Influence of a silyl group on an allylic position. A theoretical approach

Allylsilanes show in certain cases a behaviour towards electrophiles which is opposite to that of its carbon homologues. Theoretical calculations using Dewar's MINDO/3 method performed on 3-methyl 3-butenyl trimethylsilane and 2-methyl 2-butene show that geometrical optimization leads to a silicon-allylic carbon bond nearly parallel to the double bond π cloud, and both net atomic charges and HOMO coefficients indicate an inversion between these two substrates.     

Measurements of inelastic cross sections for the (j,m) = (2,0)→(3,0) rotational transition of CsF in collisions with atoms and molecules

Individual state-to-state rotational transitions have been resolved in small angle scattering of polarized CsF molecules on Ne, Ar, C₂, H₆, N₂, CO, CO₂, CHF₃ at center of mass energies of about 0.1 eV. The absolute inelastic cross sections range from 5Ų up to 600Ų.     

Comportement thermique de polyamides et polysulfonamides “semi-aromatiques”

Various techniques (thermal analysis, dilatometry, X-ray diffraction, nuclear magnetic resonance, mass spectrometry, electrical measurements) have been used to study the thermal behaviour of several “half-aromatic” polyamides and polysulphonamides. Three transition phenomena were revealed and related to morphological modification of polymers.     

Electrochemical systems for galvanic cells in organic aprotic solvents: V. Electrochemical behaviour of gamma-butyrolactone

Gamma-butyrolactone (GBL) was shown to decompose on the clean surface of Li, Na, K, and their amalgams. Polarization curves were obtained on Pt and “Kovar” electrodes at potentials from 4 to ?4 V vs. Li?Hg in 0.5 M LiClO₄ or vs. K?Hg in 0.5 M KPF₆. GBL was found to reduce electrochemically at potentials more positive than 1 V. Various passivation phenomena provoked by the decomposition of the solvent were observed, hindering cathodic deposition of the alkali metals from solutions of their salts in GBL. The presence of a high-molecular surfactant in the electrolyte suppresses the decomposition of GBL and suggests a path to the deposition of Li on the electrode.     

Spectres de vibration et champs de force de valence de quelques composes π benzoate de methyle Cr(CO)3-nLn: II. Benzoate de methyle chrome tricarbonyle

A valence force field of methyl benzoate tricarbonylchromium is determined from the force field of methyl benzoate and that of hexacarbonylchromium. The results show the perturbation made both to the aromatic ring and to the carbonyl bonds by the chromiumring bond. This work is the first complete analysis of the vibrational spectra of methyl benzoate tricarbonylchromium.     

The pyrolysis of trimethylgermane and trimethylsilane

The number of products and the H₂/CH₄ ratio obtained from the flow pyrolyses of (CH₃)₃GeH and (CH₃)₃SiH were very different. The (CH₃)₃GeH decomposition is consistent with the following mechanism:

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The pyrolysis of (CH₃)₃SiH was found to be much more complex, presumably due to the formation of silicon-carbon double bonded intermediates and the (CH₃)₂Si(H)CH₂ radical. We also present data which supports the presence of a H atom chain sequence during this pyrolysis.     

Anionic polymerization of 1,2-butylene oxide

Anionic polymerizations of 1,2-butylene oxide were carried out in vacuum-sealed dilatometers in the range of 30–60°C. Potassium terbutoxide and dimsyl sodium were used as initiators; dimethyl sulfoxide (DMSO) and mixtures of DMSO with tetrahydrofuran were solvents. The polymer products were analyzed by gel permeation chromatography and infrared spectroscopy. The object of the investigation was to obtain information on the mechanism of the reaction and to elucidate some of its kinetic aspects. It has been shown that the polymerizations occur by two different processes, depending on the choice of experimental conditions. One of the processes involves free ions and ion-pairs, the other, ion-pairs alone. In the first case, where dimethyl sulfoxide is used as solvent, the order of the reaction with respect to the initiator concentration far exceeds unity (～1.8), while in the second case, involving mixed solvents, the order of the reaction, for all practical purposes, is one.     

Chemical structure of cow kappa-casein: study of the soluble tryptic peptides

The sequences of 13 tryptic peptides of cow ?_A-casein (accounting for about one half of the amino acid residues present in the protein) were established. The rennin sensitive linkage could be located in a large fragment (36 residues). ?-casein consists of a hydrophilic part (?-caseino-glycopeptide) and of a hydrophobic moiety (para-?-casein); in this latter, however, several quite hydrophilic sequences were characterized. Another feature of the ?-casein structure is the frequent duplication or triplication of certain amino acids (Pro-Pro; Phe-Phe; Gln-Gln-Gln-Asn-Glu-Glu-Glu; Pro-Pro-Lys-Lys-Asn-Gln-; etc. …).     

Maßanalytische Bestimmung von Merkapto-Benzthiazol im Wärmeaustauscher eines Reaktors

Zusammenfassung Eine volumetrische Methode zur Bestimmung geringer Mengen Merkapto-Benzthiazol in der Kühlflüssigkeit von Reaktoren wurde ausgearbeitet. Es wird in ammoniakalischem Medium mit ammoniakalisehem Silbernitrat titriert. Das Merkapto-Benzthiazol bildet mit Silberionen einen weißen, flockigen Niederschlag. Der Endpunkt der Titration wird mit Hilfe der Dead-stop-Indikation bestimmt. Er wird durch eine sprunghafte Stromstärkeerhöhung (Pt-Pt-Elektrode, 500 mV und 10^–7 A Empfindlichkeit des Galvanometers) angezeigt. Die Methode wird durch Triäthanolamin, Glykol, geringe Mengen von Chlorid und Phosphat nicht gestört.

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Summary A volumetric method has been developed for determining slight amounts of mercapto-benzthiazol in the cooling liquid of reactors. It is titrated in ammoniacal medium with ammoniacal silver nitrate. The mercapto-benzthiazol yields a colorless flocculent precipitate with silver ions. The endpoint of the titration is found by the dead stop indication. It is signalled by a sudden jump in the current strength (Pt-Pt-electrode, 500 mV and 10^–7 amp sensitivity of the galvanometer). The method is not impaired by triethanolamine, glycol, slight amounts of chloride, nor by phosphate.

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Résumé On a mis au point une méthode volumétrique pour le dosage de faibles quantités de mercaptobenzothiazole dans le liquide de refroidissement des réacteurs. On titre en milieu ammoniacal par le nitrate d'argent ammoniacal. Le mercaptobenzothiazole forme un précipité blanc, floconneux avec les ions argent. On détermine le point d'équivalence du titrage par la méthode du «dead stop end point». Il se trouve signalé par une augmentation brusque de l'intensité (électrodes Pt-Pt, 500 mv et 10^–7 A de sensibilité du galvanomètre). La triéthanolamine, le glycol, de petites quantités de chlorures et de phosphates, ne gênent pas.

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Vorgetragen beim Symposium für analytische Chemie in Graz, 29. September bis 1. Oktober 1965.