6(5H)-phenanthridinones. II. Preparation of substituted 6(5h)-phenanthridinones from 9-oxofluorenes

A number of 6(5H)-phenanthridinones have been conveniently prepared from 9-oxofluorenes through the Schmidt reaction. It has been found that all amino and nitro 9-oxofluorenes thus far tried gave substituted 6(5H)-phenanthridinones with the amino or nitro group situated in the benzene ring attached to the nitrogen of the lactam group. UV and IR spectral data are presented for these compounds.     

Pharmacologically interesting compounds—I: High resolution mass spectra of phenothiazines

The mass spectra of twenty-six commercially available medicinal phenothiazines have been determined at high resolution. In each compound, the side chain attached to the 10-position of the phenothiazine ring contains nitrogen and fission of the C? C bond α to this nitrogen gives in most cases the base peak. Some of the compounds are also substituted at the 2-position and this substituent generally remains intact, though some substituents such as acetyl, propionyl, methoxyl and methylthio can undergo fragmentation. Fragmentations fall into three groups; those which give ions representing a part of the side chain; those which give ions representing the intact phenothiazine ring with part of the side chain attached; those which give ions representing a partially fragmented ring system.     

About changes of electrical conductance by warming in some diluted polymethylmethacrylate and polystyrene solutions

Summary The conductivity of polystyrene solutions (2 g/l) in decahydronaphthalene (decaline), ethylbenzene and dichloroethane as a function of temperature, and of polymethylmetacrylate in benzene (2 g/l) and acetone as a function of both temperature and concentration ((0,25–4 g/l) was investigated. Two kinds of the conductivity-temperature dependence could be observed. One, obeing the Arrhenius law, the other leading to maximum values of the conductivity in the transition temperature ranges. That behaviour is mainly dependent on the polarisability of the components. The tacticity of the polymers is important too.

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Zusammenfassung Die elektrische Leitf?higkeit von Polystyroll?sungen (2 g/l) in Decahydronaphthalin (Dekalin), ?thylbenzol und Dichlor?than als Temperaturfunktion und Polymethylmethacrylatl?sungen in Benzol und Aceton als Konzentration (0,25–4 g/1) und Temperaturfunktionen wurde untersucht. Der Temperaturbereich entspricht dem bekannten Konformationsübergangsbereich. Zwei Arten von Leitf?higkeits?nderungen bei Erw?rmung wurden beobachtet. Die eine entspricht der Arrhenius-Gleichung für Temperatur?nderungen mit einem Knick im Bereich der Konformationsumwandlung, die zweite zeigt ein Leitf?higkeitsmaximum in demselben Temperaturbereich. Dieses Verhalten scheint haupts?chlich von der Polarisierbarkeit der Komponenten abh?ngig zu sein. Neben der Polarisierbarkeit spielt bei diesen Erscheinungen die Taktizit?t der Polymeren eine wichtige Rolle.

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With 8 figures and 3 tables     

Crystal structure,Mössbauer,and magnetic behavior of mixed valence compounds in the BaFeS system: Ba3(Ba1−xAlx)Fe2S6[S1−y(S2)y]

The compounds $\text{Ba}{}_4\text{Fe}{}_2\text{S}{}_6\text{[S}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{(}\text{S}{}_2\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{]}$ and Ba_3.6Al_0.4Fe₂S₆[S_0.6(S₂)_0.4], designated I and II, were prepared by reacting BaS, Fe, and S powders and Al foils in graphite containers sealed in evacuated quartz ampoules at approximately 1100°C. The crystal structure of I was determined using 1682 independent, nonzero X-ray reflections, while 3589 were used for II. They are triclinic, $\text{A}\text{l}$:

$\text{a=9.002(2)}\text{A}\text{?}\text{,b=6.7086(8)}\text{A}\text{?}\text{,c=24.658(4)}\text{A}\text{?}\text{α91.49(2)°,}$

$\text{β=105.10(2)°y=90.74(2)°,ψ}{}_{\mathrm{calc}}\text{=4.15g/cm}{}^3\text{,for I:}$

$\text{a=8.993(6)}\text{A}\text{?}\text{,b=6.708(7)}\text{A}\text{?}\text{,c=24.70(1)}\text{A}\text{?}\text{α91.11(6)°,}$

$\text{β=105.04(6)°y=90.90(9)°,ψ}{}_{\mathrm{calc}}\text{=3.90g/cm}{}^3\text{,for II:}$

BaS₆ trigonal prisms share edges to form distorted hexagonal rings which form one-dimensional chains leaving two free lateral edges. The chains link in a stairstep manner with the rings offset along the [301] direction. These stairsteps join in a complicated manner to form a three-dimensional network. Fe ions are in two sites forming isolated FeS₄ tetrahedra and isolated Fe₂S₆ dimers by edge-sharing tetrahedra. The Al substitution occurs in the trigonal prisms which have free edges with Al replacing Ba. Room-temperature Mössbauer isomer shifts are 0.20 mm/sec. for I and 0.30 mm/sec for II. These data indicate that upon Al substitution charge compensation occurs by reducing Fe³⁺. Valence calculations indicate that Fe in edge-sharing tetrahedra are reduced while the Fe in the isolated tetrahedron remains unchanged. The effective charge distribution in the Al substituted compound is approximately Fe³⁺, Fe^2.5+ with electron delocalization across the shared edge. Room temperature electrical resistivity is 10⁵ ohm/cm. The compositions of the crystals are best represented by the formulas $\text{[}\text{Ba}{}_4\text{Fe}{}_2\text{S}{}_7\text{]}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{·[}\text{Ba}{}_4\text{Fe}{}_2\text{S}{}_6\text{(S}{}_2\text{)]}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}$ and [Ba₃AlFe₂S₇]_0.4·[Ba₄Fe₂S₇]_0.2·[Ba₄Fe₂S₆(S₂)]_0.4. The replacement of a sulfide by a disulfide ion is thought to be strongly dependent on the sulfur activity during the preparation.     

Comparison of figures of merit for fluorimetric analysis of rhodamine complexes of gallium and indium by excitation with pulsed laser and by xenon arc sources

Optimum conditions have been established for formation and extraction of indium-Rhodamine complexes, and limits of detection found for fluorimetric determination of gallium and indium by means of Rhodamine dyes, using the excitation with pulsed laser and xenon arc sources.     

Synthetic analogues of wedelolactone

The syntheses of 7′-methoxy- and 5′,7′,6-trimethoxy-coumarino(3′,4′:3,2)coumarones (IIa and IIb) are described.     

Determination of equilibrium constants of alkaline earth metal ion chelates with Dowex A-1 chelating resin

A complexation chemistry model is applied to chelating ion-exchange systems and a method is presented for the determination of equilibrium constants for metal ion chelates with these resins. Protonation constants for the iminodiacetic based chelating resin Dowex A-1 were determined from potentiometric pH-data. Equilibrium constants were determined for 1:1 beryllium, magnesium, calcium, strontium and barium chelates with the resin in a wide pH range by measuring the concentrations of respective metal ions in the aqueous phase with direct current plasma atomic emission spectrometry (DCP-AES). A batch technique was used for the equilibrium experiments. At pH below 7 protonated 1:1 species were also found to be formed with the resin. From the obtained equilibrium constants, theoretical distribution coefficients were calculated as function of pH for respective metal ion resin system.     

Form of the dihedral angle dependence of the spin-spin coupling constant JHNNH

Cyclic hydrazides (derivatives of phtalhydrazide,pyrozolidone-3, indazolone, cyclic hydrazide camphoric acid) are studied by the NMR¹H method. The size of the dihedral HNNH angle of several model compounds (pyrozolidone-3, cyclic hydrazide norcamphoric acid) are calculated by the MINDO/3 SSF MO LCAO method. It is shown that in the hydrazides with HNNH dihedral angle 0–70° the magnitude of the HNNH spin-spin interaction constant does not exceed 1 Hz. The form of its dependence on the dihedral angle is determined.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 3, pp. 363–366, 1989.     

A deuterium nuclear quadrupole double resonance study of the ferroelectric phase transition in potassium dihydrogen phosphate

A study has been made of the nuclear quadrupole double resonance (NQDR) spectrum of deuterium in a powdered sample of potassium dihydrogen phosphate, KH₂PO₄ or KDP for short, both as a function of temperature and of percentage deuteration. Double transitions have also been observed and these enable the orientation of the ferroelectric electric field gradient (EFG) tensor to be determined.