Zur Umsetzung des 3,4,5,6-Tetrahydro-6-hydroxy-4,4,6-trimethyl-1,3-thiazin-2-thions mit sekundären Aminen

Tetrahydro-6-hydroxy-trimethyl-1,3-thiazine-2-thione (1) reacts with secondary amines via the dialkylammonium-3-oxoalkyldithiocarbamate3, either via isothiocyanates6 to 4-dialkylaminodihydro-2(1H)-pyridinethiones7 or to dialkylammonium dithiocarbamates (13), depending on the amine used and the reaction conditions. Subsequently, 6-dialkylaminotetrahydro-1,3-thiazine-2-thiones11 or tetrahydro-6-mercapto-1,3-thiazine-2-thione10 are formed. On being heated to reflux,11 reacts to pyridinethione7 and 4-dialkylaminodihydrothiopyranthione19. With secondary amines only13 is formed from tetrahydro-6-hydroxytetramethyl-1,3-thiazine-2-thione20. The reaction of dihydrotrimethyl-1,3-thiazine-2-thione21 with secondary amines leads to N,N-dialkylthioureas16 or dialkylammonium thiocyanates17 and with dialkylformamides 4-dialkylaminodihydropyridinethiones7 are formed. Dihydrotetramethyl-1,3-thiazine-2-thione24 reacts neither with secondary amines nor with dialkylformamides.     

Koordinationschemie von Dinitroresorcin mit Kupfer-, Kobalt-, Nickel-, Eisen- und Zinksalzen

The reactions of the bidentate dinitrosoresorcinol (DNR) with copper, cobalt, nickel, iron and zinc salts were investigated. This ligand was found to react with these metal salts in aqueous media where hydrogen ion was confirmed to be liberated except in case of iron. The solid complexes were prepared in alcoholic media. Chemical analyses, magnetic and spectral data were compatible to determine the structure of these complexes and their mode of chelation.

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Beiträge zur Chemie der Pyrrolpigmente, 19. Mitt.: Die elektrochemische Oxidation von Pyrromethenonen und Pyrromethenen (Gallenpigment-Partialstrukturen)

The electrochemical oxidation of arylmethylene-pyrrolinones, pyrromethenones and pyrromethenes as representative bile pigment partial structure models was investigated by means of a rotating disc platinum electrode using acetonitrile as the solvent. Two different oxidation reactions were found. The first reaction being a reversible one-electron oxidation with compounds of the arylmethylene-pyrrolinone series and pyrromethenones which are unsubstituted in position 5 of the pyrrole ring. A two step reaction (the first one reversible, the second irreversible) on the other hand was found to be typical for pyrromethenones bearing a methyl group in this position.Through protonation the first step is at a higher potential, whereas the second one is lowered and becomes reversible. The resulting oxidation pattern can be interpreted analogous to the oxidation of hydroquinones in aprotic solvents.The geometrical isomers of a pyrromethenone were oxidized at appr. the same potential, but there is a strong dependence of the potential of the first oxidation step on the substitution: a higher degree of alkylation favours oxidation by lowering the oxidation potential.

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Intramolecular Diels-Alder Reactions of Decatrienoates: Remote Stereocontrol and Conformational Activation(1)

The intramolecular Diels-Alder (IMDA) reactions of C(8)-substituted decatrienoates have been studied. The stereospecific formation of 11 via an endo-boat-9 transition state attests to the powerful directing influence of a C(8) substituent in the IMDA of decatrienoate. In addition, the contrasting observations that stereospecific 9 --> 11 occurs at room temperature while the nor-tert-butyl substrate (4a) requires 125 degrees C/5 h reaction conditions and produces a 60:40 mixture of diastereomers provide clear evidence that a bulky C(8) substituent is a powerful conformational activator of the IMDA.     

Correlating second harmonic optical responses of single Ag nanoparticles with morphology

Femtosecond laser excited second harmonic (SH) activity from single Ag nanoparticles is reported. A correlation of SH single-particle measurements with high-resolution imaging of particle morphology by TEM was achieved by creating position markers on an optical and electron transparent substrate (Si3N4 thin film, approximately 100 nm). We compared the SH activity of single Ag nanoparticles (nanospheres versus nanorods) and cluster structures (composed of two or multiple particles, e.g., dimers and trimers). The direct correlation of single-particle structures and SH activity, spectral and power dependence, strongly suggests one-photon resonant driven nonlinear oscillator response mechanism.     

N-Monobromamide: Darstellung durch Bromierung mit „Dibromisocyanursäure”, Eigenschaften

By reaction of primary carboxamides with “dibromoisocyanuric acid” (DBI) N-monobromoamides can be readily obtained as well as the N,N-dibromoamides described in an earlier paper¹. Reactions, some of them new, and properties of these compounds are described and compared with those of the N,N-dibromoamides. Like other compounds bearing the NHBr group^{2, 3} the N-monobromocarboxamides disproportionate at room temperature according to: 2 RCONHBr ? ? RCONH₂+RCONBr₂. For CH₃CONHBr the equilibrium constant was found to beK=0.02. In aqueous solution they behave as weak acids. The dissociation constants of eight compounds [R=?CH₃, ?C₂H₅, ?CH₂Cl, ?CHCl₂, ?CCl₃, ?CF₃, ?C(CH₃)₃ and ?C₆H₅] were measured: they differ from those of the corresponding carboxylic acids by about three powers of ten.     

Influence of extended π-conjugation units on carrier mobilities in conducting polymers

Carrier mobilities in thin films of copolymers with repeat units consisting of oligothiophenes bridged by Si atoms are measured over a range of doping levels, where the numbers of thienylenes in the repeat unit are 7, 8, 10, 12, and 14. The mobilities for these polymer films increased with the increase in doping level and the mobility enhancement followed an increasing order of the π-conjugation length. The magnitude of the mobility increase for the Si polymer comprising 14 thiophene units reached ca. 10⁴, implying that this π-conjugation length is almost sufficient to reproduce transport properties of polythiophenes.     

Synthesis of 5,6,8,9,14,14a-hexahydroisoquino[1,2-b][3]benzazepines

Syntheses of 5,6,8,9,14,14a-hexahydroisoquino[1,2-b][3]benzazepine-2,3,11,12-tetrol and related compounds are described. Key steps involve an initial construction of the isoquinoline ring under the Bischler-Napieralski conditions, which is followed by the building of the azepine ring via an intramolecular lactam formation on to the isoquinoline nucleus.     

Use of long-chain alkylamines for preconcentration and determination of traces of molybdenum, tungsten and rhenium by atomic-absorption spectroscopy-II: molybdenum in soils, sediments and natural waters

Molybdenum is extracted as the thiocyanate complex with the quaternary long-chain aliphatic amine Aliquat 336 in chloroform, followed by evaporation of the solvent, dissolution in MIBK, and atomic-absorption spectroscopy. The method is simple, rapid and sensitive, with few interference problems for the determination of the Mo content of soils and sediments in the range 0.1-1.0 ppm with a relative standard deviation better than 5% when 1-g samples are used. Quantitative extraction from large volumes of aqueous solution has also been confirmed, allowing the determination of Mo in natural waters in the ppM range.