Sur les dérivés de la fluorénone. IX. La (pyridyl-2)-3-fluorénone,la méthyl-2-(pyridyl-2)-3-fluorénone et la méthyl-3-(pyridyl-2)-3-fluorénone

Fluorenone Derivatives. IX. 3-(Pyrid-2-yl)-fluorenone, 2-methyl-3-(pyrid-2-yl)-fluorenone, and 2-(3-methyl-pyrid-2-yl)fluorenone Unsuccessful attempts to synthesize an aza-cis-fluorenacene system starting from 2-aza-chalcone or 6-methyl-2-aza-chalcone led to the title compounds.     

Alkylation par des dérivés d'indole. N-Ethylation de pipéridines par le méthyl-1 ethoxy-2 indole carboxylate-3 d'éthyle

Ethyl 1-methyl 2-ethoxy 3-indole carboxylate behaves as an alkylating reagent with nucleophiles such as piperidine and 2-methylpiperidine. The reaction is very sensitive to steric effects, as demonstrated by the difference in rates of ethylation of these two amines. Amidification of the ester function is also observed with piperidine, but the 2-ethoxy group is attacked predominantly.     

Complexes macrocycliques des lanthanides: Stabilité et comportement électrochimique dans le méthanol et le carbonate de propylène

Macrocyclic Complexes of Lanthanides: Stability and Electrochemical Behaviour in Methanol and Propylene Carbonate The stabilities of the 1:1 complexes of the trivalent lanthanides with the diazapolyoxamacrocycles (2.1.) and (2.2.1.) in anhydrous methanol and propylene carbonate have been determined at 25°, by competitive potentiometric methods using H⁺ or Ag⁺ as auxiliary cations, with Et₄NClO₄ as supporting-electrolyte. Additional data are also reported for the crown ethers 15C5 and 18C6 in propylene carbonate. It is shown that the diazapolyoxamacrocycles are much stronger complexing agents for trivalent lanthanides than macrocyclic polyethers, and that the bicyclic (2.2.1.) cryptates are more stable than the monocyclic (2.1.) complexes. With increasing atomic number of the lanthanides, the stability increases with diazapolyoxamacrocycles and decreases with cyclic polyethers. The electrochemical reduction of the trivalent samarium and europium cryptates has been investigated by polarography on a dropping Hg-electrode, in water and methanol. In both solvating solvents, the +2 oxidation states of the cations are stabilized by complexation.     

Stabilité dans le méthanol et propriétés thermodynamiques de transfert des cryptates de certains cations de transition et de métaux lourds

Stability in Methanol and Thermodynamic Transfer Properties of the Cryptates of some Transition Cations and Heavy Metals The nature and stability of the macrocyclic and macrobicyclic complexes of Ag⁺, Cd²⁺, and Pb²⁺ (Mⁿ⁺) with 21, 22, 211, 221 and 222 in anhydrous methanol 0.05M in Et₄N⁺ClO^?₄, at 25° (see Scheme) have been determined by potentiometry and spectrophotometry. Binuclear complexes M₂L²ⁿ⁺ have been observed in all cases, besides the mononuclear MLⁿ⁺ complexes. The macrobicyclic 1:1 complexes MLⁿ⁺ exhibit an important ‘cryptate effect’ with Mⁿ⁺=Ag⁺, Pb²⁺ and Cd²⁺, but not with Cu²⁺ and Zn²⁺; their stability is in all cases maximum with 221. The applicability to our results of the recent extrathermodynamic hypothesis involving MLⁿ⁺ cryptates is examined.     

Note sur le mécanisme réactionnel de la transposition de Dimroth. Une étude ab initio

An ab initio study of the Dimorth rerarrangement of the -amino-1,2,3,4-tetrazole leads to the conclusion teht in vapour phase the rate determining step is not the ring-chain isomerism, but is either the Z-E iomerism around the C?N double bond or the 1,3-sigmatropic shift of the proton.     

Sur l'acylation des méthylfluorènes VI. Formylation du méthyl-2-fluorène et du méthyl-3-fluorène selon Rieche

The formylation of 2-methylfluorene and of 3-methylfluorene according Rieche yields 2-methyl-7-fluorene-carbaldehyde and 3-methyl-2-fluorenecarbaldehyde respectively. The constitution of the obtained aldehydes is proved by their conversion into the known 2,7-dimethyl-fluorene and 2,7-dimethyl-9-fluorenone, respectively into the known 2,3-dimethylfluorene and 2,3-dimethyl-9-fluorenone.     

Action du phényllithium en série pyrazine: Piégeage des intermédiaires réactionnels par le benzoate de méthyle

The action of phenyllithium on pyrazine, 2-methyl pyrazine and acetonyl pyrazine gave mono- or di-addition products with azomethines bonds of pyrazine. The adducts can be condensed with methyl benzoate to give C or N condensed derivatives. No product with initial metalation of methyl or acetonyl groups was observed.     

Sur le mécanisme de la réaction de meth-cohn-tarnowski de préparation des thiocoumarines

Reaction of 2-t-butylthiobenzaldehyde with N-(2-dialkylaminoethyl)-cyanacetamides followed by heating of the resulting 3-(2-t-butylthiophenyl)-2-cyanoacrylamides in polyphosphoric acid leads to the formation of 3-carboxamido-2-imino-2H-benzo[b][l]thiopyrann intermediates which afford thiocoumarins on hydrolysis. The authors postulate the intermediate formation of a thiophenate ion by an electronic mechanism involving six centers.     

Structure du méthyl-3 phénylamino-4 phényl-5 triazole-1,2,4

The crystal structure or 3-methyl-4-phenylamino-5-phenyl-1,2,4-triazole has been determined by X-ray diffraction. It allows one to choose between the two reaction mechanisms which can be taken into account for the reaction of hydrazine upon N-acylated hydrezonates.     

La luminescence différée du styrène en solution vitreuse dans le méthylcyclohexane

The trapping of electrons and styrene cations and anions has been studied in a methylcyclohexane glass by the techniques of deferred luminescence. Radiothermoluminescence curves consist of two peaks, at 90 and 95°K, in this matrix. The second peak increases linearly with styrene concentration up to 2 × 10^?2M when it reaches a constant value, whereas the first peak increases from 10^?4 to 10^?3M and then decreases at higher concentrations and is not discernible at concentrations above 10^?2M. We propose two mechanisms which are qualitatively consistent with this behavior and are based essentially on the recombination of styrene cations with thermally detrapped electrons in the first peak and with anions in the second peak. Photothermoluminescence (i.e., thermoluminescence after photoionization with ultraviolet light) similarly consists of the 90 and 95°K peaks for a 10^?3M solution and of the 95° peak alone for a 10^?d M solution. Radiophotoluminescence excitation spectra at 77°K, corresponding to absorption spectra of trapped electrons and styrene anions, show that anions are the predominant negative species in 10^?2 molar solution, and trapped electrons in 10^?3 molar solution. Spectral analysis of radiothermoluminescenece shows the presence of two emission bands, one of which is identical with styrene fluorescence excited by the 254 Nm mercury line (λ_max = 292, 302, 307, and 317 Nm). The other band has three fairly poorly resolved maxima at 474, 486 and 496 nm and seems to correspond to the fluorescence of C₆H₅?H-CH₃ radicals formed during radiolysis.     

Composés d'addition des chlorures de terres rares avec le méthanol,l'éthanol et le propanol-2. Préparations,solubilités et réactions de transsolvatation

By reaction of hydrated rare earths chlorides (M = La, Nd, Sm, Gd, Dy, Er, Yb, Y) with orthoformates, the following adducts have been prepared: MCl₃· 4MeOH, MCl₃ ·3EtOH (M = La, Nd, Sm, Gd, Yb), MCl₄ · 4 EtOH (M = Dy, Er, Y); adducts MCl₃ · 3iso-PrOH have been prepared by successive action of methyl orthoformate and of 2-propanol. The solubilities of these adducts in the corresponding alcohols at 25° (for the lanthanum adducts equally at 0 and 50°) are given. Two examples of the transsolvatation of these compounds, yielding adducts with weakligands, are described.     

Action d'organolithiens sur la méthyl-2 quinoxaline. Etude de la réactivité des adduits

The action of organolithium reagents such as phenyllithium or n-bulyllithium on 2-methylquinoxaline gave lithiation of the methyl group which upon reaction with electtropholesphiles produce side chain alkenyl derivatives. On the other hand organolithium reagents react with the quinoxaline azomethine bond to give I-lithio-2-alkyl)or ary-1)-3 methylquinoxalines which can be further loithiated on the methyl group to give 2-alkyl(or aryl)-3-alkenylquinoxaline derivatives. The adducts can be condensed with clectrophiles such as benzonitrile or methlyl benzoate but only methyl benzoate leads to N condensed derivatives. Furthermore substituted 1,2,3,4-terahydroqinoxalines are available via the above lithio intermediates.     

Polymérisation anionique du méthacrylate de méthyle par les organo-alcalins-I : Polymérisation en milieu solvant aprotonique, étude des tacticités

Anionic polymerizations of methylmethacrylate, initiated by fluorenyl-alkali metals in ether media or in hexamethyl phosphotriamide, give syndiotactic polymers. Calculated differential entropies and enthalpies of activation between the iso- and syndiotactic placements reveal that in dioxane, tetrahydropyrane and tetrahydrofurane the syndiotacticity increases from K⁺ to Li⁺. With solvents having higher dielectric constant (such as hexamethyl phosphotriamide) or higher donating power (such as glyme 4), the tacticity of the polymers is not affected by the nature of the counter-ions.

It has been suggested that, with dioxane, tetrahydropyrane and tetrahydrofurane, the donating power is not strong enough to destroy the coordination bonds between the C=O groups of the living polymer chains and the counter-ions.