Zur Darstellung von Imidazolidin-thionen-(4) und Imidazolin-(3)-thionen-(5)

Zusammenfassung 2,2,5-Trisubstituierte Imidazolidin-thione-(4) lassen sich mittels Schwefels mit guten Ausbeuten zu Imidazolin-(3)-thionen-(5) dehydrieren. Hierüber sowie über einige Verbesserungen der bisher bekannten Synthesen für insbesondere 2,2,5-trisubstituierte Imidazolidin-thione-(4) wird berichtet.

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Dehydration of 2.2.5-trisubstituted imidazolidine-(4)-thiones with elementary sulfur gives in good yields 3-imidazoline-(5)-thiones. This reaction and improved methods of the well known syntheses of especially 2.2.5-trisubstituted imidazolidine-(4)-thiones are described.

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Mitt.:F. Asinger, W. Schäfer undH. Triem, Mh. Chem.97, 1510 (1966).

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Teil der Dissertation vonH. Meisel, Techn. Hochschule Aachen, 1963.

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Teil der Dipl.-Arbeit vonHilde Kersten, Techn. Hochschule Aachen, 1963, und Teil der Dissertation vonHilde Kersten, Techn. Hochschule Aachen, 1965.     

1-Chlor-3-(di)alkylamino-disilazane

The 1-chloro-3-(di)alkylamino-disilazanes1–18 were prepared according to equ. (2), characterized in their properties (Tab. 1) and confirmed in their structure (Tab. 2, 3). They could be transformed easily into disiltriazanes (equ. 3), but not be condensed into cyclotri- or-tetrasilazanes.

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116. Mitt.:U. Wannagat undD. Labuhn, Mh. Chem.104, 1453 (1973).

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Sonderdrucke über Prof. Dr.U. Wannagat, Inst. f. Anorg. Chemie der Techn. Univ., Pockelsstraße 4, D-3300 Braunschweig, Bundesrepublik Deutschland.

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Mit Auszügen aus der DissertationD. Labuhn, Techn. Univ. Braunschweig 1973.     

Polarographische Bestimmung von Guanabenzacetat (Wytensin)

Zusammenfassung Guanabenzacetat 1 wird an der Quecksilbertropfelektrode reduziert und kann auch in Gegenwart der Hydrolyseprodukte 2,6-Dichlorbenzaldehyd 2 und 2,6-Dichlorbenzaldehydsemicarbazon 3 polarographisch quantitativ bestimmt werden. Die Gehaltsbestimmung von 1 in Wytensin-Tabletten wird beschrieben (relative Standardabweichung 2,05%).

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Polarographic determination of guanabenz acetate (Wytensin)

Summary Guanabenz acetate 1 is reduced at the dropping mercury electrode and can be determined also in presence of its hydrolysis products 2,6-dichlorobenzaldehyde 2 and 2,6-dichlorobenzaldehydesemicarbazone 3. The assay of guanabenz acetate in Wytensin tablets is described (relative standard deviation 2.05%).

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Herrn Prof. Dr. H. Oelschläger zum 65. Geburtstag in freundlicher Verbundenheit gewidmet

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Teil der zukünftigen Dissertation A. Zeller

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Dem Fonds der Chemischen Industrie danken wir für finanzielle Unterstützung     

Synthesen von 3-Imidazolin-thionen-(5)

Zusammenfassung Es wird über die Darstellung neuer 2-Methyl-2,4-diaryl-3-imidazolin-thione-(5) berichtet. Sie entstehen bei Einwirkung von Ammoniak und Schwefel im Überschuß auf kernsubstituierte Acetophenonderivate bzw. acetylierte Heterocyclen in methanol. Lösung im Raumtemperaturbereich.

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The preparation of new 2-methyl-2,4-diaryl-3-imidazolin-thions-(5) is reported. These compounds are formed when ammonia und sulphur in excess react with nucleus substituted acetophenone derivatives or with acetylated heterocycles in methyl alcohol solution of room temperature.

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Herrn Professor Dr.W. Langenbeck zu seinem 65. Geburtstag gewidmet.

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44. Mitt.:F. Asinger, H. Diem undW. Schäfer, Mh. Chem.95, 1391 (1964).

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DiplomarbeitG. Kriebel, Techn. Hochschule Aachen, 1963.     

Magnetische Messungen in den Systemen (Zr,Hf)—(Fe,Co,Ni)—O

The phases Zr₃Fe, Zr₃CoO _x (x=0,35;1);Zr₃NiO _x (x=0,2; 1); Hf₃NiO are measured magnetically in the range between 1300°K and 90°K. Whereas Zr₃Fe is ferromagnetic, the other isotypical structures are paramagnetic.

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Mit 2 Abbildungen     

Fluorargentate(II) der Alkalimetalle

Zusammenfassung Dargestellt wurden die bislang unbekannten Verbindungen KAgF₃ (braun, orthorhombisch,a=6.48₉ [Å],b=6.27₀ [Å],c=8.30 [Å]), RbAgF₃ (braun, tetragonal,a=6.33₅ [Å],c=8.44 [Å]), CsAgF₃ (braun, tetragonal,a=6.48₉ [Å],c=8.52 [Å]) sowie blau-violettes K₂AgF₄.Guinier-Aufnahmen zeigen, daß die VerbindungenM[AgF₃] mit KCuF₃ strukturell verwandt sind. Die magnetischen Eigenschaften und derMadelunganteil der Gitterenergie (MAPLE) werden diskutiert.

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Fluoroargentates(II) of alkali metals

The hitherto unknown compounds KAgF₃ (brown, orthorhombic,a=6.48₉ [Å],b=6.27₀ [Å],c=8.30 [Å]), RbAgF₃ (brown, tetragonal,a=6.33₅ [Å],c=8.44 [Å]), CsAgF₃ (brown, tetragonal,a=6.48₉ [Å],c=8.52 [Å]) and blue-violet K₂AgF₄ could been prepared.Guinier-patterns show, that the compoundsM[AgF₃] are structural related with KCuF₃. The magnetic behaviour and theMadelung Part of Lattice Energy [MAPLE] are discussed.

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Herrn Prof. Dr.H. Nowotny gewidmet.

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Teil der DissertationR.-H. Odenthal, Univ. Gießen 1971, D26; bez. näherer Einzelheiten vgl. dort.

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Vgl. auchR.-H. Odenthal undR. Hoppe, Z. anorg. allgem. Chem., im Druck.     

Triacetoxysilan und Tris(trifluoracetoxy)silan

Zusammenfassung Die Darstellung der bisher unbekannten Verbindungen (CH₃COO)₃SiH und (CF₃COO)₃SiH wird beschrieben, ihre Schwingungs- und Kernresonanzspektren werden mitgeteilt. Die extrem liegenden Werte der Fluorverbindung werden im Zusammenhang mit den bisher bekannten Werten diskutiert.

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Triacetoxy silane and tris(trifluoroacetoxy) silane

The preparation of the formerly unknown compounds (CH₃COO)₃SiH and (CF₃COO)₃SiH is described, their vibrational and NMR-spectra are reported. Some extreme values of the latter compound are discussed.

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Mit 1 Abbildung

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Herrn Prof. Dr.A. Wacek zum 75. Geburtstag gewidmet.     

Characterization and Molecular Structure of Bis(Isopropyl Xanthate) Bis(1,10-Phenanthroline) Nickel(II): [Ni(phen)2(CH3)2CHOCSS](CH3)2CHOCSS

The crystal and molecular structure of the title compound, [Ni(phen)₂(CH₃)₂CHOCSS](CH₃)₂CHOCSS has been determined by X-ray diffraction. The brown crystal is triclinic of space group Pi, with parameters a = 11.790(2), b = 12.410(3), c = 12.680(3) Å, α = 92.49(3), β = 96.54(3), γ = 117.43(3)° and Z = 2. The compound contains a six-coordinate cation and an isopropyl xanthate anion (CH₃)₂CHOCSS^?, the central Ni atom is chelated by four nitrogen atoms of two phenanthroline ligands and two sulfur atoms of an isopropyl xanthate ligand. The TG data indicate that it decomposed completely at 734°C.     

Reactions of (E)-(3-Aryl-3-oxoprop-1-en-1-yl)triphenylphosphonium Bromides with Arylhydrazines

(E)-(3-Aryl-3-oxoprop-1en-1-yl)triphenylphosphonium bromides reacted with arylhydrazines in an acidic medium to form hydrazones, the intramolecular heterocyclization of which led to the formation of (2,5- diaryl-2,3-dihydro-1H-pyrazol-3-yl)triphenylphosphonium bromides. Under the action of hydrobromic acid, the resulting quaternary phosphonium salts produced saturated (3-aryl-3-oxopropyl)triphenylphosphonium salts.

     

Poly[Ni(II)Protoporphyrin IX] Modified Electrode for Amperometric Detection of Acetylcholine (Ach) and Choline (Ch)

Abstract

Poly[Ni(II)Protoporphyrin IX] (pNiPP) modified electrode can be used as an alternative method for direct amperometric detection of Acetylcholine (Ach) and Choline (Ch). This response is highly dependent on the electrode potential, that must be higher than +0.4 V versus Ag/AgCl with a maximum at +0.6 V.

Other amino derivatives such as ethanolamine and tetrabutyl ammonium hydroxide did not show amperometric response in the same experimental conditions. On the contrary, KCl shows an increasing amperometric signal in flow injection for a concentration range of 10^?3 to 1 M, indicating certain sensitivity of membrane to Cl^? ions. The lowest detection limit corresponds to the highest cationic volume. The response for acetylcholine is slightly higher than for choline and is almost completely non‐linear for both substrates. The proposed model for the response is Y=(A×X)/(B+X) according to AICc Akaike method.

Choline, in a complex solution, was analyzed by HPLC with the chemically modified electrode as detector.     

Neue Derivate der 2-Acylamino-thiophen-(und-benzo[b]thiophen-)-3-carbonsäure sowie des ([1]Benzo-)Thieno[2,3-d]-pyrimidin-4(3H)-ons

The title substances1 and2 were prepared by acylation of the corresponding ethyl 2-amino-thiophene- (or:-4,5,6,7-tetrahydro-benzo[b]thiophene)-3-carboxylates, in some cases followed by reactions introducing a basic substituent.Additionally a group of 2-aroylamino-thiophene-(or:-4,5,6,7-tetrahydro-benzo[b]thiophene)-3-carboxamides was subjected to ring closure reactions, yielding the corresponding 2-aryl-thieno[2,3-d]pyrimidin-4(3H)-ones and 2-aryl-[1]benzothieno[2,3-d]pyrimidin-4(3H)-ones (both:3).

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Zum Teil unter Mitarbeit vonFerdinand Fuhrmann     

Kinetik der thermischen Zersetzung von Cs2Zn(N3)4 und K2Zn(N3)4

The thermal decomposition of two complex inorganic azides, i.e. Cs₂Zn(N₃)₄ and K₂Zn(N₃)₄, has been studied. Decomposition proceeds from the melt in the temperature range from 285–330°C and 310–360°C, resp., the main reaction products being N₂ and small solid particles of Zn₃N₂ containing minor amounts of finely divided metallic zinc. The alkali metal component (CsN₃ and KN₃) is stable to decomposition in the temperature region investigated. The kinetics of the decomposition process are described in terms of the acceleratory action of the solid Zn₃N₂(Zn)-particles and their mutual agglomeration with increasing fractional decompositionX (kinetic models I and III). In the final stages of decomposition the metal azide component may crystallize from the melt. This situation is accounted for within the kinetic model IV. The experimental data [X(t)-isotherms] have been analyzed with respect to the postulated kinetic models by statistical techniques (nonlinear regression).

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Mit 5 Abbildungen

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Herrn Professor Dr.R. Kieffer zum 70. Geburtstag gewidmet.     

Synthesis of New Iminosugar Derivatives Based on (S)-(1,2,3,6-Tetrahydropyridazin-3-yl)methanol

(S)-(1,2,3,6-Tetrahydropyridazin-3-yl)methanol was synthesized in two steps by the Diels-Alder reaction of penta-2,4-dien-1-ol with diethyl azodicarboxylate in the presence of (S)-BINOL as chiral catalyst. The subsequent Boc-protection of the 2-position of the pyridazine ring, ring-closing carbonylation of the hydroxy group, and deprotection afforded a bicyclic iminosugar analog. The structure of the isolated compounds was proved by NMR, IR, and mass spectra and elemental analyses.

     

Crystal Structures of (18-Crown-6)-(2-Hydroxyethylammonium) Tetracyanonickelate(Ii) and 10-Amino-Decylammonium Tetracyanonickeltate(II)

Abstract

The crystal structures of the two title tetracyanonickelate(II) salts of organic ammonium ions, (18-crown-6)-(2-hydroxyethylammonium) tetracyanonickelate(II), I, and 10-aminodecylammonium tetracyano nick-elate(II), II, have been analyzed. I crystallizes in the monoclinic space group P2₁/n with a = 10.458(2), b = 8.267(3), c = 24.045(2) Å, β = 94.09(1)°, V = 2074(1) ų, Z = 2, R = 0.061 for 2274 reflections; II is triclinic P ₁ with a = 9.437(3), b = 10.094(3), c = 9.205(3)Å,a = 110.16(2), β = 112.72(3), γ = 69.16(2)°, V = 733.7(5) ų 2=1, R = 0.040 including all the hydrogen atoms refined for 2724 reflections. The square planar tetracyanonickelate(II) anion is in a favourable position to form hydrogen bonds via N with the hydroxyl group in I and the ammonio group in II, respectively.     

Biological evaluations and spectroscopic characterizations of 3-(4-ethoxyphenyl)-2-methylacrylate based organotin(IV) carboxylates derivatives

Six new organotin(IV) carboxylates, [Me₂SnL₂] (1), [n-Bu₂SnL₂] (2), [n-Oct₂SnL₂] (3), [Me₃SnL] (4), [n-Bu₃SnL] (5) and [Ph₃SnL] (6), where L = 3-(4-ethoxyphenyl)-2-methylacrylate, have been synthesized and characterized by FT-IR, NMR spectroscopy and elemental analyses. The synthesized compounds were tested for in vitro antibacterial and antifungal activities. The complexes 4–6 demonstrated higher activity than the complexes 1–3. UV-Vis absorption spectroscopy indicated that the ligand and its complexes interacted with DNA via partial intercalation as well as minor groove binding.

     

Isomere Kupfer(II)-Chelate mit Liganden vom Cuprointyp

Two pairs of isomeric copper(II) chelates of the composition Cu(dm)(NO₃)₂ and Cu(dp)(NO₃)₂, resp., have been prepared (dm=6,7-dihydro-5,8-dimethyl-dibenzo[b,j][1,10]phenanthroline), anddp=6,7-dihydro-5,8-diphenyl-dibenzo[b,j][1, 10]-phenanthroline). By ESR, IR, and visible reflectance spectra the structures of the first coordination sphere of these chelates have been established, the two Cu(dm) (NO₃)₂ chelates and the brown -Cu(dp) (NO₃)₂, having coordination number six while the green -Cu(dp) (NO₃)₂ has coordination number seven. In comparison with the diamagnetically diluted complexes (solution, powder) the isomerism is found to be typical only for undiluted copper(II) complexes.

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Mit 2 Abbildungen

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19. Mitt.:D. Rehorek, H. Spindler undPh. Thomas, Z. Chem.15, 281 (1975).     

Die Kinetik der Entladung von Thorium (IV) in Gegenwart von Äthylen-bis(3-mercaptopropionat) an der Quecksilbertropfelektrode

The reduction of thorium at the dropping mercury electrode in presence of ethylene bis(3-mercaptopropionate) has been found to be irreversible and kinetically controlled. The kinetics of the electrode reaction has been investigated adopting the treatment followed byKoutecky.

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Synthesis of (E)-4-(4-chlorobenzylidene)-3,4-dihydro-2H-pyrrole-based pyrrolinium salts

Pyrrolinium salts containing 3-arylidene fragment were obtained. Their synthesis is based on the reaction of (E)-4-(4-chlorobenzylidene)-3,4-dihydro-2H-pyrrole with various bromo-alkanes. Structures of the obtained compounds were confirmed by a set of physico-chemical analysis methods.

     

Acylgruppenwanderung in N-Acyl-2H-imidazol-4(3H)-thionen

On acylating 2H-imidazole-4(3H)-thiones the orange to violet crystalline N-1-acyl-2H-imidazole-4(3H)-thiones1 a–18 a are formed, the thermal stability of which depends on the acyl group and the substituents in the heterocyclic ring system. Thus the N-aroyl-2,2,5-trimethyl-2H-imidazole-4(3H)-thiones13 a–16 a are stable on being heated to the melting point, while1 a–12 a are converted quantitatively to the corresponding S-aroyl-2H-imidazole-4-thiols1–12. Rearrangement is faster when the heterocyclic ring bears bulky substituents. The aliphatic N-acyl compounds17 a and18 a are thermally unstable. This N S acyl group migration, described here for the first time, is shown to proceed by an intermolecular mechanism.

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Herrn Prof. Dr. Dr. h. c. mult.Hermann F. Mark zum 80. Geburtstag in Verehrung gewidmet.

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88. Mitt.:F. Asinger, A. Saus, H.-J. Gräber, E. Fichtner undW. Leuchtenberger, Mh. Chem.106, 1449 (1975).

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Teil der DissertationE. Fichtner, Techn. Hochschule Aachen, 1974.     

SYNTHESIS AND STRUCTURES OF DICHLOROTETRAKIS-(PHENYLTHIOUREA) CADMIUM(II) AND CATENA-BIS(THIOCYANATE) BIS(PHENYLTHIOUREA)CADMIUM(II)

Abstract

Two new cadmium(II) complexes with phenylthiourea (PTU), namely Cd(PTU)₄Cl₂ (1) and [Cd₂(NCS)₂(μ₂-SCN)₂(PTU)₂(μ₂-PTU)₂] _n (2), have been prepared and characterized structurally by X-ray diffaction. Complex 1 crystallizes in the monoclinic space group C2/c, with a = 27.057(13), b = 8.108(3), c = 16.751(8) Å, β = 114.46°, V = 3345(3) ų, Z = 4. Complex 2 crystallizes in the triclinic space group P-1, with a = 9.336(3), b = 14.686(5), c = 16.911(5) Å, α = 71.36(2), β = 84.31(2), γ = 72.470(10)°, V = 2095.0(12) ų Z = 4. The structural analysis shows that each metal atom in both the mononuclear complex 1 and polynuclear complex 2 is octahedrally coordinated by four sulfur atoms and two chloro ligands or two nitrogen atoms from the thiocyanate groups, respectively. The PTU ligand can serve as either a monodentate ligand or a μ₂-bridging ligand upon coordination to a metal atom.