Cycloadditionsreaktionen der aminofluorsilane

Aminofluorsilanes are obtained by the reaction of fluorosilanes with the lithium salts of the corresponding amines. The reaction of aminofluorosilanes with butyllithium in a (2 + 2)cyclo addition reaction leads to the formation of fourmembered silicon-nitrogen ring compounds. The mechanism of the reaction is discussed, the mass, ¹H and ¹⁹F NMR spectra of the compounds are reported.     

Beitrag zum problem der bandenverschiebung in den i.r.-spektren von dialkyldithiocarbamidaten : Teil III. Pyrroldithiocarboxylate. der bereich von 4000–300 cm-1

An i.r. spectrometric study of specially prepared pyrroledithiocarboxylates is described. These compounds were selected as being very similar in mass and structure to the previously studied tetramethylenedithiocarbamates (TMDTC) except for the presence of a single C-N bond. The i.r. spectra of the new compounds show very intense bands in the region of 1300 cm^-1, which can be ascribed to the C-N bond. The corresponding bands in the spectra of the TMDTC compounds are shifted by ca. 150 cm^-1 to higher wavenumbers. hence it seems correct to suggest that the C-N bond in such compounds has the character of a partial double bond.     

Vergleichende Betrachtung der bisher bekannten cis-Dihydrogenchalkogenido-Komplexe der d8-Metalle

Comparision of the Hitherto Known cis-Dihydrogenchalcogenido Complexes of d⁸ Metals Phosphine-coordinated d⁸ metal dichlorides react in different ways with hydrogen-sulfide, sodium hydrogensulfide and sodium hydrogenselenide respectively. The phosphine ligand and the YH-providing reactand cut a great figure to get the monomere products. Some reactions of the dihydrogenchalcogenido platinum(II) compounds with sodium ethanolat and elemental sulfur respectively are investigated. I.r. and ¹H-n.m.r. spectra are reported.     

Intramolekulare Cycloadditionen in der Reihe der Binaphthyle

Intramolecular cyloadditions of binaphtyl compounds Three new bridged ketones, 7,8 and 9 , have been isolated in 44%, 3% and 19% yields respectively (Scheme 2) by heating 2,2′-bis-allyloxy-1,1′-binaphthyl ( 5 ) at 215° for 16 hours. These compounds could be epimerized about C(16) by bases, and in particular 9 yielded the new epimer 10 . The structures of the alcohols obtained by reduction of the keto group are also given (Scheme 2). The constitution of all compounds was derived from spectroscopic data, chiefly from their ¹H-NMR, spectra (tab. 2, 3 and fig. 1). The assignments were based on the observed long-range coupling constant between H(endo)-C(16) and H(endo)-C(5) in 7 and 10 and on the analysis of chemical shifts and coupling constants in both the ketones and their derivatives. Moreover, the structures of the compounds investigated have been proved by x-ray analysis of ketone 8 (chap. 3, fig. 2). The thermal conversion of binaphthylether 5 to the bridged ketones proceeds via an intramolecular Diels-Alder reaction, followed by Claisen rearrangement (Scheme 8). On heating, the bis-beta-methylallyl ether 20 yielded the ketone 21 and a small amount of the ether 23 (Schemes 5 and 7). Ether 23 and binaphthyl monoallyl ether 26 were converted thermally to the bridged ketones 31 (Scheme 7) and 27 (Scheme 6) respectively. In addition, 26 underwent an intramolecular ene-reaction to give the spiroketone 28 (Schemes 6 and 9). The structures of these compounds were also established, mainly by analysis of their ¹H-NMR. spectra.     

13C-NMR.-Spektren N-acylierter Indoline. Einfluss der Orientierung der Carbonylgruppe auf die chemische Verschiebung

¹³C-NMR. spectra of N-acylated indolines. Effect of the orientation of the carbonyl group on the chemical shift Large downfield shifts are observed in the ¹³C-NMR. spectra of indolines and related compounds induced by electric field effects of carbonyl and oxime groups.     

N-Alkyl-5,5-diorganodiptychoxazstannolidone,intramolekular pentakoordinierte stannylester der N-methylminodiessigsäure

The reaction of dialkyltin oxides or dialkyltin dialkoxides with N-methyliminodiacetic acid in dimethylformamide/toluene gives the title compounds in 80–90% yields. The structure of these compounds was investigated by NMR, IR and mass spectroscopy. The temperature dependent ¹H and ¹³C NMR spectra are interpreted by a dissociation—inversion mechanism.     

Metallorganische verbindungen der lanthanoiden: XX. Cyclopentadienyllutetiumderivate von triphenylmethylenphosphoran

Tricyclopentadienyllutetium tetrahydrofuranate reacts with triphenylmethylenephosphorane with the formation of tricyclopentadienyllutetium triphenylmethylenephosphorane. A lutetium-containing metallacycle, 1,1-diphenyl-3,3-dicyclopentadienyl-1-phospha-3-luteto-indane, is formed by the decomposition of dicyclopentadienyl(methyl)lutetium triphenylmethylenephosphorane, by the reaction of dicyclopentadienylchlorolutetium triphenylmethylenephosphorane with sodium hydride or by the reaction of dicyclopentadienyllutetium chloride with lithium triphenylphosphonium methylide, respectively. The ¹H and ¹³C NMR spectra of the new compounds are discussed.     

Aufkl?rung der 1H- und 13C-NMR-spektren sowie der kristallstruktur unges?ttigter glycosylphosphonate und konformationsberechnungen an modellen1

By application of a modified LAOCN-3 program a complete elucidation of the ¹H NMR spectra of 2,3-unsaturated glycosyl phosphonates 1–5 could be achieved. The exactly determined ⁿJ(H, H) and novel ⁿJ(C, P) coupling constants are discussed, and permit a conclusive deduction of the conformations. The ¹³C NMR spectra of 1 to 6 can be fully interpreted. By a close inspection of chemical shifts as well as ¹J(C-H) and ⁿJ(C, P) coupling constants the conformational assignment is supported. For all the derivatives the correlations ¹J(C-1,H_e)>¹J(C-1, H_a) and ¹J(C-1, P_e) >¹J(C-1, P_a) can be used for the assignment of anomers. The crystal structure of 1 is in accordance with this assignment of anomers and displays an unexpected conformation. Calculations by MINDO-3 in resembling model compounds serve to elucidate such conformative effects.     

Synthese und Struktur der Stannatrane

Synthesis and Structure of Stannatranes The reactions of stannonic acids, (RSn(O)OH)_n or diorganotinoxides, (R₂SnO)_n with triethanolamines yields stannatranes (I) in a simple manner. The structure of these compounds in verified by measurements of dipole-moment and ¹H-n.m.r. spectra.     

Austauschreaktionen an komplexgebundenen liganden von elementen der IV. Hauptgruppe : II. Aminolyse von cyclopentadienyl-dicarbonyl-trichlorsilyl-eisen

The ¹H and ¹³C NMR spectra of the following six compounds have been examined over a wide range of temperatures: four derivatives of 3,5-dimethylpyrazole substituted at the nitrogen atom by organometallic groups such as Si(CH₃)₃ (I), Si(C₂H₅)₃ (II), Si(OC₂H₅)₃ (III), Ge(CH₃)₃ (IV), 3,5-dimethyl-1-trimethylsilyl-1,2,4-triazole (V) and 1-trimethylsilylimidazole (VI). Activation energies of the metal migration have been found for the compounds (I–V) by the total NMR line-shape analysis. Proton and carbon spectra of the compound (VI) show equivalence of the positions 4 and 5 in the imidazole ring. No temperature-dependent changes in the spectra were observed at –80 to +80°. These facts may be interpreted by assuming that the organometallic group undergoes an intermolecular exchange.     

Darstellung und Charakterisierung der Trisilylphosphane (Ph 3Si) n P(SiMe 3)3−n,n=1,2,3

A simple preparation of the title compounds is achieved by reacting Na₃P/K₃P with stoichiometric mixtures of chlorotriphenylsilane and chlorotrimethylsilane.³¹P- and²⁹Si-NMR-Data as well as Ir and Raman spectra of the compounds are reported.

     

Synthese und Struktur der Diptychoxazstannolidine und Diptychthiazstannolidine

Synthesis and Structure of Diptychoxazstannolidines and Diptychthiazstannolidines The reactions of diorganotinhalides, oxides and alkoxides with diethanolamines or diethanthiolamines yields diptychoxazstannolidines (I) and diptychthiazstannolidines (II). The structure of these compounds is verified by dipolemoment measurements and ¹H n.m.r. spectra.     

N-Methyl-N-diäthoxyphosphorylamido-Derivate des Hexachlorocyclotriphosphazatriens. IV. NMR-spektroskopische Untersuchungen zur Konstitution der Ammonolyseprodukte von N-Methyl-N-diäthoxyphosphorylamido-chloro-cyclotriphosphazatrienen

N-Methyl-N-Diethoxyphosphorylamido Derivatives of Hexachlorocyclotriphosphazatriens. IV N.M.R. Spectroscopic Investigations of the Products of the Ammonolysis of N-methyl-N-diethoxyphosphorylamindo-chloro-cyclotriphosphazatrienes Broad band ¹H decoupled ³¹P n.m.r. spectra of products obtained by ammonolysis of N-methyl-N-diethoxyphosphorylamido-chloro-cyclotriphosphazatrienes provide essential hints at the constitution of these compounds. In this connection it may be easily demonstrated, both amino groups of N₃P₃Cl₃[NCH₃P(O)(OC₂H₅)₂][NH₂]₂ as well as of N₃P₃Cl₂[NCH₃P(O)(OC₂H₅)₂]₂ [NH₂]₂ are arranged geminally. The spectral parameters were found and verified by simulation of spectra. The simulated ³¹P spectra agree closely with the observed ones. The conclusions from the ³¹P n.m.r. spectra are complemented by these from the ¹H n.m.r. spectra.     

Zur Kenntnis der Strontiumpolysulfide Präparative,röntgenographische und schwingungsspektroskopische Untersuchungen

X-ray, I.R., and Raman Data of Strontium Polysulfides The strontium polysulfides SrS₂, SrS₃A, and SrS₃B were studied in terms of preparation, thermal decomposition, and phase transition. The i.r. and Raman spectra of the strontium polysulfides as well as the normal coordinates of the phonon modes are presented and discussed in comparison with the respective barium compounds. From the spectra it is shown that S₃^2? entities are present in SrS₃A as in SrS₃B.     

Vier- und achtgliedrige metallhaltige Bor–Stickstoff-Heterocyclen. Bildung und Strukturen in Abhängigkeit von der Raumerfüllung der Substituenten

Four and Eight Membered Metal Containing Boron–Nitrogen-Heterocycles. Formation and Structures in Dependence on the Steric Requirement of their Substituents TripB(NRLi)₂ (Trip = 2,4,6-triisopropylphenyl, R = Me ( II a ), CH₂Me ( II b ), CHMe₂ ( II c ), CMe₃ ( II d ) reacts with dibromo(dimethyl)tin to give eight membered ( III a , III b ) and four membered metallacycles ( IV c and IV d ). If tetrahalides (GeCl₄, SnCl₄) are the reaction partners, the spiro compounds V c and VI d are obtained from II c and II d resp. The compounds are characterized by their m.s. and n.m.r. (¹H, ¹¹B, ¹³C, ¹⁹F, ¹¹⁹Sn) spectra and by elemental analyses. An X-ray structure analysis was performed for III a .     

A 13C-NMR. Study of cis-trans isomeric vitamins A, carotenoids and related compounds.

The ¹H-decoupled ¹³C-NMR. spectra of 35 all-trans, 17 mono-cis vitamin A compounds (acetates, alcohols, aldehydes, acids and esters) and of one 11, 13-di-cis compound (11, 13-di-cis retinol) are reported. Included in this investigation are desmethyl-, desmethylethyl, and aryl-vitamin A analogues and others as well as 30 reference compounds of smaller molecular weight. Furthermore, the ¹³C-NMR. spectra of 23 β-apo- and other carotenoids were studied. A complete assignment of the signals of all 106 compounds to the specific carbon atoms was achieved by extensive application of lanthanide shift reagents, mainly Yb(dpm)₃, by CW-offset and selective ¹H-decoupling experiments, by comparison of the shifts of related compounds, and in three cases by utilization of specifically deuteriated compounds (11, 12-D₂-retinol and retinyl acetate, 15, 15′-D₂-β-carotene). The chemical shift differences between the cis- and trans-vitamin A compounds and the applicability of the shift reagents for the assignment of the ¹³C-NMR. spectra are discussed.     

Beitrag zur Aufklärung der Beziehungen zwischen der Zusammensetzung,der Struktur und den Redox-Veränderungen der Komplexverbindungen von CuCl2 mit aliphatischen Aminen als Liganden

Contribution to the Study of the Correlations between Composition, Structure, and Redox Changes of Complex Compounds of CuCl₂ with Aliphatic Amines as Ligands Complex compounds of the composition CuCl₂L₂L₄(L = methylamine and ethylamine) and CuCl₂L₂ (L = methylamine, ethylamine, ethylamine and diethylamine) were prepared. The structure of these complexes was studied by means of electronic, infrared and e:p.r. spectra. The results of the applied methods showed that the degree of distortion of the coordination polyhedra of Cu^II increased with the basicity and dimension of The ligands. The thermal stability of the complexes as well as the reduction temperature of the Cu^II decreased in the same order. These results are discussed with respect to the mutual influence of ligands in Cu^II complexes and to its effects on the course of their redox reactions.     

Zur Frage der Isomorphie der Wasserfreien Doppelsulfate von CuII

On the Isomorphism of Anhydrous Double Sulphates of Cu^II Structural properties of MCu(SO₄)₂ (where M^I = Na, K, Rb, Cs and Tl) compounds were studied, using their i.r. spectra and X-ray powder diffractograms. It was found that the compounds, unlike their hexa- or dihydrates, are not isomorphous. This result is consistent with i.r. data, which show that the bonding mode of the sulphate groups is different for various M^I.     

Zur Kenntnis der Hexafluoromanganate(III)

The preparation of the up to now unknown compounds [Co(NH₃)₆]MnF₆, [Cr(NH₃)₆]MnF₆ and [Rh(NH₃)₆]MnF₆ is reported. The compounds crystallize in the space group T_h⁶–Pa3, with four formula units in a cell. The magnetic moment of [Co(NH₃)₆]MnF₆ has been measured (4,94 B.M.). The spectra of the above compounds and of K₃MnF₆ and K₂NaMnF₆ in the ultraviolet, visible and infrared region have been measured and discussed. The static distortion of MnF^3?₆ in K₃MnF₆ and K₂NaMnF₆ and a dynamic effect of the compounds with a complex cation due to the JAHN -TELLER theorem show two different types of infrared spectra.     

Über Chalkogenolate. 101. Untersuchungen über Halbester der Monothiokohlensäure. 1. Darstellung und Eigenschaften von Oxoxanthaten

On Chalcogenolates. 101. Studies on Hemiesters of Monothiocarbonic Acid. 1. Preparation and Properties of Oxoxanthates Alkyl oxoxanthates of alkali metals have been prepared by reaction of COS with the corresponding alkoxides. The reaction of ethyl oxoxanthate with methyl iodide leads to S-methyl-O-ethyl ester of monothiocarbonic acid. The oxidation of [SOC? OC₂H₅]^? ions with iodine forms bis(ethoxycarbonyl)-disulfide (S? CO? OC₂H₅)₂. The prepared compounds have been characterized with chemical and thermoanalytical methods as well as by means of electron absorption spectra, infrared spectra, ¹H-NMR spectra, and mass spectra.