Fluxional behaviour of π-bonded acetylenes

Some cationic five coordinate complexes of formula [Os(CO)(NO)L₂A]PF₆ (L = tertiary phosphine, A = an acetylene) have been prepared by reaction of the appropriate acetylene with [Os(CO)(NO)L₂(acetone)]PF₆; the variable temperature ¹H NMR spectra of some of these indicate that the coordinated π-acetylene undergoes fluxional behaviour.     

The synthesis of 2,2'-Dinor-carotenoids (author's transl)]

The Synthesis of 2,2′-Dinor-carotenoids. 2,2′-Dinor-carotenoids which include the naturally occurring actinioerythrol ( 1 ) and the blue carotenoid violerythrin ( 2 ) have been obtained by total synthesis. The synthesis starts with acetone and acetylene and yields compounds 1 and 2 as well as other carotenoids of the same type.     

Syntheses based on 5-methylfurfural

Conclusions A series of derivatives of furan and tetrahydrofuran were synthesized on the basis of 5-methylfurfural: alkyl(5-methylfuryl)carbinols, alkyl(5-methyltetrahydrofuryl)carbinols, 2-methyl-5-alkenylfurans, 2-methyl-5-alkylfurans, and 2-methyl-5-alkyltetrahydrofurans.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 1829–1831, October 1966.     

Fast and simple radiochemical method for the separation of uranium,thorium and lanthanum

The concept of using paper chromatography on papers impregnated with liquid anion or cation exchangers is extended to the separation of trace elements through filtration on filter papers loaded with suitable extractant. The uptake of uranium, thorium and lanthanum from HCl and HNO₃ media of different molarities by a filter paper treated with tri-octyl amine (TOA) is investigated. The effect of the different parameters on the uptake of the studied elements is experimented. A simple and fast radiochemical procedure is developed for the separation of La, Th and U from each other.     

Behavior and characteristics of biogenic amines, ornithine and lysine derivatized with the o-phthalaldehyde-ethanethiol-fluorenylmethyl chloroformate reagent

The stability and characteristics of the ornithine (Orn), lysine (Lys), putrescine (Put), cadaverine (Cad), 1,7-diaminoheptane (Diah), spermidine (Spd) and spermine (Spm) derivatives obtained with the o-phthalaldehyde (OPA)-ethanethiol (ET)-fluorenylmethyl chloroformate (FMOC) reagent has been investigated. The stoichiometry of the introduced, two-step derivatization process has been followed by photodiode array (DAD) and fluorescence (FL) detections, simultaneously, while the composition of derivatives was confirmed by on-line HPLC-electrospray ionization (ESI) MS measurements. Depending on the composition of the OPA reagents, in addition to the secondary amino group-containing Spd and Spm, under common aqueous conditions also Orn and Lys do react with FMOC resulting in derivatives of various compositions. Applying the OPA-ET reagent of increasing methanol (Met) content (38-80%, v/v) the formation of the FMOC group containing Orn and Lys derivatives could be considerably decreased. Optimum elution condition (18 min, including equilibration) was developed for the simultaneous quantitation of Orn, Lys, Put, Cad, Diah, Spd and Spm, in the presence of the rest of protein amino acids. The practical utility of the method was demonstrated by the analysis of mouse tissues. Average reproducibility of quantitations, characterized with the relative standard deviation percentages of fluorescence intensities and UV responses, in order of listing, proved to be 2.1% and 2.1%, respectively.     

ESR study of free radicals chemically generated at high pressure

Free radicals generated by the thermal decomposition of benzoyl peroxide in polyacrylnitrile were studied by the ESR method at 700 MPa between 100 and 130°C. The formation and decay of macroradicals were investigated and the mechanism of macroradical generation is discussed.

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700 MPa 100 130°C. .

     

Reactions of molybdenum and tungsten halides with acetylenic hydrocarbons: an approach to the structure and pathways of formation of metathesis catalysts

A number of acetylene and mixed acetylene-nitrile complexes of tungsten and molybdenum halides have been prepared and investigated. Depending on the acetylene and the reaction conditions, one or more acetylene molecules may be coordinated to the metal. In the latter case acetylenes are coordinated not as single molecules but in systems of conjugated non-aromatic double bonds. On the basis of the supposed structure of such species and on their pyrolysis products a decomposition scheme is proposed, which consider the formation of apparent metathesis products as a side reaction of the cyclotrimerization of acetylenes to aromatic hydrocarbons.     

Absolute configuration of cryptostylines I,II, and III by x-ray analysis and aromatic chirality method

The S-configuration of the alkaloids cryptostylines I, II, and III was assigned on the basis of a single crystal X-ray analysis of unnatural cryptostyline II hydrobromide (5.HBr: orthorhombic, P2₁2₁2₁a = 10·162, b = 12·352, c = 16·456 Å) and confirmed by application of the aromatic chirality method. Further evidence for the configurational assignment was provided by the CD spectra of the monophenolic derivatives of unnatural cryptostyline II (14).     

Acid deuterium exchange in benzazoles

The kinetics of acid deuterium exchange in benzazoles carrying electron-donor substituents in the 5-, 6-, or 7-positions have been studied. Mass spectrometric studies have shown that exchange in 5-methoxy-1, 2-dimethylbenzimidazole takes place exclusively at one position in the benzene ring, in 5-chloro-, 7-chloro-,5-methoxy-2-methylbenzothiazole and 6-methoxy-2-methylbenzoxazole simultaneously in two positions, and in 6-methoxy-2-methylbenzothiazole the hydrogen at all three possible positions is exchangeable. Using quantum chemical reactivity indices (CNDO/2) in dynamic and state approximations, the orientational features of the reaction have been ascertained. The lack of agreement between the reactivities of the most reactive sites to exchange in heteroaromatic bicycles of similar structure and electrophilic localization energies is explained by differences in the energy profile of the reaction.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 679–687, May, 1986.     

Analytical aspects of absorption spectroelectrochemistry at a platinum electrode-I Study of metal ions

An apparatus has been built with which the intensity of a light-beam passing at grazing incidence over a platinum electrode can be monitored. The absorption of light which occurs during the electrolysis of dilute aqueous metal ion solutions has been studied as a function of a number of parameters including wavelength, potential difference and concentration. The theories of metal deposition and processes occurring at the electrode surface and in the diffusion layer have been examined and a mechanism for the production of the absorbing species in terms of increase in pH of the catholyte is proposed. The analytical potential of the technique is discussed.