Sur l'acylation des méthylfluorènes II [1]. Benzoylation et acétylation du méthyl-2-fluorène

Benzoylation and acetylation of 2-methyl-fluorene according of Friedel-Crafts in carbon disulfide with aluminium chloride yielded the corresponding 7-acylderivatives. By oxydation the benzoyl derivative gave 7-benzoyl-9-oxo-fluorene-2-carboxylic acid, which was decarboxylated to the known 2-benzoyl-9-oxo-fluorene. By reduction according to Clemmensen the acetyl derivative gave 2-methyl-7-ethylfluorene.     

Sur l'acylation des métylfuorènes I. Benzoylation et acétylation du méthyl-1-fluorène

Benzoylation and acetylation of 1-methylfluorene according Friedel-Crafts in carbon disulfide with aluminium chloride yielded the corresponding 2-acyl derivatives. By oxydation the benzoyl derivative gave 2-benzoyl-9-oxo-fluorene-1-carboxylic acid, cyclizable into 1,2-phthalyl-fluorenone.     

Sur l'acylation des méthylfluorènes IV. [1] Benzoylation du méthyl-4-fluorène

Benzoylation of 4-methylfluorene according to Friedel-Crafts in carbon disulfide with aluminium chloride yielded two benzoyl derivatives: 5-methyl-2-benzoyl-fluorene (II) (major product), and 4-methyl-2-benzoyl-fluorene (III). By oxidation II and III gave the corresponding 9-oxo-derivatives, the structure of the last compounds being proved by an independent way.     

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.     

Sur l'acylation des mäthylfluorànes V. Formylation selon Rieche du mäthy1-1-fluoráne

The formylation of 1-methylfluorene according Rieche yields 1-methyl-2-fluorene-carbaldehyde, the constitution of which being proved by three independent ways.     

Sur 1'o-chlorobenzylidène-9-fluorène

9-o-Chlorobenzylidenefluorene is obtained in good yield from fluorene and o-chlorobenzaldehyde by condensation in methanol in the presence of sodium methoxide, while in ethanol containing sodium ethoxide 9-o-chlorocinnamylidenefluorene is formed as a by-product. The latter is absent in the methanol condensation system.     

Synthèse du mèthyl-1 diformyl-2,3 pyrrole,de la méthyl-1 pyrrolo[2,3-d] pyridazine et de la méthyl-1 oxo-6 (6h)cycloheptatrieno[b] pyrrole

This communication describes the synthesis of l-methyl-2,3-diformylpyrrole. This new compound is used to prepare a new heterocycle, l-methylcyclohepta[b]pyrrol-6-one and thus allows a new synthesis of l-methylpyrrolo[2,3-d]pyridazine.     

Synthèse d'analogues bihétérocycliques du phénanthrène: Les méthyl-1-[1]benzothinéo,benzoséléno[2,3-b ]pyrroles,et méthyl-1-[1]benzofuro,benzothiéno et benzoséléno[3,2-b ]pyrroles

The condensation of ethyl sarcosinate on 2- or 3-halogeno 3- or 2-formyl[1]benzofuran. benzothiophene or benzoselenophene, and on the related 2h-[1]-3-benzoheteroyclanones is described. In the last instances the resulting compounds were formylated in teh 2-position with subsequent. After hydrolysis and decarboxylation, the I1methy][1]benzothieno-, benzoseleno [2,3-b]pyrroles were were thus 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,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.     

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.     

Formation d'hydroxy-5 méthyl-5 isoxazolidinones-3 par action du dicétène sur les hydroxylamines

The reaction of diketene with N-monosubstituted hydroxyl-amines provides cyclic derivatives of the 5-hydroxy-5-methyl-isoxazolidin-3-one type.     

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.     

Sur les dérivés de la fluorénone VI Les acides bromo-3-fluorénonecarboxylique-2 et bromo-2-fluorénonecarboxylique-3 et la bromo-3-méthyl-4-fluorénone

Starting from 2-amino-3-bromo-9-oxofluorene and from 3-methylfluorene respectively the preparation of 3-bromo-9-oxofluorene-2-carboxylic acid and of 2-bromo-9-oxofluorene-3-carboxylic acid is described. A synthesis of 3-bromo-4-methyl-9-oxofluorene is also given.