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  • Chemistry  (15)
  • Diazadiphosphetine
  • Methanediphosphonic Acid Derivatives
  • Wiley-Blackwell  (15)
  • 1980-1984  (4)
  • 1975-1979  (11)
Collection
Keywords
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  • Wiley-Blackwell  (15)
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Year
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 320 (1978), S. 389-394 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: α-Substituted Phosphonates. XXXI. The Reaction of N,N,N′,N′-Tetramethyl Chloroformamidinium Chloride with P(III) CompoundsN,N,N′,N′-Tetramethyl chloroformamidiniumchloride (4) does not react with triethyl phosphite (TEP) or isopropyl diphenylphosphinate to give the expected bisphosphoryl derivatives 7 and 11, respectively, but primarily the monophosphorylated amidinium salts 6 and 10 respectively. The phosphine oxide 10 is stable, while 6 undergoes an elimination of ethyl chloride to the betain 8. Even under more drastic conditions the reaction of 4 or 8 with TEP does not lead to the expected bis(dimethylamino)bisphosphonate 7, but to the monoaminated bisphosphonate 1, involving a reduction step. Similar reduction has been observed under mild conditions in Michaelis-Arbusov reaction of dichloromethylenimonium chloride, yielding the expected trisphosphonate 2 and the bisphosphonate 1 as a by-product.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 411 (1975), S. 148-152 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Properties of Lineary PhosphorylchlorphosphazenesThe phosphorylchlorphosphazenes, Cl2(O)P - [N=PCl2]n - Cl, (n = 1, 2, 3) react like POCl3 with hexamethyldisilazan forming silylamides, Cl2(O)P - [N = PCl2]n - NHSi(CH3)3, (n = 0, 1, 2, 3). From these are obtained the phosphorylchlorphosphazenes by reaction with PCl5 containing one group  - N = PCl2 more.
    Notes: Die Phosphorylchlorphosphazene, Cl2(O)P - [N=PCI2]n - Cl, (n = 1, 2, 3) reagieren ebenso wie POCl3 mit Hexamethyldisilazan zu den Silylamiden, Cl2(O)P - [N=PCl2]n - NHSi(CH3)3, (n = 0, 1, 2, 3), aus denen mit PCl5 die um eine Phosphazengruppe verlängerten Phosphorylchlorphosphazene erhalten werden.
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  • 3
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Temperature Dependence Investigations of 31P Chemical Shifts of Trialkoxyphosphazene N-phosphoryldialkylestersThe 31P NMR spectra of a series of trialkoxyphosphazene-N-phosphoryldialkylesters, (RO)3P=N—P(O)(OR′)2, where R = R′ = Et; R = Et, R′ = Bu; R = Bu, R′ = Et; R = R′ = Bu; and R = R = R′ = Hex respectively, and of trichlorophosphazene-N-phosphoryldichloride were investigated at various temperatures. The temperature dependence of chemical shift of phosphorus belonging to the phosphazene group is multiplicately larger than that of phosphorus belonging to the phosphoryl group. This fact also could be confirmed for other simple phosphazene and phosphoryl compounds. As discussed this different temperature dependence of 31P chemical shift is not a consequence of the medium but of the molecular structure.
    Notes: Für eine Reihe von Trialkoxyphosphazen-N-phosphoryldialkylestern, (PO)3P=N—P(O)(OR′)2, wobei R = R′ = Et; R = Et, R′ = Bu; R = Bu, R′ = Et; R = R′ = Bu bzw. R = R′ = Hex waren, sowie für Trichlorphosphazen-N-phosphoryldichlorid wurden jeweils 31P-NMR-Spektren bei verschiedenen Temperaturen aufgenommen. Es zeigte sich, daß die Temperaturabhängigkeit der chemischen Verschiebung für den Phosphor der Phosphazen-Gruppierung um ein mehrfaches größer ist als die für den Phosphor der Phosphoryl-Gruppierung. Dies konnte auch allgemein für andere einfache Phosphazen- und Phosphoryl-Verbindungen bestätigt werden. Es wird diskutiert. daß diese unterschiedliche Temperaturabhängigkeit der 31P-chemischen Verschiebung nicht auf Medieneinflüsse, sondern auf die molekulare Struktur zurückzuführen ist.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 415 (1975), S. 1-7 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the „HCl- Condensation“ of Phosphorus OxytriamideThe reaction of HCl with phosphorus oxytriamide suspended in ether leads to highly cross-linked imidopolyphosphates. By substitution of amido group by chlorine atoms amidochlorides of phosphoric acid are also formed which are soluble in ether. Only traces of oligomeric μ-imidophosphoric acid amides are obtained. The intermediate formation of phosphorylimide amide, OP(=NH)NH2, and phosphoryl imide chloride, OP(=NH)CI, is assumed to explain the experimental results.
    Notes: Die Reaktion von HCl mit Phosphoroxidtrimid in ätherischer Suspension führt zur Bildung stark vernetzter Imidopolyphosphate. Durch Substitution von Amidgruppen durch Chloratome entstehen außerdem ätherlösliche Amidchloride der Phosphorsäure. Oligomere μ-Imidophosphorsäureamide werden nur in Spuren erhalten. Zur Interpretation der experimentellen Befunde wird die intermediäre Bildung von Phosphorylimidamid, OP(=NH)NH2, und Phosphorylimidchlorid, OP(=NH)CI, angenommen.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 433 (1977), S. 200-206 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Constitution of the Trimethylsilyl Derivatives of Imidodiphosphoryl CompoundsEsters and dialkylamides of the imidodiphosphoric acid react with hexamethyl-disilazane to form trimethylsilyl derivatives. 1H-, 29Si-, and 31P-NMR data show the trimethylsilyl group to be bond to oxygen with rapid reversible exchange between both phosphoryloxygen atoms.
    Notes: Ester und Dialkylamide der Imidodiphosphorsäure reagieren mit Hexamethyldisilazan zu den Trimethylsilylderivaten. Aus 1H-, 29Si- und 31P-NMR-Daten folgt, daß die Trimethylsilylgruppe über Sauerstoff gebunden ist und einem schnellen reversiblen Austausch zwischen den beiden Phosphorylsauerstoffatomen unterliegt.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 437 (1977), S. 269-274 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Formation and Constitution of a Heterocyclic Phosphorus BetaineThe zwitter ionic 2,2,6,6-tetrakis(diethylamido)-4,4-Dioxo-1,3,5,2λ5,4λ5,6λ5-azadioxatriphosphorin (3) is formed as a cristalline byproduct in the reaction of octaethyl imidodiphosphoryl tetramide derivatives, {[(Et2N)2P(O)]2N}Y (Y = H, Na, SiMe3), with phosphorus(V) chlorides (PCl5, POCl3, ClP(O)(OEt)2). It is obtained from the primary reaction products in a secondary reaction. Its constitution was revealed by 31P-n.m.r.-spectroscopy and by synthesis of the 15N-labeled compound. From O-Diethoxyphosphorylated octaethyl imidodiphosphoryl tetramide the compound 3 is obtained only in presence of water traces and agents providing HCl like e. g. ClSiMe3 or ClP(O)(OEt)2.
    Notes: Bei der Umsetzung von Octaäthylimidodiphosphoryltetramid-Derivaten, {[(Et2N)2P(O)]2N}Y (Y = H, Na, SiMe3), mit Phosphor(V)-chloriden (PCl5, POCl3, ClP(O)(OEt)2) entsteht aus den primären Reaktionsprodukten in einer Folgereaktion das zwitterionische 2,2,6,6-Tetrakis(diäthylamido)-4,4-Dioxo-1,3,5,2λ5,4λ5,6λ5-azadioxatriphosphorin (3) als kristallines Nebenprodukt. Die Konstitutionsermittlung erfolgte mittels 31P-NMR-Spektroskopie und durch Synthese der 15N-markierten Verbindung. Aus dem O-Diäthoxyphosphorylierten Octaäthylimidodiphosphoryltetramid bildet sich 3 nur in Gegenwart von Wasserspuren und HCl-liefernden Reagenzien, wie ClSiMe3 oder ClP(O)(OEt)2.
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  • 7
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Formation and N.M.R.-Spectroscopic Characterization of Alk-(ar-)oxy Derivatives of Trichlorophosphazene-N-phosphoryldichloride, Cl3P=N—P(O)Cl2, Imido- and N-Methylimidodiphosphoryltetrachloride, Cl2P(O)NHP(O)Cl2 and Cl2P(O)N(CH3)P(O)Cl2The ester chlorides and esters P2NOCl5-x(OR)x (x = 1-5), P2(NH)O2Cl4-x(OR)x (x = 1-4) and P2(NCH3)O2Cl4-x(OR)x (x = 1-4) derived from the title compounds by substitution of chlorine atoms by alk- or aroxy groups are characterized by their 31P-n.m.r. data. The possibilities for forming these compounds by alcoholysis, chloridolysis, dealkylation and P—N-bond formation are discussed.
    Notes: Die sich von den Titelverbindungen durch Substitution der Chloratome durch Alk- bzw. Aroxygruppen ableitenden Esterchloride und Ester P2NOCl5-x(OR)x (x = 1-5), P2(NH)O2Cl4-x(OR)x (x = 1-4) und P2(NCH3)O2Cl4-x(OR)x(x = 1-4) werden 31P-NMR-spektroskopisch charakterisiert. Die Möglichkeiten zur Bildung dieser Verbindungen durch Alkoholyse, Chloridolyse, Entalkylierungs- und P—N-Bindungsknüpfungsreaktionen werden vorgestellt.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 465 (1980), S. 120-126 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of Lineary and Branched Phosphazenes from N-silylated Phosphoryl AmidesThe use of N-silylated phosphoryl amides in the reaction with PCl5 favours the KIRSANOV reaction and reduces undesirable substitution reactions. However, silylated monoamides, X2P(O)NHSiMe3 (X = OEt, NEt2), do not give the expected trichlorophosphazenes but the isomeric N-dichlorophosphoryl phosphazenes, Cl2P(O)—N=PClX2, which are also formed in the reaction of (EtO)2P(O)NCl2 with PCl5. As the first phosphoryl-P, P-bis(trichlorophosphazene) (EtO)P(O)(N=PCl3)2 could be obtained in the reaction of PCl5 with the silylated diamide (EtO)P(O)(NHSiMe3)2. Tris reactivity of silylated amides to P—Cl compounds decreases in the row PCl5 〉 POCl3 〉 CIP(O)(OEt)2 〉 ClP(O)(NEt2)2. In the reaction with phosphoryl chlorides the preferred formation of compounds with P—NH—P bridges could not be observed.
    Notes: Die Verwendung N-silylierter Phosphorylamide begünstigt bei der Umsetzung mit PCl5 die KIRSANOV-Reaktion und drängt unerwünschte Substitutionsreaktionen zurück. Silylierte Monoamide, X2P(O)NHSiMe3 (X = OEt, NEt2), geben mit PCl5jedoch nicht die erwarteten Trichlorphosphazene, sondern die isomeren N-Dichlorphosphorylphosphazene, Cl2P(O)-N=PClX2, die auch bei der Reaktion von (EtO)2P(O)NCl2 mit PCl5 entstehen. Als erstes Phosphoryl-P, P-bis-(trichlorphosphazen) konnte (EtO)P(O)(N=PCl3)2 durch Umsetzung des silylierten Diamids (EtO)P(O)(NHSiMe3)2 mit PCl5 erhalten werden. Tris(trimethylsilyl)phosphoryltriamid, OP(NHSiMe3)3, bildet mit PCl5 das Triphosphazen [ClP(N=PCl3)3]Cl. Die Reaktivität der silylierten Amide gegenüber P—Cl-Verbindungen nimmt in der Reihe PCl5 〉 POCl3 〉 ClP(O)(OEt)2 〉 ClP(O)(NEt2)2 ab. Eine bevorzugte Bildung von Verbindungen mit P—NH—P-Brücken konnte bei der Umsetzung mit Phosphorylchloriden nicht beobachtet werden.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 502 (1983), S. 21-28 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of N-Di(alk-, ar-)oxyphosphoryl-tri(alk-, ar-)oxyphosphazenes, (RO)2P(O)—N=P(OR)3, by P—N-Bond FormationThe title compounds can be prepared from di- and triesters of phosphorous acid, sodium azide, and carbon tetrachloride in a single step procedure and in high yields. Due to the combination of the Atherton-Todd and the Staudinger reaction toxic phosphoric acid ester azides are formed only in situ and their concentration is kept very small. As by-products trichloromethane phosphonic acid esters, (RO)2P(O)CCl3, esters of phosphoric acid and condensed phosphoric acids as well as N-alkylimidodiphosphoric acid esters, [(RO)2P(O)]2NR, are formed. Their formation can be avoided or reduced by choosing suitable reaction conditions. The mechanism of the reaction is discussed.
    Notes: Die Darstellung der Titelverbindungen ist nach einer kombinierten Atherton-Todd- und Staudinger-Reaktion in einem Verfahrensschritt aus Di- und Triestern der phosphorigen Säure, Natriumazid und Tetrachlorkohlenstoff in hohen Ausbeuten möglich. Toxische Phosphorsäureesterazide, (RO)2P(O)N3, werden nur in situ gebildet, wodurch ihre Konzentration extrem niedrig gehalten wird. Als Nebenprodukte treten Trichlormethanphosphonsäureester, Cl3CP(O)(OR)2, Ester der Phosphorsäure und kondensierter Phosphorsäuren sowie N-Alkylimidodiphosphorsäureester, [(RO)2P(O)]2NR, auf. Ihre Bildung kann durch die Wahl geeigneter Reaktionsbedingungen vermieden bzw. vermindert werden. Der Mechanismus der Reaktion wird diskutiert.
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  • 10
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of the Two-component System Triethylphosphite/Carbon Tetrachloride with Nucleophiles Containing Hydrogen. 1. Reaction with Acyl AmidesAcyl amides react with the two-component system triethylphosphite/carbon tetrachloride yielding N-acyl phosphazenes, (EtO)3P=N—Ac. In this way (EtO)3P=N—P(O)(OEt)2, (EtO)3P=N—CN, (EtO)3P=N—C(O)Ph, and (EtO)3P=N—SO2Ph were prepared. Ethyl esters of phosphoric acid and trichloromethane phosphonic acid were obtained as by-products.
    Notes: Säureamide reagieren mit dem Zweikomponentensystem Triethylphosphat/Tetrachlorkohlenstoff zu N-Acylphosphazenen, (EtO)3P=N—Ac. Auf diese Weise wurden aus entsprechenden Amiden (EtO)3P=N—P(O)(OEt)2, (EtO)3P=N—CN, (EtO)3P=N—C(O)Ph und (EtO)3P=N—SO2Ph dargestellt. Als Nebenprodukte werden Phosphorsäureethylester und Trichlormethanphosphonsäureester erhalten.
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