IR spectroscopic study of substituent effects in N,N-dimethylhydrazides of aromatic acids

Conclusions An IR spectroscopic study showed that the C=0 values in the spectra of N,N-dimethylhydrazides of aromatic acids, RCONHN(Me)₂, correlate linearly with a regression equation obtained for the unsubstituted hydrazides of aromatic acids, RCONHNH₂. This dependence differs significantly from that for N-methyl-N-aroylhydrazines, in which ,-conjugation in the RC(O)N group is more pronounced.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2353–2355, October, 1987.     

Effects of stereoisomerism in the mass spectra of 2,4-disubstituted thiacyclohexanes

The mass spectra of cis- (Ia-c) and trans-2-methyl-4-R-thiacyclohexanes (IIa-c; a R = n-C₄H₉, b R = n-C₅H₁₁, c R = Ph) were studied. It was established that [M-CH₃]⁺ ions, which correspond to the loss of a methyl group from the 2 position, are formed more readily in the case of the less stable trans isomers IIa-c than in the case of cis isomers Ia-c. The three-dimensional structures of the substances have no effect on the degree of elimination of the R substituent. The relative ionization energies (RIE) for Ia,b and IIa,b and the relative appearance energies (RAE) of the [M-CH₃]⁺ ions were measured by the electron impact method. It was found that the RIE are almost 0.05 eV lower and that the RAE of the [M-CH₃]⁺ ions are 0.1 eV lower for trans isomers IIa,b than for cis isomers Ia,b.Communication 4 from the series Ionization and appearance energies in organic chemistry, See [1] for Communication 3.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 333–338, March, 1981.     

Nitrobenzene oxidation of fractions of cotton-plant dioxane lignin

Summary Analysis of the products of alkaline nitrobenzene oxidation of lignin fractions has confirmed their chemical inhomogeneity and has shown that in the various fractions the amounts of condensed syringly and guaiacyl structures differed markedly.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii No. 1, pp. 82–84, January–February, 1979.     

Preparation and reactions of the (dicarbonyl)(η5-cyclopentadienyl)(tetrahydrofuran)iron cation: A convenient route to (dicarbonyl)(η5-cyclopentadiemyl)(η2-olefin)iron cations and related complexes

The versatile reagent [η⁵-C₅H₅)Fe(CO)₂(THF)]BF₄ has been isolated from the reaction of (η₅-C₅H₅)Fe(CO)₂I and AgBF₄ in THF and shown to react in CH₂Cl₂ with olefins to yield [(η⁵-C₅H₅)Fe(CO)₂(η²-olefin)]BF₄ complexes. For most olefins the yields are high. The yield in these reactions can be increased by treating the CH₂Cl₂ solution of [(η⁵-C₅H₅)Fe(Co)₂(THF)]BF₄ and olefin with gaseous BF₃ in order to complex the THF as the BF₃-THF adduct. Most striking is the increase in yield for the cyclohexene complex from 17% to 92%.     

Research on a number of substituted arylamides of dithiocarboxylic acids

Dithiomalonic acid diarylamldes are cyclized to 3,5-diarylamino-1,2-dithiolium halides by oxidation with an equivalent amount of bromine (iodine) in chloroform solution; the same amides are cyclized to 4-bromo-3,5-diarylamino-1,2-dithiolium bromides with excess bromine and to 3-arylamino-5-arylimino-1,2-dithiols in alkaline media with potassium ferricyanide. The behavior of the synthesized substituted 1,2-dithiols with respect to various reagents was studied.     

On the chromophore of polyacrylonitrile

Further evidence is presented to show that the chromophore of polyacrylonitrile is formed by polymerization of the nitrile groups, rather than by dehydrogenation of the polymer backbone. The polyimine structure formed is resistant to hydrolysis; hence, the nitrogen content of hydrolyzed polymer increases with increased chromophore formation.     

Selektivierung geringer Mengen Kupfer mit Polyäthylenimin-Zellulose

Zusammenfassung Polyäthyleniminzellulosen sorbieren Cu²⁺ durch koordinative Bindung als Zentralion des sekundären Stickstoffs des Polyäthylenimins im P_H-Bereich 3,5 bis 4,5 selektiv aus verd. Lösungen. 10g Kupfer können von 10⁵fachen Überschüssen anderer Übergangsmetalle separiert, mit verd. Salzsäure eluiert und mit Diäthyldithiocarbamat photometrisch bestimmt werden. Das Verfahren eignet sich zur Erfassung von 0,001% Kupfer in Zink, Mangan, Kobalt, Nickel, Cadmium und Aluminium sowie aus Lösungen, deren Kupfergehalt 0,02 ppm beträgt.

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Selectivation of small amounts of copper with polyethyleneimine-cellulose

Summary Polyethyleneimine celluloses selectively sorb Cu²⁺ from dilute solutions through coordinative bonding as central ion of the secondary nitrogen of polyethyleneimine in the p_H-range of 3.5–4.5. 10g of copper may be separated from 10₅-fold excesses of other transition metals, then eluted with dilute hydrochloric acid and determined photometrically with diethyldithiocarbamate. The method is suitable for determining 0.001% copper in zinc, manganese, cobalt, nickel, cadmium, and aluminium as well as in solutions whose coppercontent is 0.02 ppm.

     

Schnellbestimmung von Hexachlorcyklohexan neben DDT mit Hilfe der Mikrobrechungsindexbestimmung nach Kofler

Zusammenfassung Eine Bestimmung von HCH und DDT aus Pulvergemischen und Streupudern wird beschrieben. Die beiden Insektizide werden über einer Säule, die mit Aluminiumoxyd neutral beschickt ist, mit Äther oder n-Hexan eluiert und das Eluat im Vakuum vorsichtig getrocknet. Aus der Schmelze des Rückstandes wird mit Hilfe der Glaspulvermethode die prozentuelle Zusammensetzung an Hand von Eichkurven ermittelt.

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Summary A method is described for determining HCH and DDT obtained from mixed powders and dusting powders. The two insecticides are passed through a column packed with neutral aluminium oxide, and then eluted with ether or n-hexane, and the eluate then carefully dried in vacuo. The percentage composition is found by means of standard curves when the glass powder method is applied to the melt of the residue.

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Résumé On décrit un dosade de HCH et de DDT sur le mélange des poudres et sur des poudres d'épandage. On réalise l'élution des deux insecticides avec l'éther ou le n-hexane, sur une colonne remplie d'oxyde d'aluminium neutre et l'on sèche avec prudence l'éluat dans le vide. On obtient la composition en pour-cent sur la partie fondue du résidu, au moyen de la méthode à la poudre de verre et en se servant de courbes d'étalonnage.

     

On the symmetry of iron(III) tris-acetylacetonate crystals

The crystal structure of iron tris-acetylacetonate is re-determined. Crystal data at 293 K are: a = 15.4524(5) Å, b = 13.5876(4) Å, c = 16.5729(7) Å, Z = 8; at 150 K: a = 15.2541(4) Å, b = 13.4451(3) Å, c = 16.4256(5) Å, Z = 8. The structure is molecular and comprises isolated molecules. The coordination polyhderon of iron is an almost regular octahedron, Fe-O bond lengths are 1.977–2.003 Å (293 K) and 1.982–2.006 Å (150 K). In the crystalline state, the molecules are arranged in layers, and iron atoms are located on a plane yielding an almost regular trigonal net with the Fe...Fe separations of 7.558–8.103 Å (293 K) and 7.472–8.017 Å (150 K). The adjacent layer is positioned exactly over the first one with a Fe...Fe distance of 8.303 Å (293 K) and 8.236 Å (150 K).