On the behavior of α-brominated dimethyl o-benzenediacetate toward nitrogen nucleophiles. Part II. Reaction of dimethyl α-bromo-o-benzenediacetate with hydrazines

Dimethyl α-bromo-o-benzenediacetate ( 1 ) condensed with hydrazine and acetylhydrazine to give respectively 1-carbomethoxy-2-amino-1,4-dihydro-3-(2H)isoquinolinone (2) and its N-acetyl derivative ( 9 ). Replacement of the bromine atom of 1 with the N-1-methylhydrazino ( 3 ) and the N-1-phenylhydrazino ( 5 ) groups occurred by allowing 1 to react respectively with methylhydrazine and phenylhydrazine. In the latter case alkylation by 1 at the N-2 also occurred which led to the formation of the 2-phenylaminoisoquinolinone ( 8 ). Derivatives 3 and 5 smoothly cyclized to the 1-earbomethoxy-5(H)-1,2,3,4-tetrahydro-2,3-benzodiazepin-4-ones 4 and 6 . A series of derivatives of 2 were also pharmacologically tested as antiinflammatory and CNS depressant agents.     

Thermal decomposition of copolymers of styrene and halogenated monomers

Copolymers of 1,2,2,2-tetrachloroethyl esters of unsaturated acids and halogenated N-phenyl maleimides with styrene were pyrolyzed; volatile products were analyzed with a mass spectrometer combined with a gas chromatograph. Hydrogen halide and carbon dioxide in the volatile products were determined during the thermal decomposition of copolymers in glass ampoules; the acyl chloride groups were determined in the residues. The thermal decomposition of copolymers of tetrachloroethyl esters with styrene sets in at ca. 230° by the release of chloral from the copolymer and splitting of some of the CCl bonds in the copolymer. The decomposition of copolymers of styrene with halogenated N-phenyl maleimides starts above 300° by depolymerization of the polystyrene chain sections and by splitting of some of the carbon-halogen bonds. At 310 and 500° for copolymers of tetrachloroethyl esters and at 500° for halogenated N-phenyl maleimides, there is radical dehydrohalogenation of the copolymers, with depolymerization of polystyrene blocks and splitting of carbon-carbon bonds in the main chain.     

Substituent effects in mass spectrometry—II. The effect of substituents on the dissociation of para and meta disubstituted benzenes

The effect of substituents on the activation energy for primary dissociation processes in the molecular ions of mono- and para and meta di-substituted benzenes has been examined. Where the daughter ion retains the substituent group, variation of the energy of activation derives from a combination of the effects of substituents on the ionisation potential of the molecular ion and the appearance potential of the daughter ion. An equation relating the energy of activation for the fragmentation of the molecular ion of a mono-substituted benzene to that of related para and meta di-substituted benzenes is presented.     

Phase diagram and X-ray diffraction analysis of the acrylic acid–acrylamide system

The phase diagram of the acrylic acid–acrylamide system as determined by DTA and the supporting x-ray diffraction data are presented. This diagram shows that the system forms a 1 : 1 addition compound which decomposes above 0°C. There is also one eutectic point at a 67 mole-% acrylic acid composition.     

Interaction of 1, 3-dioxa-2-silacyclanes and their oligomers with alklymagnesium and arylmagnesium halides

Conclusions Cyclic alkoxysilanes — 1,3-dioxa-2-silacyclanes — and their oligomers are decomposed by organomagnesium compounds with the formation of the corresponding silanols (disiloxanes) and tetraalkylsilanols.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1283–1285, July, 1966.     

Über die Konstitution eines Nebenalkaloides aus Adhatoda vasica Nees

Zusammenfassung Das in der vorangehenden Mitt. vonE. Späth undF. Gandini-Kesztler beschriebene Nebenalkaloid wird auf synthetischem Wege mit dem 6-Hydroxy-peganin identifiziert. Die phenolische OH-Gruppe steht also, bezogen auf Formel III, nicht an der Stelle, welche dem CH₃O des Harmins entspricht.     

Iterative degenerate perturbation theory

A fairly general degenerate perturbation theory has been considered which involves two versions, i.e., the Rayleigh-Schrodinger and Brillouin-Wigner treatments. The simple recursive formulas have been found for effective Hamiltonians which allow one to split the degenerate energy levels in any orders of this theory.     

FIBER-OPTIC PLANT TISSUES: SPECTRAL DEPENDENCE IN DARK-GROWN AND GREEN TISSUES*

Abstract— The fiber-optic properties of etiolated plant tissues can be used to detect and characterize pigment absorption in vivo. Transmission spectra of light guided through several monocot and dicot etiolated tissues show a decreasing red/far red ratio with increasing tissue length. Absorption bands attributable both to vacuolar pigments such as anthocyanins and to chloroplast pigments lead to the conclusion that the guided light passes through both vacuole and cytoplasm. As etiolated tissue becomes green under white light treatment, the red/far red ratio also changes, the nature of the change depending upon the tissue involved. The blue/red ratio also changes both with increasing length of etiolated tissue and during the greening process, with the changes again dependent on the tissue involved. The spectral dependence of the light-guiding phenomenon in dark grown and green plants may have implications for physiological responses mediated by phytochrome.     

Investigations under quasi-isothermal and quasi-isobaric conditions by means of the Derivatograph

It is proved that under the conditions of dynamic thermoanalytical examinations the course of a decomposition reaction is determined primarily by the gas- and heattransfer partial processes, i.e. indirectly by the experimental conditions. This raises the question of whether it is justified to make kinetic calculations based on the shapes of similar curves. A new measuring technique is reported which uses a slightly modified Derivatograph. With this new method decomposition reactions can be examined under “quasi-isothermal” and “quasi-isobaric” conditions. The pernicious effects of the gas- and heat-transfer processes are thus eliminated, and the shapes of the curves obtained provide the possibility of studying the decomposition reactions in a new and more thorough way.