Showing papers in "Phosphorus Sulfur and Silicon and The Related Elements in 1980"

Synthesis of phosphonic dichlorides and correlation of their p-31 chemical shifts

Abstract: Various mono-substituted diethyl arylphosphonates were prepared in good yield by treatment of aryl bromides or iodides with triethyl phosphite in the presence of NiCl2 or alternatively, addition of the aryl grignard reagent to diethyl phosphorochloridate. These esters were then converted into the appropriate phosphonic dichlorides by standard methods. Para-substituted phosphonic dichlorides were also prepared by dimethylsulfoxide oxidation of phosphonous dichlorides which were prepared by Friedel-Crafts reaction of PCl3 with the substituted benzene. The P-31 chemical shifts of these phosphonic dichlorides were correlated with Hammett (σn) and Taft (σo) values. The shielding of the phosphorus resonance signal by electron withdrawing groups was rationalized by increased P[dbnd]O bonding. The observed shielding of ortho-substituted arylphosphonic dichlorides was rationalized by a gamma effect.

Structure of Antimony tris-(O,O-Diethyl Phosphorodithioate), a Passivation Agent for Contaminant Metals in the Catalytic Cracking of Crude Petroleum

Abstract: The coordination polyhedron of the antimony atom in antimony tris-(O,O-diethyl phosphorodithioate) is a distorted capped octahedron with a stereochemically active lone pair in the capping position and approximately on a molecular pseudo triad axis which passes through the antimony atom.

Phosphororganische verbindungen 931

Abstract: Optisch aktives Ethyl-phenyl-phosphinigsaurediethylamid 1 wird in racemische literaturbekannte Verbindungen uber-gefuhrt bei der Einwirkung von HCl, HBF4, Alkoholen, Thioalkoholen, Carbonsauren, Carbonsaureestern, Carbonsaureanhydriden, Carbonsaurehalogeniden, Verbindungen mit Pl und sekundaren Phosphinen. p-Kresol, Trifluoressigsaure-p-kresylester sowie Trifluoressigsaure-s,s,s-trifluorethylester setzen sich mit optisch aktivem Ethyl-phenyl-phosphinigsaure-diethylamid 1 unter Erhaltung der Konfiguration zu den entsprechenden optisch aktiven Ethyl-phenyl-phosphingsaureestern um. Optically active ethyl-phenyl-phosphinous acid diethylamide 1 was treated with HCl, HBF4, alcohols, thiols, carboxylic acids, esters, anhydrides, acid chloride, compounds with the structure element P[sbnd]Cl and secondary phosphines to give in each case a racemic mixture of the corresponding, previously described, reaction products. Reaction of optically active 1 with para-cresol, para-cresyltrifluoro-acetate or 2,2,2-tri...

Phosphororganische verbindungen 921

Abstract: Optisch aktive Phosphinigsaureamide R1R2PNR2 4 (R1 [dbnd] Ph, R2 [dbnd] Me bzw. Et, R [dbnd] Et) sind durch kathodische Spaltung bzw.Cyanolyse optisch aktiver Amidophosphoniumsalze [R1R2R3PNR2]X (R...

Synthese et proprietes de nouveaux spirophosphoranes. reaction des dioxa et oxazaphospholanes avec l'azodicarboxylate d'ethyle

Abstract: La reaction de l'azodicarboxylate d'ethyle avec des phosphites et des aminophosphines cycliques conduit a des nouveaux spirophosphoranes 2. Les spirophosphoranes 2 se condensent avec la 5′-0-trityluridine, l'aminoethanol ou le N-methylaminoethanol pour donner des nouveaux spirophosphoranes 3 et 5. The reaction of phosphites and cyclics aminophosphites with diethylazodicarboxylate lead to news spirophosphoranes 2. Spirophosphoranes 2 condenses with 5′-0-trityluridine, aminoethanol or N-methylaminoethanol to form news spirophosphoranes 3 and 5.

Physicochemical properties and structural study of 1,2-dithiolylium-4-olates and isothiazolium-4-olates

Abstract: The physicochemical properties of two series of mesoionic compounds, 1,2-dithiolylium-4-olates 3 and isothiazolium-4-olates 4 have been examined. The negative solvatochromy shown by 3 and 4 in u.v.-vis. is discussed. The unusual i.r. band of 3g (1488 cm−1 in KBr) and 4 (1530 cm−1 in KBr) is identified by its large solvent shift. The experimental dipole moments of a few compounds of series 3 and 4 are compared with the theoretical values corresponding to the canonical structures A, B and C. Carbon-13 NMR chemical shift data are given for a number of 3 compounds and compared with data from related 1,2-dithiolylium salts. In connection with the geometry of compound 3a, determined by X-ray diffraction, the CO group is found to be intermediate between a carbonyl and a single bond C[sbnd]O. The discussion deals with the comparison of the CO group in compounds 3 and in tropone 10 or in (4H) thiopyran-4-one 11 and with the comparison of the experimental data with a theoretical electronic structure publis...

Reactions des dioxo-2,4 et oxo-4 thioxo-2 diazaphospholidines-1,3,2 avec divers nucleophiles

Abstract: L'ouverture par les nucleophiles des dioxo-2,4 diazaphospholidines-1,3,2 non substituees et substituees a l'azote N1 (respectivement 1 et 2), s'effectue avec rupture de la liaison P2[sbnd]N3. Elle est rapide avec l'eau et les alcools et conduit aux sels 4 ou 6 et aux esters 7. Avec les amines, cette rupture est lente (cas des heterocycles 1) ou negligeable (cas des heterocycles 2). Ces resultats sont interpretes par l'intervention de deux mecanismes reactionnels: addition-elimination, de facon generale, et elimination-addition, dans le cas de l'aminolyse des cycles 1. Nucleophilic ring-opening of unsubstituted and N1-substituted 2,4-dioxo-1,3,2 diazaphospholidines (1 and 2 respectively) occurs with cleavage of the P2[sbnd]N3 bond. Water and alcohols rapidly lead to salts 4 or 6 and to esters 7. The rate of aminolysis is slow (heterocycles 1) or negligible (heterocycles 2). An interpretation based on a general addition-elimination mechanism and a particular elimination-addition pathway in the case...

SYNTHESIS, REACTIVITY AND CONFORMATION OF 10,11-DIHYDRODIBENZO-[b,f]PHOSPHEPIN AND DIBENZO[b,f]PHOSPHEPIN DERIVATIVES. PHOSPHORUS ANALOGUES OF IMINOBIBENZYL ANTIDEPRESSANTS

Abstract: Derivatives of the novel dibenzo[b,f]phosphepin system are prepared from 10,11-dihydro-5-phenyl-5H-bibenzo[b,f]phosphepin 5-oxide (2). New members in the 10,11-dihydro-5H-dibenzo[b,f]phosphepin series, including phosphorus analogues (7, 10) of the andidepressant drug imipramine (30), are also reported. Products of nucleophilic substitution at tetrahedral phosphorus in 2 appear to be determined by the relative apicophilicity of the nucleophile. Conformational analysis based on 1H NMR data suggests folded (“butterfly”) conformation for the tricyclic compounds. The twisted boat conformation of the central ring in the 10,11-dihydro compounds bears a pseudo-equatorial P[dbnd]O oxygen or a P[dbnd]S sulfur, in solution. Symmetric AA‘BB’ spin systems are found in 4,5 and 7, and their solution conformations appear to be similar to those of analogous 10,11-dihydrodibenzo[b,f]azepine derivatives. The interaction of some compounds with NMR shift reagents and their mass spectral fragmentations are discussed.

Reactions of sulfur dioxide with aminophosphines

Abstract: The reactions of SO2 with tris-dimethylaminophosphine, bis-dimethylaminofluorophosphine, bis-dimethylaminochlorophosphine, dimethylaminodifluorophosphine, dimethylaminodichlorophosphine, 1,3-dimethyl-2-fluoro-1,3,2-diazaphospholidine and 1,3-dimethyl-2-chloro-1,3,2-diazaphospholidine have been investigated. The complex reactions are dominated by facile oxidation of the respective phosphine to phosphoryl and thiophosphoryl derivatives. The new heterocyclic phosphines CH3 NCH2CH2N(CH3)P(O)F and CH3 NCH2CH2N(CH3)P(S)F have been isolated and characterized by NMR, infrared, and mass spectrometry.

The reaction between ketones and thionyl chloride

Abstract: The reaction between thionyl chloride and ketones gives rise to a variety of products depending both on the structure of the ketone and on the reaction conditions. Two rules have been formulated enabling the initial reaction product to be predicted. Some reactions involving sulphuryl chloride have also been discussed.

Organoarsenverbindungen: 39 substituierte benzylphosphine und -arsine als leicht zugängliche bidentate liganden

Abstract: 2-Hydroxybenzylamine bzw. 2- und 4-Aminobenzylamine reagieren mit Diphenylphosphin bei hoheren Temperaturen zu hydroxy- bzw. aminosubstituierten Benzylphosphinen. Im Falle der Alkoxy- bzw. Dialkylaminobenzylamine versagt diese Reaktion. Nach Uberfuhrung der Benzylamine in ihre quarternaren Ammoniumsalze und nachfolgende Umsetzung mit Natriumdiphenylphosphid werden die entsprechenden Alkoxy- bzw. Dialkylaminobenzylphosphine erhalten. In analoger Weise sind-auch 2-Alkylmercaptobenzylphosphine zuganglich. Aufgrund der unterschiedlichen Reaktionsbedingungen wird ein Eliminierungs-Additions-Mechanismus bzw. ein Substitutions-mechanismus diskutiert. Nach beiden Reaktionswegen sind auch die Stickstoff- bzw. Sauerstoff-substituierten Benzylarsine erhaltlich. 3-Dimethylaminomethylindol reagiert mit sekundaren Phosphinen und Arsinen entsprechend dem vorgegebenen Mechanismus zu 3-Indolylmethylphosphinen und -arsinen. 2-Hydroxybenzylamines or 2- and 4-aminobenzylamines react with diphenylphosphine at higher ...

A direct synthesis of heterocyclic thiols

Abstract: Heterocyclic thiols (thiones) are conveniently synthesized in good yields by the reaction of heterocyclic halides with sodium thiosulfate. The reaction requires the presence of acid, either added or liberated during the reaction, to hydrolyze the intermediate thiosulfate to thiol.

Synthese de trioxo-2,4,5-diaza-1,3-phospholidines-2-trisubstitutees et reactions avec les alcools et les amines

Abstract: Les trioxo-2,4,5-diaza-1,3-phospholidines-2-trisubstituees, 3, sont synthetisees par reaction, en absence de base, du chlorure d'oxalyle avec les phosphordiamides primaires 1. Les cycles 3 sont ouverts avec rupture d'une liaison [dbnd]P(O)+N'CO[sbnd]par les alcools et [dbnd]P(O)[sbnd]N'°CO[dbnd]par les amines. Ces resultats sont interpretes par la formation d'un complexe pentacoordine X dont la decomposition, dans le cas des amines, est plus lente que l'attaque au niveau de l'un ou l'autre des carbonyles. The 2,4,5-trioxo-1,3-diaza-2-phospholidine trisubstituted, 3, are synthetized in the absence of any base, by the reaction of oxalyle chloride on the primary phosphordiamides 1. The 3 cycles are opened with a [dbnd]P(O)+N'CO[sbnd] bond cleavage in the presence of alcohols and a [dbnd]P(O)[sbnd]N'°CO one in the presence of amines. It can be assumed from the results that + pentacoordinate X complex is formed, whose breakdown in the case of amines is slower than the attack on one or the other of the...

Synthèse de Fluorosulfates D'Aryle Encombres

Abstract: Par action du fluorure de sulfuryle sur les sels de lithium des phenols (1a[sbnd]c), a -60°, nous avons synthetise, avec des rendements tres eleves, les premiers fluorosulfates d'aryl encombres (2a[sbnd]c) renfermant en positions 2 et 6 un groupe tertiobutyle. By reaction of sulfuryl fluoride with the lithium salts of phenols (1[sbnd]c), at -60°, we have synthetized, in high yield, the first sterically hindered aryl fluorosulfates (2a[sbnd]c) having a t-butyl group in the 2 and 6 positions.

CYCLIC ORGANOPHOSPHORUS COMPOUNDS. PART XV.1 4-t-BUTYL-2,6,7-TRIOXA-1-PHOSPHABICYCLO[2,2,2]OCTANE AND ITS OXIDE

Abstract: Treatment of 4-t-butyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2]octane with sulphuryl chloride yields merely its P-oxide and not the expected 5-t-butyl-2-chloro-5-chloromethyl-1,3,2-dioxaphosphorinan 2-oxide. The mass spectra of the bicyclic phosphite and its oxide are discussed.

Tris 2,4,6-trimethylphenyl-phosphine and arsine radical cations

Abstract: The character of electrochemical oxidation of trimesitylphosphine and trimesitylarsine in acetonitrile has been studied on the rotating platinum electrode. Their oxidation has been shown to involve two stages, the first one being the one-electron reversible wave. Characteristics of common anodic and cathodic waves of degassed solution of substances on stationary electrodes and symmetry of their cyclic voltammetry polarograms indicate the stability of radical cations formed. Electrochemically generated radical cations of tris 2,4,6-trimethylphenyl-phosphine (Mes3P+) and -arsine (Mes3As+) were studied by ESR spectroscopy. Hyperfine splitting was found to be a P = 250 gauss, a As = 279 gauss and hybridisation ratios C2 p /C2 s = 13.8 and 12.3 were established from analyses of anisotropic spectra.

Beiträge zur chemie des phosphors 901 1,2,3-triphenyltriphosphan

Abstract: Bei der Alkoholyse von 1,2,3-Triphenyl-1,3-bis(trimethylsilyl)-triphosphan, (Me3Si)2(PPh)3, entsteht als Hauptprodukt die Titelverbindung 1. Das Triphosphan ist in Losung unterhalb von - 30°C verhaltnismaβig bestandig. Bei Raumtemperatur disproportioniert 1 in PhPH2, H2(PPh)2 und (PPh)5, wobei als Zwischenprodukte auch hohere Homologe der Reihe H2(PPh)n gebildet werden. Die betreffenden Umlagerungen erfolgen nach einem Vierzentrenmechanismus unter bevorzugter Beteiligung von P[sbnd]P-Bindungen. In Losung bildet 1 die drei Diastereomeren 1a (threo/threo), 1b (threo/erythro) und 1c (erythro/erythro) im Verhaltnis von etwa 3:4:1. Ihre Zuordnung zu den 31P-NMR-spektroskopisch beobachteten Spinsystemen ergibt sich aufgrund der Diederwinkelabhangigkeit der 1Jpp-Kopplungskonstanten sowie aus dem Isomerenverhaltnis unmittelbar nach der stereospezifischen Solvolysereaktion. The title compound 1 is formed as the main product of alcoholysis of 1,2,3-triphenyl-1,3-bis(trimethylsilyl)-triphosphane, (Me3Si)2(P...

Phosphoranes monocycliques a ligand hydrogene i-etude de l'equilibre de formation

Abstract: Addition of compounds containing a mobile hydrogen (alcohols, amines …) to derivatives of tetramethyldioxaphos-pholane leads to monocyclic phosphoranes including a P[sbnd]H bond in equilibrium with the starting phospholane: Study of this equilibrium by 31P, 1H and 13C NMR shows a real dependence on solvent, temperature and concentrations of the reagents. Keeping in mind a BPT structure, the NMR data suggest an apical position for the H bonded to P in phosphoranes obtained by reaction with amines. L'addition de composes a hydrogene mobile (alcools, amines …) sur des derives du tetramethyldioxaphospholane conduit a des phosphoranes monocycliques a ligand PH en equilibre avec le phospholane de depart: Cet equilibre etudie par RMN de 31P, 1H, 13C montre une nette dependance vis-a-vis des concentrations relatives des reactifs, des solvants et de la temperature. Les parametres de RMN conduisent, dans l'hypothese d'une bipyramide trigonale, a proposer une position apicale pour l'hydrogene lie au phospho...

The reactions of sulfur dioxide with excess ammonia

Abstract: The reaction of sulfur dioxide with excess ammonia was studied during warm-up of rare gas matrices and in sealed pressure tubes containing various isotropic species. In the matrix experiments six IR bands belonging to ammonium thionylimide, NH4: NSO, were observed in the temperature range between 40°K and 90°K. Above 80°K the spectrum of ammonium sulfite, NH4SO3 prevails. In sealed tubes containing liquid ammonia at room temperature several step-wise reactions can be followed. They consist of ammonolysis of SO2, followed by auto-redox disproportionation of SIV into a range of oxidation states. Raman spectra show the presence of sulfate, dithionate, thiosulfate, and the polythionates. Isotope substitution indicates that ammonia does not participate in redox reactions and acts merely as a nucleophilic catalyst. The composition of the samples changes over a period of at least 2 years. In some tubes with NH3:SO2 <7 a spontaneous reaction occurs after 1 ½ to 2 years and the colorless or pale yellow so...

DIBENZO(d,f)-1,3,2-DIOXAPHOSPHOREPINE UND METALLKOMPLEXE VON 2,2′-BIPHENYLYLENPHOSPHORSÄUREN

Abstract: Synthese und Eigenschaften von Dibenzo(d,f)-1,3,2-dioxaphosphorepinen des Typs R = 2.2′-Biphenylylen werden beschrieben. Die Verbindungen mit Y[dbnd]OH bzw. SH, die auch als 2.2′-Biphenylylenphosphorsauren bezeichnet werden konnen, bilden Metallkomplexe, in denen das Saureanion je nach Art der Donatoratome (S und/oder O) als Chelat-oder Bruckenligand fungiert. Synthesis and properties of dibenzo(d,f)-1,3,2-dioxaphosphorepines of general formula R = 2,2′-biphenylylen are reported. The compounds with Y[dbnd]OH or SH, which may be also named 2.2′-biphenylylenphosphoric acids, form metal complexes in which, depending on the type of donor atom (S and/or 0), the acid anion acts as a chelating or bridging hgdnd

The reaction of anhydrous hci/chloroform with diaryl sulfoxides

Abstract: The reaction of variously substituted diaryl sulfoxides with anhydrous HCl in chloroform was examined. The products ranged from the corresponding sulfides to mono- and dichlorinated sulfides and sulfoxides. The same reaction in the presence of phenol afforded primarily the corresponding sulfides accompanied by o- and p-chlorophenol. The latter reaction is an efficient means for deoxygenating diaryl sulfoxides. The mechanism of the reaction and the nature of the chlorinating species are discussed.

Synthese de derives diamidiques n-phosphoryles d'aminoacides

Abstract: Vingt sept phosphordiamides incorporant un (3, 3') ou deux (5) residus d'α aminoesters et sept diesters phosphoriques d' α aminoamides (6), ont ete generalement synthetises a partir les chlorures d'acide du phosphore tetraedrique correspondant respectivement 1 et 7. Twenty seven phosphordiamides incorporating one (3, 3') or two (5) α aminoester residues and seven aminoamide phosphodiesters (6) were synthetised starting generally from the corresponding tetrahedral phosphorus chlorides 1 and 7, respectively.

Organophosphorus compounds, xxx. the reaction of fluorenylidenetriphenylphosphorane with maleic, phthalic and thiophthalic anhydrides

Abstract: Fluoroenylidenetriphenylphosphorane (1a) reacts with maleic and phthalic anhydrides to give lactones 2a and 3, respectively. The same reagent (1a) extrudes sulphur from thiophthalic anhydride yielding the spiro-1,3-indandione derivative 4. The infrared and mass spectra of the new products are discussed.

Polydentate Ligands Containing Phosphorus. 5. Some Derivatives of Tris(diphenylphosphino)methane

Abstract: Phosphorus-31 and proton nuclear magnetic resonance data are reported for a series of chalcogen derivatives of tris(diphenylphosphino)methane, Tdppm. Tdppm also behaves as a bidentate ligand when coordinated to Group 6 metal carbonyls in the compounds [Tdppm]M(CO)4, where M is Cr or W. Five of the compounds are previously unreported.

Studies in the heterocyclic compounds: ii. the mass spectra of some thiophene-sulfonyl derivatives

Abstract: Mass spectra of five 2-thiophenesulfonyl derivatives are determined and the interpretations given are based on mechanistic analogy and supported in most cases by metastable peaks. There are reports in the literature of the effect of electron-impact on thiophene,1 alkylthiophenes,2 2-acyl, 2-aroyl and nitroaroylthiophenes.3–5 However, there has been no report on the mass spectra of 2-thiophenesulfonyl derivatives. The present paper reports an examination of the mass spectra of five 2-thiophenesulfonyl compounds (1–5), figure 1, in order to assess the similarity between the fragmentation pattern of these compounds and those of other reported arysulfonyl derivatives.

Some sulfonyl derivatives of salicylic acid and related compounds

Abstract: o-Methoxybenzamide, salicyclic acid, salicylamide and N-acetylsalicylamide have been converted to the corresponding 5-sulfonyl chlorides, and p-hydroxybenzoic acid to the 3-sulfonyl chloride. The sulfonyl chlorides were characterized by the preparation of various derivatives, e.g. amides, hydrazides, hydrazones and azides. Chlorosulfonation of O-acetyl compounds showed either complete or partial deacetylation. O-Acetyl compounds were therefore obtained by subsequent acetylation. O-Acetylsalicylamide on heating was converted to the N-acetyl derivative and the isomerization was followed by h.p.l.c. In contrast both m-and p-acetoxybenzamides were relatively stable. Salicylanilide and O-methylsalicylanilide, with chlorosulfonic acid gave the 1,4′-disulfonyl chlorides. On the other hand, 4′-chloro- and 4′-chloro-O-methyl-salicylanilides afforded the corresponding monosulfonyl chlorides. The i.r., n.m.r. and mass spectra, together with the algaecidal and antibacterial results are briefly discussed.

New 2h-1,2,3-diazaphosphole derivatives and related ring-opened compounds

Abstract: The addition of phosphites to the azoalkene 1 gives mixtures of diazaphosphole derivatives 4 and related ring-opened compounds 3 in different proportions depending on the phosphite used. The compounds 3 have the Z-configuration, while cyclic compounds 4 are a mixture of isomers in which predominates the isomer bearing the C4-Ph and OR groups in a trans configuration. When P(OPh)3 is used in dry hexane with rigorous exclusion of moisture the new diazaphosphole derivative 5 is obtained. The results are explained in terms of the relative apicophilicities in the pentacoordinated intermediates.

Electrochemical synthesis of organophosphorus compounds

Abstract: The electrolysis of tertiary phosphines in the presence of aromatic or heteroaromatic compounds made it possible to carry out the electrochemical synthesis of the respective aryl(heteroaryl)phosphonium salts with good yield. The anodic oxidation of the esters of phosphorous acids in the presence of aromatic compounds led to the formation of respective esters of arylphosphonic acid.

Mindo/3-berechnungen von phosphororganischen verbindungen. iv.1

Abstract: Es wird uber die Bestimmung der Parameter αXY fur die Kernabstosung und B XY fur das Resonanzintegral der Bindungen P[sbnd]O, P[sbnd]F, und P[sbnd]Cl im MINDO/3-Verfahren berichtet. Die berechneten Werte fur die Bildungsenthalpien, Ionisationspotentiale und Geometrien werden mit experimentellen Daten verglichen. The parameters αXY and B XY for the core repulsion and the resonance integrals in MINDO/3 are reported for the P[sbnd]O, P[sbnd]F, and P[sbnd]Cl bondings. The heat of formation, ionization potentials and geometries are compared to experimental data.