Fluordiazadiphosphetidine, 7. Mitt. Die reaktion von 2,2,2,4,4,4-Hexafluoro-1,3-dimethyl-1,3,2λ5,4λ5-diazadiphosphetidin mit mono-und bissilyliertemN,N′-Dimethylharnstoff

The reaction of (CH₃NPF₃)₂ with mono-and bissilylatedN,N-dimethylurea yields a crystalline solid which has been identified as a cuban-like P-N-compound with two dimethylurea-bridges. The conditions of formation and the NMR-spectra are discussed.

     

Lumineszierende Cu(I)- und Ag(I)-Cluster mit Thionoliganden

Zusammenfassung Cu(I) bildet mit zahlreichen nicht lumineszierenden Thionoliganden (N-monosubstituierten N-Sulfonylthioharnstoffen, N,N-Dialkyl-N-phenylthioharnstoffen und N,N-Dialkylmonothiocarbamaten) rot lumineszierende oktaedrische Cluster (CuL)₆. Die Lumineszenz tritt sowohl im Festzustand als auch in Lösungen auf. Abklingzeiten von 10^–5s deuten auf kurzlebige Phosphoreszenz hin. Der Einfluß verschiedener Strukturelemente auf die Lage der Emissionsmaxima wird diskutiert. Dabei bewirken Veränderungen in der Metall-Ligand-Koordination die stärkste Verschiebung der Lumineszenzbanden. Tetraedrische (CuL)₄-Cluster mit den obigen Thionoliganden zeigen keine Lumineszenz. Generelle Unterschiede in der Struktur oktaedrischer und tetraedrischer Cluster werden diskutiert.Ag(I) bildet nur mit N-Alkyl-N-sulfonylthioharnstoffen lumineszierende Cluster (AgL)₆. Die Lumineszenz ist im Gegensatz zu den Cu-Clustern auf den Festzustand beschränkt.

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Luminescent Cu(I) and Ag(I) clusters with thiono ligands

Summary Octahedrical (CuL)₆ clusters with several non luminescent thiono ligands (N-monosubstituted N-sulfonylthioureas, N,N-dialkyl-N-phenylthioureas and N,N-dialkylmonothiocarbamates) show red luminescence in the solid state and in solution. The luminescence lifetimes of 10^–5s are typical of short lived phosphorescence. The emission bands are affected by structural variation of the ligand. Changes of the coordination bonds cause the strongest shifts of the luminescence maxima. Tetrahedrical (CuL)₄ clusters with the same thiono ligands are not luminescent. General structural differences between octahedral and tetrahedral clusters are discussed.(AgL)₆ clusters are only luminescent in the solid state and if the ligand is a N-monosubstituted N-sulfonylthiourea

     

Fluordiazadiphosphetidine, 20. Mitt. Die Dehydrofluorierung zwitterionischer und die Hydrofluorierung neutraler,hydrazinsubstituierter Fluordiazadiphosphetidine

In the presence ofEt ₃N·PF₅, F₄P^–(CH₃N)₂PF₂NHNH⁺(CH₃)₂ (I) looses one molecule of HF to yield F₃P(CH₃N)₂PF₂NHN(CH₃)₂ (II). The reaction ofI withDABCO (1,4-diazabicyclo[2.2.2]octane) yieldsDABCO·2H⁺⁺(CH₃NPF₄) ₂ ^–– (III) and [CH₃NPF₂NHN(CH₃)₂]₂ (IV). Even in the presence of CsF,II does not react with HF.

     

Strukturelle Abwandlungen anN-Acetylneuraminsäure, 4. Mitt. Transformationen am Diethyl-dithioketal desN-Acetylneuraminsäure-γ-lactons

Partial protection of diethyldithioketal ofN-acetylneuraminic acid--lactone using one or two equivalents oft-butyldimethylchlorosilane leads to the 9-O-silyletherderivative7 and the 8,9-bis-O-silylderivative5, resp. The reaction of1 as well as7 with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TIPSiCl₂) yields selectively the protected products4 and9. The 9,8,7,6-tetra-O-acetyl-N-acetylneuraminic acid--lactone derivative3 is formed by the oxidative desulfurazation of the peracteylated form of1 (i. e.2) by means ofNBS. By reaction of5 withTPPDEAD the 6,7-carbonato compound6 arises instead of the expected 6,7-epoxyderivative. The analogous carbonate8 is formed by treating7 with bisimidazolylcarbonate.

     

Notiz zur [1,2]-Heterorest-Verschiebung in einem Sulfinamidin

Reaction of methyl 1-pyrroline-2-carboxylate (3 a) with N,N-Ditosylsulphur-diimide affords the pyrrol-2-carboxylic acid derivative7. The sulfenamide function in7 is cleaved by trimethyl phosphite leading to8. Presumably the reaction sequence (3 a 7) takes its course via the sulfinamidine4 a and the rearrangement product5 a followed by elimination of tosylamide. An analogous reaction starting with the dimethyl-1-pyrrolin-2-carboxylate3 b yields the stable sulfinamidine4 b, which undergoes a rearrangement reaction with base producing6 b with the thioaminal5 b as the intermediate.

Herrn Prof. Dr. Dr. h. c.K. Kratzl zum 70. Geburtstag herzlich gewidmet.     

Synthesis,crystal structure and conformation of N-acetyl-Cα,α-diethylglycine-N′-methylamide

Summary Synthesis and X-ray structure analysis of N-acetyl-^,-diethylglycine-N-methylamide [CH₃-Co-NH-C(C₂H₅)₂-CO-NHCH₃] are described. The compound was obtained from the corresponding N-acetyl derivative [CH₃-CO-NH-C(C₂H₅)₂-COOH] through the mixed anhydride procedure. It crystallizes as monohydrate (C₉H₁₈N₂O₂·H₂O) in space group P2₁/c,a=7.139(1),b=11.823(2),c=15.778(3) Å, =122.23(1)°,V=1126.53 ų,D _m=1.20 Mgm^–3 (room temperature),R=0.046 for 1523 reflections. The crystal packing is dominated by two strong hydrogen bonds between the water molecule and two carbonyl oxygen atoms and two weak H-bonds to two amide-N-atoms of symmetry-equivalent molecules. The molecular conformation is closer to a 3₁₀-helix then ana-helix.

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Synthese, Kristallstruktur und Konformation von N-Acetyl-^,-diethylglycin-N-methylamid

Zusammenfassung Es wird über Synthese und die röntgenographische Strukturbestimmung von N-Acetyl-^,-diethylglycin-N-methyl-amid [CH₃-CO-NH-C(C₂H₅)₂-CO-NH-CH₃] berichtet. Die Verbindung wurde unter Anwendung der Methode der gemischten Anhydride aus dem entsprechenden N-Acetylderivat [CH₃-CO-NH-C(C₂H₅)₂-COOH] erhalten. Sie kristallisiert als Monohydrat (C₉H₁₈N₂O₂·H₂O) in der Raumgruppe P2₁/c mita=7.139(1),b=11.823(2),c=15.778(3) Å, =122.23(1)°,V=1126.53 ų,D _m=1.20 Mgm^–3,D _x=1.204 Mgm^–3 (Raumtemperatur).R=0.046 für 1523 Reflexe. Die Kristallpackung ist dominiert durch zwei starke H-Brücken vom Wassermolekül zu zwei Carbonylsauerstoffatomen sowie zwei schwachen H-Brücken zu zwei Amid-N-atomen symmetrieequivalenter Moleküle. Die Konformation des Peptidgerüstes ist näher einer 3₁₀ als einera-Helix.

     

Ein einfacher Weg zu α-substituierten (E)-3-Oxo-1-alkenylphosphonsäureestern

Zusammenfassung -Substituierte -Acylvinylphosphonate3 mitE-Konfiguration [R ²CO-CH=C(R ¹)-P(O)(OR)₂], werden in guten Ausbeuten durchWittig-Reaktion von Acylphosphonsäureestern1 [R ¹CO-P(O)(OR)₂,R ¹=Alkyl oder Aryl] mit (2-Oxoalkyliden)triphenylphosphoranen2 [R ²CO-CH=PPh ₃,R ²=Alkyl, O-Alkyl oder CH₂ X (X=Br, OMe, CO₂ Et)] erhalten.

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A convenient route to -substituted dialkyl (E)-3-oxo-1-alkenylphosphonates

-Substituted dialkyl (E)--acylvinylphosphonates [R ²CO-CH=C(R ¹)-P(O)(OR)₂,3], are easily obtained in good yields byWittig-reaction of dialkyl acylphosphonates1 [R ¹CO-P(O)(OR)₂,R ¹=alkyl or aryl) with 2-oxoalkylidene triphenylphosphoranes2 [R ²CO-CH=PPh ₃,R ²=alkyl, O-alkyl and CH₂ X (X=Br, OMe, CO₂ Et)].

     

Synthesis and crystal structure of copper halide complexes with triethylallylammonium (teaa) chloride: [(teaa)Cu3ICl4], [(teaa)Cu3IBr3.86Cl0.14], and (teaa)2CuIICl4

The results of X-ray diffraction analysis of novel triethylallylammonium chloride compounds with copper(I) chloride, copper(I) bromide, and copper(II) chloride are reported. The [(CH₃CH₂)₃(CH₂=CHCH₂xN]Cu ₃ ^I Cl₄ and [(CH₃CH₂)₃(CH₂=CHCH₂Cu ₃ ^I Br_3.86)Cl_0.14 -complexes are isostructural: space group P2₁/a; a= 17.58(1) Å, b = 12.059(8)Å, c = 7.184(4) Å, = 98.37(5)° and a = 17.972(9) Å, b=12.479(8) Å, c = 7.290(5) Å, = 98.81(5)°, respectively. ²-Coordination of the copper atom by the olefinic bond plays a key role in the structural ordering of the tetraalkylammonium cation. In contrast, the structure of {(CH₃CH₂)₃x(CH₂=CHCH₂)N}₂Cu^IICl₄ (P4₂/nmc; a = 8.839(3) Å, c =15.660(9) Å) follows the ionic salt pattern.Original Russian Text Copyright © 2004 by L. M. Babkov, I. I. Gnatyuk, G. A. Puchkovskaya, and S. V. TrukhachevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 398–405, May–June, 2004.     

Synthesis and crystal structure ofN,N′-DicyclohexylpiperazineN,N′-dioxide octahydrate

N,N-DicyclohexylpiperazineN,N-dioxide octahydrate, C₁₆H₄₆N₂O₁₀,M _r=426.55, monoclinic, space groupC2/m (No. 12),a=12.961(4),b=11.533(4),c=7.907(1) Å, =98.37(2)^o,V=1169.3(6) ų,Z=2. The structure was solved by the direct method and refined toR=0.045 for 1192 observed MoK reflections. TheN,N-dioxide molecule occupies a site of symmetry 2/m. The piperazine ring takes the chair form with the two N–O bonds oriented axially in atrans configuration. Hydrogen bonding between the water molecules, as well as between theN-oxide groups and water molecules, gives rise to a puckered layer composed of edge-sharing four-membered, five-membered, six-membered, and eight-membered rings. Adjacent layers are cross-linked by theN,N-dicyclohexylpiperazine moieties lying between them, thereby generating a sandwich structure consolidated by covalent and hydrogen bonding. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82062 (8 pages).     

Theoretical study of the electronic structure of diazomethane

The least-energy dissociation path of the ground state of CH₂N₂ was determined fromab initio calculations using in a complementary way basis sets of minimal size (STO-3G) and double-zeta (DZ) quality. The results indicate that the least-energy point of attack of the N₂ molecule on CH₂ (¹ A ₁) is roughly perpendicular to the molecular plane (93 °), the C and N atoms being almost co-linear (angle C-N-N203 ° with outermost N atom pointing away from CH₂). The potential barrier of 1.2 eV found previously on theC _2v dissociation path, disappears completely along the least-energy dissociation path (point groupC _s (out-of-plane)). These findings corroborate the Woodward-Hoffman rules for this process since the outermost orbitals of the two intersecting states found in point groupC _2v (...2b ₁ and ...8a ₁) both correlate to the same irreducible representation (10á) in point groupC _s (out-of-plane).Larger basis set calculations (DZ + polarization functions on all centers, 3d _c and 3d _N developed here), were also carried out on CH₂N₂ (¹ A ₁,³ A ₂ and¹ A ₂) at the¹ A ₁ equilibrium geometry and on CH₂ (³ B ₁) and N₂ (¹ _g ⁺ ) at their respective equilibrium geometries. These calculations, together with consideration of correlation energy differences, yieldD ₀ ⁰ (CH₂N₂,¹ A ₁) = 19 kcal/mole and vertical excitation energies of 67 and 73 kcal/mole for the³ A ₂ and¹ A ₂ states respectively. The latter value is in good agreement with the measured experimental value: 72.4 kcal/mole corresponding to the maximum of intensity in the¹ A ₂¹ A ₁ absorption band.     

Untersuchungen zur Cyclisierung von „3-Aza-1,5-dicarbonylverbindungen”

From1b, 1c and1d no 1,4-oxazines are available under dehydrating conditions. Only reaction of1c withPPA at room temperature yields7, while1 d in dependence of the reaction time withPPA at 100°C undergoes cyclisation to the indoles3 b and3 c and the pyrroloindole4 b, resp.

Teile der DiplomarbeitHaubold G., Wien 1977. Teile der DissertationHaubold G., Wien 1980.     

Fluordiazadiphosphetidine, 18. Mitt. Neue zwitterionische Fluordiazadiphosphetidinderivate

The reaction of (CH₃NPF₃)₂ with substituted hydrazines yields a new type of a P/N/P/N ring system by addition of one molecule hydrogenfluorid to the substituted molecule. These betain-like compounds are the first examples of a P/N/P/N ring system with one P-atom in ⁵- and the other in ⁶-conformation.

     

Addition products of hydrazine derivatives to azo-alkenes,part V: The reaction of α-(1-phenylhydrazino)alkanone phyenylhydrazones with acids and acid derivatives

Summary The bifunctional title compounds2 react with acylating, carbamoylating and sulfonylating reagents mostly at the primary amino group of the hydrazine function. Both functional groups of2 are attacked by N,N-carbonyldiimidazole converting it into 1H-1,2,4,5-tetrazepin-3-one derivatives8. The acid-induced 1,4-elimination of phenylhydrazine from2 gives rise to the formation of phenylosazones3. In the presence of thiocyanic acid the intermediately formed phenylazo-alkenes1 undergo [3+2]-cycloaddition furnishing 1-anilino-imidazoline-2-thiones13.

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Additionsprodukte von Hydrazin-Derivaten an Phenylazo-alkene, 5. Mitt.: Umsetzung von -(1-Phenylhydrazino)alkanon phenylhydrazonen mit Säuren und Säurederivaten

Zusammenfassung Die bifunktionellen Titelverbindungen2 reagieren mit Acylierungs-, Carbamoylierungs-und Sulfinylierungs-Reagenzien meist an der primären Amino-Gruppe der Hydrazin-Funktion. N,N-Carbonyldiimidazol greift beide funktionelle Gruppen von2 an und bedingt die Umwandlung in 1H-1,2,4,5-Tetrazepin-3-on-Derivate8. Die säureinduzierte 1,4-Eliminierung von Phenylhydrazin aus2 führt zur Bildung der Phenylosazone3. In Gegenwart von Thiocyansäure erfolgt [3+2]-Cycloaddition an die intermediär gebildeten Phenylazo-alkene1, sodaß 1-Anilino-imidazolin-2-thione13 entstehen.

     

Schiff base derivatives of lanthanons-synthesis of La(III), Pr(III) and Nd(III) derivatives of β-ketoimines derived from 2,4-pentanedione

Reactions of the isopropoxides of some of the lighter lanthanons with bidentate -ketoimines, such asAAH-n-C₄H₉ andAAH-C₆H₅ (donor system: N,OH) and tridentate -ketoimines such asAA(CH₂CH₂)H₂ andAA(CH₂CHCH₃)H₂ (donor system: HO,N.OH) have led to products of the typesLn(O-i-C₃H₇)_3n (AA-R) _n ,Ln(Oi-C₃H₇) (AAR') andLn ₂(AAR')₃ [Ln=La(III), Pr(III) or Nd(III);n=1 or 2;R=-n-C₄H₉ or-C₆H₅ andR'=-CH₂CH₂-or-CH₂CHCH₃-]. Some undergo exchange reactions with an excess oftert-butanol, leading to the corresponding complexesLn(O-tert-C₄H₉)_3n (AA-n-C₄H₉) _n andLn(O-tert-C₄H₉) (AA-CH₂CH₂). All these have been characterised by elemental analysis, molecular weight determinations and their ir spectra. A thermogravimetric analysis of the diisopropoxy derivatives has also been carried out.

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Schiff-Basen Derivate von Lanthaniden-Synthese von La(III), Pr(III) und Nd(III) chelaten mit -Ketoiminen

Zusammenfassung Reaktionen von Lanthanid-Isopropoxiden mit zweizähnigen -Ketoiminen [AAH-n-C₄H₉ undAAH-C₆H₅; Donorsystem: N,OH] und dreizähnigen -Ketoiminen [AA(CH₂CH₂)H₂ undAA(CH₂CHCH₃)H₂; Donorsystem: OH, N,OH] führten zu Produkten vom, TypLn(O-i-C₃H₇)_3-n (AA-R) _n ,Ln(O-i-C₃H₇) (AAR') undLn ₂(AAR')₃ [Ln=La(III), Pr(III) oder Nd(III);n=1 oder 2;R=n-C₄H₉ oder C₆H₅ undR'=CH₂CH₂ oder CH₂CHCH₃]. Einige Komplexe unterliegen bei Behandlung mit einem Überschuß vontert-Butanol einer Austauschreaktion, die zu den entsprechenden Butoxid-Komplexen führt [Ln(O-tert-C₄H₉)_3-n , (AA-n-C₄H₉) _n undLn(O-tert-C₄H₉) (AACH₂CH₂)]. Alle Derivate wurden mittels Elementaranalyse, Molgewichtsbestimmung und IR-Spektroskopie charakterisiert. Eine thermogravimetrische Analyse der Diisopropoxi-Derivate wurde ebenfalls ausgeführt.

     

β-Tricarbonyl compounds. I. 2,4-Disubstituted 1,3-cyclopentanediones

Summary Stable enolic isomers of 2-aroyl-4-aracyl-1,3-cyclopentanediones such as3 and4 were prepared by condensation of aryl methyl ketones and diethyl maleate using an excess of sodium ethoxide (Aryl=C₆H₅, 4-C₆H₄CH₃, 4-C₆H₄Br and 4-C₆H₄Cl).

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-Tricarbonyl Verbindungen. I. 2,4-Disubstituierte 1,3-Cyclopentandione

Zusammenfassung Stabile Enol-Isomere von 2-Aroyl-4-aracyl-1,3-cyclopentandionen wie3 und4 wurden durch Kondensation von Arylmethylketonen und Diethylmaleat mit einem Überschuß von Natriumethoxid dargestellt (Aryl=C₆H₅, 4-C₆H₄CH₃, 4-C₆H₄Br und 4-C₆H₄Cl).

     

Synthesis and Crystal Structure of a New Copper–PMIDA Compound (H4PMIDA=H2O3PCH2N(CH2CO2H)2)

A new Cu(II)PMIDA compound [Cu(H₂PMIDA)(phen)] 3H₂O (1) (H₄PMIDA = H₂O₃PCH₂N (CH₂CO₂H)₂,phen = 1,10-phenanthroline) has been successfully synthesized and structurally characterized. In complex 1, Cu (II) is six coordinated by chelation in a tetradentate fashion by a PMIDA ligand and by two N atoms of a phen ligand. Every phen–Cu(II)–PMIDA group connects with each other via a hydrogen bond and the edge-to-face -stacking interaction. Complex 1 crystallized in triclinic P-1 with cell dimensions of a = 7.5817(6) Å, b = 10.6980(8) Å, c = 13.1852(10) Å, =82.350(2)°, = 84.151(2)°, =78.4250(2), V= 1035.25(14) ų, Z = 2, Dc = 1.677 Mg/m³.     

Aromatische Spirane, 16. Mitt.: Darstellung von monound dianellierten 2,2′-Spirobiindan-1,1′-dionen

Summary The spiroketones19, 21, 24, 27, and31 were prepared by cyclisation of the dicarboxylic acids and their acid chlorides, resp., (18, 20, 22, 23, 25, 26, 28, and30) with polyphosphoric acid (PPA) or SnCl₄. The latter compounds were synthesized by alkylation of the appropriate -keto esters10, 11, 12, and13 with the benzyl chlorides14, 15, 16, and subsequent retro-Claisen-reaction. The spiro compounds21a and39 were obtained byPPA-cyclisation of the keto acids35 and38, which in turn were prepared by aldol-reaction of the ketoness-hydrindacen-1-on and9a with phthalaldehydic acid to the olefinic keto acids33 and36 followed by catalytic hydrogenation.

     

Über die Synthese von Dihydro-1,2,3,5-thiatriazol-1,1-dioxiden, 2. Mitt.

By reaction of several N-phenyl-benzamidrazones with SO₂F₂ 2-phenyl-2,5-dihydro-1,2,3,5-thiatriazole-1,1-dioxides2 a–c are formed. By reaction of N,N-diethyl-N-chlorosulfonyl-chloroformamidine8 with hydrazines the corresponding 4-diethylamino-substituted derivatives9 a–d are obtained. Methylation of2 b yields two isomeric products5 and6, whereas by methylation of9 d only one product9 b is obtained.

     

Fluordiazadiphosphetidine, 10. Mitt.: Die Reaktion von 1,3-Dialkyl-2,2,2,4,4,4-hexaflouro-1,3,2λ5,4λ5-diazadiphosphetidine mitN-Trimethylsilylmethylamin

Reaction of (RNPF₃)₂ compounds (R=CH₃, C₂H₅,n-C₃H₇,n-C₄H₉,i-C₄H₉) withN-trimethylsilyl-methylamine leads to nucleophilic substitution of one or two fluorine atoms by the methylamino group, depending on the molar amounts of the reactants. In the case ofR=CH₃, two by-products are formed: in the first step a compound with coordination numbers IV, V and VI for the three phosphorus atoms in C₅H₁₇F₇N₅P₃ and in the second step a monospiroflourodiaza-⁵, ⁵-diphosphetidine.

9. Mitteilung:Utvary, K., Kubjacek, M., Varmuza, K. Z. anorg. allg. Chem.458, 281 (1979).