Organische Phosphorverbindungen XXII. Darstellung und Eigenschaften von diprimären α,ω-Bis-phosphino-alkanen

The preparation and properties of diprimary α,ω-bis-phosphino-alkanes of the general structure H₂P(CH₂)_n PH₂ (n = 1, 2, 3, 4) are described. Their reactions with N-hydroxymethyl-dialkylamines and with olefins, which yield ditertiary α,ω-bisphosphino-alkanes, (R₂NCH₂)₂P(CH₂)_nP(CH₂NR₂)₂ and R₂P(CH₂)_nPR₂, respectively, are also reported. The physical properties of two new α,ω-bis-dialkylphosphinyl-alkanes have been determined.     

Organische Phosphorverbindungen 44 Darstellung und Eigenschaften von Bis-(ß-chloräthyl)-phosphinsäure-Derivaten [1]

Reaction of ClCH₂CH₂PCl₂ with ethylene oxide gives the phosphonous acid ester ClCH₂CH₂P (OCH₂CH₂Cl)₂ which on heating to 120° rearranges to the phosphinic acid ester (ClCH₂CH₂)₂P(O)OCH₂CH₂Cl ( 3 ). Chlorination of 3 with PCl₅ in CCl₄-solution yields the phosphinic chloride (ClCH₂CH₂)P(O)Cl ( 4 ), which on treatment with P₂S₅ at 170° produces the thioderivative, (ClCH₂CH₂)₂P(S)Cl, (₅). Treatment of 4 and 5 with alcohols, mercaptanes, or amines in the presence of an acid binding agent leads to the corresponding phosphinic and thiophosphinic acid derivatives, (ClCH₂CH₂) P (X)Y, (X = O, S; Y = OR, SR, NR₂) ( 6 ). Reaction of 6 with excess base yields the corresponding divinylphosphinic and divinylthiophosphinic acid derivatives (CH₂ = CH)₂P (X) Y (X = O, S; Y = OR, SR, NR₂) ( 7 ). Bis-(ß-chloroethyl)-phosphinates, e. g. (ClCH₂CH₂)₂P (O) OEt, undergo a Michaelis-Arbuzov reaction when heated with phosphites to 160–170° to give bis-(phosphonylethyl)-phosphinates, e.g. (EtO) (O)P[CH₂CH₂CH₂P(O)(OEt)₂]₂ ( 8 ), which on hydrolysis with conc. HCl under reflux yield the corresponding acid HO₂P(CH₂CH₂PO₃H₂)₂.     

Organische Phosphorverbindungen XXIV Darstellung und Struktur von ketten- und ringförmigen Polyphosphinen

The new triphosphine CH₃P[P(C₆H₅)₂]₂, m. p. 130–134º, has been prepared in high yield by the interaction of (C₆H₅)₂PH and CH₃P[N(CH₃)₂]₂. This triphosphine is cleaved by CH₃J and Br₂. With sulfur it yields an adduct of the probable structure CH₃P[P(S)(C₆H₅)₂]₂, m. p. 163,5–166º.     

Organische Phosphorverbindungen 41. Synthese und Eigenschaften von Polyphosphinaten und Polyphosphinsäuren [1]

A process for the preparation of alkyl chloromethylphosphonites, ClCH₂P(OR)₂ (R = Et, Bu), diethyl β-chloroethylphosphonite, ClCH₂CH₂P(OEt)₂, and their conversion to polyphosphinates with the back-bone structures ? [? CH₂PO₂R? ]? _x and ? [? CH₂CH₂P(O₂R)? ]? _x, respectively, by an Arbuzov type reaction is described. Hydrolysis to the corresponding polyphosphinic acids is effected by refluxing the esters with conc. HCl for extended periods. The polyphosphinic acid with structure V is an excellent chelating agent for Ca ions.     

Organische Phosphorverbindungen XXVIII. Die α-Aminoalkylierung von elementarem weissem Phosphor. Eine einfache Methode zur Darstellung von tertiären Phosphinoxiden,Phosphinsäuren und Phosphonsäuren [1]

White phosphorus reacts with N-hydroxymethyl-dialkylamines to give mainly three products, i.e., tris(dialkylaminomethyl) phosphine oxides, bis(dialkylamino-methyl) phosphinic acids, and dialkylaminomethyl phosphonic acids, according to the equation: The yield of the various products depends mainly upon the ratio of the reactants, the pH, and the solvents used.     

Darstellung und Eigenschaften von Chlorozinksäuren

Contributions to the Chemistry of Hydrazine and its Derivatives. 53. Synthesis of P-, As-, and Sb-substituted Hydrazines by Addition of P? H, As? H, and Sb? H Groups to N?N Double Bonds Addition of diphenylphosphinous acid, diphenylthiophosphinous acid, methyl hydrogen phenylphosphonite, diethyl hydrogen phosphite, diphenylphosphane, dibutylphosphane, diphenylarsane, diethylarsane, and diphenylstibane to the N?N double bond of diethyl azodicarboxylate, dimethyl azodicarboxylate, ethyl phenylazocarboxylate, and azobenzene yields the P-, As-, and Sb- substituted hydrazines 1–23 . The spectroscopic data agree with the structural formulae. The course of the reactions suggests a polar reaction mechanism except in the case of the synthesis of 15 , which probably proceeds via radical intermediates. The azo systems employed show a distinct graduation in their ability to add to the element-hydrogen groups used.     

Phosphinsubstituierte Chelatliganden. XVIII. Penta- und Tetracarbonylmetall-Komplexe des Chroms,Molybdäns und Wolframs mit sekundären und tertiären Phosphinothioformamid-Liganden

Phosphine Substituted Chelate Ligands. XVIII. Penta- and Tetracarbonylmetal Complexes of Chromium, Molybdenum, and Tungsten with Secondary and Tertiary Phosphinothioformamide Ligands Mono- and bidentately coordinated phosphinothioformamide complexes are obtained by photochemical substitution of the metal hexacarbonyls M(CO)₆ (M ? Cr ( a ), Mo ( b ), W ( c )). The M(CO)₅ · THF adducts react with secondary thioamides under exclusion of light to give the P-coordinate pentacarbonyl complexes [(CO)₅MPPh₂C(S)NHR¹] (R¹ ? Ph ( 1a – c ), Me ( 2a )). The photoreaction of M(CO)₅ · THF with secondary and tertiary thioamides at low temperatures leads to the formation of the P, S-chelate complexes . The corresponding N-silylated complexes 6a – c (R¹ ? Me₃Si, R² ? Ph) are obtained by direct photosubstitution of M(CO)₆ in cyclohexane solution. The labile bis(thioformamide) complexes [(CO)₄M(PPh₂C(S)NHMe)₂] ( 7a – c , cis-trans isomers) are synthesized in low yields according to the same procedure. The attempted alkylation of the chelate complexes 3a – c remains unsuccessful, whereas the secondary thioformamides react with n-BuLi/CH₂Br₂ to give the methylene bis(thioformirnidoesters) [Ph₂PC(NR¹)S]₂CH₂ (R¹ ? Ph (8), Me ( 9 )) in quantitative yields.     

Massenspektren von sekundären Vinylcarbinolen

The mass spectra of secondary vinylcarbinols of the structure R? CH(OH)? CH?CH₂ show the same fragments as those of the isomeric ethylketones R? CO? C₂H₅. This is the result of a rearrangement of the molecular ions of the vinylcarbinols to molecular ions of the ethylketones before fragmentation occurs. Compounds of the two classes differ only slightly from one another in the intensity values.     

Darstellung,Kristallstruktur und Eigenschaften von Cäsiumozonid

Synthesis, Crystal Structure and Properties of Cesium Ozonide By reaction between CsO₂ and mixtures of O₂ and O₃ in the temperature range from 25°C to ?70°C and subsequent extraction with liquid ammonia pure CsO₃ was obtained in grammeamounts. By X-ray powder and thermal techniques a reversible, structural phase transition was detected at +8°C, and decomposition into CsO₂ and O₂ at +53°C. The low-temperature form (T? CsO₃) is isostructural to RbO₃ (P2₁/c; a = 675.1(2), c = 901.5(3) pm, β = 120.74(3)°l Z = 4), the crystal structure of H? CsO₃, which shows orientational disorder with respect to the ozonide ion, corresponds to the CsCl-type of structure (a = 436.06(3) pm). Using the geometry as determined for KO₃ and RbO₃, and the vibrational frequencies of different isotopomeres, the force constants of O₃^? have been redetermined.     

Darstellung und Eigenschaften von Carbonylisocyanat

Zusammenfassung Es wird über die erstmalige Darstellung von Carbonylisocyanat, CO(NCO)₂, durch thermische Zersetzung von Trichlorisocyanursäure berichtet; einige physikalische Eigenschaften der neuen Verbindung werden mitgeteilt. Ihre Reaktionen mit Alkali, Wasser, Ammoniak und Äthanol wurden untersucht. Durch Reaktion mit Wasser im Verhältnis 1: 1 wurde 2,4,6-Trioxo-tetrahydro-1,3,5-oxadiazin bzw. Carbonyldicarbamidsäureanhydrid als neue Verbindung erhalten.

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Carbonyl isocyanate has been prepared the first time by thermolysis of trichlorisocyanuric acid and some of its physical properties have been determined. Its reactions with alkali, water, ammonia and ethanol have been investigated. By reaction with equimolar amounts of water the novel compound 2,4,6-trioxotetrahydro 1,3,5-oxadiazine (carbonyl-dicarbamic acid anhydride) was obtained.

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Auszugsweise vorgetragen auf der Vortragstagung des VOeCh. am 28. 9. 1965 in Graz.     

Darstellung und Eigenschaften von Trifluormethylmercaptothiophosphoryldichlorid

Preparation and Properties of Trifluoromethylmercaptothiophosphoryldichloride The reaction of CF₃SP(O)Cl₂ with SPCl₃ leads to a CF₃S-chlorine exchange and gives CF₃SP(S)Cl₂ in 50% yield. A controlled hydrolysis of CF₃SP(O)Cl₂ affords CF₃SP(O)(OH)₂, that cannot be isolated as such, but it condenses to CF₃SP(O)(OH)O? [P(SCF₃)(O)? O]_nP(O)(OH)SCF₃. On the other hand, CF₃SP(S)Cl₂ reacts with water to yield H₃PO₄, CF₃SH, S₈, and HCl. CF₃SP(X)Cl₂ reacts with alcohols to give CF₃SP(X)(OR)₂ [R = CH₃, C₂H₅, n-C₃H₇, CH(CH₃)₂, n-C₄H₉ and for X = O, R = C₆H₅, too]. The formation of semi-esters CF₃SP(X)Cl(OR′) could be proven for X = O, R′ = CH₃, C₆H₅ and for X = S, R′ = R. While CF₃SP(O)(OC₂H₅)₂ rapidly decomposes into SCF₂ and FP(O)(OC₂H₅)₂, the other compounds and primarily CF₃SP(O)(OCH₃)₂ and CF₃SP(S)(OR)₂ ar stable. The reaction between CF₃SCl and CH₃SPCl₂ results in CF₃SCH₂SPCl₂ and that between CF₃SP(O)Cl₂ and AlCl₃ gives [CF₃SP(O)Cl]⁺[AlCl₄]^?. Physical and spectroscopical data are given for the newly formed compounds.     

Darstellung und Eigenschaften von Phenyljodcyclopentasilanen

Zusammenfassung Dekaphenylcyclopentasilan reagiert mit wasserfreiem HJ im Bombenrohr unter Benzolabspaltung zu Phenyljodcyclopentasilanen. Der Grad der Phenylabspaltung hängt von der Reaktionszeit ab. Reaktion mit Methanol führt zu entsprechenden Methoxyphenylcyclopentasilanen.Die Hydrolyse ergibt gelbe, fluoreszierende, polymere Hydrolysenprodukte, in denen Si₅-Ringe über Sauerstoff verknüpft sind. Die Farbe der Hydrolysenprodukte wird im Zusammenhang mit den Ergebnissen der Siloxenchemie diskutiert.

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Synthesis and properties of phenyliodocyclopentasilanes

Decaphenylcyclopentasilane reacts with anhydrous HJ in a sealed tube to give phenyliodocyclopentasilanes and benzene, and the degree of phenyl cleavage was found to depend on the reaction time. The corresponding methoxyphenylcyclosilanes are obtained in the reaction with methanol. Hydrolysis yields a yellow, fluorescent, polymeric compound containing Si₅-rings coupled by oxygen. The colour of the hydrolysis products is discussed in connection with pertinent results in siloxene chemistry.