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 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,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 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,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.     

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-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.     

Synthèses dans la série des bis-indéno-anthracènes,II [1] Le dihydro-9,16-bis-indéno[2.1-α; 1′,2′-c]anthracène

Starting from 3,3′-bi-indenyle and 1,4-naphthoquinone the title compound, III, has been synthesized in 3 steps (overall yield 54.6%).     

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.     

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.     

Synthèses dans la série des bis-indéno-anthracènes,III. Le dioxo-15,16-dihydro-15, 16-bis-indéno[1.2-a;2′.1′-c]anthracène et le tétraoxo-5,10,15,16-tétrahydro-5,10,15,16-bis-indéno[1.2-a; 2′.1′-c]anthracène

The title compounds, a dioxo (XVIII) and a tetraoxoderivative (VI) of a new diindenoanthracene, are synthesized in several steps (overall yield 35 and 26%, respectively) starting from 2,3-dimethyl-1,4-diphenyl-butadiene-1,3 (VIII). The corresponding hydrocarbon could not be obtained by reduction.     

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,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.     

Recherches dans la série des cyclitols,XLI. Synthèses de deux cyclopentane-pentols

Two new cyclopentane-pentols, namely the 1, 2, 3, 4/5- and 1, 2, 3/4, 5-isomers have been prepared by hydroxylation of the three 3, 4, 5-trihydroxy-1-cyclopentenes. The stereoselectivity of some hydroxylating agents is discussed.     

Thio-I ehromannones 5,8-disubstituées et synthèses dans la série du thiéno[4,3,2-de] thiochromanne

With the aim of obtaining the thieno[4,3,2-de] thiochromane structure, various 5,8-disubstituted derivatives of [1]thiochromanone have been synthesized. The structures of the compounds thus obtained and of the intermediates used in their syntheses were confirmed by nmr spectroscopy or by chemical procedures.     

Synthesis of new guanidine derivatives from 2′,3′,4′,9′-tetrahydrospiro[piperidine-4,1′-[1H]pyrido[3,4-b]indole]

The reaction of the isothiourea derivative 2 with methylaminc or pyrrolidine resulted in guanidines 3a-3b . Using hydrazine under the same conditions the tetrazole derivative 4 was obtained. On reacting 2 with piperidine, morpholine, methylhydrazine, phenylhydrazine, hydroxylamine or sodium hydroxide, cycliza-tion took place leading to the novel 4-cyanimino-1,2,3,4,6,7,12,12b-octahydro-3,12b-ethanopyrim-ido[1′,6′:1,2]pyrido[3,4-b]indole ( 5 ). Some structural aspects of 5 and other model compounds were analysed mainly by ¹³C nmr spectroscopy.