Thermal Behavior of Pyridinium Salt of 2,4-Dimer-Capto-2,4-Dithioxo-1,3-Bis(Trimethylsilyl)-1,3-Diaza-2λ5, 4λ5-Diphosphetidine

Abstract

The reaction of P₄S₁₀with PSCL₃ in pyridine leads to Py.PS₂Cl (1). This substance yields by the reaction with hexamethyldiailazane in molar ratio 1:l a new subatance that was identified as pyridiniwn salt of 2,4-dimercapto-2,4-dithioxo-1,3-bis(trimethylsilyl)-1,3-diaza-2λ⁵,4λ⁵-diphosphetidine (PYH)₂/S₂P(NSiMe₃)₂PS₂/ (I). (2).     

Röntgenstrukturanalyse des 1,3-Bis(diethylamino)-1,3-dibenzyl-2,4-diphenyl-1λ5, 3λ5-diphosphets

X-Ray Crystal Structure Determination of 1,3-Bis(diethylamino)-1,3-dibenzyl-2,4-diphenyl-1λ⁵, 3λ⁵-diphosphete Benzylidene-diethylamino-benzylfuorophosphorane, 1 , reacts with lithium bis(trimethylsilyl)amide to give the title compounds 2 and 1-diethylamino-2,3-diphenylphosphirane, 3 . Only one of the stereoisomers of 2 is formed in which the two benzyl groups are located on the same side of the planar four-membered ring. 2 crystallizes in the monoclinic space group P2₁/n.     

A 1,5-diaza-2,4-(λ4P+, λ6P−)-diphosphorinane

The oxidation of the 1,3-diaza-4,6-diphosphorine 1 with tetrachloroorthobenzoquinone 2 led, unexpectedly, to the formation of 1,5-dimethyl-2,2-bis(dimethyl-amino)-4,4,4,4-bis-(tetrachloro-o-phenylenedioxa)-1,5-diaza-2,4-λ⁴, λ⁶-diphosphorinane-6-one 4 , containing two phosphorus atoms of opposite formal charge and different coordination number. The X-ray crystal structure analysis of 4 revealed the presence of a six-membered ring with an unusual conformation.     

2,2-Difluor-1,2,3-trimethyl-1,3-diaza-2λ5-phospholidin

2,2-Difluoro-1,2,3-trimethyl-1,3-diaza-2λ⁵-phospholidine The title compound 1 is obtained in about 50% yield by oxidative fluorination of 1,2,3-trimethyl-1,3-diaza-2λ³-phospholidine, 6 , with IF₅. 1 is characterized by its nmr, mass, and ir spectra.     

Mono- und Bis(difluorphosphoranyl)ethylen,n-Hexyliden-fluorphosphoran und ein 2,4-Di-n-pentyl-1λ5,3λ5-diphosphet

Mono- and Bis(difluorophosphoranyl)ethylene, n-Hexylidene-fluorophosphorane, and a 2,4-Di-n-pentyl-1λ⁵, 3λ⁵ -diphosphete Bis(diethylamino)phosphanylethylene, 1 , is converted by SF₄ into bis(diethylamino)difluorophosphoranylethylene, 2. Analogously trans-1,2-bis(diphenylphosphanyl)ethylene, 3 , is converted into trans-1,2-bis(difluorodiphenylphoranyl)ethylene, 4. 2 reacts with n-butyllithium to give n-hexylidene-bis(diethylamino)fluorophosphorane, 5. With more n-butyllithium, the main product n-hexylidene-bis(diethylamino)-n-butylphosphorane, 7 , and the by-product 2,4-di-n-pentyl-1,1,3,3-tetrakis(diethylamino)-1λ⁵, 3λ⁵ -diphosphete, 8 , are formed. With t-butyllithium 2 yields 3,3-dimethyl-butylidene-bis(diethylamino)fluorophosphorane, 6. All new compounds 1, 2, 4–8 are characterized by their nmr and ir spectra.     

2,4-Bis(4-methylpheylthio)-1,3,2λ5,4λ5-dithiadiphosphetan-2,4-dithion: Ein neues Reagens zur Schwefelung von N,N-disubstituierten Amiden

2,4-Bis(4-methylphenylthio)-1,3,2λ⁵,4λ⁵-dithiadiphosphetane-2,4-dithione: A New Reagent for Thiation of N,N-Disubstituted Amides As a new reagent for the thiation of amides, the easily accessible 2,4-bis(4-methylphenylthio)-1,3,2λ⁵,4λ⁵-dithiadiphosphetane-2,4-dithione ( 9 ) shows a remarkable selectivity. This selectivity – the preferred thiation of N,N-disubstituted amides – is complementary to the one of the well known Lawesson reagent. Thiation of diamides of type 2 with 9 leads via cyclization of the corresponding dithiodiamides to 1,3-thiazole-5(4H)-thiones 1 (Scheme 3).     

Die Reaktion von λ5-Diphospheten mit COS und CO2 Dihydro-λ5-Phosphete

Reactions of λ⁵-Diphosphetes with COS and CO₂. Dihydro-λ⁵-Phosphetes 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , reacts with COS to yield the (3-oxo-3,4-dihydro-1λ⁵-phosphete-2-yl)-phosphonothioic bis(dimethylamide) 7 . Reaction of dimethyl substituted 1 , i.e. 1,1,3,3-tetrakis(dimethylamino)-2,4-dimethyl-1λ⁵,3λ⁵-diphosphete 4 , with COS and CO₂ results in (3-oxo-2,3-dihydro-1λ⁵-phosphete-2-yl)-phosphonothioic bis(dimethylamide) 9 , and (3-oxo-2,3-dihydro-1λ⁵-phosphete-2-yl)-phosphonic bis(dimethylamide) 10 , respectively. Reaction mechanisms are suggested. 7, 9 and 10 are characterized by their properties, and their nmr, mass-, and ir-spectra. The results of X-ray structural analyses of 9 and 10 are reported and discussed.     

Übergangsmetall-Komplexe des 1,1,3,3-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphets

Transition Metal Complexes of 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-Diphosphete 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3aλ⁵-diphosphete, 1 , reacts with W(CO)₆ to yield the isomeric complexes {1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete}(pentacarbonyl)tungsten 4 and {1,1,3,3-tetrakis(dimethylamino)-1,4-dihydro-1λ⁵,3λ⁵-[1,3]diphosphetium}(pentacarbonyl)tungsten 5 . With Cr(CO)₆ the complex {1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete}(pentacarbonyl)chromium 6 is formed. From the reaction products of Fe₃(CO)₁₂ and Fe₂(CO)₉ with 1 the complex {1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete}(pentacarbonyl)iron 7 could be isolated. Properties, nmr, ir and mass spectra of the new compounds are reported. 6 and 7 were characterized by X-ray structure determinations.     

Synthese und NMR-Spektren von λ5-Diphospheten Die Struktur des 2,4-Diphenyl-1,1,3,3-tetrakis(diethylamino)-1λ5,3λ5-diphosphets

Synthesis and NMR Spectra of λ⁵-Diphosphets. Structure of 2,4-Diphenyl-1,1,3,3-tetrakis (diethylamino)-1λ⁵, 3λ⁵-diphosphete Preparation, properties, and n.m.r. spectra of C₂H₅PF₂[N(C₂H₅)₂]₂, CH₂?PF[N(C₂H₅)₂]₂, and the diphosphetes {RC?P[N(C₂H₅)₂]₂}₂ (R) ? H ( 5a ), CH₃ [( 5b )] are described. The λ⁵-diphosphete {HC?P(NR₂)₂}₂ (R ? CH₃) reacts with BF₃ · O(C₂H₅)₂ to give which is transformed into by n-C₄H₉Li. The crystal and molecular structure of 2,4-diphenyl-1,3,3-tetrakis(diethylamino)-1λ⁵,3λ⁵-diphosphete 2 are reported and discussed.     

1,1,3,3-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphet als Ligand in Koordinationsverbindungen

1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete as Ligand in Coordination Compounds 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , reacts with GeCl₂ · 1,4-dioxane, SnCl₂, and (CO)₅W(Z-cyclooctene) to give the complexes {HCP[N(CH₃)₂]₂}₂ · GeCl₂, 3 , {HCP[N(CH₃)₂]₂}₂ · SnCl₂, 4 , and {HCP[N(CH₃)₂]₂}₂ · W(CO)₅, 5 , respectively. The n.m.r., mass, and i.r. spectra of the new compounds as well as the crystal and molecular structures of 3 and 4 are reported and the bonding situation in compounds 3–5 is discussed.     

Synthese von Fluoro-λ5-monophosphazenen und Fluoro-1, 3-diaza-2λ5, 4λ5-diphosphetidinen mittels der Staudinger-Reaktion

Synthesis of Fluoro-λ⁵-monophosphazenes and Fluoro-1,3-diaza-2λ⁵,4λ⁵-diphosphetidines by Means of the Staudinger Reaction 35 Tetrafluoro- and 2 difluorodiaza-diphosphetidines as well as 4 difluoro- and 30 monofluoro-λ⁵-monophosphazenes were prepared by the Staudinger reaction between tervalent phosphorus fluorides, R_nPF_3?n (n = 1, 2; R = R₂N, (CH₂)₅N, O(CH₂)₄N, RO, (CH₂O)₂, alkyl, aryl) and phenylazides, X? C₆H₄N₃ (X = H, 4-CH₃, 4-Cl, 4-Br, 4-NO₂, 3-NO₂). PF₃ does not react with phenylazide The influence of substituents on the structure of the reaction products is discussed. Kinetic measurements allowed to determine the constants λ^P_I of the substituents (CH₂)₅N, O(CH₂)₄N and R(C₆H₅)N (R = CH₃, C₂H₅, n-C₄H₉).     

Reactions of 1,1,3,3-tetrakis(dimethylamino)-1λ5,3λ5-diphosphete with diphenylchlorophosphane and methyl iodide

1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1, reacts with diphenylchlorophosphane to yield 1,1,3,3-tetrakis(dimethylamino)-4-diphenylphosphanyl-1,2-dihydro-3λ⁵-[1,3]diphosphetium chloride, 2, or, depending on the reaction conditions, the isomer compound 3. The cation of 2 is deprotonated by LiN[Si(CH₃)₃]₂ to give the diphenylphosphanyl-substituted derivative of 1, i.e., compound 4. Methyl iodide adds to 1 to form 1,1,3,3-tetrakis(dimethylamino)-4-methyl-1,2-dihydro-3λ⁵-[1,3]diphosphetium iodide, 6. Deprotonation of 6 with n-butyllithium leads to the monomethyl derivative of 1, i.e., compound 7. Physical properties, NMR spectra, and mass spectra of compounds 2–4, 6, and 7 are described. The results of the X-ray structural analysis of 6 are reported and discussed. © 1996 John Wiley & Sons, Inc.     

Thermal decomposition of the pyridinium salt of 1,3-bis(trimethylsilyl)-2,4-dimercapto-2,4-dithioxo-1,3-diaza-2λ5, 4λ5-diphosphetidine

It was found that the first step of thermal decomposition of the pyridinium salt of 1,3-bis(trimethylsilyl)-2, 4-dimercapto-2,4-dithioxo-1,3-diaza-2⁵,4⁵-diphosphetidine (I) most probably involves breakdown to the acid form HS(S)P(NHSiMe₃)₂P(S)SH (II). The latter is very unstable and decomposes further, the end-product being a polymer (PNS)_x. In this work, the mechanism of this process is investigated.

---

Zusammenfassung Man fand, daß der erste Schritt der thermischen Zersetzung des Pyridiniumsalzes von 1,3-Bis(trimethylsilyl)-2,4-dimercapto-2,4-dithioxo-1,3-diaza-25,45-diphosphetidin (I) sehr wahrscheinlich einen Abbau zur Säureform HS(S)P(NHSiMe₃)₂P(S)SH (II) beinhaltet. Letztere ist sehr unbeständig und zersetzt sich, wobei als Endprodukt ein (PNS)_x-Polymer entsteht. In vorliegendem Manuskript wird der Mechanismus dieses Prozesses näher untersucht.

     

1λ6,2,4-Thiadiazetidine und 1,2λ6,3-Oxathiazetidine

1λ⁶,2,4-Thiadiazetidines and 1,2λ⁶,3-Oxathiazetidines From the reaction of the sulfur triimides (RN?)₃S ( 2a R?(CH₃)₃C, 2b R?(CH₃)₃Si) with pentafluoroazapropene ( 11 ) the appropriate 1λ⁶,2,4 thiadiazetidines ( 13a, 13b ) are formed, while from ClSO₂N?CCl₂ ( 14 ) and 2a (CH₃)₃C? N?C?N? SO₂Cl ( 17 ) is isolated. 2b and hexafluoroacetone ( 18 ) give the rather unstable 1,2λ⁶,3-oxathiazetidine ( 20 ).     

2,4-Dimethoxycarbonyl-1,1,3,3-tetrakis(dimethylamino)-1λ5,3λ5-diphosphete

1,1,3,3 - Tetrakis(dimethylamino) - 1λ⁵,3λ⁵ - diphosphete, 1 , reacts with cyanoformic acid methyl ester to form two isomers of the title compound 2 . Properties, NMR, mass, and IR spectra of 2 , as well as the molecular and crystal structure of the E isomer of 2 , are described and discussed.     

Synthesis of 6aλ4-thia-1,6-diselena-3,4-diazapentalenes, 1,6,6aλ4-triselena-3,4-diazapentalenes, 6aλ4-thia-1,3,4,6-tetraazapentalenes,and 6aλ4-Selena-1,3,4,6-tetraazapentalenes from cyclic thioureas and selenoureas

Imidazolidine-2-thione (7a) and the corresponding 2-selone (7b), hexahydropyrimidine-2-thione (7c) and 2-selone (7d), and hexahydro-1H-1,3-diazepine-2-thione (7e) and 2-selone (7f) reacted with 2,4-dinitrobenzyl chloride to give the 2-(2,4-dinitrobenzylthio) and 2-(2,4-dinitrobenzylseleno) derivatives (8a)-(8f) of 4,5-dihydroimidazolium chloride, 1,4,5,6-tetrahydropyr-imidinium chloride, and 4,5,6,7-tetrahydro-1H-1,3-diazepinium chloride. Deprotonation of the chlorides (8a)-(8f) gave, respectively, 2-(2,4-dinitrobenzylthio)-and 2-(2,4-dinitrobenzylseleno)-4,5-dihydroimidazole (9a) and (9b), 2-(2,4-dinitrobenzylthio)- and 2-(2,4-dinitrobenzylseleno)-1,4,5,6-tetrahydropyrimidine (9c) and (9d), and 2-(2,4-dinitrobenzylthio)- and 2-(2,4-dinitrobenzylseleno)-4,5,6,7-tetrahydro-1H-1,3-diazepine (9e) and (9f). The bases (9a)-(9f) reacted with isoselenocyanates with elimination of 2,4-dinitrotoluene and concomitant addition of two molecules of the isoselenocyanate to give 1,6,6aλ⁴-triheterapentalenes of two structural types, depending on the size of the heteroring in the bases (9a)-(9f). The imidazoles (9a) and (9b) gave 6aλ⁴-thia-1,6-diselena-3,4-diazapentalenes (10a)-(10j) and 1,6,6aλ⁴-triselena-3,4-diazapentalenes (11a)-(11h), respectively. The sulfur-containing bases (9c) and (9e) gave 6aλ⁴-thia-1,3,4,6-tetraazapentalenes (12a)-(12j) and (14a)-(14d), respectively, and the selenium-containing bases (9d) and (9f) gave 6aλ⁴-selena-1,3,4,6-tetraazapentalenes (13a)-(13j) and (15a)-(15d). Heteroatom-heteroatom covalent bond energies have been estimated for representative members of the series (10)-(14) by using the Huggins equation and experimentally determined bond lengths. © 1997 John Wiley & Sons, Inc.     

Neue 1λ5, 3λ5-[1,3]Diphosphinine mit Thio- und Selenophosphonsäureresten – Darstellung,Kristallstruktur, NMR-Daten und Komplexbildung mit PdII

Diphosphabenzenes. VI. New 1λ⁵, 3λ⁵-[1,3]Diphosphinines with Thio and Seleno Phosphonic Acid Groups – Preparation, Crystal Structure, NMR Data, and Coordination to Pd^II Preparation of N,N,N′,N′-tetraethyl-P-phenylethinyl phosphonothioacid diamide ( 2 ) and the corresponding phosphonoselenoacid diamide ( 3 ) are described. 2 and 3 react with 1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete ( 1 ) to yield 1λ⁵,3λ⁵-[1,3]diphosphinine derivatives 4 and 5 . With (bzl)₂Cl₂Pd 5 forms the coordination compound 6 . All new compounds 2–6 are characterized by their nmr and ir spectra, the structures of 4–6 are further elucidated by X-ray structural analyses.     

1, 2λ5-azaphosphinines and a new 1λ5, 3λ5-. Diphosphinine

The 1,2-azaphosphinine, 9 , and the 1,3-diphosphinine, 10 , can be isolated from a mixture resulting from the reaction of 1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , and ethyl isothiocyanate. The reaction of 1 with phenyl isothiocyanate yields the 1,2-azaphosphinine, 16 . Mechanisms for the formation of the compounds 9 , 10 , and 16 are suggested. The properties, the NMR, mass, and IR spectra, and the molecular and crystal structures of 9 and 10 are described and discussed.     

Reaktionen von 1,1,3,3‐Tetrakis(dimethylamino)‐1 λ5, 3 λ5‐diphosphet mit 5‐Cyano‐1‐pentin und mit 2‐(Cyanmethyl)‐1‐methylpyrrol

Diphosphabenzenes. VII. Reactions of 1,1,3,3‐Tetrakis(dimethylamino)‐1 λ⁵, 3 λ⁵‐diphosphete with 5‐Cyano‐1‐pentine and 2‐(Cyanomethyl)‐1‐methylpyrrol 5‐Cyano‐1‐pentine reacts with the equimolar amount of the λ⁵‐diphosphete 1 to give the λ⁵‐diphosphinine (λ⁵‐diphosphabenzene) ( 3 ), while reaction with the double equimolar amount of 1 yields the λ⁵‐diphosphinine ( 4 ). The acyclic compount 6 is the main product of the reaction between 1 and 2‐(cyanomethyl)‐1‐methylpyrrol, 5 . Melting points of 4 · CH₃CN and 6 , and mass, nmr and ir spectra of 3 , 4 , and 6 are reported. The crystal structure of 4 · CH₃CN shows an open‐chain ylidic CPCP‐sequence, which is linked to a λ⁵‐diphosphinine via an ethylene bridge. The X‐ray structure analysis of 6 confirms the existence as an acyclic conjugated double ylid.     

Reaction of chlorodithiophosphoric acid pyridiniumbetaine with adamantane derivatives containing amino group

Reactions of chlorodithiophosphoric acid pyridiniumbetaine, py.PS₂Cl (I) with 1-aminoadamantane (amantadine, Am) and 1-amino-3,5-dimethyladamantane (memantine, Mem), 1-(adamant-1-yl)ethylamine (rimantadine, Rim), and 1-aminomethyladamantane (amAd) were studied. New compounds – N,N′,N′′,N′′′-tetrakis(adamant-1-yl)trithiophosphoric acic tetraamide (II), N,N′,N′′,N′′′-tetrakis(3,5-dimethyladamant-1-yl)trithiophosphoric acid tetraamide (III), chlorodithiophosphoric acid 1-(adamant-1-yl)ethylamide pyridiniumbetaine (IV), pyridinium salt of 1,3-bis(adamant-1-yl)ethane-2,4-mercapto-2,4-dithioxo-1,3-diaza-2λ⁵,4λ⁵-diphosphetidine (V), N,N′,N′′,N′′′-tetrakis(adamant-1-ylmethyl)trithiophosphoric acid tetraamide (VI), and pyridinium salt of 1,2-bis(adamant-1-ylmethane)-4-mercapto-2,4-dithioxo-1-aza-3-thia-2λ⁵,4λ⁵-diphosphetidine (VII) – were prepared and characterized either/or by ³¹P NMR and infrared spectroscopy, the substances II a IV by X-ray diffraction analysis, III, V, VI, VII by MALDI TOF MS.