Fluorénacènes et fluorénaphènes Synthèses dans la série des indéno-fluorènes,XIX Dérivés tétraméthylés du trans-fluorénaphène et du trans-fluorénacène

By condensation of isophthaloyldichloride resp. of terephthaloyldichloride with 4-bromo-1,2-xylene according Friedel-Crafts, followed in each case by a double cyclisation and a final reduction, the 2,3,9,10-tetramethyl-7,12-dihydro-indeno[1,2-a]fluorene resp. the 2,3,8,9-tetramethyl-6, 12-dihydro-indeno[1,2-b]fluorene are synthesized.     

Fluorénacènes et fluorénaphènes synthèses dans la série des indéno-fluorènes,XVII. Dérivés méthylés du cis-fluorénacène,du trans-fluorénacène et du trans-fluorénaphène

By condensation of the chlorides of the three 9-oxo-fluorene-2-, -3-, and -4-carboxylic acids with 4-bromo-1,2-xylene on one side, and of the chlorides of o-bromobenzoic acid, 2-bromo-4-methyl-benzoic acid and 2-bromo-4,5-dimethyl-benzoic acid with fluorene, 2-methylfluorene and 3-methylfluorene on the other side, followed by direct or indirect cyclisation and by final reduction, several new methyl derivatives of the indenofluorenes I, II and IV are synthesized.     

Fluorénacènes et fluorénaphènes Synthèses dans la série des indéno-fluorènes XIV [1] Nouvelle synthèse du trans-fluorénacène

A new synthesis of 6, 12-dihydro-indeno [1,2-b] fluorene (trans-fluorenacene) in 9 steps starting from fluorene (overall yield 24,5%) is recorded. By partial oxidation of the hydrocarbon its 6-oxo derivative is also obtained.     

Fluorénacènes et fluorénaphènes Synthèses dans la série des indéno-fluorènes,XV [1] Méthyl-5-dihydro-10, 12-indéno [2, 1-b]fluorène

Starting from α-methylchalcone and diethyl ketone the title compound, II, has been synthesized in 6 steps (overall yield 26%). As an intermediate compound the gold yellow 10, 12-dioxoderivative of II was also obtained.     

Fluorénacènes et fluorénaphènes Synthèses dans la série des indéno-fluorènes,XVIII. Le diméthyl-5, 6-dihydro-7, 12-indéno[1, 2-a]fluorène

Starting from 3, 4-dimethylfluorene the title compound, 5, 6-dimethyl-7, 12-dihydro-indeno[1,2-a]fluorene (IV), is synthesized in four steps (overall yield 9%). The same hydrocarbon is also obtained in four steps starting from the phthalaconecarboxylic acid of Gabriel. This corroborates the structure of IV.     

Fluorénacènes et fluorénaphènes Synthèses dans la série des indéno-fluorènes,XVI. Méthyl-5-, diméthyl-5, 6- et diphényl-5, 6-dihydro-11, 12-indéno [2.1-a] fluorène

Starting from 2-methyl- and from 2,3-dimethyl-1,4-diphenyl-butadiene-1, 3 respectively, the 5-methyl- and the 5,6-dimethyl-11, 12-dihydro-indeno[2.1-a]fluorene are synthesized in 4 steps. The 5, 6-diphenyl-11, 12-dihydro-indeno[2.1-a]fluorene is obtained by reduction of the already known 11, 12-dioxoderivative. Accesorily a new preparation of the unsubstituted hydrocarbon is described.     

Étude thermochimique des méthylnaphtalènes

Calorimetric measurements of enthalpies of change of state (sublimation or vaporization) of methylnaphthalenes gave the following results:

1-methylnaphthalene: (ΔH√_vap)_m=(57.32±0.42) kJ mol⁻¹

2-methylnaphthalene: (ΔH√_sub)_m=(65.69±0.84) kJ mol⁻¹

Combination of these values with those obtained by Speros and Rossini¹ for enthalpies of combustion of these compounds makes it possible to determine their energy of isomerization more accurately. This energy is (2.97±2.41) kJ mol⁻¹ and should be attributed to steric hindrance in the 1-methylnaphthalene molecule.

The comparison of energies of conjugation, theoretical as well as experimental, which we have determine for both molecules studied, confirms the present result.     

Synthèse d'azido dithiényl-1,2 éthènes et éthanes

Two convenient preparations of azido-1,2-dithienylethenes are described. The synthesis of azido-1,2-dithienylethanes proceeds via metalation (n-Buli) and subsequent treatment by tosylazide of bromo-1,2-dithienyl-ethanes. The structures of the obtained derivatives were established on the basis of ¹H nmr, ir, and mass spectral data.     

Recherches sur la stéréochimie des diènes fonctionnels—X: Etude par Résonance Magnétique Nucléaire d'alcoxybutadiènes 1,3

The nuclear magnetic resonance parameters of 1,3 alkoxy-butadienes are strongly dependent on the cis or trans configuration of the ethylenic systems. A discussion of the different types of coupling constants and of the additivity of substituent effects on the chemical shift is proposed. The results are applied to the identification of isomers and to the study of the electronic and stereochemical structure of each configuration. The conformational equilibrium about the C? C and C? O bonds is discussed with special reference to the aromatic solvent and temperature effects.     

Triazènes et benzotriazines dérivés de sucres

Sugar triazenes and benzotriazines Several triazenylsugars have been prepared, generally in good yields, by treating an amino sugar with a substituted benzenediazonium salt. The triazenylsugars bearing a hydrogen atom on the triazenyl group are acetylated on the nitrogen atom closest to the glycosyl moiety (N(1)), even when the proton exchanged sites between N(1) and N(3). When an acetyl or a methoxycarbonyl group was present in the ortho position of the benzene ring cyclization took place leading to a 3,4-dihydro-4-methylidene-1,2,3-benzo[d]triazine or a 3,4-dihydro-1,2,3-benzo[d]triazin-4-one respectively.     

Synthèses et caractérisation de germylènes difonctionnels

Syntheses and caracterization of bifunctional germylenes Several synthetic methods of bifunctional germylenes GeY₂ (Y = RO, PhO, RS, CH₃COO, Acac; Y₂ = OCH₂CH₂O, SCH₂CH₂S) or GeXY (Y = RO, X = Cl; Y = RS, X = Cl; Y = Acac, X = Cl) such as exchange reactions, dechlorhydratation reactions and nucleophilic substitutions from GeCl₂ · dioxane are described. Some more synthesis of divalent species GeY₂ from Ge(OR)₂ by transalcoxylation and from Ge(Cp)₂ by cleavage using protic species will be presented. The stability and reactivity of these germylenes are discussed. Difunctionnal germylenes give generally a selfpolycondensation reactions. However, their reactivity in situ shows a effective participation of monomeric species GeY₂.     

Transpositions de doubles liaisons de p-menthènes et de p-menthadiènes catalysées par des bases

The displacements of double bonds by basic catalysts (N-lithioethylene diamine with an excess of ethylene diamine, potassium t-butylate in dimethylsulfoxide, benzyl-sodium in boiling xylene) are studied on p-menthenes and p-menthadienes. The isomerizations of p-menthadienes are accompanied by dehydrogenation. A representative mechanism of isomerization and dehydrogenation according to the catalyst is proposed for limonene.     

Synthèse d'amino-3 thiophènes a partir d'aryl-et d'hétaryl-acétonitrile

Applying Fiesselman's condensation to α-hydroxymethylene nitriles the authors describe a synthesis of substituted aminothiophenes.     

Réaction de l''oxygène singulet avec quelques vinylallènes

The dye sensitized photooxidation of three diversely substituted vinylallenes leads to Δ-4 tetrahydropyrane-3-ones.     

Synthèse d'oxaphénalènes substitués en position 2 par un groupement électro-attractif

Up to now, little is known about naphtho[1,8-bc]pyran (oxaphenalene) derivatives, although some of them have been detected in the vegetable kingdom. However, very recently [6], 2-nitronaphtho[1,8-bc]pyran and 6-methoxy-2-nitronaphtho[1,8-bc]pyran proved to be powerful mutagenic agents (the most efficient on mammal cells in culture hitherto known). This fact prompted us to investigate further this class of products by studying compounds bearing an electron-withdrawing group in the 2-position. We report in the present paper that, in certain cases, this synthesis can be achieved by the yet unattempted péri-heterocyclization of 8-hydroxy-1-naphthaldehydes with an halogenated active methylene compound in acetone in the presence of potassium carbonate. Thus, among others, 2-acetyl, 2-benzoyl and (4-methoxybenzoyl)naphtho[1,8-bc]pyrans, as well as the corresponding derivatives bearing a methoxy group in the 6-position have been prepared. Nevertheless, such a condensation according to Rap [1] cannot be carried out in certain cases, particularly with acetonitrile.     

Action du monoxyde d'azote sur le phényléthylène et sur quelques arylalcènes

Nitric oxide reacts with phenylethylene and arylalkenes under the action of sunlight and at room temperature giving dimeric nitronitroso compounds prouved by IR. spectroscopy (see Table 2) and the corresponding nitroolefins. The main gaseous product is nitrogen as prouved by gaz liquid chromatography (see Table 1). The dimeric nitronitroso compounds can also be obtained by the reaction of dinitrogen trioxide with olefins. The structure of the nitronitroso compounds was further discussed. They may be reduced to give monoamines corresponding to the nitrogroup and may be also converted into nitroolefins.     

Additions radicalaires. 16 Additions d'hétérocycles oxygénés aux allènes

Free radical addition of tetrahydrofuran and tetrahydropyran to various allenes gives mainly 1:1 adducts. Increasing substitution on the allenic triad involves a change in ratio of adduct formed by way of central attack (1% with propadiene, 99% with 2,4-dimethyl-2,3-pentadiene).