Perfluorinated para-element imido derivatives

The comparative reaction chemistry between first and second derivative paraelement analogs ( (CF₃)₂PH, (CF₃S)₂PH, CF₃SH, CF₃SSH, CF₃SNH₂, (CF₃S)₂NH, (CF₃S) ₃N) and F-N-isopropylacetimidoyl chloride [CF₃CCl=NCF(CF₃)₂, I] has been investigated. Reaction schemes are presented. The reactions of I with NH₃ and NaI are also reported. Analytical data is provided for previously unreported compounds along with more detailed analysis of known compounds.     

Darstellung von polyfluororganotrichlorsilanen

The following substances could be prepared by Grignard reactions or by conversions with trichlorosilane: C₆F₅CH₂CHCH₂, C₆F₅(CH₂)₃SiCl₃, CF₃(CF₂)₉CH₂CHCH₂, CF₃(CF₂)₇(CH₂)₂SiCl₃, CF₃(CF₂)₁₁(CH₂)₃CHCH₂ und CF₃(CF₂)₁₁(CH₂)₅SiCl₃.They were characterized by spectroscopical and microanalytical methods.     

(Perhalogenmethylthio)heterocyclen. X. Säurekatalysierte Substitutionen an (Perchlorfluormethylthio)pyrrolen und deren agrobiologische Wirkung

(Perhalomethylthio)heterocycles. X

1 IX. Mitt.: s. [1].

. Acid-catalyzed substitutions on (perchlorofluoromethylthio)pyrroles and their agro-biological activities In the presence of C₄F₉SO₃H the (perhalomethylthio)pyrroles 1a–c react with Cl_3?nF_nCSCl (n = 1–3) to give mixtures of the 2,5- and 2,4-disubstituted pyrroles 2a–f and 3a–h . 2a and 3a react with CF₃SCl (catalyst CF₃SO₃H) yielding 2,3,5-tris (trifloromethylthio)pyrrole ( 4a ), which under similar conditions reacts further to give 2,3,4,5-tetrakis (trifluoromethylthio)pyrrole ( 5 ). As a by-product during the conversion of 3a to 4a 2,3,4-tris (trifluoromethylthio)pyrrole ( 4b ) is formed. The pyrroles 2a , 4a and 5 form the mercury salts 6a–c ; compound 5 yields also a silver salt 7 . The ¹H- and ¹⁹F-NMR. spectra are discussed and the agro-biological properties of the compounds investigated.     

Pseudohalogenverbindungen. XX. Perfluorierte alkan- und phenylsulfonylpseudohalogenide

The pseudohalide CF₃SO₂NCO has been synthesized by means of a new reaction involving trifluoromethanesulphonamide and chlorosulphonylisocyanate. This method may be used for preparing other perfluorinated alkanesulphonyl-, arenesulphonyl- and alkanecarbonyl-amides. Reactions of CF₃SO₂NCO with alcohols, thiols, phenols and amines lead to the corresponding carbonic acid esters, thio-esters, phenyl esters and ureas. Reactions with carbonic acids, aldehydes and dimethylsulphoxide gave CO₂ and the corresponding acid amides, azomethines and imino-dimethylsulphurane. Under pressure at 160°C, CF₃SO₂NCO reacts with phosphorus pentasulphide to give the previously unknown compound CF₃SO₂NCS; with phosphorus pentachloride under the same conditions, CF₃SO₂NCCl₂ is formed.     

Die Oxidation von 3-(1-Nitro-2-oxocycloalkyl)propanal

The Oxidation of 3-(1-Nitro-2-oxocycloalkyl)propanal Oxidation of the title compound 1 with KMnO₄ under neutral conditions led to the corresponding acid 2 , 5-(2,3,4,5-tetrahydro-2-nitro-5-oxo-2-furyl)pentanoic acid ( 4 ), and 4-oxononadioic acid ( 6 ). On the basis of experimental results the mechanism of the formation of 4 is discussed (Scheme 1). Oxidation of 1 with KMnO₄ under basic conditions gave 6 which was transformed to (E)-4,5-dihydro-5(2′-oxocyclopentyliden)furan-2(3H)-one ( 12 ) with benzene/TsOH (Scheme 3). In contrast to this result the corresponding 4-oxoheptandioic acid ( 22 ) yields 1,6-dioxaspiro[4,4]nonan-2,7-dione ( 23 ) only (Scheme 4).     

Michael additions to trifluoromethylvinyl sulfone

Michael addition reactions of trifluoromethyl vinyl sulfone with organic compounds with labile hydrogen atoms are studied. Such additions can be successfully accomplished using potassium fluoride and 18-crown-6-ether or benzyltrimethylammonium hydroxide (Triton B) as catalysts.     

Diaminocarbene- and Fischer-carbene complexes of palladium and nickel by oxidative insertion: preparation, structure, and catalytic activity

Oxidative insertion of [Pd(PPh3)4] or [Ni(cod)2]/PPh3 into the C-Cl bond of various 2-chloroimidazolinium- and other -amidinium salts affords metal-diaminocarbene complexes in good to excellent yields. This procedure is complementary to existing methodology in which the central metal does not change its oxidation state, and therefore allows to incorporate carbene fragments that are difficult to access otherwise. The preparation of a variety of achiral as well as enantiomerically pure, chiral metal-NHC complexes (NHC = N-heterocyclic carbene) and metal complexes with acyclic diaminocarbene ligands illustrates this aspect. Furthermore it is shown that oxidative insertion also paves a way to prototype Fischer carbenes of Pd(II). Since the required starting materials are readily available from urea- or thiourea derivatives, this novel approach allows for substantial structural variations of the ligand backbone. The catalytic performance of the resulting library of nickel- and palladium-carbene complexes has been evaluated by applications to prototype Suzuki-, Heck-, and Kumada-Corriu cross-coupling reactions as well as Buchwald-Hartwig aminations. It was found that even Fischer carbenes show appreciable catalytic activity. Moreover, representative examples of all types of neutral and cationic metal-carbene complexes formed in this study have been characterized by X-ray crystallography.     

Ergebnisse aus versuchen zur darstellung von bis(trifluormethylsulphanyl)thioketen (CF3S)2C=C=S

The attempted preparation of bis(trifluoromethylsulphanyl)thioketene is described. Mono-and di-(trifluoromethylsulphanyl)-substituted orthothioesters may be prepared fromCH₃C(SC₂H₅)₃ and CF₃SCl in the presence of anhydrous ZnCl₂. The unstable compoundshave been isolated and characterized. The corresponding CF₃Se and CF₃SO₂ derivativesare only formed as intermediates which decompose to ketene diethylmercaptal. Suchmono- and di-substituted products are obtained in good yield from H₂C=C(SC₂H₅)₂ andCF₃ECl (E=S, Se). The reaction of H₂C=C(SC₂H₅)₂ with CF₃SO₂F gave only poor yieldsof (CF₃SO₂)_nCH_2−n=C(SC₂H₅)₂ (n=1, 2) which were only capable of characterizationin etheral solution by spectral means. Attempts to prepare (CF₃S)₂C=C=S by refluxing(CF₃S)₂CHC(O)Cl, (CF₃S)₂CHC(O)OH or (CF₃S)₂C=C=O with P₄S₁₀ in toluene yieldedonly the cyclic dimer and the corresponding 1,3,4-trithiolan.