bluuebunny/crossref_metadata_2025 huggingface dataset:
Die Kristallstrukturen von [(CH3)P(C6H5)3][C(NO2)3] und [(ICH2)P(C6H5)3][C(NO2)3]
Authors: Dieter Scherfise Klaus , Weller Frank , Dehnicke Kurt
Published: March 2015

The title compounds and the trinitro methanide salts with PPh4
⊕ and N-methyl pyridinium cations are prepared from K[C(NO2)3] and the chlorides of the organic cations in aqueous solution. They form thermally stable, yellow crystalline solids. The IR spectra are reported. The crystal structures of [(CH3)P(C6H5)3][C(NO2)3] (2) and [(ICH2)P(C6H5)3][C(NO2)3] (3) are determined by the aid of X-ray methods.
Fluorboryl- und Fluorborandiyl-Cyclosilazane
Authors: Klingebiel Uwe , Skoda Lutz
Published: March 2015

Hexamethylcyclotrisilazanes and their lithium salts react with F2BN(SiMe3)2 to give the corresponding mono-, bis-, and tris(fluoroboryl)cyclotrisilazanes. Di-fluoroboryl-substituted rings are obtained in the reaction of 1,3-bis(silyl)- and 1-boryl-cyclotrisilazanes with BF3-etherate. A compound consisting of two cyclodisilazanes connected by a (SiNBNSi)-bridge is formed in the reaction of lithiated bis(silyl)cyclotrisilazane with BF3-etherate. Ring coupling of two six membered rings occurs in the reaction of lithiated cyclotrisilazane with 1-difluoroboryl-cyclotrisilazane and in the reaction of lithiated bis(fluoroboryl)cyclotrisilazane with BF3-etherate in a molar ratio 2:1. Ring expansion takes place in the reaction of the lithium salt of a four membered SiN-ring with F2BN(SiMe3)2. Substitution occurs in the same reaction with F3SiN(SiMe3)2.
Reaktive E =C (p—p) π-Systeme, IV [1]: Retro-Dienspaltung von Diels-Alder-Addukten des Phosphaalkens F3CP=CF2
Authors: Binnewies Michael , Grobe Joseph , Van Duc Le
Published: March 2015

Pyrolysis of the Diels-Alder adducts 2-4 yields F3CP = CF2 (1) and the corresponding dienes. For the thermal cleavage of 3 an alternative pathway in addition to the retro-diene reaction is observed, giving the new phosphetane F3 [xxx] and C4H4 dimers. The enthalpy of the cycloreversion reaction of 2 as well as estimated bond energies for the phosphorus-carbon σ- and π-bond have been determined from appearance potentials and thermochemical literature data. The products were characterized by mass and NMR spectra.
Über bicyclische Diacyloxy-pentafluoro-μ3-oxotriborane 2.2.6.10.10-Pentafluoro-4.8-dialkyl-1.3.5.7.9-pentaoxa-2.6.10-triborabicyclo(4.4.0)decadiene: Darstellung, Molekül- und Kristallstruktur
Authors: Binder Herbert , Matheis Walter , Heckmann Gernot , Deiseroth Hans-Jörg , Fu-Son Han
Published: March 2015

Bicyclic acyloxyfluoroboranes 3 react with BF3 by an insertion reaction to form bicyclic diacyloxy- pentafluoro-μ3-oxotriboranes of the 2.2.6.10.10-pentafluoro-4.8-dialkyl-1.3.5.7.9-pentaoxa- 2.6.10-tribora-bicyclo(4.4.0)decadiene type 4. A X-ray crystal structure determination of 4b is reported. NM R data of 4b in the solid state and in solution are discussed.
15N- und 11B-NMR-Untersuchungen an 8-gliedrigen Bor-Stickstoff-Sauerstoff-Heterocyclen
Authors: Csuk René , Müller Norbert , Sterk Heinz
Published: March 2015

Keywords

N-Alkyl-2-phenyl-1,3,6,2-perhydro-dioxazaborocines were investigated by means of 11B and 15N NMR spectroscopy. 11B and 15N NMR spectroscopy is proven to be a powerful tool for the estimation of hydrolytic stabilities of the title com pounds; good correlatations between the hydrolytic stability of the compounds and δ15N , resp. or δ11B as well as the size of the nitrogen substituent could be found.
Grignard Reaction of 2-Substituted-3-Cyanoquinolines
Authors: Neelima  , Bhat Balkrishen , Bhaduri A. P.
Published: March 2015

Grignard reactions of 2-morpholino and 2-methylthio-3-cyanoquinoline, 2-chloro-3-cyanoquinoline, 2-chloro-3-cyano-6-methoxyquinoline and 2-chloro-3-cyano-7-methylquinoline with alkyl or aryl magnesium halides have been studied. It was found that 2-morpholino and 2-methylthio- 3-cyanoquinolines gave 1,4-addition products followed by rapid aromatisation. 2-Chloro-3- cyanoquinoline with alkyl magnesium halides furnished 1,4-addition products but with aryl magnesium halides 1,4- and 1,2-addition products were obtained. The cyano group of 4-aryl-2-chloro- 3-cyano-1,4-dihydroquinolines was found to participate in the Grignard reaction to yield 1,2- addition products. 2-Chloro-3-cyano-6-m ethoxyquinoline with alkyl and phenyl magnesium halides yielded exclusively 1,4-addition products. Similarly with p-m ethoxyphenyl magnesium bromide, 1,4-addition products were isolated which participated in the Grignard reaction to yield the expected adducts. Unlike the other chloroquinoline derivatives, 2-chloro-3-cyano-7-methylquinoline with alkyl magnesium halide formed 1 ,2-addition products but with aryl magnesium halides, 1,4-addition products were isolated. The 4-alkyl-2-chloro-3-cyano-l,4-dihydroquinolines were unstable as compared to their 4-aryl analogs. A couple of the Grignard reaction products were found to be unstable on activated surface.
Synthese und Kristallstruktur des dreikernigen μ-Nitridokomplexes (PPh4)2[W3N2Cl14] · CCl4 · CH2Cl2/ Synthesis and Crystal Structure of the Trinuclear μ-Nitrido Complex (PPh4)2[W3N2Cl14] · CCl4 · CH2Cl2
Authors: Godemeyer Thomas , Dehnicke Kurt , Fenske Dieter
Published: March 2015

The title compound results from a slow reaction between two m oles of PPh4[W2NCl10], dissolved in dichlorom ethane, upon addition of carbon tetrachloride. The red crystals are characterized by X-ray diffraction. (PPh4)2[W3N2Cl14] · CCl4 · CH2Cl2 crystallizes triclinically in the space group P1̄ with two formula units per unit cell. The cell dimensions at -100 °C are: a = 1430, b = 1462, c = 1655 pm , α = 74.6°, β = 79.0°, γ = 82.4° (10,908 independent, observed reflexions, R = 0.078). The structure consists of PPh4
⊕ ions, trinuclear finitrido anions [W3N2Cl14]2⊝ and enclosed molecules of CCl4 and CH2Cl2. The tungsten atom s of the anion are linked by almost linear nitrido bridges (~176°) with different WN bond lengths (mean values 184 pm and 207 pm ), corresponding to double and single bonds. The equatorial WCl4 groups are in eclipsed conformation; the two chlorine atoms in trans-position to the nitrido groups have mean bond lengths of 240 pm which is 9 pm longer than the equatorial W -Cl bonds. The IR spectrum is reported.
Darstellung und Schwingungsspektren von Thiotrichlorosilicat und -germanat. Die Kristallstruktur von NEt4[SiSCl3] · 0,5 CCl4/ Preparation and Synthesis of Thiotrichloro Silicate and Germanate. Crystal Structure of NEt4[SiSCl3] · 0.5 CCl4
Authors: Müller Ulrich , Krug Volker
Published: March 2015

NEt4[SiSCl3] · 0.5CCl4 was obtained from NEt4SH and SiCl4 in liquid H2S and subsequent crystallization from CH2Cl2/CCl4. The analogous reaction with GeCl4 was performed without solvent at room temperature. Raman and IR spectra are in accord with simple anionic species with C3v symmetry. The crystal structure of NEt4[SiSCl3] · 0.5 CCl4 was determined from X-ray diffraction data (849 independent observed reflexions, R - 0.030). Crystal data: tetragonal, space group P4̄c2 , Z = 4, a = 1196.0, c = 1200.7 pm. Both, cation and anion occupy positions on twofold rotation axes, with the consequence of positional disorder for the [SiSCl3]- ion by statistical superposition of the sulfur and one chlorine position. The general packing of cations and anions resembles the NaCl type, the CCl4 molecules occupying interstices. NEt4[GeSCl3] · 0.5 CCl4 is isotypic (a = 1204, c = 1201 pm); NEt4[GeSCl3] also crystallizes in the tetragonal system (a = 1048.4, c = 1274.4 pm).
Darstellung von m- und p-Phenylen-bis(dichlorstiban)/ Synthesis of m- and p-Phenylene-bis(dichlorostibane)
Authors: Stricker-Lennartz Rainer , Latscha H. P.
Published: March 2015

The reaction of antimony(III)-chloride with lithiumdiisopropylamide in the molar ratio 1:2 in ether gives monochloro-bis(diisopropylamino)stibane (4). m -Bromophenyl-bis(diisopropylamino)stibane (2a) is prepared by reaction of m-bromophenyllithium with 4. p-Bromophenylbis(diisopropylamino)stibane (2b) can be obtained by reaction of p-brom ophenyl-dichlorostibane with lithium-diisopropylamide, or from p-brom ophenyllithium and 4. The metal-halogen-exchange of 2a, b by butyllithium in ether gives m- or p-Lithium phenyl-bis(diisopropylamino)- stibane (3a, b), respectively. Without isolation of the lithiated com pound m-/p-phenylene-bis[bis- (diisopropylamino)stibane] (5a, b) are prepared by reaction o f 3a, b with 4. Esterification of 5a, b with C2H5OH (1:4) yields m-/p-phenylene-bis(diethoxystibane) (6a, b). The reaction of 6a, b with acetylchloride in chloroform gives m -/p-phenylene-bis(dichlorostibane) (7a, b).

The new compounds 2-7 are characterized by elemental analysis, NM R- and IR-spectra. 7a, b are also characterized by MS.
Sekundäre Aminophosphane – Synthese und Reaktivität/ Secondary Aminophosphanes – Synthesis and Reactivity
Authors: Niecke Edgar , Rüger Reinhold , Güth Werner
Published: March 2015

Secondary diaminophosphanes 1c-e as well as alkylaminophosphanes 1g , h are available by the reaction of the corresponding chlorophosphanes with lithium-tetrahydridoaluminate. With triethylamine containing three equivalents of hydrogen fluoride, the aminophosphanes 1d , g are converted into the secondary fluorophosphanes 2a, b. While 1c -e are thermally quite stable, 1f -h and 2a, b decompose to give diphosphanes through elimination of amine and hydrogen fluoride.
Menthylsubstituierte Phosphorverbindungen, II. L-Men(R)P(X)Cl (R = Cl, L-Men, D-Men; X = :, S). Charakterisierung singulärer, diastereotoper und enantiotoper Menthylgruppen durch 1H-, 13C- und 31P-NMR-Techniken/ Menthyl-Substituted Phosphorus Compounds, II L-M en(R)P(X)Cl (R = Cl, L-Men, D-Men; X =:, S). Characterization of Singular, Diastereotopic and Enantiotopic Menthyl-Groups by 1H, 13C and 31P NMR Techniques
Authors: Hägele Gerhard , Kückelhaus Wolfgang , Seega Jürgen , Tossing Gudrun , Kessler Horst , Schuck Regina
Published: March 2015

Menthyl-substituted phosphorus compounds L-M en(R )P(X )Cl(R = Cl, L-M en, D -Men ; X = :, S) are synthesized. ID and 2 D NMR studies on nuclei 1H , 13C and 31P were used to characterize singular, diastereotopic and enantiotopic menthylgroups.
Synthese und Struktur des Ethendithiolato-Komplexes [(CO)3FeSCH2]2, einem Dihydrobenzvalen-Analogon/ Synthesis and Structure of the Ethenedithiolato Complex [(CO)3FeSCH2]2, an Analogon of Dihydrobenzvalene
Authors: Messelhäuser Johannes , Lorenz Ingo-Peter , Haug Klaus , Hiller Wolfgang
Published: March 2015

The ethenedithiolato complex [(CO)3FeSCH2]2 (1) is obtained by thermal fragmentation of thiirane-S-oxide in the presence of Fe3(CO)12 in THF and by photolytic reaction of [(CO)3FeS]2 (3) with ethene, respectively. According to an X-ray structure analysis, complex 1 has the same symmetric polyhedron structure as dihydrobenzvalene 2 .
Phosphorverbindungen ungewöhnlicher Koordination, 5 [3+2]- sowie [4+2]-Cycloadditionsreaktionen an ein kinetisch stabilisiertes Phosphaalken/ Phosphorus Compounds with Unusual Coordination, 5 [3+2]- as well as [4+2]-Cycloaddition Reactions to a Kinetically Stabilized Phosphaalkene
Authors: Zurmühlen Frank , Rösch Wolfgang , Regitz Manfred
Published: March 2015

Aliphatic diazo compounds display different reactivity towards the phosphaalkene 9: diazomethane, diazoethane and terf-butyl diazoacetate (10a-c) formally react with Si/P-insertion to give the hitherto unknown phosphaalkenes 12a-c. In contrast, 1-diazo-2.2-dim ethylpropane (10d) and diazotrimethylsilylmethane (10e) lead to the 1.2.4-diazaphospholes 15 and 17, respectively, if the primary products (11d , 14) are treated with sodium hydroxide in tetrahydrofuran. T he reaction of the nitrile oxides 18a-c with 9 yields the 1.2.4-oxazaphospholes 20a-c; the [3+2] cycloadducts 19a-c are assumed to occur as intermediates, which eliminate hexamethylsiloxane either spontaneously (19a, b) or with OH- -catalysis. Azide dipoles (21a-c) add to 9 with formation of 4.5-dihydro-1.2.3.4-phospholes (22a-c) which - instead of aromatization by hexamethyldisiloxane elimination - prefer fragmentation to 23 (→25 ) and imidoesters 24a-c; hydrolysis produces the pivaloyl amides 26a-c. The 1:2 reaction between 9 and the o-quinones 31a-d proceeds via [4+2] cycloadducts (32a-d) to produce the phosphoranes 34a-d by a subsequent [4+1] cycloaddition process.
Notizen: Beiträge zur Chemie des Phosphors, 158. Über die Hexadecaphosphane P16Et2 und P16Me2/ Contributions to the Chemistry of Phosphorus, 158. On the Hexadecaphosphanes P16Et2 and P16Me2
Authors: Bäudler Marianne , Becher Rainer
Published: March 2015

Diethyl-hexadecaphosphane (2) and dimethylhexadecaphosphane (3) have been synthesized by reacting dilithium-hexadecaphosphide, Li2P16 (1 ), with ethylbromide and methylbromide, respectively. 2 and 3 are the first polycyclic organophosphanes with 16P atoms in the molecule.
Darstellung und Struktur von Rb2As8S13·H2O und (NH4)2As8S13·H2O / Preparation and Structure of Rb2As8S13·H2O and (NH4)2As8S13·H2O
Authors: Sheldrick W. S. , Kaub J.
Published: March 2015

The rubidium and ammonium thioarsenates(III) Rb2As8S13·H2O and (NH4)2As8S13·H2O have been prepared by the reaction of the alkali carbonates with As2S3 in aqueous solution in sealed ampoules at respective temperatures of 200 °C and 220 °C. The structure of Rb2As8S13·H2O has been established by X-ray structural analysis. The polymeric anion (As8S13
2-)n is composed of individual As3S3-rings, which are connected to one another via bridging AsS3-pyramids, so giving rise to infinite loop-branched dreier double chains. (NH4)2As8S13·H2O is isotypic with Rb2As8S13·H2O.
Tin (IV ) and Organotin(IV) Coordination Complexes with Nitrogen and Oxygen (Sulfur) Containing Ligands
Authors: Sakuntala E. N. , Vasanta E. N.
Published: March 2015

Reactions of tin tetraacetate with various bifunctional tetradentate Schiff bases have been carried out in refluxing toluene (with the azeotropic removal of the liberated acetic acid) in 1:1 and 1:2 molar ratios. But only the diacetate derivatives of tin have been isolated as stable monomeric compounds. Benzoxazine, a potentially bifunctional tetradentate ligand, is found to undergo a rearrangement when reacted with tin tetraacetate as well as with organotin compounds. All the new compounds are characterised by NMR and IR spectral data.
Synthesis and Crystal Structure of Di[bis(triphenylphosphine)iminium]-biscyanophthalocyaninato-ferrate(II)- dichloromethane
Authors: Küppers H. , Eulert H.-H . , Hesse K.-F. , Kalz W. , Homborg H.
Published: March 2015

Black-green crystals of [[(C6H5),P]2N]2Fe(CN)2(C32H16N8)] · CH2Cl2 (triclinic. P1̄; a = 14.306, b = 13.205, c = 12.081 Å; α = 98.77, β = 92.15, γ = 92.60°; Z = 1) are prepared by the reaction of [[(C6H5),P];N]CN and chlorophthalocyaninato-iron(III) in basic media. The crystal structure was refined to Rw = 4.6% for 3617 reflections measured at 180 K. The Fe(II) ion is coordinated by six nearly equidistant ligands that form an almost regular octahedron suggesting low-spin configuration.
Darstellung und Struktur des N-Thiobis-N′ -(phenylsulfonyl)schwefeldiimids / Synthesis and Structure of N-Thiobis-N′-(phenylsulfonyl)sulfurdiimide
Authors: Roesky Herbert W. , Sundermeyer Jörg , Noltemeyer Mathias , Sheldrick George M. , Meyer-Bäse Karen , Jones Peter G.
Published: March 2015

The reaction of S4N4 with PhSO2NCl2 proceeds with formation of (PhSO2NSN)2S 2. The main product 2 was characterized by an X-ray structure determination. [P21/c, a = 996.8(2), b = 1733.0(2), c = 1131.2(1) pm, β = 114.69(1)°, Z = 4, R = 0.044 for 1911 reflections.] 2 contains a sulfur-nitrogen chain with a planar central N4S3-Unit. The substituents at the NSN-groups are in cis-trans positions.

2 reacts with AgAsF6 to yield the 1:1 complex 3; attempts to recrystallise this from CH2Cl2 led to 2 · CH2Cl2, which was also subjected to a crystal structure determination [P1̄, a = 554.4(2), b = 1313.5(4), c = 1541.3(4) pm, α = 111.05(2), β = 94.61(2), γ = 92.24(2)°. Z = 2. R = 0.088 for 1728 reflections]. Minor differences between the two forms of 2 are observed.
π-Olefin-Iridium-Komplexe, XIII [1] Neuartige metallzentrierte Verknüpfung zweier Tolan-Moleküle / π-Olefin Iridium Complexes, XIII [1] Novel Metal-Centered Linkage of Two Tolane Molecules
Authors: Müller Jörn , Tschampel Matthias , Pickardt Joachim
Published: March 2015

Reaction of [(cod)IrI]2 (cod = 1,5-cyclooctadiene) with methyllithium in the presence of diphenylacetylene (tolane) yields a (cod)Ir complex (3) with a 1-benzyl-2.3-diphenyl-7-methyl-indenyl ligand which is formed by a novel cyclization of two tolane units with participation of a methyl group. The compound was characterized by spectroscopic methods and by X-ray diffraction analysis.
Nature and Composition of Fe(III) Complexes with Some Polyphenolic Ligands
Authors: Dhar M. L. , Singh Onkar
Published: March 2015

The chelated complexes of Fe(III) of the type FeL3 [where L is the mononegative anion of phloroacetophenone (PHA); 2.4-dimethoxyphloroacetophenone (DMPHA); 4-benzvloxyres-acetophenone (BRP); 2,6-dihydroxyphenylbenzylketone (DHPBK); 2,4,6-trihydroxyphenyl-4′-methoxybenzylketone (THPBK); 2-hydroxy-4,6-dibenzyloxyphenyl-3′,4′-dioxymethylenebenzyl- ketone (HBMK); 2-hydroxy-3-prenyl-4′,6′-dibenzyloxyphenyl-3′,4′-dioxymethylenebenzyl- ketone (HPBMK); naringenin (NG); 2-methyl-5,7-dihydroxychromone (MDHC) and methyl-β-resorcylate (MR)] have been prepared and characterized by elemental, magnetic, infrared and electronic spectral studies.
Synthese und Eigenschaften von 4-Alkoxy-4,5-dihydro-2H-thieno[3.2-b]pyrrol-5-onen Synthesis and Properties of 4-Alkoxy-4,5-dihydro-2H-thieno[3.2-b]pyrrole-5-ones / Synthesis and Properties of 4-Alkoxy-4,5-dihydro-2H-thieno[3.2-b]pyrrole-5-ones
Authors: Geffken Detlef , Strohauer Knuth
Published: March 2015

The reaction of (2-thienyl)substituted N-alkoxyglycolam ides (4) with dicyclohexylcarbodiimide at ambient temperature gives 4-alkoxy-4,5-dihydro-2H -thieno[3.2-b]pyrrole-5-ones (5) in moderate yields.
Synthesis of Some New 2-Substituted Thiazolid-4-ones
Authors: Younes Mansour I. , El-Zohry Maher F. , Metwally Saoud A.
Published: March 2015

2-Substituted thiazolid-4-ones were prepared by interaction of thioglycolic acid with certain acyl derivatives in presence of ammonium carbonate and dry benzene. The reaction mechanism is discussed.
Bis(oxalato)platinate des Bis(oxamidoxim)platin: Anisotrope Festkörper mit gemischten und mit getrennten Stapeln/Bis(oxalato)platinate Salts of Bis(oxamide-oxime)platinum: A nisotropie Solids with Mixed and with Segregated Stacks
Authors: Endres Helmut , Liebich-Brudy Gisela
Published: March 2015

Three different phases of bis(oxalato)platinate salts of bis(oxamide-oxime)platinum have been obtained by diffusion techniques and have been characterized by X-ray methods; α-phase: [Pt(C2O4)2][Pt(C2H6N4O2)2] · 2H2O, monoclinic P21/n, a = 15.073(13), b = 3.660(1), c = 16.759(14) Å , β = 96.03(4)°, V = 919 Å3, Z = 2; β-phase: [Pt(C2O4)2][Pt(C2H6N4O2)2] · nH2O, monoclinic P21/n, a = 6.718(1), b = 18.885(4), c = 7.412(2) Å, β = 107.06(2)°, V = 930 Å3, Z = 2; γ-phase: [Pt(C2O4)2][Pt(C2H6N4O2)2] · 3H2O, orthorhombic Pnca, a = 13.694(3), b = 19.210(5), c = 15.225(5) Å, V = 4005 Å3, Z = 8. The α-phase contains segregated stacks of the planar cations and anions, the β- and γ-phases mixed stacks. The well-refined structure of the γ-phase is discussed in detail and compared with the gross structural features of the α- and β-phases.
Über die Nichtexistenz eines einfachen μ-oxo-Diphosphorans mit zwei 1.3.5.7-Tetramethyl-1.3.5.7-tetra-aza-4λ5-phosphaspiro[3.3]heptan- 2.6-dion-Gruppierungen: Darstellung und Struktur eines zweifach mit N,Nʹ-Dimethylharnstoff überbrückten λ5P–O–λ5P-Diphosphorans/On the Nonexistence of a Simple μ-Oxo-diphosphorane Involving two 1,3.5.7-Tetramethyl-1.3.5.7-tetra-aza-4λ5-phospha-spiro[3.3]heptane-2.6-dione Groupings: Preparation and Structure of a λ5P–O–λ5P Diphosphorane Doubly Bridged with N.Nʹ-Dimethylurea
Authors: Schomburg Dietmar , Wermuth Ulrich , Schmutzler Reinhard
Published: March 2015

The reaction between the spiro-chlorophosphorane, [O = C (NMe)2]2PX (X = Cl), and the related trimethylsiloxy compound (X = OSiMe3) was expected to give rise to the formation of a μ-oxo-bis(spirophosphorane), [[O = C(NMe)2]2P]2O. Instead, an isomer of the expected compound, with two N.Nʹ-dimethylurea bridges across a λ5P-O-λ5P bond system was obtained. The identity of the product was established by spectroscopic means (IR , NMR, mass spectroscopy), and by a single crystal X-ray diffraction study.
Synthese und Eigenschaften von 5-BenzoyItetramsäuren/Synthesis and Properties of 5-Benzoyltetramic Acids
Authors: Poschenrieder Hermann , Stachel Hans-Dietrich
Published: March 2015

The synthesis of the title compounds 4a/b and their enolethers 4c/d respectively by hydrolysis of the α-methoxybenzylidene-pyrrolinones 3 is reported. Methylation by diazomethane preferentially yields the benzoylpyrroles 7. Analogously, hydrolysis of the α-methoxybenzylidene-pyrrolidinone 9 followed by methylation leads to the isomeric enolethers 10b and 11.
Synthesis of Quaternary Salts from 2,3ʹ-Bipyridine and Dibromoalkanes
Authors: Singh Shyam K. , Summers Lindsay A.
Published: March 2015

Reaction of 2,3ʹ-bipyridine with dibromoalkanes affords both 1ʹ-bromoalkyl-2,3ʹ-bipyridinium bromides and 1ʹ,1‴-(alkanediyl)-bis-2,3ʹ-bipyridinium dibromides. The latter diquaternary salts react with dimethyl sulfate to afford 1ʹ,1‴-(alkanediyl)-bis-(1-methyl-2,3ʹ-bipyridinium) tetraquaternary salts which are reduced to diradical dications at potentials (E0) of about -0.47 V to -0.62 V.
Chlorination of 3,5-Di-tert-butylphenol+ Crystal Structure of the Keto Tautomer of a Sterically Hindered Phenol
Authors: Hillera Wolfgang , Hörner Manfredo , Rieker Anton , Streich Edgar
Published: March 2015

IR, UV and NMR data reveal that the dichlorination product of 3,5-di-tert-butylphenol is the keto tautomer (1a) of 3,5-di-tert-butyl-2,4-di-chlorophenol (3) instead of the ortho-quinol dichloride (2a), as assumed by Hewitt et al. (1972). According to the crystal structure determination, the first one of a monocyclic keto tautomer, 1a crystallizes in the space group P1̄ with Z = 4; a = 1052.6(3), b = 1202.6(4), c = 1207.4(4) pm, α = 90.52(4)°, β = 95.13(4)° and γ = 108.59(4)°. The structure was solved by direct methods and refined by full-matrix least squares to R = 0.094 for 2176 reflections (I > 3 · δ(I)). Bond lengths and angles show no unusual features; the conformation is discussed with respect to the acidity of the sp3-s CH bond. Suggestions for the mechanism of formation of 1a are presented.
Notizen: Notiz zur Blitzthermolyse von peri-Bis(chlormethyl)-aromaten/Note on the Flash Pyrolysis of peri-Bis(chloromethyl)-aromatic Compounds
Authors: Dehmlow Eckehard V. , Kramer Roland
Published: March 2015

Vacuum pyrolysis of 1,8-bis-(chloromethyl)naphthalene yields acenaphthylene and a little acenaphthene.
Notizen: Darstellung und Schwingungsspektrum von Hexaiodoiridat(III), Cs3[IrI6]/Preparation and Vibrational Spectrum of Hexaiodoiridate(III), Cs3[IrI6]
Authors: Preetz W. , Steinebach H.-J.
Published: March 2015

On tempering heterogeneous pellets of Cs3[IrBr6] and NaI at 160 °C for several days, Cs3[IrI6] is formed by solid state ligand exchange. Because of the slow diffusion rate of the halide ions within the NaI phase, the reaction has to be repeated several times in order to accomplish complete iodation. The embedding material is removed with anhydrous acetone or methanol. Cs3[IrI6] is very slightly soluble in water and immediately hydrolyzed. The IR bands and Raman lines are assigned according to point group Oh.
Notizen: A New , Short Synthesis of Z-Jasmone
Authors: Mikolajczyk Marian , Midura Wanda
Published: March 2015

Z-Jasmone (1) was prepared from ethylene ketal of 0,0-diethyl-4-oxo-pentanephosphonate (2) in four steps in 36% overall yield. A key step in this synthesis is the oxygenation of the α-phosphonate carbanion generated from the monoalkylation product of 2 with Z-3-hexen-1-yl iodide (3).
Notizen: Zur Photochromie des N-Isopropyl-4- nitrothiobenzimidsäure-methylesters/The Photochromic Reaction of Methyl N-Isopropyl-4-nitrothiobenzimidate
Authors: Meese Claus O. , Güsten Hans
Published: March 2015

Methyl N-isopropyl-4-nitrothiobenzimidate (1) exhibits reversible photochromism to a dark blue coloured species in the crystalline state only. Experimental evidence for a topochemically controlled nitro-aci-nitro tautomerism of 1 in the electronic excited state is presented.
Notizen: Darstellung und Eigenschaften des Br2VS2N3 / Synthesis and Properties of Br2VS2N3
Authors: Roesky Herbert W. , Schimkowiak Jürgen , Walther Fred
Published: March 2015

The metallacycle Br2VS2N3, has been obtained from the reaction of S4N4 with VBr, in CH2Br2. The 51V NMR spectrum reveals a singulet at 445.6 ppm and the field ionisation mass spectrum shows only the molecular ion at 317 m/e.
Darstellung und Röntgenstrukturanalyse von (DichIoro)-(1,3,5,7-tetramethyI-2,4,6,8,9,10-hexathiaadamantan)palladium(II), PdCl2(CH3)4C4S6 Preparation and X-Ray Structure Analysis of (D ichloro)-(l,3,5,7-tetram ethyl-2,4,6,8,9,10-hexathiaadam antane)palladium (II), PdCl2(CH3)4C4S6
Authors: Pickardt Joachim , Rautenberg Norbert
Published: March 2015

By reaction of PdCl2(C6H5CN) 2 with 1,3,5,7-tetram ethyl-2,4,6,8,9,10-hexathiaadam antane, (CH3)4C4S6, (“TMTA”), the complex PdCl2-TMTA could be obtained. X-ray structure analyses were performed for the free ligand TMTA as well as for the adduct. Both com pounds crystallize monoclinically, space group P21/n, lattice parameters for TMTA are a= 845.9(5), b= 1225.8(7), c= 1314.8(8) pm, ß= 93.28(5)°; for PdCl2-TMTA a= 1262.3(3), b= 1376.3(4), c= 939.1(3) pm, and ß= 92.86(5)°. In the palladium complex TMTA acts as a bidentate chelating ligand. The coordination about the Pd atom is approximately square planar, but the bond angle S -Pd -S is only 76.2°
1,2-Diphosphonio-diphosphirane / 1,2-Diphosphonio-diphosphiranes
Authors: Lochschmidt Siegfried , Müller Gerhard , Huber Brigitte , Schmidpeter Alfred
Published: March 2015

The addition of AlCl3, to a dichloromethane solution of a triphosphenium tetrachloroaluminate R3P-P-PR3 AICI4 leads to chloromethylation of the latter, and in a subsequent reaction to the formation of 1,2-diphosphonio-diphosphirane tetrachloroalum inates. It is essential for this second step, that at least one R3P group of the two triphosphenium ions entering the reaction is aminosubstituted. The structure o f the diphosphonio-diphosphirane ions is established by NMR spectroscopy and in one case by X-ray investigation
Kinetics of Pb(IV) Oxidation of Substituted Methyl Mandelates — A L.F. E. R. Study
Authors: Banerjee Sudheer K. , Shanker R. , Sachdeva Om P.
Published: March 2015

Lead tetra acetate (Pb(IV) or LTA) oxidation of the esters X -C6H4-CH(OH)-COOCH3(X = H, m-NO2, p-NO2, m-Cl, p-Cl, p-Br. p-CH3 and p-C2H5) gives corresponding keto esters. The reaction is first order in [Pb(IV)] and second order in [Ester], and is catalysed by pyridine and 2,6-lutidine. The pyridine catalysed reaction is first order each in [Pb(IV)]. [Ester] and [Pyridine]. A kinetic isotope effect is observed in oxidation of methyl m andelate for both uncatalysed reaction (kH/kD = 4.2) and pyridine catalysed reaction (kH/kD = 1.8). Activation param eters for both uncatalysed and pyridine catalysed reactions are evaluated. The results are in accord with Linear Free Energy Relationship (L.F.E.R.) and the reaction constant (ϱ = +0.75) obtained supports proton transfer in the ɑ-C-H bond rupture in the rate limiting step. The role pf pyridine in catalysis, as a ligand or as a base is discussed
Diels-Alder Reaction in the Presence of Zeolite
Authors: Ipaktschi Junes
Published: March 2015

Cu(I) ion exchanged Y-zeolite catalyzed Diels-Alder reaction of furan, cyclopentadiene, 1.3-cyclohexadiene, isoprene and 2.3-dimethylbutadiene with a series of acrylic and acetylenic dienophiles is reported. The cycloadducts are obtained in high yield and selectivity
Catalytic Hydrogenation of Pyrylium Salts: A Convenient Route to Alkyl-Substituted Tetrahydropyrans
Authors: Mihai Gheorghe , Balaban Teodor-Silviu
Published: March 2015

2,4.6-Trialkylpyrylium perchlorates afford in high yields by hydrogenation on palladium catalyst at room tem perature the corresponding all-dis-2,4.6-trialkyltetrahydropyrans, whereas other reaction conditions lead to mixtures of tetrahydropyrans and hydrogenolyzed products
Synthesen ortho-nitrosubstituierter Bis(phenyl)platin(II)-Verbindungen / Syntheses of ort/zo-Nitro-Substituted Bis(phenyl)platinum(II) Compounds
Authors: Stapp Bernhard , Schmidtberg Günther , Brune Hans Albert
Published: March 2015

Syntheses of the com pounds cis-{Pt[P(C6H5)3]2(2-O2N-C6H4)(X-C6H4)}(X=4-CH3O; 4-CH3; 4-CF3; 4-O2N; 2-CH3O; 2-CH3; 2-CF3; 2-O2N), [Pt(1,2,5,6-η4-C0D)(2-O2N-C6H4)(X-C6H4)](X=4-CH3O; 4-CH3; COD= 1,5-cyclooctadiene) and [Pt(1,2,5,6-η4-COD)(X-C6H4)Cl](X= 2-CH3O; 2-CH3; 2-CF3)are reported
Cuticular Hydrocarbons of the Colorado Beetle Leptinotarsa decemlineata say
Authors: Maliński Edmund , Kuśmierz Jósef , Szafranek Janusz , Dubis Eligiusz , Poplawski Janusz , Wróbel Jerzy T. , König Wilfried A.
Published: March 2015

The cuticular hydrocarbons of the Colorado beetle Leptinotarsa decemlineata say consist of 2-methylalkanes, internally branched monomethylalkanes, dimethyl-, trimethyl-and tetramethyl-alkanes. The hydrocarbons differ from those of most of the other insects so far investigated. The major components were found to be the dim ethyl branched alkanes, 2,6-and/or 7,22-dimethyl-octacosane and the tetram ethylalkane, 3,10,16,23-tetram ethyltritriacontane. The hydrocarbons identified are members of homologous series which differ by two m ethylene groups. The identification of hydrocarbons was achieved by mass spectrom etry and gas chromatographic determination of Kovats retention indices on two high efficiency capillary columns coated with Dexsil 300 and OV-1.
Solutions of Aluminium Trichloride in Tetramethylurea and the Molecular Structure of an Aluminium Trichloride Tetramethylurea Adduct
Authors: Bittner Astrid , Männig Detlef , Nöth Heinrich
Published: March 2015

Aluminium trichloride forms a 1:1 addition product with tetramethylurea (1) the structure of which has been determined by X-ray methods. Tetramethylurea is bound to the AlCl3 unit via its oxygen atom; consequently, a lengthening of the CO bond is observed. The (CH3)2N units are less twisted relative to the OCN2 plane than in the free ligand.

Solutions of AlCl3·OC(NMe2)2 in diethylether contain both the initial molecular adduct 1 and the ether adduct AlCl3·OEt2. In tetramethyl urea, compound 1 dissociates predominantly into the ions AlCl4- and {Cl2Al[OC(NMe2)2]2}+ . These solutions have been studied by 27Al NMR spectroscopy.
Die Kristallstruktur von [(CH3)4N]2TeCl6 und über die Einschlußverbindung [(CH3)4N]2(CH3CN)TeCl6 / The Crystal Structure of [(CH3)4N]2TeCl6 and the Inclusion Compound [(CH3)4N]2(CH3CN)TeCl6
Authors: Abriel Walter
Published: March 2015

Both title com pounds show an antifluorite-like arrangement of (CH3)4N+ cations and TeCl6
2- anions. The remaining octahedral holes in this array can be filled with CH3CN molecules forming the inclusion com pound by crystallization from CH3CN solution. [(CH3)4N]2TeCl6 (space group Fd3̄c with a = 25.791(3) Å at 265(5) K and Z = 32) contains almost regular TeCl6
2-octahedra. In contrast, in [(CH3)4N]2(CH3CN)TeCl6 (space group Cmcm with a = 12.765(6), b = 14.349(7), c = 12.716(3) Å and Z = 4) the anion is statically distorted with the approximate point symmetry 4 mm. At temperatures above 320 K the solvent molecules can be removed yielding the Fd3c phase. Finally, structural relationships between antifluorite-like phases A2BX6 and elpasolites A2B′BX6 considering halogenides and cyanides are discussed.
Zur Reaktivität von Natrium-bis-trimethylsilylamid gegenüber Metallcarbonylkomplexen mit Metall-Metall-Bindungen, I ER2-verbrückte Dicyano- und Diisonitril-octacarbonyl-dimanganate (E = Sn, Pb) / The Reactivity of Sodium Bis-trimethylsilylamide against Metal Carbonyl Complexes with Metal Metal Bonds, I ER2 Bridged Dicyano or Diisonitrile Octacarbonyl Dim anganates (E = Sn, Pb)
Authors: Moll Matthias , Behrens Helmut , Merbach Peter , Trümmer Karl-Heinz , Thiele Gerhard , Wittmann Kurt
Published: March 2015

EPh2 bridged dicyano octacarbonyl dimetalates {Ph2E[Mn(CO)4CN]2}2- are formed by the reaction of bis(carbonyl-metalates) of tin and lead Ph2E[Mn(CO)5]2 with NaN(SiMe3)2. The new dicyano anions can be transformed with trialkyloxonium tetrafluoroborates [R′3O]BF4 or chlor-trimethylsilane and -germane into the corresponding diisonitrile complexes Ph2E[Mn(CO)4CNR′]2 (R′=Me, Et, SiMe3, GeMe3). In the case of Ph2E [Mn(CO)4CNR′]2 (R′=Me, Et; E=Sn, Pb) the two phenyl groups can be removed with dry hydrogenchloride to give Cl2E[Mn(CO)4CNR′]2.NMR and mass spectra are discussed. The vibrational spectra of the new compounds show cis-coordination of the Sn atoms and the cyano or isonitrile ligands in the carbonylmetalate fragments. This is confirmed by the X-ray structure analysis of Ph2Sn[Mn(CO)4CNMe]2 (space group P21/n).
Magnesiumorganische Innerkomplexe, Teil II [1]. Ethyl(dialkylaminoalkyl)- und Ethyl(4-alkoxybutyl)magnesium-Verbindungen / Organomagnesium Inner Complexes, Part II [1]. Ethyl(dialkylaminoalkyl)- and Ethyl(4-alkoxybutyl)magnesium Compounds
Authors: Bogdanović Borislav , Koppetsch Gudrun , Krüger Carl , Mynott Richard
Published: March 2015

The reaction of bis(dialkylaminoalkyl)-and bis(4-alkoxybutyl)magnesium inner complexes with MgEt2 leads to the formation of ethyl(dialkylaminoalkyl)-and ethyl(4-alkoxybutyl)magnesium compounds. The X-ray crystal structures of ethyl(3-N,N-dimethylam inopropyl)magnesium and ethyl(3-N-cyclohexyl-3-N-methylaminopropyl)magnesium confirm that the com pounds are dimeric with the α-C-atom of the chelating ligand bridging the magnesium atoms.

The difference in reactivity of the Mg-Et and Mg-CnH2nX bonds (X = NR′R″, OR) makes itself apparent in the reaction of these complexes with ethylene: up to six ethylene molecules are inserted, whereby in the case of the ethyl(4-alkoxybutyl)magnesium compounds insertion occurs preferentially into the Mg-Et bond whereas in the case o f the ethyl(dialkylaminoalkyl)magnesium compounds both bonds are equally reactive.
Synthese von 5-Alkyliden-3-pyrrolin-2-onen / Synthesis of 5-Alkylidene-3-pyrrolin-2-ones
Authors: Stachel Hans-Dietrich , Poschenrieder Hermann , Burghard Hans
Published: March 2015

By reduction of the tetramic acids 1 or their derivatives 5 and 6 with complex borohydrides the pyrrolidinones 2 and 7 are obtained. Dehydration of 2 and 7 leads to the title compounds 3 and 8, respectively.
Sila-Pharmaka, 34. Mitt. [1]. Sila-Analoga des Triparanols und Ethamoxytriphetols: Synthese sowie pharmakologische und toxikologische Eigenschaften / Sila-Pharmaca, 34th Communication [1]. Sila-Analogues of Triparanol and Etham oxytriphetol: Synthesis as well as Pharmacological and Toxicological Properties
Authors: Tacke Reinhold , Bentlage-Felten Anke , Linoh Haryanto , Magda Stephen
Published: March 2015

Starting from tetramethoxysilane, sila-triparanol 4b and sila-ethamoxytriphetol 8b were synthesized by four-step syntheses. 4b and 8b exhibit a strong hypolipidemic activity in mice after p.o. administration. Whereas 4b and its carbon analogue triparanol (4a) show a similar hypolipidemic potency, 8b was found to be less potent than its carbon analogue ethamoxy­-triphetol (8a). The silicon com pounds 4b and 8b are less toxic (repeated administration over a period o f 8 days) than the corresponding carbon analogues 4a and 8a, respectively.
Das Phasendiagramm des Systems Aluminiumchlorid-Pyridiniumchlorid / Determination of the Phase Diagram Aluminiumchloride-Pyridiniumchloride
Authors: Seemann Gerd , Hensen Karl
Published: March 2015

A phase equilibrium study of the system aluminiumchloride and pyridiniumchloride has been carried out. The phase diagram of the system indicates the existence of four congruently melting compounds of the molar ratio AlCl3/PyHCl 1:1, 1:2, 1:3, 2:3 .
Synthese und Konformationsstudien ringsubstituierter Titanocen-Dithiolen-Chelate / Synthesis and Conform ational Studies of Ring-Substituted Titanocene Dithiolene Chelates
Authors: Köpf Hartmut , Klapötke Thomas
Published: March 2015

The titanocene dithiolenato chelates Cp′2Ti(S2C6H3CH3-4) and CpCp′Ti(S2C6H3CH3-4) (Cp = η5-C5H5, Cp′ = η5-C5H4CH3) were prepared by reaction o f Cp′2TiCl2 or CpCp′TiCl2 with equiva­lent amounts of 1,2 -(LiS)2C6H3CH3-4. The structure and the conform ational mobility of the η5-bonded and of the chelating ligands of the dithiolenato complexes are discussed on the basis of their temperature-dependent 1H NMR spectra. The mass spectra show metastable transitions for the fragmentation processes.
Intermediates in the Palladium-Catalysed Reactions of 1,3-Dienes, Part 5 [1] Butadiene Complexes of Nickel, Palladium and Platinum
Authors: Benn R. , Jolly P. W. , Joswig T. , Mynott R. , Schick K.-P.
Published: March 2015

A series of [M(R2PC2H4PR2)(butadiene)] complexes of Ni, Pd and Pt has been prepared and their structures investigated NMR-spectroscopically. The nickel and palladium complexes, irre­spective of the substituents at phosphorus, contain a fluxional η2-bonded butadiene molecule. In the case of platinum the bonding mode is ligand dependent: an η2-arrangement is observed where R is tert-butyl or cyclohexyl while when R is isopropyl the butadiene adopts an η1, η1-arrangement to give a platinacyclopentene derivative.
Oligophosphan-Liganden, XX [1] Reduktion von CO2 am Trisphosphanrhodium(I)-Komplex RhCl[t-BuP(CH2CH2CH2PMe2)2] Oligophosphine Ligands, X X [1] Reduction of Carbon Dioxide by the Trisphosphinerhodium (I) Complex RhCl[t-BuP(CH2CH2CH2PMe2)2]
Authors: Dahlenburg Lutz , Prengel Constanze , Höck Nils
Published: March 2015

The reaction of Rh2Cl2(cyclo-C8H 12)2 with t-BuP(CH2CH2CH2PMe2)2 gave RhCl[t-BuP(CH2CH2CH2PMe2)2] (1) which was characterized by its 1H and 31P NMR spectra. 1 interacted with carbon dioxide to produce Rh(O2CO)Cl[t-BuP(CH2CH2CH2PMe2)2](2) and CO. 2 was studied by IR and 13C and 31P NMR spectroscopy as well as by an X-ray structure analysis. There is no evidence for any production of carbon dioxide derivatives containing C- or C- and O- bound integer CO2 ligands.
Das Ketocarben-Oxiren-Gleichgewicht unter einem präparativen Aspekt≠ / The Oxiren-Oxo Carbene Interconversion from a More Preparative Point of View≠
Authors: Rühl Wolfgang , Bölsing Friedrich , Hofer Edgar , Speer Dietrich , Jansen Martin
Published: March 2015

The photochemical decomposition of α-diazoketone 1 in toluene gives rise to the formation of the well known keto carbene-oxirene equilibrium from which not only the product of the Wolff rearrangem ent can be derived but also the com pounds 5, 6 and 7 which are formed directly via the corresponding keto carbenes A and B respectively. Formation of the azulene 6 is unexpected in this context, it's structure could be revealed by X-ray analysis. The results may be regarded as an additional contribution to the mechanism of the Wolff rearrangement, but what is more, they could serve as a model for the feasibility of mechanistic oxirene chemistry in a more preparative aspect.
ESR-und ENDOR-Untersuchungen der Autoxidationsprodukte des Adrenalons und analoger Verbindungen / ESR and ENDOR Investigations of the Autoxidation Products of Adrenalone and Related Compounds
Authors: Stegmann Hartmut B. , Stolze Klaus , Scheffler Klaus
Published: March 2015

The signs of the proton coupling constants of adrenalone semiquinone and related compounds were determined by ENDOR and TRIPLE resonance studies, thereby verifying the increment system described in our previous paper [2], Comparison of the spin-distribution of several substituted acylcatechols showed the conformational influence on the coupling constants due to mesomeric interaction of the carbonyl group with the aromatic π-system.

Adrenalone and other N -monosubstituted catecholamines showed rather stable secondary radi­cals after the decay of the primary semiquinone radical. They were identified as substituted dihydropyrazinium cation radicals after selective deuteration and comparison of their ESR-, ENDOR- and TRIPLE-resonance spectra with those of the non-deuterated species. They are formed by cyclic condensation of two molecules with subsequent oxidation.
Analogues of Methyl D̲-Ribo-and D̲-Arabino-furanosides Having Phosphorus in the Anomeric Position+
Authors: Wróblewski Andrzej E.
Published: March 2015

Acid-catalysed cyclisation of (1S̲J-and (1R̲)-1-C̲-(dimethoxyphosphinyl)-D-erythritols gave exclu­sively P-epimeric analogues of methyl D-ribo- and D-arabino-furanosides with phosphorus in the anomeric position.
Synthese und Kristallstruktur von [WCl3(N 3S2)(Pyridin)] / Synthesis and Crystal Structure of [WCl3(N3S2)(Pyridine)]
Authors: Wadle Heribert , Conradi Elke , Müller Ulrich , Dehnicke Kurt
Published: March 2015

[WCl3(N3S2)(pyridine)] was obtained by the reaction of a mixture of S5N5[WCl4(N3S2)] and S4N3[WCl4(N3S2)] with pyridine in dichloromethane. It forms brown, moisture-sensitive crystal plates and was characterized by its IR spectrum and an X-ray crystal structure determination (1404 ob­served reflexions. R = 0.052). Crystal data: ortho­rhombic, space group Pbca. Z = 8, a = 708.3, b = 1275.4, c = 2628.6 pm. The tungsten atom has a distorted octahedral coordination and is part of a planar WN3S2 ring with WN bond lengths of 176 and 186 pm. The pyridine ligand (W−N 232 pm) is in trans position to the shorter WN bond.
Bis[tetraethylammonium]-meso-bis[dichloro-μ-chloro-oxo-aquavanadat(IV)], [(C2H5)4N]2[{VOCl2(OH2)}2(μ-Cl)2]: Molekülstruktur und spektroskopische Charakteristika/ Tetraethylammonium raeso-Bis[dichloro-μ-chloro-oxo-aquavanadate(IV)], [(C2H5)4N]2[{VOCl2(OH2)}2(μ-Cl)2]: Molecular Structure and Spectroscopic Characteristics
Authors: Priebsch Wolfgang , Weidemann Carola , Rehder Dieter , Kopf Jürgen
Published: March 2015

The title compound crystallizes in the monoclinic space group P21/c with a = 822.0(1), b = 1126.4(2), c = 1629.0(2) pm and β = 103.54(1)°. The two vanadium centers of the anion, which is an edge-bridged bioctahedron, are asymmetrically connected by bridging chloroligands; V -(μ -Cl) bond lengths are 238.4 und 278.3 pm , respectively. ESR and IR characteristics are discussed.
Diphenyl[mono(per)fluoracyI- und aroyl(oxy)]phosphan(oxid)e – neue Synthesen, neue Verbindungen/ Diphenyl[mono(per)fluoroacyl- and aroyl(oxy)]phosphan(oxid)es – New Synthetic Methods, New Compounds
Authors: Hennig Heinz-Werner , Neu Peter , Sartori Peter
Published: March 2015

Diphenylpentafluorobenzoyloxyphosphane 2 a was prepared by reacting diphenylchlorophosphane with sodium pentafluorobenzoate. Reaction of diphenylchlorophosphane with sodium salts of trifluoroacetic acid and of 4-ethoxy-2,3,5,6-tetrafluorobenzoic acid leads to diphenyl trifluoroacetyl phosphane oxide 3b and to diphenyl 4-ethoxy-2,3,5,6-tetrafluoro benzoyl phosphane oxide 3 e. IR data, 19F and 31P {1H } NMR data are given.
Interpretation of Substituent Angular Parameters of Monosubstituted Benzenes by Means of ab initio STO-3G Fully Optimized Molecular Structures and Charges Densities. Part VI of the Series: “Crystallographic Studies and Physicochemical Properties of π-Electron Systems”
Authors: Krygowski Tadeusz Marek , Häfelinger Günter , Schüle Josef
Published: March 2015

The angular variations of molecular structures calculated for 17 monosubstituted derivatives of benzene by use of ab initio analytical gradient optimization at the STO -3G level have been correlated by multiple linear regression analysis with Mulliken σ- and π-electron charge densities at corresponding ring carbon atoms. Variations of angles γ at meta positions are solely due to π-electron effects (R = 0.961). Changes in angles β at ortho positions are independent of σ- or π-electron effects but may be related to steric effects (R = 0.719) alone or additionally to charge densities on ortho protons (for dual regression R = 0.846). Angles a at ipso atom s depend significantly on both, σ- and π-electron charge densities in the ratio of 70% to 21% with R = 0.974 for dual regression. Variations of angles δ para-positions depend on all three effects considered (with correlation coefficient for a triple regression R = 0.951) in the ratio 37.6% :2 8 .3% : 34.1% for steric effects, σ- and π-electron charge densities, respectively.
Die Photoreaktion von Re2(CO)10 mit Ethylen und Ethylenderivaten/ The Photoreaction of Re2(CO)10 with Ethylene and Ethylene Derivatives
Authors: Kreiter Cornelius G. , Franzreb Karl Heinz , Sheldrick William S.
Published: March 2015

Re2(CO)10 (1) has been photolyzed at reduced temperature in the presence of ethylene (2), styrene (3) or 2-methyl-1,3-butadiene (4), respectively. Main products of these reactions are the octacarbonyl-μ-hydrido-μ-η2:1-olefinyl-dirhenium (6, 9, 12, 13, 15) and tridecacarbonyl-μ-η2:1- olefinyl-trirhenium complexes (7, 14, 16). In lesser amounts, three isomeric undecacarbonyl-μ- hydrido-bis(μ-η2:1-vinyl)trirhenium com pounds (8 a, 8 b, 8 c), enneacarbonyl-η2-ethylenedirhenium (5) and three octacarbonyl-η4-diene-dirhenium complexes (10,17,18) are formed. The reaction products were separated by HPL chromatography. They were characterized by IR and NM R spectroscopy (1H , 13C) and by C, H elemental analyses. The molecular and crystal structure of tridecacarbonyl-η2:1-E-3-methyl-1,3-butadien-1-yl-trirhenium was determined by X-ray structure analysis.
Phosphorverbindungen ungewöhnlicher Koordination, 13. Abfangreaktionen von Phenyl-thioxophosphan durch [4+1]-CycIoaddition mit o-Chinonen/ Phosphorus Compounds with Unusual Coordination, 13 [1] Trapping Reactions of Phenyl Thioxophosphane by [4+1] Cycloaddition with o-Quinones
Authors: Hussong Rita , Heydt Heinrich , Regitz Manfred
Published: March 2015

Phenyl thioxophosphane (1) - generated by thermal cycloreversion from 7 along with the dihydropyridazine 8 - is trapped by [4+1] cycloaddition with the o-quinones 9a-f by formation of the dioxaphospholsulfides 10a-f. Solvolysis of 10a-c, e and f with m ethanol yields the phenol derivatives 12a-e (in the case of 10b the isomer 12b′ is formed, too). This reaction is reversible (12a-c→10a-c) and accompanied by formation of the isomers 13a-c. The phenanthrene quinone methanide 14 is also suitable for the trapping reaction of 1 (→15→17).
Studies on the Chemical Constituents of Azadirachta indica A. Juss (Meliaceae), Part VII
Authors: Siddiqui Salimuzzaman , Faizi Shaheen , Siddiqui Bina Shaheen
Published: March 2015

A new limonoid, nim bocinol, has been isolated from the fresh, undried, ripe fruits of Azadirachta indica (neem ) along with known com ponents, azadirone, epoxyazadiradione, azadiradione, gedunin, 17-hydroxyazadiradione and cholesterol. It is the first report of the isolation of cholesterol from any part of the neem tree.
Notizen: Eine neue Synthese und das IR-Spektrum von [SNBr0,4]x/ A New Synthesis and the IR Spectrum of [SNBr0,4]x
Authors: Demant Udo , Dehnicke Kurt
Published: March 2015

[SNBr0,4]x was prepared by the reaction of trithiazyl chloride with BrSiMe3 in CH2Cl2 solution at -60 °C. The IR spectrum is recorded and discussed. The mass spectrum is in agreement with samples prepared by other pathways.
Die Kristallstruktur von [Mg(H2O)6](N3)2 / The Crystal Structure of [Mg(H2O)6](N3)2
Authors: Mautner Franz A. , Krischner Harald , Kratky Christoph
Published: March 2015

The crystal structure of [Mg(H2O)6](N3)2 was determined by single crystal X-ray diffraction (421 independent observed MoKα-counter reflections. R = 0.037). The crystals are orthorhombic, space group Fmmm, Z = 4, a = 644.3(1), b = 1134.4(1), c = 1333.5(3) pm. The magnesium atoms are octahedrally coordinated to six oxygen atom s of water molecules, the azide groups are not coordinated to metal atoms, N -N = 117.0(2) pm.