Synthese und eigenschaften von dialkylaminodifluorarsinen

The reactions of secondary amines with AsF₃ lead to the formation of dialkylaminodifluorarsines F₂As-NR₂. Eight aminoarsines have been prepared by this method and are describe. IR, ₁₉F and ₁H-NMR and mas spectral data are presented for these compounds and discussed. The fluorination of aminodicholorarsines Cl₂As-Nr₂ with SbF₃ or ZnF₂ produces only small yields of the difluorarsines F₂As-NR₂; fluorination of AsCl₃ under the same conditions, however, is a suitable preparative method for the synthesis of AsF₃.     

Synthese und eigenschaften von ortho-verbrückten diarylcyclopropenonen

A series of ortho-bridged diaryl cyclopropenones is prepared by straightforward synthetic pathways. The spectroscopic and chemical properties of the new cyclopropenones are reported.     

Anthelminthika,III Synthese und 13C-NMR-spektroskopische eigenschaften von (fluor- und iodanilino)ethentricarbonitrilen)

The reaction of ethenetetracarbonitrile with the appropriate haloanilines leads to anilinoethenetricarbonitriles comprising halogen substitutions as follows: 2-fluoro-, 3-fluoro-, 4-fluoro-, 2,4-difluoro-, 3-iodo-, and 4-iodo. The new (fluoro- and iodoanilino)ethenetricarbonitriles are capable of exerting anthelminthic, fungicidal, and herbicidal activity. The structures of the reaction products were established spectroscopically (IR, ¹H-NMR, ¹³C-NMR, and mass).     

Darstellung und eigenschaften von und reaktionen mit metallhaltigen heterocyclen: XXV. Synthese und eigenschaften neuer platina- und rhodacycloalkane durch substitution und oxidative addition einer CCl-bindung

The platinacyclopentane derivative [Cl(CH₂)₃R₂P](Cl)$\text{PtPR}{}_2\text{CH}{}_2\text{CH}{}_2\text{CH}{}_2$ is formed by action of Cl(CH₂)₃PR₂ on Pt(COD)₂ in n-hexane via the not isolable Pt[PR₂(CH₂)₃Cl]₂ (R  C₆H₁₁) by oxidative addition of a CCl bond to platinum. [μ-CIRh(CO)₂]₂ reacts in benzene with Cl(CH₂)₃PR₂ under partially CO substitution to give the stable intermediate Cl(OC)Rh[PR₂(CH₂)₃Cl]₂. In boiling toluene oxidative addition of a CCl bond to rhodium occurs under formation of the phospharhodacyclopentane [CI(CH₂)₃R₂P] Cl₂(OC)-$\text{RhPR}{}_2\text{CH}{}_2\text{CH}{}_2\text{CH}{}_2$ (R  C₆H₅). The ³¹P{¹H}-NMR spectra of the rhodium compound is characterized by an ABX system, that of the platinum by superposition of an ABX pattern with an AB spectrum.     

Darstellung und eigenschaften von und reaktionen mit metallhaltigen heterocyclen: V. Synthese,reaktionen und struktur neuartiger manganacycloalkane

The colourless, six- and seven-membered manganacycloalkanes (OC)₄$\text{MnPR}{}_2\text{OCH}{}_2\text{XC}$H₂ are obtained by reaction of Na₂[(OC)₄MnPR₂O] with the bis(triflate)alkanes (YCH₂)₂X (R = C₆H₅; X = CH₂, C(CH₃)₂, CH₂CH₂; Y = CF₃SO₃). CO or SO₂ can be inserted into the reactive MnC-σ bonds under ring expansion. Some characteristic IR and ¹H NMR data are discussed. (OC)₄$\text{MnPR}{}_2\text{OCH}{}_2\text{CH}{}_2\text{C}$H₂ crystallizes monoclinic in the space group P2₁/c with Z = 4.     

Synthese,eigenschaften und carbonyl-insertions-reaktionen von tetracarbonyleisen(0)-komplexen para-substituierter styrole

The Fe(CO)₄ η²-complexes of para-substituted styrenes (substituent  H, CH₃, OCH₃, Cl, F) can be obtained in good yields. Complexation changes drastically the chemical shifts and coupling constants of the vinyl protons. Reaction of the complexes with one mole equivalent of bromine in methanol liberates styrenes, but using two equivalents esters and diesters are formed via intermediate complexes of iron(III). For these carbonyl insertion reactions no systematic influence of the substituent on yield and product distribution was observed.     

(Perhalogenmethylthio)heterocyclen. XVIII . Synthese und eigenschaften von halogenierten (perhalogenmethylthio)pyrrolen

(Trifluoromethyltho)pyrroles 1-5 and (chlorodifluoromethylthio)pyrroles 6 were chlorinated by sulfuryl chloride, sulfuryl chloride/silicon dioxide, sulfuryl chloride/disulfur dichloried/aluminium trichloried to give the corresponding chloropyrroles 1a-d , 2a,b , 3a,b , 4a , 5a , and 6a-c Bromination with bromine or iodination with iodine/potassium iodide of 2, 3, 4 , and 6 yielded the derivatives 2c,d, 3c,d, 4b, 6d , and 2e, 3e, f, 4c , 6e respectively. Mixed halogenated pyrroles 3g and h were obtained from 3a and bromne or 3a and iodine/potassium iodide. During some chlorination reactions 7, 8 , and 9 were fromed in low yield asbyproducts. The ¹H-nmr, ¹⁹F-nmr and ir spectroscopic data are presented.     

Darstellung und eigenschaften von diphenylalkylthio- und diphenylarylthio-gallanen. Kristallstruktur von diphenylethylthiogallan

Triphenylgallane reacts with alkyl- and aryl-thiols, respectively, with formation of the corresponding diphenylalkyl- and diphenylaryl-thiogallanes. Spectra and some physical and chemical properties of the new compounds are given. The results of the X-ray structure determination of diphenylethylthiogallane are discussed.     

Chemische eigenschaften und synthese-verfahren von 3-vinylindolen

Selectively functionalized 3-vinylindoles are mostly stable compounds, which may serve as potent building blocks for anellation of the indole nucleus, in particular for synthesis of carbazole alkaloides and to obtain pharmacologically active compounds. This review describes from a great number of the permanent increasing literature of vinylheterocycles the chemical properties, the most important principles of the synthetic methods and the synthetic applications of 3-vinylindoles. Among the synthetic methods to obtain 3-vinylindoles the classical condensation, the Wittig-Horner-/Wadsworth-Emmons-Olefination and the recently developed Pd-catalyzed vinylation should be considered as reliable standard methods. Depending on the special functionalization in the desired product some others methodologies are developed, so the thermolysis or the acid catalyzed ipso-cleavage of hetarylindolylethanes for deriving 1-hetaryl-1-indolylethenes.     

Darstellung und eigenschaften von diorganogermaniumdisulfinsäureestern

Diorganogermaniumdisulfinic esters of the type R₂Ge(O₂SR′)₂ (R = CH₃, R′ = CH₃, C₆H₅, p-CH₃C₆H₄; R = C₆H₅, R′ = CH₃, p-CH₃C₆H₄) which are sensitive to hydrolysis are obtained by reaction of the corresponding diorganogermanium dichlorides with anhydrous silver sulfinates. The newly prepared compounds are thoroughly investigated on the basis of their ¹H NMR, mass, IR and Raman spectra. The methyl ester (CH₃)₂Ge(O₂SCH₃)₂ is compared with the already known sulfinato complex of tin with the same formal composition.     

Die fluorierung von perfluoralkyljodiden: Darstellungen und eigenschaften von perfluoralkyljod-difluoriden und perfluoralkyljod-tetrafluoriden

The fluorination of perfluoroalkyliodides: preparation and properties of perfluoroalkyliodine-difluorides and perfluoroalkyliodine-tetrafluorides. The perfluoroalkyliodine-difluorides RIF₂ (R = CF₃, C₂F₅, C₃F₇) may be prepared by the direct fluorination of perfluoroalkyliodides at −78°C in CCl₃F in high yields. From the fluorination at ca. −40°C the perfluoroalkyliodine-tetrafluorides RIF₄ are formed as final products. The preparation and properties are described.     

Synthese von Betenamin und von Betalain-Modellsubstanzen

Synthesis of Betenamine and of Betalaine Model Substances For comparisons of color, spectroscopic properties, pK_a values, and stabilities, a number of model substances containing the 1,7-diazaheptamethinium chromophore 8 of the yellow and red betalaine plant pigments were prepared by the thermal or photolytic ring opening of simple pyridine derivatives (such as 2 and 14-16 ), followed by the introduction of amines. Among the novel compounds prepared were betenamine perchlorate ( 5 ), the ‘naked’ ring system of the beet-pigment betanine ( C ) as well as two 1,7-diazaheptamethinium salts 25 and 27 with terminal amono acids. The synthesis of 5 started with 4-(2-aminoethyl)pyridine ( 1 ) and proceeded via 2 , ring opening with indoline to 4 , saponification, and intramolecular amine replacement (Scheme 1). The syntheses of 25 and 27 involved only one step, namely ring opening of γ-picoline using (S)-cyclodopa ( 24 ) and (S)-proline ( 26 ), respectively (Scheme 3).