Schwefel-Phosphor Heterocyclen RP(S)Sn,Darstellung, Struktur und Eigenschaften

Sulfur-Phosphorus Heterocycles RP(S)S_n, Synthesis, Structure, and Properties Sulfur-phosphorus heterocycles of the composition RP(S)S_n (R = Me, t-Bu; n = 7–5) 1a, b–3a, b have been synthesized in ring-closing reactions between the silyl or stannyl esters of trithiophosphonic acids RP(S)(SEMe₃)₂ (E = Si, Sn) and chlorosulfanes S_xCl₂ (x = 5–3). The heterocycles are fairly stable in crystalline state, in solution disproportionation to ring compounds with larger and smaller number of S-atoms, respectively, as well as oligomerization is observed. According to NMR spectroscopic investigations the S? P heterocycles exhibit the following structures 1. MeP(S)S₇ ( 1a ), eight-membered ring showing two crown conformations that differ in the orientation (axial, equatorial) of the Me-group; t-BuP(S)S₇ ( 1b ), eight-membered ring with crown conformation (t-Bu = equatorial). 2. RP(S)S₆ ( 2a, b ), seven-membered rings with twist-chair conformation. 3. RP(S)S₅, six-membered rings, R = Me ( 3a ) chair conformation (Me = axial), R = t-Bu ( 3b ) chair conformation (t-Bu = equatorial) and twist-boat conformation. In crystalline state 1a only exists in the crown conformation with axial orientation of the Me-group. In solution a fast conformational interconversion between the two isomers of 1a and of 3b has been detected by dynamic NMR measurements. Furthermore t-BuP(S)S₅ ( 3b ) is in a temperature and concentration dependent equilibrium with its dimer and probably also with oligomeric forms.     

Darstellung und spektroskopische Eigenschaften von Nitridophthalocyaninatorhenium(V)

Preparation and Spectroscopical Properties of Nitridophthalocyaninatorhenium(V) Nitridophthalocyaninatorhenium(V) ([ReNPc^2?]) is prepared by the reaction of dirheniumheptoxide with ammoniumiodide in molten 1,2-dicyano-benzene. The diamagnetic complex is chemically und thermically extremely stable. In the Uv-vis spectra the typical π-π*-transitions of the Pc^2? ligand are observed. Extra bands in the solid state spectrum are due to strong excitonic coupling of ca. 2.8 kK. In the resonance Raman spectra the intensity of the Re≡N stretching vibration (v(Re≡N)) at 969 cm^?1 is selectively enhanced by laser excitations above 19.0 kK. v(Re≡N) is a dominant m.i.r. absorption at 976 cm^?1.     

Darstellung,Eigenschaften und Molekülstruktur eines Titan-tris(diazadien)-Komplexes

Preparation, Properties, and Molecular Structure of a Titanium-tris(diazadiene) Complex (R = i-C₃H₇) 1 was obtained by reaction of TiCl₄ · 2 THF with Li₂(NR? CH = CH? NR) in the presence of the ligand molecules. The compound was characterized by ¹H-, ¹³C-n.m.r., and mass spectroscopy. The molecular structure was determined by X-ray diffraction. The bonding distances in the identically coordinated diazadiene ligands are similar to those of radical.     

Synthesen von Heterocyclen, 103. Mitt.: Über Reaktionen mit Oxalylchlorid (Kurze Mitteilung)

Ohne Zusammenfassung     

Synthesen von Heterocyclen, 21. Mitt.: Reaktionen mit cyclischen Ketonen

Zusammenfassung Den Cyclanonen analog reagieren mit Benzylmalonsäure-bis-(2,4-dichlorphenol)-ester II folgende cyclische Ketone: Menthon, Benzosuberon, -Tetralon, Cyclohexandion-(1,4), 1-Hydrindon, Thionindoxyl, Cumaranon, 1-Phenyl-3-methyl-pyrazolon-(5), peri-Naphthindandion und Flavanon. E. Ziegler, H. Junek undE. Nölken, Mh. Chem.89, 678 (1958).     

Trivalent-pentavalente Phosphorverbindungen/Phosphazene. V. Darstellung,Eigenschaften und Reaktionen neuer Phosphonig- und Phosphinigsäureester

Trivalent-Pentavalent Phosphorus Compounds/Phosphazenes. V. Preparation, Properties, and Reactions of New Phosphonous- and Phosphinous Acid Esters Phosphonous diesters R? P(OR′)₂ (R ? CH₃, Ph and R′ ? CH₂? CF₃) have been synthetized by reaction of phosphonous dichlorides with 2, 2, 2-trifluoroethanol in the presence of a base. These diesters react with trimethyl(trimethylsilylimino)phosphorane, (CH₃)₃P?N? Si(CH₃)₃ by desilylation and N? P-linking to phosphinous acid esters (CH₃)₃P?N? P(OR′)R. The phosphinous acid esters react with methyl iodide to the quaternary salts [(CH₃)₃P? N? P(OR′)(R)CH₃]⁺I^?. The compounds are characterized by elementary analysis and spectroscopical methods.     

Über Reaktionen mit Kohlensuboxid (C3O2) Synthesen von Heterocyclen, 154. Mitt.

Zusammenfassung Das vonDashkevich undKuvaeva ¹ aus Benzalanilin und C₃O₂ dargestellte Produkt (22) besitzt nicht die SpirostrukturB, sondern ist als eine quasi mesoionische Verbindung vom Typ1 (11) anzusehen. Solche Substanzen lassen sich auch aus Benzalanilinen und Malonylchlorid synthetisieren.

---

Syntheses of heterocycles, CLVI: Reactions with carbon suboxide

The compound first obtained byDashkevich undKuvaeva ¹ from benzalanilíne and C₃O₂ has the quasi mesoionic structure1 and not the proposed spiro structureB. This class of compounds can also be synthesized from benzalanilines and malonyl chloride.

---

---

Herrn Prof. Dr.M. Pailer, Universität Wien, zum 60. Geburtstag gewidmet.     

Synthesen von Heterocyclen, 62. Mitt.: Über Reaktionen mit Betain

Zusammenfassung Beim Erhitzen von Betain mit Phenylisocyanat (12) auf 140–160° entsteht Diphenylimidazolidin-dion-(2,4) (I).

---

Diphenylimidazolidine-dion-2,4 (I) was obtained by the reaction of betaine with phenylisocyanate (12) at 140–160°.

     

Darstellung und Eigenschaften einiger Nickel(0)-Komplexe mit stickstoffhaltigen Alkinverbindungen

Preparation and Properties of Some Nickel(0) Complexes with Nitrogen-containing Acetylenic Compounds Compounds of the type (ligand)₂Ni(acetylene) have been prepared by reactions of complexes (ligand)₂Ni(C₂H₄) with disubstituted nitrogen-containing acetylenes. The new complexes are characterized by some chemical reactions and physical methods and compared with recently prepared hydroxy-acetylene compounds.     

Synthesen von Heterocyclen, 118. Mitt.: Über Reaktionen mit heterocyclischen Aminalen

Zusammenfassung Aminale einer Reihe von Mesoxalylheterocyclen, welche leicht aus den entsprechenden Dichlormalonylderivaten zugänglich sind, werden mit verd. Säuren in die vic. Tricarbonylverbindungen (bzw. deren Hydrate) gespalten. Die Reduktion der Aminale in neutralem Medium mit Na₂S₂O₄ liefert Monomorpholino-(bzw. Monopiperidino-)-malonylheterocyclen, während die Reduktion mit Zn/HCl in Äthanol zu Reduktonen führt.

---

Aminals of a number of heterocyclics derived from mesoxalic acid and obtainable from derivatives of dichloromalonic acid readily undergo cleavage with dil. acids to give the vic. tricarbonyl compounds or their hydrates. Reduction of aminals in neutral media by means of sodium dithionite, Na₂S₂O₄, yields mono-morpholino- or mono-piperidinomalonyl heterocyclics. Reduction with Zn/HCl in ethanol leads to the formation of reductones.

     

Darstellung und Untersuchung von Aminoschwefeltrifluoriden sowie eines Hydrolyseprodukts, 1-(Fluorooxothio)-2,5-dihydropyrrol

Synthesis and Investigation of Aminosulphur Trifluorides and of a Hydrolysis Product 1-(Fluorooxothio)-2,5-dihydropyrrole The reaction of previously unknown (trimethylsilyl)amines with sulphur tetrafluoride gives some new aminosulphurtrifluorides. Experiments to cleaver 1-(Trifluorothio)-2,5-dihydropyrrole and 1-(trifluorothio)pyrrolidin into butadiene and ethylene respectively and NSF₃ by way of a chelotrope cycloelimination were unsuccessful. ¹H-NMR and ¹⁹F-NMR spectra revealed the nitrogen in the aminosulphur trifluorides must be regarded sp³ hybridized rather than sp².     

Darstellung einer molekularen,monomeren thallium(I)-Verbindung mit einem neuen chelatisierenden Liganden

The chelating ligand Me₃COSiMe₂N(CMe₃)H (III) can easily be prepared in high yields and has been employed for the synthesis of some metal derivatives. With n-butyllithium III forms [Me₂Si(Me₃CO)(Me₃CNLi)]₂ (IV), which is found to be dimeric in solution and in the gas phase. When IV is allowed to react with thallium(I) chloride in diethyl ether the monomeric, highly reactive Me₂Si- (Me₃C$\text{O)(Me}{}_3\text{CNTl}$) (II) is formed under precipitation of lithium chloride. The cyclic structure and the physical properties of II can be understood on the basis of isosteric relation to cyclic diazasilastannylenes. II forms the tetramer (TlOMe)₄ with methanol and does not add methyl iodide to the metal, the thalium containing product being TII. With magnesium dichloride in diethyl ether yields thallium(I) chloride and the spiro compound [Me₂Si(Me₃CO)(Me₃CN)]₂-Mg (VI), in which magnesium exhibits 4-fold coordination.     

Synthesen von Heterocyclen, 64.Mitt.: Über Reaktionen mit Schwefelsäurediamid

Zusammenfassung Es wird über Umsetzungen von - und -Diketonen mit Schwefelsäurediamid zu Derivaten des 1,2,5-Thiadiazols bzw. 1,2,6-Thiadiazins berichtet.

---

The reaction of - and -diketones with sulfamide yields 1.2.5-thiadiazole and 1.2.6-thiadiazine derivatives respectively.

---

---

Herrn KollegenF. Kuffner, Wien, mit Grüßen und herzlichen Wünschen zum 60. Geburtstag.     

Synthesen von Heterocyclen, 136. Mitt.: Über Reaktionen mit Salicylsäurechlorid

Zusammenfassung N,N-Äthylen- bzw. N,N-Trimethylen-S-äthyl-isothioharnstoff (2 bzw.3) reagieren mit der doppeltmolaren Menge Salicyl-säurechlorid (1) zu den pentacyclischen Verbindungen4 und5.

---

Syntheses of heterocycles, CXXXVI: Reactions with salicoyl-chloride

N,N-Ethylene- or N,N-trimethylene-S-ethyl-isothiourea (2 or3) react with 2 molecules of salicoyl chloride (1) yielding the pentacyclic compounds4 and5, resp.

     

Synthesen von Heterocyclen, 134. Mitt.: Über Reaktionen mit Salicylsäurechlorid

Zusammenfassung N,N-Diphenyl-S-äthyl-isothioharnstoff (2) reagiert mit Salicylsäurechlorid (1) zum 2-Phenylimino-3-phenyl-2,3-dihydro-1,3-benzoxazin-4-on (4), das auch aus Diphenylcarbodiimid und1 erhalten werden kann.

---

Syntheses of heterocycles, CXXXIV: Reactions starting with salicoyl chloride

The reaction of salicylic acid chloride (1) with S-ethyl-N,N-diphenyl-isothiourea (2) or diphenyl-carbodiimide gives 2-phenylimino-3-phenyl-2.3-dihydro-1.3-benzoxazin-4-one (4).

     

Synthesen von Heterocyclen, 79. Mitt.: Über Reaktionen mit Ketensäurechloriden

Zusammenfassung Monosubstituierte Malonsäurechloride reagieren mit Nitrilen bzw. Isocyanaten zu 1,3-Oxazinen¹. Malonylchlorid setzt sich mit den gleichen Reaktionspartnern sowie mit Phenylsenföl in einer komplizierteren Reaktionsfolge zu bicyclischen Pyrono-1,3-oxazinen^1–3 um.

---

Monosubstituted malonyl chlorides react with nitriles and isocyanates to 1.3-oxazines. Malonyl chloride itself reacts with nitriles, isocyanates, and iso-thiocyanates in a complicated manner yielding bicyclic pyrono-1.3-oxazines.

---

---

Herrn KollegenA. Wacek, Techn Hochschule Graz, mit den besten Wünschen zum 70. Geburtstag.     

Synthesen von Heterocyclen, 108. Mitt.: Über Reaktionen mit Salicylsäurechlorid

Zusammenfassung Salicylsäurechlorid (1) reagiert mit Campherimin ·HCl bzw. Campheranil oder mit Aldazinen zu Derivaten des 1,3-Benzoxazin-4-ons.

---

Salicoyl chloride reacts with camphorimine hydrochloride and camphoranile or with aldazines to give derivatives of 1.3-benzoxazin-4-ones.