A Photoelectron-spectroscopic investigation of the Homoconjugative Interaction between π- and Walsh-Orbitals in endo- and exo-Cyclopropano-norbornene

Photoelectron spectra of endo- and exo-cyclopropano-norbornene ( = endo- and exo-tricyclo[3.2.1.0^2.4]octa-6-ene) show that a significant homoconjugation exists between the π-orbital of the double bond and the symmetric Walsh-es-orbital of the cyclopropane ring in the exo-isomer, whereas the interaction is negligeable in the endo-derivative.     

The method of non-paired spatial orbitals

The calculation of non-paired spatial orbitals and alternant molecular orbital wavefunctions for the benzyl radical is described. The NPSO and AMO methods give comparable energy lowerings which indicate that they make substantial allowance for electron correlation. The calculated spin densities are not in very good accord with experiment and it is thought that this reflects inadequacies in the integral approximations used.     

Intramolecular hydrogen bond in substituted 3-hydroxypyridines

To explain the character of the intramolecular hydrogen bond in substituted 3-hydroxypyridines, the chemical shifts in the NMR spectra of the hydroxyl group and the IR spectra were studied. It was established that the stability of the intramolecular hydrogen bond of the O-HNR₂ type in substituted 3-hydroxypyridines increases when compared with the corresponding phenols, while an opposite pattern is observed for bonds of the O-H0₂ N type. An approximate evaluation of the energy of the intramolecular hydrogen bond in substituted 3-hydroxypyridines was achieved. When reacting with bases of the same strength, 3-hydroxypyridine forms more stable complexes than phenol.     

On the photochemistry of alpha, beta-unsaturated gamma-aldehydoketones. I. The UVirradiation of 3, 19-dioxo-17-beta-acetoxy-delta-4-androstene

Irradiation of 3,19-dioxo-17β-acetoxy-Δ⁴-androstene ( 2 ) at room temperature in either of its two absorption bands centered at about 245 and 315 nm, respectively, led to products 21, 22 , and 23 (Chart 3). Compounds 21 and 22 result from rearrangements involving intramolecular formal 1,2- (→ 21 ) and 1,3-shifts (→ 22 ) of the angular formyl group, and the formation of compound 23 proceeds through the elimination of the formyl radical and the incorporation of a hydrogen from the medium. Evidence favors the latter process to be a secondary radical reaction rather than a primary photochemical step.     

Titrimetric methods for the microdetermination of halogens in organic compounds by the rapid combustion procedure: The determination of individual halogens

A critical study has been carried out of titrimetric methods suitable for the microdetermination of each of the halogens, chlorine, bromine and iodine, in their possible organic combinations with the elements, oxygen, nitrogen and sulphur, following organic decomposition by the rapid empty tube combustion procedure.     

Influence de la temperature de polymerisation sur le taux de branchement de divers polybenzofurannes obtenus par amorçage cationique

Several polybenzofuranes, obtained by cationic initiation at various temperatures, have been fractionated by preparative G.P.C. The fractions have been studied by various physical methods, mainly osmometry, light scattering, viscometry and G.P.C. These determinations have been made in benzene and the Mark-Houwink relations have been obtained. From the differences observed between these various relations, the gyration radii and the determination of branching indexes, we have found very numerous branches in the samples obtained at the highest temperatures. These branches very probably result from a Friedel-Crafts attack on benzene rings by the carbocations of growing chains. Quantum chemistry determinations are in agreement with this view.     

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.     

Über Trichlorphosphazo-Verbindungen aus Nitrilen. III. Die Reaktion zwischen Acrylnitril und PCl3

On Trichlorophosphazo Compounds from Nitriles. III. The Reaction between Acrylonitrile and PCl₃. The reaction of PCl₃ with acrylonitrile at higher temperatures gives CH₂Cl? CCl₂? CCl₂? N? PCl₃ ( II ). On pyrolysis of (II), CH₂Cl? CCl₂? CN (IV) is form- ed. Treatment of (II) with SO, results in CHzCL? CCl₂? CCl?N-P(0)Cl₂ ( III ). At lower temperatures and/or in the presence of PCl₃, acrylonitrile reacts with PCl₃ to give the cis/ trans isomers VIa and VIb .     

Zur Hemmung der katalytischen Jodwirkung auf das system Cer(IV)-sulfat—arsenige Säure

Zusammenfassung Die Hemmung der katalytischen Jodwirkung auf die Redoxreaktion Cer(IV)-sulfat—arsenige Säure wird hinsichtlich ihrer Vorund Nachteile bei analytischer Anwendung untersucht. Brucinacetat gibt mit Ceriion in schwefelsaurer Lösung nachFischl eine quantitativ auswertbare Farbreaktion. Kritische Untersuchungen hierzu ergeben, daß die Lösungen zur vollen Entwicklung und Stabilität der orangeroten Farbe (Absorptionsmaximum 470 nm) mindestens 10 bis höchstens 12 Min. auf 105° zu erhitzen sind. Die Anwendung auf die Jodbestimmung im Blutserum nachSpitzy, Reese undSkrube bietet infolge methodischer Komplizierung keinen besonderen Vorteil.

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Summary The inhibition of the catalytic action of iodine on the redox-reaction ceric sulphate—arsenious acid was investigated with regard to the advantages and disadvantages in its analytical application. Brucine acetate gives, according toFischl, a quantitative colour reaction with ceric ions in sulphuric acid. Critical investigations carried out show that the solution only develops a stable, orange-red colour (absorption maximum 470 nm) between 10 and 12 minutes heating. Application of this procedure to the determination of iodine in blood serum by the method ofSpitzy, Reese, andSkrube introduces complications and has, therefore, no special advantage.

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Résumé Etude des avantages et des inconvénients de l'emploi en chimie analytique de l'inhibition de l'effet catalytique de l'iode sur la réaction d'oxydo-réduction cerium(IV)-sulfate—acide arsenieux. Avec les ions cériques l'acétate de brucine donne, en solution sulfurique, d'aprèsFischl, une réaction colorée susceptible d'être employée pour une détermination quantitative. Des recherches critiques ont montré que les solutions devaient être chauffées pendant au moins 10 min. et au plus 12 min. à 105° pour développer complètement la couleur rouge orangé et obtenir sa stabilité (maximum d'absorption à 470 nm). L'application à la détermination de l'iode dans le sérum sanguin d'aprèsSpitzy, Reese etSkrube n'offre aucun avantage particulier du fait de la complication de la méthode.