Mechanism of the oxidation of cycloheptanone by chloramine-T

The oxidation kinetics of cycloheptanone by chloramine-T in alkaline media has been investigated. A mechanism involving the formation of an intermediate by the interaction between the enolic anion of cycloheptanone and chloramine-T in a slow step followed by its interaction with another molecule of chloramine-T in a fast step leading to products has been proposed. The scheme satisfactorily accords with the observed stoichiometry, negligible influence of ionic strength and a positive dielectric effect. Various rate parameters have been computed and 1.2-cycloheptanedione identified as the end product.With 2 Figures     

Ring-chain tautomerism of substituted hydrazones

1-Hydrazino-2-propanol reacts with aliphatic carbonyl compounds to form the corresponding (2-hydroxypropyl)hydrazones. 1-(N-Alkylhydrazino)-2-propanols, on the other hand, give tautomeric mixtures of alkyl-substituted perhydro-1,3,4-oxadiazines and N-alkyl-N-(2-hydroxypropyl)hydrazones. As compared with derivatives of 2-(N-alkylhydrazino)ethanols, the position of the equilibrium in the investigated cases is shifted to favor the cyclic forms.See [1] for communication I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 301–308, March, 1971.     

Über die Einwirkung von elementarem Schwefel und Schwefelwasserstoff auf Acetophenon oder Propiophenon in Gegenwart von Aminen oder Ammoniak

Zusammenfassung Bei Einwirkung von H₂S und Aminen bzw. NH₃ auf Acetophenon bzw. Propiophenon entstehen in Gegenwart elementaren Schwefels Bis-[1-phenylalkyl-(1)]-polysulfide, ohne Zusatz von Schwefel in der Hauptsache Bis-[1-phenylalkyl-(1)-]-disulfide. Die Struktur der linearen Di- und Polysulfide wurde durch Chlorolyse und Vergleich mit auf anderem Wege hergestellten Polysulfiden ermittelt.Die Reaktionen verlaufen über Ketimine als Zwischenstufe. Diese Intermediärprodukte wurden synthetisiert und geben bei der H₂S-Behandlung gleichfalls Bis-[1-phenylalkyl-(1)]-disulfide. Die Frage des Auftretens von Enaminen bei Verwendung von Morpholin als Aminkomponente wird diskutiert.Teil der Dissertation vonK. Halcour, T. H. Aachen, 1961.     

Infrared spectra of cyclic ethers and their derivatives

Data for the characteristic bands of cyclic ethers are reviewed. The infrared spectra of a number of 2-mono- and 2, 5-di-substituted derivatives of tetrahydrofuran are investigated. Absorption bands at about 900 cm⁻¹ are related to pulsation vibrations, and those at about 1200 cm⁻¹ to antisymmetric skeletal vibrations, of the tetrahydrofuran ring. It is shown that to confirm the presence of a tetrahydrofuran ring in a molecule, it is necessary to take into account not only the band of valence antisymmetric vibrations of the group C-O-C (ν _C-O-C ^as 1075 cm⁻¹), but also bands due to ring pulsation vibrations (ring symmetric valence vibrations ν _sk ^s ∼ 900 cm¹).     

Determination of betamethasone and triamcinolone acetonide by GC-NCI-MS in excreta of treated animals and development of a fast oxidation procedure for derivatisation of corticosteroids.

The use of corticosteroids in combination with other hormonal substances has long been known to result in increased mass gain with bovines. Practice has demonstrated, however, that even the single use of a glucocorticoid may result in growth promoting effects. In addition to the popular dexamethasone, more recently other corticosteroids have also been misused for fattening purposes. The first part of this study deals with the detection of two of them, namely betamethasone and triamcinolone acetonide. Betamethasone was administered orally to a cow at a dose of 50 mg d-1 for 5 d, then later the same cow was injected intramuscularly with a dose of 50 mg of betamethasone dipropionate. Excretion in urine and faeces was followed with both HPLC-enzyme immunoassay and a previously described method based on negative chemical ionization mass spectrometry (NCI-MS) after oxidation. For the triamcinolone acetonide study a cow was treated with 50 mg d-1 of the drug during a 7 d period. Excretion in faeces was followed with GC-NCI-MS. As triamcinolone acetonide is resistant to the previously described oxidation procedure, however, a hydrolysis step had to be introduced prior to oxidation. In addition to this specific modification necessary for triamcinolone acetonide, in a subsequent part of this study the original oxidation procedure with pyridinium chlorochromate was re-investigated especially to shorten the procedure. With the introduction of potassium dichromate the reaction time could be decreased from 3 h to 10 min.     

Some investigations on the photostabilization of polypropylene

The effect of substituted hydroxybenzophenone, benzotriazole and organic metal complexes on the photooxidation of PP films has been studied. It has been established that NiDBTC added in 1.0 wt. % is the most effective photostabilizer.While in the case of other stabilizers there is a slight increase in the Co content even during the induction period, with the application of NiDBTC practically no oxidation can be observed before the stabilizer completely disappears. This means that NiDBTC inhibits the photooxidation of the polymer even in low concentration.

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Ab initio scf and CI study of the ground and excited states of the HN2 radical

Non-empirical SCF and CI calculations are reported for the HN₂, free radical in various low-lying electronic states. The nature of the angular and N-N and N-H stretching potential curves of each of these species is investigated, including a study of the dissociative behavior of such states. The ground state is found to be only very slightly bound with respect to NH stretch, in contrast to what is observed for isoelectronic HCO, The vertical electronic spectrum of HN₂, appears to be marked by a single long wavelength transition (1.95 eV) from the bent (124°) ‘A’ ground state to the linear ²Π excited species, but at least four other intra-valence and an additional n → 3s Rydberg species are indicated in the 5.5–8.0 eV absorbing region.     

Vibrational and lifetime line broadenings in ESCA

The line profile of the narrow, symmetric 1s line from neon, recorded with the new ESCA instrument with X-ray monochromatization, is analyzed. The natural linewidth of this line is found to be 0.23 ± 0.02 eV, in good agreement with theoretical calculations of the oscillator strengths for Auger transitions and X-ray emission. Spectra from molecules show frequently asymmetric core electron lines under high resolution. This rules out previous explanations based on a chemical influence on the natural lifetime. Contrary to earlier assumptions, vibrational excitations are shown to be important in core electron spectra. For methane, the vibrational energy spacing is large enough to allow the vibrational lines to be partly resolved. Recent results from accurate PNO CI calculations on methane agree well with the experimental findings. The Franck-Condon transitions in the C1s and N1s lines from CO and N₂ are shown to be well described in the harmonic approximation and approximating the potential curves of the highly excited core hole states with the potential curve for the ground state of NO⁺, X¹ Σ⁺. Knowledge of vibrational excitations in core electron spectra is shown to be valuable in the analysis of high resolution X-ray emission spectra of free molecules.     

Determination of sulphur in fly ash by instrumental proton activation analysis

A method for the determination of sulphur in fly ash by instrumental proton activation analysis using the³⁴S/p,n/^34mCl reaction was developed. The 2128.5 keV and 3305.0 keV -rays of^34mCl /t=32.0 min/ were measured on a Ge/Li/ -spectrometer, shielded with a lead absorber to attenuate low energy -rays. Irradiation and measuring conditions were optimized. The detection limit for instrumental analysis is 0.3 to 1 mg g^–1 and the standard deviation is cca. 4% for a typical sample.     

Thermal properties of flame retardant viscose fibers

This paper discusses the problem of the thermal properties of flame retarding additives based on phosphazene derivatives and of the commercial agents TomflamB, FlammexT23P and StockhausenW-20949, as well as of flame resistant viscose fibers containing the above agents. Results of this investigation showed the action of FlammexT23P, StockhausenW-20949 and phosphazene derivatives at lower temperature. TomflamB acted within a much wider range of temperatures. The flame retardant additives applied to viscose fibers change the thermal properties of the fiber material.