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  • 1
    ISSN: 0044-2313
    Keywords: Diphenoxyphosphorylchloride ; N′,N′-dialkyl-N-diphenoxyphosphoryl urea ; N-diphenoxyphosphoryl-N″,N″-dipropyl biuret ; X-ray crystal structure analysis ; n.m.r. spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Diphenoxyphosphorylchloride with N,N-disubstituted Ureas - Formation of Phosphorylated Biuret CompoundsN′,N′-disubstituted N-diphenoxyphosphorylureas, (PhO)2P(O)—NH—CO—NR1R2 (R1 = R2 = Et, 1; n-Pr, 2; n-Bu, 3; i-Bu, 4; R1 = Me and R2 = Ph, 5) as well as phosphorylated biuret compounds, (PhO)2P(O)—NH—CO—NH—CO—NR1R2 are obtained in the reaction of diphenoxyphosphorylchloride with N,N-disubstituted ureas and triethylamine. The biuret derivatives are formed via (PhO)2P(O)NCO. Their yield rises if the reaction is carried out without amine. The X-ray crystal structure analysis of (PhO)2P(O)—NH—CO—NH—CO—NPr2, 8, shows that dimers exist in the crystal with intermolecular as well as intramolecular hydrogen bonds. The framework formed by atoms P—N1—C1(O4)—N2—C2(O5)—N3(C3)C6 is planar. The existence of a rotation barrier along the bond C2-N3 was detected by NMR spectroscopy.
    Notes: Bei der Umsetzung von Diphenoxyphosphorylchlorid mit N,N-disubstituierten Harnstoffen in Gegenwart von Triethylamin treten neben N′,N′-disubstituierten N-Diphenoxyphosphorylharnstoffen, (PhO)2P(O)—NH—CO—NR1R2 (R1 = R2 = Et, 1; n-Pr, 2; n-Bu, 3; i-Bu, 4; R1 = Me u. R2 = Ph, 5), immer auch N″,N″-disubstituierte N-Diphenoxyphosphorylbiuret-Verbindungen, (PhO)2P(O)—NH—CO—NH—CO—NR1R2 auf. Sie entstehen über intermediär gebildetes (PhO)2P(O)NCO. Die Ausbeute an Biuretderivaten steigt, wenn ohne Aminzusatz gearbeitet wird. Die Röntgen-Kristallstrukturanalyse von (PhO)2P(O)—NH—CO—NH—CO—NPr2, 8, zeigt, daß im Kristall Dimere mit sowohl inter- als auch intramolekularen Wasserstoffbrücken vorliegen. Das Gerüst von 8 mit der Atomfolge P—N1—C1(O4)—N2—C2(O5)—N3(C3)C6 ist nahezu planar. NMR-Untersuchungen beweisen die Existenz einer Rotationsbarriere um die Bindung C2-N3.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 601 (1991), S. 111-119 
    ISSN: 0044-2313
    Keywords: Sulfonyl amines ; bis(dimesylamino)dimethyl silane ; bis(dimesylamino)dimethyl stannane ; preparation ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polysulfonyl Amines. XXIV. Preparation and Crystal Structures of Bis(dimesylamino)dimethyl Silane and Bis(dimesylamino)dimethyl StannaneThe new compounds (CH3)2E[N(SO2CH3)2]2 with E = Si (3), m.p. 162 °C, and E = Sn (4), m.p. 194-196 ° were prepared by metathesis of AgN(SO2CH3)2 with (CH3)2ECl2 and subjected to X-ray structure determinations. 3 crystallizes in the monoclinic space group C2/c with a = 1714.3(4), b = 679.6(2), c = 1389.9(4) pm, β = 97.50(2)° and Z = 4, 4 in the same space group with a = 2093.8(8), b = 1320.7(6), c = 1443.9(6) pm, β = 124.28(3)° and Z = 8. The crystals of both compounds consist of discrete monomeric molecules, in which the central atom E is bonded to two carbon and two nitrogen atoms in an approximately tetrahedral geometry for 3 [angles at Si in the range (105.5⃛111.9)°] and in a severely distorted tetrahedral arrangement in 4 [CSnC 128.8°; NSnN 107.8°; NSnC in the range (99.9⃛109.4)°]. Details of the molecular structures suggest that in each molecule two intramolecular E⃛O dipole-dipole interactions are stereochemically significant [Si⃛O 291.4 pm (2x); Sn⃛O 300.9 and 303.1 pm]. The molecule of 3 displays an exact, that of 4 an approximate twofold symmetry.
    Notes: Die neuen Verbindungen (CH3)2E[N(SO2CH3)2]2 mit E = Si (3), Schmp. 162 °C, und E = Sn (4), Schmp. 194-196 °C, wurden durch Metathese von AgN(SO2CH3)2 mit (CH3)2ECl2 erhalten und röntgenstrukturanalytisch charakterisiert. 3 kristallisiert in der monoklinen Raumgruppe C2/c mit a = 1714,3(4), b = 679,6(2), c = 1389,9(4) pm, β = 97,50(2)° und Z = 4, 4 in der gleichen Raumgruppe mit a = 2093,8(8), b = 1320,7(6), c = 1443,9(6) pm, β = 124,28(3)° und Z = 8. Die Kristallpackung beider Verbindungen besteht aus diskreten monomeren Molekülen, in denen das Zentralatom E an zwei Kohlenstoff- und zwei Stickstoffatome gebunden ist. 3 weist eine annähernd tetraedrische Geometrie auf [Winkel am Siim Bereich (105,5⃛111,9)°], 4 hingegen eine stark verzerrte Tetraedergeometrie [CSnC 128,8°; NSnN 107,8°; NSnC im Bereich (99,9⃛109,4)°]. Eine Betrachtung der Molekülstrukturen legt nahe, daß in beiden Fällen je zwei intramolekulare (E⃛O)-Wechselwirkungen vom Dipol-Dipol-Typ die Stereochemie beeinflussen [Si⃛O 291,4 pm (2x) Sn⃛O 300,9 und 303,1 pm]. Das Molekül von 3 besitzt eine strenge, das von 4 eine annähernde zweizählige Symmetrie.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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