Untersuchungen an Stickstoff-Chlor-Verbindungen. VIII. N-Perchlorylverbindungen mit aromatischem System im organischen Rest

Studies on Nitrogen Chlorine Compounds. VIII. N-Perchloryl Compounds Containing an Aromatic System in the Organic Rest To the class of N-perchloryl compounds could be added two new compounds which are the first to contain one or two aromatic systems respectively in the organic rest. One of these compounds contains an acidic hydrogen atom that could be replaced by metal cations. The compounds were characterized as far as possible by analysis, IR and ¹H-NMR spectroscopy.     

Untersuchungen an Stickstoff-Chlor-Verbindungen. X. N-Perchlorylaziridin,N-Perchlorylazetidin und N-Adamantylperchlorsäureamid durch Aminolyse von Dichlorheptoxid

Studies on Nitrogen Chlorine Compounds. X. N-Perchlorylaziridine, N-Perchlorylazetidine, and N-Adamantylperchloric Acid Amide by Aminolysis of Dichlorine Heptoxide By aminolysis of dichlorine heptoxide with aziridine (ethyleneimine), azetidine (trimethyleneimine), and adamantylamine (tricyclo(3.3.1.1.^3,7)decane-1-amine) could be prepared three new N-perchloryl compounds. Furthermore several salts of N-adamantylperchloric acid amide were prepared. The compounds were characterized by i.r. and ¹H-n.m.r. spectroscopy and by analysis.     

Darstellung und Struktur von α-CrPO4. Beiträge zum thermischen Verhalten von wasserfreien Phosphaten. I

Contributions on the Thermal Behaviour of Anhydrous Phosphates. I. Preparation and Structure of α-CrPO₄ By a chemical transport reaction (1100°C → 1000°C) using chlorine as transporting agent we obtained dark-green, well shaped crystals of α-CrPO₄. The compound crystallizes in the space group Imma. The lattice constants are a = 10.403(2), b = 12.898(2), c = 6.299(1) Å. The crystal structure has been determinated from single crystal data and refined to a conventional residual of R = 0.038 (1481 unique reflections, 34 variables). The structure consists of CrO₆-octahedra and PO₄-tetrahedra. Especially remarkable are pairs of edge sharing CrO₆-octahedra which are connected with two PO₄-tetrahedra at opposite edges. Parallel to the a- and b-axis are large channels extending through the whole structure.     

Reaktion von Diphosphan(4) mit flüssigem Ammoniak und mit Aminen – ein neuer Weg zu Polyphosphiden und Hydrogenpolyphosphiden

Contributions to the Chemistry of Phosphorus. 241. On the Reaction of Diphosphane(4) with Liquid Ammonia and with Amines – a New Route to Polyphosphides and Hydrogen Polyphosphides Diphosphane(4), P₂H₄, reacts with liquid ammonia in the temperature range –76 °C to –40 °C to furnish a mixture of the ammonium polyphosphides (NH₄)₂H₂P₁₄, (NH₄)₂P₁₆, (NH₄)₃P₁₉, and (NH₄)₃P₂₁, in addition to PH₃. The first intermediate product detectable by NMR spectroscopy is the bicyclic compound NH₄H₄P₇, which reacts further with P₂H₄ to afford the more phosphorus‐rich polycyclic phosphides. On removal of the ammonia the hydrogen polyphosphide (NH₄)₂H₂P₁₄ decomposes with formation of PH₃ and hydrogen‐free, more phosphorus‐rich polyphosphides. When the reaction of diphosphane(4) with liquid ammonia is performed in the presence of tetrahydrofuran the final products are the hydrogen polyphosphides NH₄H₄P₇ and NH₄H₅P₈ together with PH₃; the hydrogen‐rich, open‐chain heptaphosphide NH₄H₈P₇ has been identified as a precursor. An investigation of the behavior of diphosphane(4) towards amines using the primary amine ethylenediamine as an example at +10 °C in the absence of a solvent or in the presence of tetrahydrofuran resulted in the formation of a polyphosphide mixture consisting of (C₂H₄N₂H₅)₂P₁₆, (C₂H₄N₂H₅)₃P₂₁, and (C₂H₄N₂H₅)₃P₁₉ as well as some PH₃. No reaction occurred with the secondary and tertiary amines diethylamine and tetramethylethylenediamine (TMEDA), respectively, even at room temperature.     

Lithiierte Siloxy-silylamino-silane – Darstellung und Reaktionen mit Chlordimethylsilan

Lithiated Siloxy-silylamino-silanes — Preparation and Reactions with Chlorodimethylsilane The siloxy-silylamino-silanes (Me₃SiO)Me_3–nSi(NHSiMe₃)_n ( 1 : n = 1, 2 : n = 2, 3 : n = 3) are obtained by coammonolysis of the chlorosiloxysilanes (Me₃SiO)Me_3–nSiCl_n (n = 1–3) with chlorotrimethylsilane. The reaction of 1, 2 , and 3 with n-butyllithium in appropriate molar ratio in n-hexane gives the siloxy-silylamido-silanes (Me₃SiO)Me_3–nSi(NLiSiMe₃)_n ( 4 : n = 1, 5 : n = 2, 6 : n = 3), which were spectroscopically characterized (IR, ¹H-, ⁷Li-, ²⁹Si-NMR) and allowed to react in solution (n-hexane, THF) with Me₂Si(H)Cl. 4 reacts to the N-substitution product (Me₃SiO)Me₂SiN(SiMe₃)SiMe₂H 7, 5 to (Me₃SiO)MeSi[N(SiMe₃)SiMe₂H](NHSiMe₃) 8 , (Me₃SiO)MeSi[N(SiMe₃)SiMe₂H]₂ 9 and to the cyclodisilazane 10. 6 gives in THF the cyclodisilazanes 11 : R = H; 12 : R = HMe₂Si) and ( 13 , in n-hexane only 11 in small amounts. An amide solution of 2 with n-butyllithium in the molar ratio 1:1 in n-hexane leads to 8 (main product), 2 and 10; in THF 10 and 2 are obtained nearly in same amounts and 8 and 9 as byproducts. The amide solutions of 3 with n-butyllithium in the molar ratio 1:1 and 1:2, resp., show nearly the same behaviour in n-hexane and THF. In THF 3, 11 , and 12 and in n-hexane 3, 11, 12 , and (Me₃SiO)Si[N(SiMe₃)SiMe₂H](NHSiMe₃)₂ 14 are formed.     

Untersuchungen an Stickstoff-Chlor-Verbindungen. VII. Neue N-Perchlorylverbindungen durch Ammono- und Aminolyse von Dichlorheptoxid

Studies on Nitrogen Chlorine Compounds. VII. New N-Perchloryl Compounds by Ammono- and Aminolysis of Dichlorine Heptoxide The reaction of dichlorine heptoxide with ammonia, primary and secondary amines leads to compounds belonging to the class of amides of perchloric acid. The remaining acidic hydrogen atoms on nitrogen could be replaced by metal cations. The compounds were characterized as far as possible by analysis, IR and ¹H-NMR spectroscopy. The changing of the bond character between nitrogen and chlorine depending on the substituents on nitrogen is discussed.     

Koordinationschemische Untersuchungen an Zinkdialkylen. X. Über die Reaktion von Zinkdimethyl mit sekundären Aminen

Dimethyl zinc reacts with diethyl amine, piperidine and morpholine forming definite 1:2- or 1:1-complexes. The weaker basic secondary amines pyrroline, pyrazolidine and imidazoline cause the evolution of methane and the formation of the corresponding zinc amides. In this way zinc pyrrolide, zinc pyrazolide and zinc imidazolide were obtained in form of pure substances.     

Untersuchungen an Stickstoff-Chlor-Verbindungen. IX. N,N′-Diperchlorylverbindungen durch Aminolyse von Dichlorheptoxid mit Diaminen

Studies on Nitrogen Chlorine Compounds. IX. N,N′-Diperchloryl Compounds by Aminolysis of Dichlorine Heptoxide with Diamines By aminolysis of dichlorine heptoxide with N,N′-disubstitutet diamines could be prepared three new compounds which contain each two perchloryl groups in the molecule. The compounds were characterized by IR and ¹H-NMR spectroscopy and partially by analysis.     

Darstellung und Untersuchung von Phosphinkomplexen mit Aluminiumtrichlorid und Aluminiumtriäthyl

Synthesis and Investigation of Complexes of Phosphines with AlCl₃ and AlEt₃ (t.-Bu)₃P and (Me₃Si)₃P form similar adducts with AlCl₃ and AlEt₃ (t.-Bu = ? C(CH₃), Me = ? CH₃, Et = ? C₂H₅). Analogous compounds are formed by reaction of (t.-Bu)₂PSiMe₃ with AlCl₃ and AlEt₃, and of (Me₃Ge)₃P and (Me₃Sn)₃ with AlEt₃. The i.r., Raman, ¹H-n.m.r. and ³¹P-n.m.r. spectroscopic data are reported and discussed.     

Darstellung und Charakterisierung von Chloroligosilanen mit mittelständigem Wasserstoff

Preparation and Characterization of Chloroligosilanes with Internal Hydrogen . Unbranched chlorinated tri-, tetra-, and pentasilanes with internal hydrogen substituent are synthesized from the corresponding phenylsilanes by cleaving off the phenyl groups with HCl/AlCl₃ and characterized by spectroscopy. Coupling of phenylsilylpotassium compounds, isolated from their mercury analogs, was used to prepare the phenylsilanes.     

Cyanohydrazonothioformiate – Darstellung und Reaktionen

Cyanohydrazonothioformate — Preparation and Reactions Sodiumcyanohydrazonothioformate-monohydrate NaSC(CN)NNH₂ · H₂O is obtained by reaction of sodiumcyanodithioformate with hydrazine. The new compound forms S-organosubstituted derivatives. Reaction with bivalent metal cations lead to coordination compounds M^II(SC(CN)NNH₂)₂ · 2H₂O, which subjected the facile reaction with carbonyl compounds yield alkylidenehydrazonocyanothioformates M^II(SC(CN)NNCRR¹)₂. The results of i.r. spectroscopic and thermogravimetric measurements are reported.     

Aminocarbonylthioformiate – Darstellung und Reaktionen

Aminocarbonylthioformates — Preparation and Reactivity Sodium aminocarbonylthioformate NaSCOCONH₂ (II) is obtained by reaction of sodium cyanodithioformate with acetone in presence of a secondary amine and water. II permits to produce the acid HSCOCONH₂ · H₂O (IX) and salts M^II(SCOCONH₂)₂ · 2H₂O. In basic aqueous solutions hydrolysis of II to oxaminate and oxalate, respectively, takes place, an excess of aqueous ammonia leads to amidino formic acid. In organic solvents the reaction of IX with N-bases yields stable ammonium salts. The results of i.r. spectroscopic and thermogravimetric measurements are discussed.     

Koordinationschemische Untersuchungen an Zinkdialkylen. XVI. Darstellung und Untersuchung von Dinorbornylzink-Verbindungen

Investigations on the Coordination Chemistry of Zinc Dialkyls. XVI. Synthesis and Investigation of Dinorbornyl Zinc Compounds Bis(1-norbornyl)-, bis(2-norbornyl)-, and bis(7-norbornyl)zinc were synthesized from zink chloride and the corresponding Grignard compounds or norbornyl lithium compounds, respectively. The properties of these compounds differ remarkably. A detailed characterization took place by the mass, IR and ¹³C-NMR spectra and by investigation of the thermal decomposition and complex formation reactions. For comparison the bis(7-norbornenyl)zinc was prepared and characterized.     

Komplexe mit aromatischen Carbonsäuren. I Darstellung und Struktur von Zinkpyromellitat-Heptahydrat

Complexes with Aromatic Carboxylic Acids. I. Synthesis and Crystal Structure of Zinc Pyromellitate Heptahydrate The crystal structure of zinc pyromellitate heptahydrate comprises features of ion exchangers, layer-like, and zeolitic structures. Single crystals of this compound were obtained by crystallization in aqueous silicagel. According to the structural properties Zn(H₂O)₅[ZnC₆H₂(COO)₄]·2H₂O is an appropriate formula. Zn(1) is coordinated tetrahedrally by four oxygen atoms of the carboxylate groups. Thus forming folded [ZnC₆H₂(COO)₄] layers to which Zn(2) is bound by only one carboxylate oxygen atom. The coordination sphere of Zn(2) is completed by five water molecules to yield a slightly distorted octahedron. Additional water is accomodated between the layers. The [ZnC₆H₂(COO)₄] layers possess channel-like cavities extending along [100] which are filled by water molecules. Hydrogen bonding is an important feature of this crystal structure.     

Darstellung und Kristallstruktur von PI4+ AlI4−

Preparation and Crystal Structure of PI₄⁺AlI₄^? PI₄⁺AlI₄^? was prepared and its crystal structure determined by single crystal X-ray data (orthorhombic, Pna2₁, a = 1109.4, b = 1048.5, c = 1529.3 pm, V = 1778.8 · 10⁶ pm³, Z = 4). The nearly tetrahedral cations and anions (mean P? I and Al? I distances: 239.6 and 251.8 pm respectively) are connected to a three-dimensional structure by weak iodine-iodine bonds (338.6–345.1 pm).     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. XXV. Reaktion der Trialkoxysilanthiole mit aromatischen Aminen und Darstellung von N-(Trialkoxysilyl)arylaminen

Contributions to the Chemistry of Silicon-Sulphur Compounds. XXV. Reaction of Trialkoxysilanethiols with Aromatic Amines and Preparation of N-(Trialkoxysilyl)arylamines Pyridine and imidazole catalyze the reaction of trialkoxysilanethiols with substituted anilines. This procedure affords a convenient method for the synthesis of N-(trialkoxysilyl)-aryl-amines. Kinetics of the reaction were investigated and rate constants and activation parameters evaluated. Relationships between the structure of amines and their reactivity were discussed. The mechanism of the reaction is discussed.