Showing papers in "Phosphorus Sulfur and Silicon and The Related Elements in 1978"

Solubility of Elemental Sulfur in Water at 298 K

Abstract: The solubility of elemental rhombic sulfur in water is 1.9(±0.6) × 10−8 mole S8·kg−1. This value is in agreement with thermodynamic considerations on the solubility of sulfur and experimental data on sulfur hydrosols.

Studies in the heterocyclic series. xiv. the chemistry and biological activity of new aza- and thia-phenothiazines, and related dibenzothiazepines

Abstract: Owing to increasing demand for phenothiazine compounds both in medicine and industry, novel rings in these series have been prepared and evaluated. The benzene rings have been replaced with pyrrole, pyrazole, pyridine, pyridazine, pyrimidine, pyrazine, thiazine and triazine rings or their combinations leading to twelve new polyaza- and thia-phenothiazines. Expansion of the central thiazine ring in these systems has also been carried out. This article therefore provides a survey of the chemistry and applications of new polyaza- and thia-phenothiazine systems and their related thiazepines and thiazocines.

Phosphazenes and phosphazanes

Abstract: Three types of phosphazene and four types of phosphazane structural units are classified on the basis of the coordination number of the phosphorus atoms involved. Phosphorus-nitrogen bond lengths are discussed in acyclic compounds and this information is used in analysing ring systems consisting wholly or partially of phosphorus-nitrogen skeletons. Four-, five-, six-, seven-, eight-, ten-, and twelve-membered rings are surveyed, as are polycyclic systems. Methods of synthesis for cyclophosphazanes, and mixed cyclo-phosphazene-phosphazanes are briefly considered, as are some of their reactions. The minimum ring size where stable phosphazenes have been observed is referred to. The effect of protonation, methylation, or coordination to a metal moiety on adjacent phosphorus-nitrogen bonds is discussed. The conformations of dimethylamino and phenyl substituents on phosphorus are considered, as is the conformations of the ring skeletons. The flexibility of a cyclic and cyclic phosphorus-nitrogen skelet...

The Reaction of Thiolates with Elemental Phosphorus

Abstract: Sodium alkanethiolates react rapidly with elemental phosphorus in tetrachloromethane to give high yields of trialkyl phosphorothioites when the thiolate is used in excess.

Phosphororganische verbindungen 871 synthese und reaktionen cyclischer phosphoniumsalze mit zwei phosphoratomen in sieben-, acht-, neun-, zehn- und elfringen sowie mit vier phosphoratomen in sechzehn-, achtzehn- und zwanzigringen

Abstract: Die im Titel gennanten cyclischen Phosphoniumsalze mit zwei und vier Phosphoratomen als Ringglieder konnen nach zwei Verfahren erhalten werden: 1. Umsetzung eines α,ω-Alkanbisphosphins A mit einen α,ω-Dihalogenalkan B, und 2. Verknupfung eines α,ω-dihalogenierten Bisphosphoniumsalzes der Struktur E mit einem Bisphosphin A. Die Anwendung des Verdunnungsprinzips fuhrt zu keiner Verbesserung der Ausbeuten an Cyclophosphoniumsalzen. Durch Einwirkung von LiAlH4 auf die Cyclophosphoniumsalze mit Benzyl-Liganden erhalt man in guten Ausbeuten die diesen entsprechenden Cyclophosphine. Mit Alkalihydroxyd entstehen aus den Cyclophosphoniumsalzen unter Abspaltung von Toluol die erwarteten Cyclophosphinoxide. Die Struktur der Cyclophosphoniumsalze wird 1H-NMR- und 31P-NMR-spektroskopisch abgesichert. Auch die massenspektrometrischen Untersuchungen an den Bis- und tetrakis-Ring-phosphinen stehen mit der Ringstruktur in bester Ubereinstimmung. The above-named title cyclic phosphonium salts with either two or fo...

The synthesis of organophosphorus compounds directly from the element

Abstract: Organophosphorus compounds were first introduced commercially as plasticizers in the 1920′s and in succeeding years their use as oil and petrol additives, anti-oxidants, stabilizers for plastics, flame retardants and flotation agents has developed rapidly.1 All organophosphorus compounds are made from elemental phosphorus, which is converted to phosphine, phosphorus tri and pentachlorides.2 phosphorus pentoxide or pentasulphide. There are obvious advantages in preparing organophosphorus compounds directly from the element, and in recent years considerable effort has been directed in this area.3–7

Phosphororganische verbindungen 851 synthese und anwendung optisch aktiver tertiärer phosphine als co-katalysatoren der homogenhydrierung mit rhodium-phosphin-komplexen

Abstract: Die Darstellung der optisch aktiven Methyl-n-propyl(bzw.-isopropyl)arylphosphine 1 bis 8 wird beschrieben. Hierbei ist Aryl: p-Methoxyphenyl (1 und 2), p-Dimethylaminophenyl (3 und 4), o-Methoxyphenyl (5 und 6), o-Dimethyl-aminophenyl (7) und o-Aminophenyl (8). Die Phosphine 1 bis 8 werden als optisch aktive Co-Katalysatoren bei der Homogenhydrierung von α- und s-Methylzimtsaureethylester, der α-Acetaminoacrylsaure und der α-Acetaminozimtsaure mit Rhodium-Phosphinkomplexen eingesetzt und jeweils die optische Induktion bestimmt. Folgende Ergebnisse (Vgl. die Tabellen 1 bis 4) wurden erhalten: 1) Die CH3O-Gruppe und N(CH3)2-Gruppe verandern unabhangig von ihrer Stellung die optische Induktion bei der Homogenhydrierung von α- und s-Methylzimtsaureethylester nur unwesentlich im Vergleich zu den entsprechenden Methyl-n-propyl (bzw.-isopropyl)-phenylphosphinen. 2) Bei der Homogenhy drierung von α-Acetaminoacrylsaure und α-Acetaminozimtsaure uben para-standige OCH3- und (CH3)2N-Gruppen in den optisch ak...

A new type of photochemical addition reaction of elemental sulfur to olefins

Abstract: Photochemical reactions of elemental sulfur with several olefins were studied. Irradiation of a mixture of elemental sulfur and norbornylene with 3500 A light afforded 3,4,5-trithiatricyclo[5.2.1.0]decane (1) and 2,3-epithionorbornane (2). Similarly, several thiane derivatives (4–6) were found to be formed by the photolysis of a mixture of cyclohexene and sulfur.

SOME DERIVATIVES OF 4-t-BUTYLCYCLOHEXYL AND 1-MENTHOL-PHOSPHOROCHLORIDATES

Abstract: cis and trans-4-t-Butylcyclohexanol and 1-menthol have been converted to the phosphorodichloridates with phosphorus oxychloride. Similar reaction with thiophosphoryl chloride afforded the phosphorodichloridothioates. By using 2 mol equivs. of 4-t-butylcyclohexanol, analogous condensations gave the corresponding phosphochloridates and chloridothioates, but with 1-menthol the reaction was unsuccessful. The various chloridates were characterized by preparation of a wide range of derivatives, e.g. amidates, azides, hydrazides, and hydrazones. These compounds are of interest as potential pesticides and their spectral features are discussed.

Dimethylarsinous acid esters of 1-thio- and -selenogalactose. a new class of potential carcinostatic agents

Abstract: The syntheses of 2,3,4,6-tetra-O-acetyl-1-S-dimethylarsino-1-thio-β-D-galactopyranose (4), 1-S-dimethylarsino-1-thio-β-D-galactopyranose (5), and 2,3,4,6-tetra-O-acetyl-1-Se-dimethylarsino-1-seleno-β-D-galactopyranose (8) are reported. An attempted preparation of 1-Se-dimethylarsino-1-seleno-β-D-galactopyranose (10) is also described. The compounds were characterized by nmr, uv, and mass spectroscopy, as well as elemental analysis. The 1H nmr spectra of these compounds were not exceptional except for the slight down-field shift of the –AsMe2 resonance noted in the selenium derivative as compared to the sulfur compound. Ultraviolet spectra of these compounds showed a relatively intense absorption which can be attributed to an n → o∗ transition associated with the As–X (X = S, Se) bond. The Δmax for the Se compounds show a slight red shift relative to analogous S compounds. The mass spectra of these compounds showed immediate loss of the aglycon, –XAsMe2, in all cases. Other fragments can be ascrib...

Preparation de composes du phosphore tri- et pentacoordine a partir d'hydroxyacides et d'aminoacides

Abstract: Des α-hydroxyacides et des aminoacides ont ete heterocyclises sur un atome de phosphore trivalent (Tableau I, composes 4a-d et 6). Les derives obtenus ont servi de point de depart pour la preparation d'acyloxyspirophosphoranes (Tableau II, composes 5a-c et 7). α-Hydroxyacids and aminoacids are cyclized on trivalent phosphorus atom (Table I, compounds 4a-d and 6). The resulting adducts used as starting material for the synthesis of acyloxysphirophosphoranes (Table II, compounds 5a-c and 7).

ALKALI-PHOSPHORVERBINDUNGEN UND IHR REAKTIVES VERHALTEN LXXVI Bildung und Reaktionsverhalten substituierter 1,2-Diphospholane und des 1,5-Diphosphabicyclo[3.3.0]octans

Abstract: Im Verlauf der Metallierung der Alkylen-bis-phosphine H2P-(CH2) n -PH2 bzw. RHP-(CH2) n -PH2 (n = 2–5) erfolgt H2-Eliminierung unter Knuipfung von P–P-Bindungen. Im Falle von Verbindungen mit n = 2 und 5 resultieren P-Polymere, mit n = 4 erfolgt teilweise Ringschlus zu 1-Lithium-1,2-diphosphorinan und mit n = 3 bilden sich ausschlieslich 1-Lithiumsubstituierte 1,2-Diphospholane. Letztere reprasentieren geeignete Ausgangssubstanzen zur Synthese verschieden substituierter 1,2-Diphospholane sowie des 1,5-Diphosphabicyclo[3.3.0]octans. Dieser neuartige P–P-Bicyclus, ohne weitere Heteroatome, verhalt sich gegenuber nucleophilen wie auch elektrophilen Agentien als bemerkenswert stabile Verbindung. Die Struktur der dargestellten Verbindungen wird anhand von P-Derivaten sowie NMR- und massenspektroskopisch gesichert. In the course of the metallation of alkylene-bis-phosphines, H2P-(CH2) n -PH2 and RHP-(CH2) n -PH2, respectively (n = 2 to 5), hydrogen is eliminated under simultaneous formation of P-P bond...

A direct synthesis of 2- and 4-hydroxydiaryl sulfoxides

Abstract: A number of 2-hydroxydiaryl sulfoxides, as well as a few 4-hydroxy analogs, have been prepared in fair to good yields by the direct arylsulfinylation of substituted phenols in the presence of anhydrous aluminum chloride.

Investigations on the alkaline degradation of the pentathionate

Abstract: Specifically 35S-labelled pentathionate is hydrolized under various reaction conditions. From the experimental activity behaviour of the hydrolization products a reaction mechanism can be deduced. Attack of the OH− occurs at the γ-S-atom of the sulfur chain leading to sulfoxylic acid and thiosulfate as reaction products. Sulfoxylic acid disproportionates to sulfur and sulfite which combine to thiosulfate.

Molecular structure of p-substituted 1,3,5-triaza-7-phosphaadamantanes: vibration spectra and crystal structure analyses

Abstract: Homologs: 1,3,5-triaza-7-phosphaadamantane-7-oxide and 1,3,5-triaza-7-phosphaadamantane-7-sulfide have been characterized by IR and Raman spectroscopy and by crystal structure analyses. The spectra and crystal structures are interpreted in comparison with the parent compound, 1,3,5-triaza-7-phosphaadamantane. The effects of the change in coordination as the result of addition of a substituent at the phosphorus atom and the influence of the character of the respective substituents on the bonding geometry of the phosphorus atom are also examined.

The mass spectra of phosphonyl compounds part 31. dimethyl and diethyl alkane- and substituted-methane phosphonates

Abstract: The electron impact mass spectra of 28 related phosphonates have been determined. Ethyl, iso-propyl and tert-butyl groups which are bound directly to phosphorus, fragment to the corresponding alkenes; similar iso-propyl and tert-butyl groups in the dimethyl esters also fragment to ethylene and propene respectively, i.e. the P-alkyl group rearranges with transfer of the elements of a methyl group to the phosphorus ion. The diethyl alkenephosphonates undergo double hydrogen rearrangements of an ethoxy group to give dihydroxyphosphonium ions. The di- and trihydroxyphosphonium ions have a characteristic fragmentation which involves loss of water. This characteristic has been used as evidence for the rearrangement of a phosphacylium ion to a dihydroxyphosphonium ion. Some other unusual rearrangements involving the combination of the groups bound to phosphorus and oxygen have been observed.

Reactivite du bromo-3 oxo-2 propyl phosphonate de diethyle dans la reaction de hantzsch

Abstract: Nous avons etudie la reactivite du bromo-3 oxo-2 propyl phosphonate de diethyle mis dans les conditions de la reaction de Hantzsch. Divers heterocycles thiazoliques et imidazothiazoliques ont ainsi ete obtenus. Testes dans plusieurs domaines biologiques (radio-protection, systeme nerveux central, phytosanitaire) ces composes n'ont presente aucune activite therapeutique interessante. The reactivity of diethyl 3-bromo 2-oxo propene phosphonate is studied in experimental conditions of the Hantzsch reaction. Various thiazolyl and imidazothiazolyl heterocycles have been obtained. In the pharmacology screening (radioprotection, C.N.S. properties,…) these compounds did not show any potential therapeutic activity.

MINDO/3–BERECHNUNGEN VON PHOSPHORORGANISCHEN VERBINDUNGEN. II. Ionisationspotentiale und Strukturdaten einfacher Phosphine

Abstract: Es wird uber die MINDO/3-Berechnungen der Verbindungen PH, PH2, PH3, P2H4, CH3PH2, (CH3)2PH, (CH3)3P, C2H4PH2, (C2H5)2PH, (C2H5)3P, HCP, CH2PH, C6H5PH2, (n-C3H7)3P, und (n-C4H9)3P berichtet. Die PE spektroskopisch ermittelten Ionisationspotentiale werden mit den niedrigsten besetzten Orbitalen verglichen. Lokalisierte Orbitale wurden nach dem Ruedenbergschen Lokalisierungsverfahren erhalten. Der Hybridisierungsgrad der P–H Bindungen und des lone-pair Orbitals am Phosphor wird mit physikalischen Eigenschaften wie Kopplungskonstante, chemical shift, Basizitat, Schwingunsfrequenz, Ionisationspotential und Geometriedaten korreliert. Die Kopplungskonstante zeigt eine uberraschende indirekte Proportionalitat mit dem Hybridisierungsgrad fur die P–H Bindung; dies unterscheidet sich zur direkten Proportionalitat fur C–H Bindungen. P2H4 wird in Abhangigkeit vom Dihedralwinkel um die P–P Achse berechnet. In Ubereinstimmung mit experimentellen Ergebnissen zeigt sich eine gauche-Konformation als stabilste; di...

DARSTELLUNG UND NMR-SPEKTROSKOPISCHE UNTERSUCHUNGEN DER 2-FLUOR-2,2-DIPHENYL-2,3-DIHYDRO-1,3,2λ5-BENZOXAZAPHOSPHOLE

Abstract: Pentakoordinierte Phosphorverbindungen vom Typ der 2.3-Dihydro-1.3.2-benzoxazaphosphole entstehen bei der Umsetzung von 2-Amino-phenolen oder N-Athyl-2-hydroxy-anilinen mit Diphenyl-trifluorphosphoran unter Verwendung von Triathylamin als Fluorwasserstoff-Akzeptor. Die Synthese einer grosen Anzahl verschieden substituierter Spezies zeigt die Allgemeingultigkeit dieses Verfahrens. Die isolierbaren Substanzen werden durch NMR-Spektren (1H, 31P, 19F) und die ublichen analytischen Methoden charakterisiert. Die Markierung einer Verbindung mit 15N tragt wesentlich zur Struktursicherung bei. Bei den 3-H-2-Fluor-2.2-diphenyl-1.3.2-benzoxazaphospholen wurde ein bemerkenswerter Zusammenhang zwischen P–F-Kopplungskonstante und dem F-shift aufgefunden, der eine lineare Korrelation dieser beiden Grosen erkennen last. Pentacoordinated phosphorus compounds of the type of 2,3-dihydro-1,3,2-benzoxazaphospholes originate from reaction of 2-aminophenol or N-ethyl-2-hydroxyaniline with diphenyl-trifluorophosphorane ...

Synthesis and properties of tetrakis(ureidomethyl)phosphonium salts

Abstract: Hydroxymethylphosphonium salts such as (HOCH2)4PCl (1), Ph3P(CH2OH)Cl (5), or (HOCH2)4PI (8) condense with urea and its methyl derivatives, giving stable ureidomethylphosphonium salts in which the quaternary structure is preserved. With few exceptions, ureas are too feebly basic to cause the dissociation to tertiary phosphine and formaldehyde that characterizes the reactions of hydroxymethylphosphonium salts with primary or secondary amines. The chemistry of the ureidomethylphosphonium salts is explored, particularly with respect to their physical and spectral properties, ion exchange, and hydrolysis with acid or base. If the phosphonium salt contains a hydrogen substituent on N-1, hydrolysis with alkali follows a β-elimination pathway, giving the tertiary phosphine, but if the N-1 position is blocked by a methyl group, the reaction follows the Cahours-Hofmann pathway, giving the tertiary phosphine oxide.

Studien zum vorgang der wasserstoffübertragung 511 raney-nickel als reagens zur hydrierenden abspaltung des chalkogenatoms aus schwefel-, selen- und tellur-verbindungen

Abstract: Thioather, Sulfoxide, Sulfone, organische Selenide und Telluride (R – Y – R': R, R', = Alkyl, Aryl, Y=S, SO, SO2, Se, Te) werden an der Grenzflache von Raney-Nickel hydrogenolysiert. Als Spaltprodukte entstehen die Verbindungen RH und R'H sowie eine Grenzflachenverbindung (Raney-Nickel-Y) (Y=S, Se, Te; S auch aus Sulfoxiden und Sulfonen. Letztere entbinden ebenfalls mit Mineralsauren YH2). Die Grose und ‘Struktur’ der Oberflache des Raney-Nickels entscheidet uber die Hydrogenolysekapazitat. Bei einer technischen Raney-Nickel-Probe liegt bei Diphenylsulfid die Sattigungsausbeute an Benzol bei 1,1 mmol/g Raney-Nickel. Die Sattigungskapazitat hangt ab von der Struktur von R bzw. R' und dem Heteroatom Y. (Auch Benzylether konnen–wenn auch langsamer als Thioether–zu Toluol aufgespalten werden). Auf Grund bekannter Daten werden Vorstellungen entwickelt, die ein Bild uber den topochemischen Verlauf der Hydrogenolyse von R–Y–R' vermitteln sollen. Vergiftetes Raney-Nickel ist im Gegensatz zum aktivierten ...

Phosphorus-nitrogen compounds. part xliv.1 cyclodiphosph(v)azanes derived from tri-alkylphosphorothioic triamides

Abstract: N, N', N'-Tri-alkylphosphorothioic triamides, P(S)(NHR)3. R = Me, Et, Pr n , Pr i , Bu n , Bu n , Bu i , Ch2Ph, cyclopentyl and cyclohexyl, decompose at 190–240°C to give cyclodiphosph(V)azanes, [RHNP(S)NR]2. The 1H nmr spectra of the cyclic dimers are reported; trans-structures are assigned to the products R = Et, Pr n , Bu n , Bu i , and CH2Ph.

XXVII. The Reaction of Fluorenylidenetriphenylphosphorane and Triphenylphosphine with 2,3-Benzofurandione, Benzo[b]thiophene-2,3-dione, and Naphtho[2,1-b]furan-1,2-dione

Abstract: Fluorenylidenetriphenylphosphorane (1) reacts with 2,3-benzofurandione (4a), benzobthiophene-2,3-dione (4b), and naphtho[2,1-b]furan-1,2-dione (5) to give the corresponding fluoren-9-ylidene derivatives (6a), (6b) and (7). Triphenylphosphine effects the deoxygenative dimerization of (4b) yielding thioindirubin (9), while no reaction has been observed with the furandiones (4a) and (5) respectively. Structural assignments are based on analytical, chemical, and spectroscopic results.

Konfigurations- und konformationsbestimmung an 1.3-oxaphosphorinanen

Abstract: The diastereomers of substituted 1,3-oxaphosphorinanes prepared by cyclocondensation of suitable 3-hydroxyalkylphosphines with aldehydes were assigned by means of the 13C- and 31P-chemical shifts, the coupling constants 1 J(P–C), 2 J(P–C–H), 2 J(P–C–C), 3 J(P–C–C–H) and the paramagnetic shift of the protons. The conformational equilibrium is mainly controlled by the substituent on position 2. In the trans-trans-isomer of 4,4,6-trimethyl-2,3-diphenyl-1,3-oxaphosphorinan we propose a participation of twist-boat-conformers. Die Diastereomere und Konformere substituierter 1.3-Oxaphosphorinane, hergestellt durch Cyclokondensation geeigneter 3-Hydroxyalkylphosphine mit Aldehyden, wurden mit Hilfe von 13C- und 31P-chemischen Verschiebungen, der Kopplungskonstanten 1 J(P–C), 2 J(P–C–H), 2 J(P–C–C), 3 J(P–C–C–H) sowie der paramagnetischen Verschiebungen der Protonen bestimmt. Die Lage der Konformerengleichgewichte hangt vorwiegend vom Substituenten in Position 2 ab. Im trans-trans-Isomeren des 4.4.6-Trime...

BOND LENGTHS AND BOND ORDERS IN π-ELECTRON HETEROCYCLES

Abstract: A comparison of bond orders calculated by different methods (Pauling, HMO, PPP, SCF-MO) with experimental bond lengths has been made for representative sets of sulfur and nitrogen π-electron heterocycles and statistical treatment of the results has been presented. Bond orders obtained by simple techniques (Pauling, HMO) are equally effective in predicting and correlating bond lengths in these heterocycles as those calculated by more sophisticated methods (PPP, SCF-MO).

Über eine Reaktion von o-Hydroxybenzylalkoholen mit Estern von Säuren des Phosphors mit der Koordinationszahl 3

Abstract: o-Hydroxybenzyl alcohol reacts with trimethyl phosphite under smooth conditions to o-hydroxyphenylmethane phosphonic acid dimethyl ester. This unusual reaction is of widest applicability. Derivatives of o-hydroxybenzyl alcohol independent of type, number or position of substituents in the ring, react with alkyl esters of phosphorous, phosphonous or phosphinous acids in an analogous process, forming the corresponding o-hydroxyphenylmethane phosphonic or phosphinic esters or phosphine oxides.

Cholesteryl phosphite and related compounds

Abstract: The preparation of cholesteryl phosphorodichloridite (2) is described; this compound with aniline (2 mol. equiv.) gave the N-phenylphosphoramidochloridite (5) and the latter by condensation with water afforded the N-phenyl-amidophosphite (6). Similarly the N-phenylphosphoramidochloridite (5) with morpholine gave the morpholidite (7); phenylhydrazine gave the hydrazinophosphite (8) and ethanol the amidoethyl phosphite (9). Cholesteryl phosphorodichloridite (2) by reaction with aniline (4 mol. equiv.) gave the N,N 1−diphenylphosphorodiamidite (10). The reaction of cholesteryl phosphorodichloridite (2) with methanol and ethanol are discussed in relation to the analogous reactions with cholesteryl phosphorodichloridate. Boiling ethanol gave cholesterol as the only isolatable product but at room temperature a low yield of the diethylphosphite (11; R=Et) was obtained. The yield of the phosphite was greatly increased in the presence of base. Similarly the dichloridite 2 with boiling water gave cholester...

MASSENSPEKTROMETRISCHE UNTERSUCHUNGEN AN ORGANOPHOSPHORVERBINDUNGEN I Zum Massenspektrometrischen Fragmentierungsverhalten von Dithio- und Thiophosphonsäureanhydriden

Abstract: 70 eV electron impact mass spectra of dimeric dithiophosphonic acid anhydrides [RP(S)S]2 (R = CH3, C6H5, p-CH3OC6H4, p-C2H5OC6H4, 2-Thienyl, 2-Naphthyl) and trimeric thiophosphonic acid anhydrides [RP(S)O]3 (R = CH3, C6H5, Cyclohexyl) are reported and discussed. General fragmentation patterns which are consistent with DADI metastable spectra are suggested for both classes of compounds. Molecular ions are observed in all cases. While in the earlier class ring fission followed by migration of R from phosphorus to sulphur is dominating, the –P–O–P– ring in the latter seems to be rather stable. Elektronenstos induzierte 70 eV Massenspektren der dimeren Dithiophosphonsaureanhydride [RP(S)S]2 (R = CH3, C6H5, p-CH3OC6H4, p-C2H5OC6H4, 2-Thienyl, 2-Naphthyl) und trimeren Thiophosphonsaureanhydride [RP(S)O]3 (R = CH3, C6H5, Cyclohexyl) werden aufgefuhrt und diskutiert. Allgemeine Fragmentierungsschemata, die durch Metastabilenspektren nach der Methode DADI erhartet worden sind, werden fur beide Verbindungs...

Investigations on the sulfite degradation of polythionates

Abstract: Sulfite attacks pentathionate at the γ-S-atom of the sulfur chain leading to thiosulfate and tetrathionate as reaction products. Excess of sulfite leads to degradation of the intermediate tetrathionate to thiosulfate and trithionate as final products. In this paper we report on the reaction of 35S-labelled tetrathionate and pentathionate with sulfite.

Preparation and nmr study of phosphorus-fluorine compounds undergoing intramolecular exchange. part 1.1 benzylmethylaminofluoro-phosphoranes

Abstract: The preparation is described of a series of benzylmethylamino-substituted fluorophosphoranes of general formula PhCH2(Me)NPF4–n R n (where R = Me, Ph; n = 0, 1, 2) from the cleavage of the silicon-nitrogen bond in benzylmethylamino-trimethylsilane by fluorophosphoranes. The structures of the new compounds are deduced from 1H, 19F and 31P nmr data. Variable temperature spectra give information about intramolecular exchange processes, and a detailed study was made of benzylmethylamino-diphenyldifluorophosphorane and of the corresponding 2-methyl-piperidyl compound.