 2015

Nb[NPPh3]Cl4 can be prepared by reacting NbCl4N3 with PPh3 in 1,2 dichloro ethane. The crystalline, yellow compound crystallizes in the monoclinic space group C2/c. The crystal structure consists of eight molecules, which are linked together via bridging chlorine atoms to centrosymmetric dimers. Thereby the niobium atoms obtain a sixfold coordination by one N and five Cl atoms. The triphenyl phosphine imine ligand is bound to niobium by its N atom. The approximate linearity of the resulting Nb-N-P group (angle Nb-N-P = 171°) and the distances Nb-N - 178 pm and N-P =164 pm can be interpreted by an sp hybridized N atom and double bonds to both the Nb and P atom.
The Crystal Structure of Eu11Sb10
Authors: Schmelczer R. , Schwarzenbach D. , Hulliger F.
Published: February 2015

Eu11Sb10 crystallizes in the tetragonal Ho11Ge10 structure type, space group I4/mmm, with a = 12.325(2), c = 18.024(4) Å; Z = 4. Large thermal parameters of certain atoms and unusual interatomic distances might suggest that the true structure is slightly distorted, but attempts to desymmetrize the structure were unsuccessful. Analogous anomalies occur in most of the other representatives of the Ho11Ge10 type. Eu11Sb10 appears to be metallic. It contains divalent Eu and is antiferromagnetic below TN ≈ 5 K. Other new representatives of the Ho11Ge10 structure type are Sr11Sb10, Sr11Bi10 and Ba11Sb10.
Ternäre Silicide des Lithiums mit Yttrium oder Neodym mit modifizierter U3Si2-Struktur /Ternary Silieides of Lithium with Yttrium or Neodymium in a Modified U3Si2-Type Structure
Authors: Steinberg Gunter , Schuster Hans-Uwe
Published: February 2015

The two isotypic compounds LiY2Si2 and LiNd2Si2 were prepared and chemically characterized. The crystal structure determination of LiY2Si2 by means of X-ray methods revealed a modified U3Si2-structure. The lattice constants of the tetragonal cells are:

LiY2Si2: a = 710.5 pm, c = 414.4 pm.

LiNd2Si2 : a = 737.0 pm, c = 424.2 pm.
Reaktionen polyhalogenierter Cyclobutane mit Trimethylphosphit /Reactions of Polyhalogenated Cyclobutenes with Trimethylphosphite
Authors: Bauer Gert , Hagele Gerhard , Sartori Peter
Published: February 2015

Polyhalogenated cyclobutanes are synthesized and dehalogenated to cyclobutenes by means of trimethylphosphite.
13C-NMR-Untersuchiingen an einigen Organosilanen /13 C NMR Studies on Some Organosilanes
Authors: Wrackmeyer Bernd , Biffar Werner
Published: February 2015

13C-NMR data (δ13C, J(13C1H), J(13C13C), J(29Si13C)) of noncyclic organosilanes CH4-n[Si(CH3)3]n (n = 1-4), (CH3)4-nC[Si(CH3)3]n (n = 1, 3, 4) and cyclic organosilanes [(CH3)2SiCH2]n (n = 2, 3), (CH3)2Si(CH2)3 are reported. Comparison of reduced coupling constants 1K proves the Fermi-contact-term to be the dominant coupling mechanism. Structural features of the four-membered heterocycles become apparent by comparison of their 13C NMR parameters with those of corresponding cycloalkanes, noncyclic organo­silanes and the 1,3,5-trisilacyclohexane derivative.
Sila-Pharmaka, 14. Mitt. Darstellung und Eigenschaften sowie Kristall-und Molekülstruktur von Sila-Difenidol /Sila-Drugs, 14th Communication Preparation and Properties as well as Crystal and Molecular Structure of Sila-Difenidol
Authors: Tacke R. , Strecker M. , Sheldrick W. S. , Heeg E. , Berndt B. , Knapstein K. M.
Published: February 2015

Sila-difenidol (6b), a sila-analogue of the drug difenidol (6a), was synthesized according to Scheme 1. 6b and its new precursors 3 and 5 were characterized by their physical and chemical properties, and their structures confirmed by elementary analyses, 1H NMR and mass spectroscopy. 6 b crystallizes orthorhombic P212121 with a = 11.523(1), b = 14.366(4), c = 11.450(1) Å, Z = 4, Dber = 1.14 gcm-3. The structure was refined to R = 0.050 for 1897 reflexions. A strong nearly linear intramolecular O-H···N hydrogen bond of 2.685 Å is observed. The anticholinergic, histaminolytic and musculotropic spasmolytic activities of 6 a and 6 b are reported.
Structure of the 1-Ethyl-3-methyl-1-alumina-indane Dimer, [C2H5(O-C6H4CH(CH3)CH2)Al]2
Authors: Brauer David J. , Krüger Carl
Published: February 2015

The molecular structure of the 1-ethyl-3-methyl-1-alumina-indane dimer has been determined from single crystal X-ray data collected by counter methods. The compound crystallizes in the monoclinic space group C2h
5-P21/c with a = 14.621(2), b = 8.3967(3), c = 8.7516(5) Å, β = 107.998(4)°, Z = 2 and dc = 1.15 gem-3 . Refinement converged with an R value of 0.037 for the 1836 reflections with I > 3 σ (I). The crystals are composed of discrete dimeric molecules possessing crystallographic 1̄ (Ci) symmetry. Each Al atom bonds to an ethyl C atom, 1.964(2) Å, as well as to alkyl 1.974(2) and aryl 2.168(1) Å C atoms of one monomer and, surprisingly, to the aryl C atom 2.104(1) Å, of the inversion related monomer. The Al-Al′ distance in the dimers is 2.6639(7) Å.
[1.3] -Hydroxylwanderung bei Radikalkationen von Allen-und Acetylenalkoholen/[1,3]-Hydroxyl Migration in Cation Radicals of Allene and Acetylene Alcohols
Authors: Ciommer Bernhard , Schwarz Helmut
Published: February 2015

Contrary to previous conclusions it is shown that the molecular ions of 1, 2, and 3 do not interconvert prior to dissociation. Investigation of labelled compounds establishes a new typ of intramolecular [1,3]-hydroxyl migration to allenic and acetylenic carbons. It is shown that both 1 and 2 undergo irreversible rearrangement to an a,β-unsaturated ketone 4. Methyl loss from the intermediate 4, which accounts for 90% of the total methyl elimination, is preceded by partial hydrogen exchange processes between the three methyl groups of 4. The actual dissociation can be described as an a-cleavage to the carbonyl function. The unusual formation of CH3CO+ " is shown to occur exclusively from 1. However, it is demonstrated that prior to CH3CO+ formation 1 rearranges to m. The mechanistic details of this as well as alternative processes are discussed.
Chemical Constituents of Corchorus capsularis and C.olitorius (Jute Plant), Part IV Isolation of Corosolic Acid, Ursolic Acid and corosin and Correlation of Corosin with Tormentic Acid
Authors: Manzoor-i-Khuda M. , Habermehl Gerhard
Published: February 2015

Three triterpenoids have for the first time been isolated from fresh undried jute root, ursolic acid as its acetate, corosolic acid as its acetate and indicated to be urs-2a,2β-diol-12-en-28-oic-acid and oxo-corosin isolated as its acetate-methyl-ester, C36H54O10, m.p. 160 °C, aD-15° (c 0.435%). The 24-carboxyl in corosin-anhydro-lactone-acetate has been reduced to the methyl group and the resultant lactone on acetylation indicated to be identical with tormentic acid lactone acetate.
Studies on Spiroheterocyclic Nitrogen Compounds, IV Synthesis of Some New Spiro Azetidinones and Spiro Thiazolidinones Containing Pyrazolines
Authors: Hassan Kh. M. , Khalil Z. H.
Published: February 2015

Condensation of isatin with 4-aminoacetophenone gave a quantitative yield of isatyl­idene - p -acetylaniline (1). Condensation of 1 with aromatic aldehydes yielded the cor­responding isatylidene azomethine chalcones (2a-f). Interaction of 2 with hydrazines afforded a new isatylidene azomethine pyrazolines (3a-f and 4a-f). Cyclocondensation of chloroacetyl chloride (or mercaptoacetic acid) on 3 giving a spiro azetidinones (5a-f) and spiro thiazolidinones (6a-f) containing a pyrazoline moiety in the para position to the phenyl ring.
Notizen: Darstellung von N-Phenylquecksilber-adenin/ Preparation of N-Phenylmercury-adenine
Authors: Peringer Paul
Published: February 2015

N-Phenylmercury-adenine is formed by the reaction of phenylmercuric hydroxide or phenyl-mercuric acetate and adenine in water at room temperature.
Konformation sterisch gehinderter Anilin-Kationradikale und Benzyl-Kationen/On the Conformation of Sterically Hindered Aniline Cation Radicals and Benzyl Cations
Authors: Woynar Helmut , Schäfer Hartmut , Berndt Armin , Thiel Walter , Schweig Armin
Published: February 2015

A series of aniline cation radicals have been generated in a flow apparatus, and their ESR spectra have been recorded and interpreted. The data show that the NR1R2 substituents are less twisted in these systems than the CR1R2 substituents in the isoelectronic but sterically less hindered benzyl radicals, in accordance with MNDO calculations. The conformations of these systems are strongly influenced by electronic π-resonance effects which limit the usefulness of steric models for structural predictions. The results suggest that the CR1R2 substituent in the benzyl cations is less twisted than in the corresponding radicals. An ESR measurement of these radicals should therefore provide an upper limit to the twist angle in the cations, which is difficult to determine otherwise by experiment.
Notizen: Studies on Metal-Metal Bonds, VI /Observations on the EAN Rule and Bond Orders for Mn-Mn Compounds
Authors: Bernal Ivan , Creswick Michael , Herrmann Wolfgang A.
Published: February 2015

The metal metal distances of a representative number of organometallic manganese complexes vary from 2.50 Å to 3.23 Å, although all these compounds are predicted by the EAN Rule to possess single metal to metal bonds. It is no longer acceptable to predict bond orders from bond lengths, and vice versa.
Das Dimethylphosphanomethanid-Ion als Brückenligand - Struktur von μ-Dimethylphosphido, μ-Dimethylphosphanomethanidotetrakis(trimethylphosphan)dicobalt / The Dimethylphosphanomethanide Ion as a Bridging Ligand - Structure of μ-Dimethylphosphido, μ-Dimethylphosphanomethanidotetrakis(trimethylphosphane)dicobalt
Authors: Klein Hans-Friedrich , Wenninger Josef , Schubert Ulrich
Published: February 2015

Dinitrogen cobaltates [(Me3P)3CoN2]2Mg(THF)4 and KN2Co(PMe3)3 react with CoCl(PMe3)3 or NiCl2(PMe3)2 to give a novel binuclear complex (Me3P)2Co(CH2PMe2)(PMe2)Co(PMe3)2 of unusual properties. Carbon monoxide produces Me3P(CO)2Co(CH2PMe2)(PMe2)Co(CO)2PMe3 but does not insert into the Co-C bond. A cleavage reaction by trimethylphosphite yields (Me3P)2[(MeO)3P]2CoP(O)(OMe)2. The molecular structure of the title compound reveals a novel heterocyclic system Co2P2C containing a CH2 group bent out of the Co2P2 plane (d(Co = Co) = 242.8(2) pm). The bond distances (d(P = C) = 171 pm, d(Co-C) = 209 pm) and angles (PCCo) = 88° suggest a type of bonding which is best described as a P-metallated phosphorane coordinated to the second Co atom via its ylide function.
Metallkomplexe der Phosphinsäuren, XV [1] Chelat- und Platin(0)-Alkin-Komplexe von Alkinyldithiophosphinsäuren RC≡C(R′)P(S)SH [2] / Metal Complexes of Phosphinic Acids, XV [1] Chelat- and Platinum(0) Alkyne Complexes of Alkynyl Dithiophosphinic Acids RC≡C(R′)P(S)SH [2]
Authors: Kuchen Wilhelm , Uppenkamp Reinhard , Diemert Klaus
Published: February 2015

By reacting RC ≡ CMgBr (R = CH3, C2H5, (CH3)Si) with perthiophosphonic anhydrides (R′PS2)2 (R′ = CH3, 4-CH3O-C6H4) alkynyl substituted dithiophosphinic acids RC ≡ C(R′)P(S)SX (X = H) are obtained, the ammonium salts of which can be converted into the esters (X = CH3) with CH3I. While the acids and their salts form numerous metal chelates (X = M/n), the corresponding esters give platinum(0) alkyne complexes [(PPh3)2Pt(RCEEC(R′)P(S)SCH3)] on reaction with Pt(PPh3)4.
[(C5H5)CO{P(0)(0C2H5)2}3]-: Eine einfache Synthese eines metallorganischen Tripodliganden und seine Reaktivität gegenüber den Kationen der III. Hauptgruppe / [(C5H5)CO{P(0)(0C2H5)2}3]-: A Convenient Synthesis of an Organometallic Tripod Ligand and its Reactivity towards the Main Group III Cations
Authors: Kläui Wolfgang
Published: February 2015

A simple two step synthesis of the salts M[(C5H5)Co{P(0)(OC2H5)2}3], M = Li, Na, K, Ag, NH4, NMe4 is described. The air stable, diamagnetic anion reacts as a tridentate 0,0,0-chelating ligand with all main group III elements. With sodium tetraphenylborate the cage-like cationic complex [(C5H5)Co{[P(0)(OC2H5)2]3BPh}]+ is obtained. With M(III) = Al,Ga, In, Tithe trinuclear sandwich compounds [{(C5H5)Co[P(0)(OC2H5)2]3}2M]+ are formed, which contain MO6 octahedra. With M(III) = TI a coupling constant 6J(T10P0CCH) = 1.0 Hz is observed.
Sila-Pharmaka, 15. Mitt. [1] Synthese und Eigenschaften des Sila-Pridinols / Sila-Drugs, 15th Communication [1] Synthesis and Properties of Sila-Pridinol
Authors: Steiling Lothar , Wannagat Ulrich
Published: February 2015

Synthesis of the silicon analogue VI b of the drug pridinol and of its homologue VI a was achieved via eq. (l-5b) (Scheme 1). The novel compounds IVa-VIb are described in their properties and confirmed in their structures (Tables I-IV). Some preliminary pharma-cological investigations suggest spasmolytical effects of sila-pridinol seeming to be somewhat better than those of pridinol itself.
Darstellung und Eigenschaften von Naphtho[1.2-d] -und Naphtho [2.3-d]-1.3-dioxolen / Preparation and Properties of Naphtho[1,2-d]-and Naphtho[2,3-d]-1,3-dioxoles
Authors: Daliacker Franz , Morcinek Ralf , Rabie Arafat
Published: February 2015

We describe the preparation of unsubstituted 1 a, of 4-methoxy- (1b), and of 5-methoxynaphtho[1,2-d]-1,3-dioxole (1 c). Treatment of 1 a with bromine leads to 5-bromo-naphtho- [1,2-d]-1,3-dioxole (1d). The carboxylic acid 1f and 5-methyl-thio-naphtho[1,2-d]-1,3- dioxole (lg) are prepared by bromine-lithium-exchange from ld. Formylation yielding 1i and bromination yielding 1h show that 4-methoxy-naphtho[1,2-d]-1,3-dioxole can easily undergo electrophilic substitution.

Because of less Ss-reactivity of 1c the carboxylic acid 1l and methyl-thio-naphtho[l,2-d]- 1,3-dioxole (In) can only be prepared from the lithium-compound as intermediate. Naphtho[2,3-d]-1,3-dioxole (2a) can easily undergo electrophilic substitution, showed by nitration yielding 2b, acetylation yielding 2c, bromination yielding 2d and 2e. The carboxylic acid 2j, the methyl-derivative 2k, the thionaphthole 2l, and the aldehyde 2m are prepared from the lithium-compound of 2d.

Treating 2e with n-butyl-lithium leads to the dilithium-naphthyl derivative, a suitable starting material to obtain the dimethyl-compound 2n, the dicarboxylic acid 2o, and the dialdehyde 2p. Monomethyl-thio- 2q) and dimethyl-thio-naphtho[2,3-d]-1,3-dioxole (2r) are prepared in the same manner.