Protonation et hydrolyse d'enamine. Epimerisation des immoniums intermediaires

At pH 5 (AcOHAcONa) protonation of the enamine of 3,6,6-trimethylnorpinane 2-one (3-methylnopinone) yields the cis immonium ion 6 (X  OAc), which isomerizes to the thermodynamically more stable trans immonium ion 6′ (X  OAc). Under more strongly acid conditions (aqueous hydrochloric or perchloric acids), the enamonium salts 7 (X  Cl or ClO₄) are formed; these isomerize, with a rate increasing with decreasing acidity to the cis immonium salts 6, stable under these conditions. Epimerization of the cis salt 6 (X  Cl), occurs in ethereal hydrogen chloride, the rate increasing also with decreasing acidity. At pH 5, hydrolysis of the enamine yields 3-methylnopinone, the proportion of the less thermodynamically stable trans isomer increasing with a rise in reaction temperature.     

Anomalous behaviour of the Landé factors and the chemical shift close to the dissociation limit of the B state of molecular iodine

Resonances in a modulated light beam have been observed on five transitions in the visible band system of I₂. Landé factors g_J and chemical shifts g₁ have been measured for levels very close to the dissociation limit of the B state.     

Determination of the pH of binary mobile phases for reversed-phase liquid chromatography

The measurement of pH in chromatographic mobile phases has been a constant subject of discussion during many years. The pH of the mobile phase is an important parameter that determines the chromatographic retention of many analytes with acid-base properties. In many instances a proper pH measurement is needed to assure the accuracy of retention-pH relationships or the reproducibility of chromatographic procedures. Three different methods are common in pH measurement of mobile phases: measurement of pH in the aqueous buffer before addition of the organic modifier, measurement of pH in the mobile phase prepared by mixing aqueous buffer and organic modifier after pH calibration with standard solutions prepared in the same mobile phase solvent, and measurement of pH in the mobile phase prepared by mixing aqueous buffer and organic modifier after pH calibration with aqueous standard solutions. This review discusses the different pH measurement and calibration procedures in terms of the theoretical and operational definitions of the different pH scales that can be applied to water-organic solvent mixtures. The advantages and disadvantages of each procedure are also presented through chromatographic examples. Finally, practical recommendations to select the most appropriate pH measurement procedure for particular chromatographic problems are given.     

Dissociation constants of phenols in methanol--water mixtures

A preferential solvation model that relates solute properties with solvent composition in binary mixtures has been applied to the dissociation pKa values of a set of 28 substituted phenols in methanol-water mixtures. The parameters of the model allow estimation of the pKa value of each phenol for any methanol-water composition. Moreover, it is demonstrated that the pKa values of the whole set of phenols at any methanol-water composition are linearly related to the pKa values of the phenols in water. Equations that relate the correlations' slope and intercept values with the solvent composition have been derived and tested with the set of phenols. The general parameters obtained for these equations allow an accurate calculation of the pKa value of any phenol, even of those not included in the original set, at any methanol-water composition solely from the pKa value of the phenol in water. These calculated pKa values can be used for quantitative structure-HPLC retention relationships. The method is tested by comparison of the calculated pKa values with the HPLC determined pKa values of 26 phenols in a polymeric column with a 50% methanol as mobile phase.     

Stéréochimie des réactions de substitution des alcoxygermanes par les organolithiens et par les réactifs de Grignard

The reactions of organolithium reagents and Grignard reagents with optically active alkoxygermanes R₃GeOR′ have been studied [R₃GeOR′ = ()-i-PrPhNpGeOCH₃, ()-i-PrPhNPGeOMen and ()-MePhNpGeOMen]. Saturated reagents (e.g. butyllithium) give retention of configuration at germanium whilst unsaturated reagents (e.g. allyl- or benzyllithium) lead to inversion.     

A field theoretical approach to calculate electronic Born-Oppenheimer coupling terms

In this paper we suggest to consider the spatial distribution of the Born-Oppenheimer nonadiabatic coupling terms as fields which are created by sources, located at degeneracy points, and which can be derived using the ordinary mathematical tools of field theory. It is shown that the curl-divergence equations as formed within a given Hilbert space [M. Baer, Chem. Phys. Lett. 35, 112 (1975)] can be converted into a set of inhomogeneous coupled Poisson equations which are solved for a given set of boundary conditions. The method is applied to the three-state Hilbert subspace of the H(3) system. The numerical results are compared with ab initio calculations for which a very encouraging fit is found.     

Molecular orbital studies on the conformation of GABA (γ-aminobutyric acid)

In distinction to Extended Hückel Theory which predicts as the most stable conformation of free zwitterionic GABA a totally extended form, PCILO and SCF ab initio studies show that the intrinsically preferred conformation of the isolated molecule is a highly folded one, resulting from strong interactions between the two charged ends. Computations are also carried out for hydrated GABA in the supermolecule approach allowing moreover for the flexibility of binding of some of the water molecules of the first hydration shell. They predict the coexistence in solution of a large number of conformations showing different degrees of folding (or extension), a result confirmed by recent NMR studies. This and a number of similar results show that we have to adapt our thinking on the role of conformations in pharmacological activity to this situation, which was frequently obscured by the more abundant results of X-ray crystallography yielding a single conformation.     

Influence of the pyridine methyl substituent position on the chemical changes of the NCS groups in the thermal decomposition of coordination compounds of the type Cu(NCS)2L2

The influence of the position of the CH₃ group in picoline and lutidine ligands on the degree of chemical change of the NCS groups in coordination compounds of the type Cu(NCS)₂L₂ (whereL=2-, 3- and 4-picoline, and 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-lutidine) is dealt with. The most marked effect of the CH₃ group is found to be exerted in position 4. This effect of the methyl group on the degree of chemical change points to the mutual influence of the ligands in coordination compounds of Cu(II).

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Zusammenfassung Der Artikel befaßt sich mit dem Einfluß der Lage der CH₃ Gruppe in Pikolinen und Lutidinen als Liganden auf den Grad der chemischen Änderungen der Gruppen NSC in Koordinationsverbindungen des Typs Cu(NCS)₂L₂ (L=2-, 3- und 4-Pikoline, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- und 3,5-Lutidine). Der ausgeprägteste Effekt der CH₃ Gruppe wurde in der Position 4 beobachtet. Dieser Einfluß der Methylgruppe auf das Ausmaß der chemischen Änderungen deutet auch auf die gegenseitige Wirkung der Liganden in Koordinationsverbindungen von Cu(II).

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Résumé L'article a trait à l'influence de la position du groupe CH₂ dans les picolines et lutidines, en tant que ligands, sur le degré des changements chimiques des groupes SCN dans les composés de coordination du type Cu(SCN)₂L₂ (L=2-, 3 et 4-picoline, 2,3-, 2,4-,2,5-, 2,6-, 3,4- et 3,6-lutidine). L'effet le plus prononcé du groupe CH₃ s'observe en position 4. Cette influence du groupe méthyle sur le degré des changements chimiques indique aussi l'influence mutuelle des ligands dans les composés de coordination du Cu(II).

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- , , NCS Cu(NCS)₂,L₂, L=2-, 3- 4- , 2.3-, 2.4-, 2.5-, 2.6-, 3.4- 3.5-. , 4. Cu(II).

     

Nachweis isomerer Phenole und Nitroaniline,von Naphthylamin und Anilin

Zusammenfassung Die mit diazotiertem p-Nitranilin hergestellten Tetrazoverbindungen von Phenolderivaten geben mit Magnesium in alkalischem Mediumfarbige Komplexe. Die Farbe des Komplexes ist verschieden bei substituierten und nicht substituierten bzw. verschieden substituierten Phenolen. Damit kann man Phenol-, Kresol- und Chlorphenol-Isomere bzw. 2,4- und 2,6-Dichlorphenol unterscheiden.Beim Diazotieren von Nitranilin und Kuppeln mit Anilin entstehen. Indikatorsäuren; p-Nitranilin bildet die stärkste Indikatorsäure, m-Nitranilin die schwächste. Auf dieser Grundlage können alle drei Isomeren nebeneinander nachgewiesen werden. Außerdem bilden die aus p- und o-Nitranilin entstandenen Indikatoren mit Magnesium verschieden gefärbte Nitronsäurekomplexe, während m-Nitranilin, das zur Nitronsäuretautomerie nicht befähigt ist, keinen Komplex bildet.Naphthylamine geben mit diazotiertem p-Nitranilin in wäßrigem. Medium eine Indikatorbase, Anilin eine Indikatorsäure. In alkoholischem Medium führt-Naphthylamin bei Kupplung von diazotiertem p-Nitranilin zu einem amphoteren Säure-Base-Indikator, aber-Naphthylamin und Anilin zu Indikatorsäuren. Damit kann man Naphthylamin und Anilin nebeneinander nachweisen. Kuppelt man Phenyldiazoniumchlorid mit Naphthylamin, so erhält man mit-Naphthylamin eine starke Indikatorbase, mit- Naphthylamin eine schwache Indikatorbase. Auf der Basis dieser Indikatorwirkung kann man-Naphthylamin neben- Naphthylamin nachweisen.

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Summary The tetrazo compounds of phenol derivatives prepared with diazotizedp-nitraniline yield colored complexes with magnesium in alkaline surroundings. The color of the complexes differs with substituted and non-substituted or variously substituted phenols. It is possible in this way to differentiate phenol, cresol and chlorophenol isomers, and also 2,4- and 2,6-dichlorophenol.Indicator acids result from diazotized nitraniline coupled with aniline;p-nitraniline yields the strongest indicator acid,m-nitraniline the weakest. With this information as a basis, all three isomers can be detected in the presence of each other. In addition, the indicators produced fromp- ando-nitraniline give nitronic acid complexes with magnesium that differ in color, whilem-nitraniline, which is not capable of nitronic acid tautomerism, forms no complex.Naphthylamines gives an indicator base in aqueous medium with diazotizedp-nitraniline, whereas aniline yields an indicator acid. In alcoholic medium, 1-naphthylamine on coupling with diazotizedp-nitraniline produces an amphoteric acid-base indicator, but 2-naphthylamine and aniline yield indicator acids. Naphthylamine and aniline can be detected in this way in the presence of each other. If phenyldiazonium chloride is coupled with naphthylamine, a strong indicator base is obtained with 1-naphthylamine, a weak indicator base with 2-naphthylamine. This indicator action is the basis of the detection of 1-naphthylamine in the presence of 2-naphthylamine.

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Résumé Les composés tétrazoïques des dérivés phénoliques qui se forment avec lap-nitraniline diazotée, donnent avec le magnésium, en milieu alcalin, des complexes colorés. La couleur du complexe diffère suivant que les phénols sont substitués, non substitués ou différemment substitués. On peut ainsi distinguer le phénol, les crésols et les chlorophénols isomères, ainsi que les dichloro-2,4 et -2,6 phénols.En diazotant la nitraniline et en copulant avec l'aniline, des acides indicateurs prennent naissance, lap-nitraniline donnant l'acide indicateur le plus fort, lam-nitraniline le plus faible. En s'appuyant sur ce fait, on peut rechercher les trois isomères en présence les uns des autres. En outre, les indicateurs qui prennent naissance à partir de lap- et de l'o-nitraniline forment avec le magnésium différents complexes colorés acinitrés, alors que lam-nitraniline, qui n'est pas susceptible d'une tautomérie de l'acide nitronique, ne donne pas de complexe.Les naphtylamines donnent avec lap-nitraniline diazotée, en milieu aqueux, une base indicateur et l'aniline, un acide indicateur. En milieu alcoolique, l'-naphtylamine conduit par copulation de lap-nitraniline diazotée à un indicateur acide-base amphotère mais la-naphtylamine et l'aniline à des acides indicateurs. On peut ainsi rechercher la naphtylamine et l'aniline en présence l'une de l'autre. Si l'on copule le chlorure de phenyldiazonium avec la naphtylamine, on obtient avec la forme une base indicateur forte et avec la forme une base indicateur faible. En se fondant sur cette action d'indicateur, on peut rechercher l'-naphtylamine en présence de-naphtylamine.