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,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.     

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.     

Synthèses dans la série des bis-indéno-anthracènes,I Le tétraoxo-5, 10, 15, 16-tétrahydro-5, 10, 15, 16-bis-indéno [2.1-a; 2′.1′-c] anthracène et le dihydro-5, 16-bis-indéno [2.1-a; 2′.1′-c] anthracène

Starting from 5-carboxy-6-methyl-7, 12-dioxo-7, 12-dihydro-indeno [1.2-a] fluorene (phthalacone-carboxylic acid) the first title compound, XI, has been synthesized in 4 steps (overall yield 28%). By anindependent way the corresponding hydrocarbon (second title compound, IV) has been obtained in 3 steps (overall yield 35%) starting from 2, 3′-bi-indenyle and 1, 4-naphthoquinone.     

Synthèses dans ka série des bis-indéno-fluorènes II. Le dihydro-10,15-5H-bis-indéno [1, 2-a;2′,1′-i] fluorène

The biangular bis-indeno-fluorene 10,15-dihydro-5H-diindeno [l, 2-a; 2′, 1′-i]-fluorene (XII) has been synthesised in 6 steps starting from 1-(o-carboxyphenyl)-fluorenone (overall yield 21%). As an intermediate the 5,10,15-trioxoderivative of XII and, accessorily, its 5,10-dioxoderivative were also obtained.     

Synthèses dans la série des bis-indéno-fluorènes I. Le dihydro-13, 15-5H-bis-indéno[1, 2-a;1′, 2′-h]fluorène

The synthesis of 13,15-dihydro-5H-diindeno[1,2-a;1′,2′-h] fluorene in six steps starting from flourenone 4-carboxylic acid and 2,4-dichlorotoluene is described. As an intermediate product the 5, 13, 15-trioxo-derivative is obtained.     

Synthèses dans la série des bis-indéno-fluorènes,VIII. Méthyl-6-dihydro-9,15-7H-bis-indéno[2.1-b;2′.1′-g]fluorène

Starting from 5-benzoyl-2,4-dibromobenzoic acid and 3-methyl-fluorene, the 6-methyl-9,15-dihydro-7H-diindeno[2.1-b; 2′,1′-g]fluorene, a derivative of a mono-angular diindenofluorene has been synthesized in 5 steps (overall yield 1,5%).     

Synthèses dans la série des bis-indéno-fluorènes,VI [1] Dihydro-12, 15–6H-bis-indéno[1. 2-b; 2′.1′-h]fluorène et dihydro-14, 15–8H-bis-indéno[2. 1-a; 2′. 1′-h]fluoréne

Starting from cyclohexene and 2, 2′, 5, 5′-tetramethylbiphenyl the linear bisindenofluorene 12, 15-dihydro-6H-diindeno [1.2-b; 2′.1′-h] fluorene (XX) has been synthesized in 5 steps (overall yield 27%). As an intermediate product the 6, 12, 15-trioxo-derivative XIX (greyish green crystals, blue alcaline vat) was obtained. By a side way, the 6-oxo-derivative of XX and the already known monoangular bis-indenofluorene 14, 15-dihydro-8H-diindeno [2.1-a; 2′.1′ -h] fluorene (XXVII) were also obtained. XX can also be prepared in several steps starting from 3-methyl-fluorene or fluorene.     

Synthèses dans la série des bis-indéno-fluorénes III [1]. Dihydro-14, 15-13H-bis-indéno[2,1-a;1′,2′,-i]fluorène et dihydro-14, 15-8H-bis-indéno [2, 1-a;2′,1′-h]fluorène

Starting from 2-bromo-9-oxo-fluorene-1-carboxylic acid the biangular bis-indenofluorene 14, 15-dihydro-13H-diindeno[2, 1-a; 1′, 2′-1]fluorene (VIII) and the monoangular 14, 15-dihydro-8H-diindeno[2, 1-a; 2′, 1′-h]fluorene (XI) have been synthesised in 6 resp. 7 steps (overall yield 22% resp. 18%). As intermediate compounds the 14-oxoderivatives of VIII and XI were also obtained.     

Synthèses dans la série des bis-indéno-fluorènes,IX. Le dihydro-13,15-7H-bis-indéno[2.1-b; 2′.1′-h]fluorène et son dérivé méthylé en position 6

By condensation according Ullmann of 2-iodo-9-oxo-fluorene with 3-bromo-2-cyano-9-oxo-fluorene, followed by cyclisation and reduction, the new linear 13,15-dihydro-7H-diindeno[2.1-b; 2′.1′-h]fluorene (III) is synthesized in 3 steps. The 6-methyl-derivative of II is also obtained in a similar way.     

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.     

Synthèses dans la série des bis-indéno-fluorènes V [1]. Dihydro-13, 15–11 H-bis-indéno[2, 1-b; 1′, 2′-h]fluorène et dihydro-13, 15–5H-bis-indéno[1, 2-a; 1′, 2′-h]fluorène

Starting from cyclohexene and 2, 2′, 4, 4′-tetramethylbiphenyl the linear bis-indenofluorene 13, 15-dihydro-11 H-diindeno [2, 1-b; 1′, 2′-h] fluorene (X) has been synthetised in 5 steps (overall yield 30%). As an intermediate product the 11, 13, 15-trioxo-derivative IX was obtained. By a side way the 13-oxo-derivative of X and the already known monoangular bis-indenofluorene 13, 15-dihydro-5 H-diindeno [1, 2-a; 1′, 2′-h] fluorene (XIX) were also obtained.     

Sur les dérivés de la fluorénone VIII. Difluorénonyl-cétones,difluorényl-cétones et difluorényl-méthanes

By condensation of the chlorides of the four isomeric fluorenecarboxylic acids, respectively of the three 1-, 3- and 4-fluorenonecarboxylic acids with fluorene, followed by reduction of the obtained mono-respectively diketones, the four difluorenylmethanes I, II, III and IV are synthesized. The oxydation of the diketones gives the corresponding triketones. Starting from the chloride of 4-fluorenecarboxylic acid and 1-methylfluorene, a methyl derivative of IV is analogically obtained.     

Synthèses dans la série des-indéno-fluorénes,VII. Le trioxo-5,12,13-dihydro-12,13-5H-bis-indéno[2.1-a; 2′.1′-g] fluoréne

Starting from 9-oxo-fluorene-1-carbaldehyde, the title compound, XII, a trioxoderivative of a new biangular diindenofluorene system, has been synthesized in 5 steps (overall yield 37,5%). The corresponding hydrocarbon could not be obtained by reduction of XII. Attempts to synthesize the isomer XX of the trioxoderivative XII are described.     

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.     

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.