1.2-Diaza-4-phospha-cyclopentane - 1.5-diaza-3.7-diphosphabicyclo-[3.3.0]octane N. N′-[bisphosphinomethylen]-N .N′-dimethylhydrazine 1.3-diaza-5-phospha-cyclohexane

N.N′-Dialkylhydrazines and hydrazine itself react with hydroxymethylphosphines to give the title compounds, bis(anilinomethylen)-phosphines form the cyclohexane-derivatives with formaldehyde.     

1.5-Diaza-3-phospha-cycloheptane N.N′-bis-[phosphinomethyl]-ethylendiamine mit optisch aktiven seitenketten

Optically active N.N′-bis[(1-phenyl)-1-ethyl]-ethylendiamine reacts with aryl- and alkyl-bis-hydroxymethylphosphines and diaryl-hydroxymethyl-phosphines to give the title compounds. The molybdenum-complexes of the diphosphines are described.     

Facile Access to Substituted 1,4-Diaza-2,3-Diborinines

Several bis(dimethylamino)-substituted 1,4-diaza-2,3-diborinines (DADBs) were synthesized with variable substituents at the backbone nitrogen atoms. By reaction with HCl or BX₃ (X=Br, I), these species were successfully converted into their synthetically more useful halide congeners. The high versatility of the generated B−X bonds in further functionalization reactions at the boron centers was demonstrated by means of salt elimination (MeLi) and commutation (NMe₂ DADBs) reactions, thus making the DADB system a general structural motif in diborane(4) chemistry. A total of 18 DADB derivatives were characterized in the solid state by X-ray diffraction, revealing a strong dependence of the heterocyclic bonding parameters from the exocyclic substitution pattern at boron. According to our experiments towards the realization of a Dipp-substituted, sterically encumbered DADB, the mechanism of DADB formation proceeds via a transient four-membered azadiboretidine intermediate that subsequently undergoes ring expansion to afford the six-membered DADB heterocycle.     

The Conformation of 1,6-Diaza-2,7-cyclodecadione in Solution

From ¹H- and ¹³C-NMR. data, a crown conformation with trans amide bonds is deduced for 1,6-diaza-2,7-cyclodecadione ( 1 ) in solution. Compound 1 was obtained by reaction of 2-pyrrolidone with POCl₃.     

IR-Spektroskopische Untersuchungen an 1,3-Dioxa- und 1,3-Diaza-2-boracyclopentanderivaten

Zusammenfassung Die IR-Spektren von mehreren Dioxa- und Diazaboracyclopentanderivaten wurden zusammen mit jenen von C-deuterierten Verbindungen untersucht. Besonderer Wert wurde auf die Klärung von Kopplungen zwischen BN-, BO- und CH₃-Schwingungen im Bereich zwischen 1550 bis 1300 cm^–1 gelegt.

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IR-spectra of several dioxa- and diaza-boracyclopentanes have been studied together with those of some C-deuterated analogues. Special attention has been given to coupling effects of BN-, BO-, and CH₃-modes in the 1550–1300 cm^–1 region.

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Mit 3 Abbildungen     

Darstellung und Molekülstruktur von 1,3-Diaza-2,4-disilacyclobutanen

Synthesis and Molecular Structures of 1,3-Diaza-2,4-disilacyclobutanes Lithio-aminofluorosilanes are obtained from the reaction of aminofluorosilanes with butyllithium. The thermal elimination of LiF from lithio-aminofluorosilanes affords a simple synthetic route to four-membered silicon-nitrogen rings. The structures of 1,3-bis(3,5-dimethylphenyl)-2,2,4,4-tetramethyl- and 2,4-di-tert-butyl-2,4-difluoro-1,3-bis(2,4,6-trimethylphenyl)-1,3-diaza-2,4-disilacyclobutanes have been determined by X-ray diffraction.     

1,5-Dimethyl-2,3,3,4-Tetrachloro-1,5-Diaza-2,4-Diphosphorinan-6-One and some derivatives

A synthesis of C-chlorinated analogues of 1,5-diaza-2,4-diphosphorinan-6-ones is described. The P-chlorophosphine 3 , a key compound for all reported substitution reactions, reacts in an unusual way with N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea to give the unsymmetrical product 5 , the formation of which is accounted for by a silatropy of the intermediate compound 4 . Compound 5 is stable in solution but rearranges quantitatively into isomer 6 without solvent at room temperature. Compound 3 , its fluoro derivative 9 , and the alkoxy derivatives 10a–d exist as cis-and trans-isomers. Some stereochemical aspects, as well as the possibility of 1,2-chlorotropy, are discussed.     

Synthesis of GdBiTe1.5Se1.5 single crystals

GdBiTe_1.5Se_1.5has been synthesized in the Gd₂Te₃-Bi₂Se₃ system at a component ratio of 1: 1. The compound congruently melts at 800 K. GdBiTe_1.5Se_1.5 single crystals have been prepared by a gas-trans-port reaction. The compound crystallizes in a tetradymite-like rhombohedral structure. The unit cell parameters are a = 4.00 Å, c = 30.36 Å, space group $R\bar 3m$ ..     

Reaktionen und Verknüpfungen von 1,2-Diaza-3-sila-5-cyclopentenen

Reactions and Bridging of 1,2-Diaza-3-sila-5-cyclopentenes 1,2-Diaza-3-sila-5-cyclopentenes react with butyllithium to give lithium salts. In reactions of the lithium salts with halosilanes ( 1–7 ), trimethyltinchloride (8) or methyliodide ( 9 ) substituted compounds are obtained by LiHal elimination. Bromosuccinimide brominates the methylene group of the ring system ( 10 ). Bridging of 1,2-diaza-3-sila-5-cyclopentenes by boryl and silyl groups are described ( 11–13 ). In the reaction of trifluorophenylsilane with lithiated 1 , 2-tert.-butyl-4-lithio-3,3,5-trimethyl-4-fluorodimethylsilyl-1,2-diaza-3-sila-5-cyclopentene, which is stable in solution, a second substitution takes place ( 14 ). The thermal elimination of LiF from lithiated 1 leads to the formation of the spirocyclic compound 15 . The n.m.r. and mass spectra of the compounds are reported.     

Fluoro-λ-Monophosphazenes and Fluoro-1.3-Diaza-2δ5,4δ5-Diphosphetidines

Abstract

34 new fluoro-λ-monophosphazenes and 37 new fluoro-1.3-diaza-2λ⁵ 4λ⁵-diphosphetidines have been prepared by applying the STAUDINGER reaction on δ³-phosphorus compounds (eq. (1)).