Synthesis in the diazasteroid group. I. A new synthesis of 8,13-diaza-2,3-dimethoxygona-1,3,5(10)triene and its mercuric acetate oxidation

From the condensation reaction of methyl butyrolactim (I) with 1-ethoxycarbonylmethyl-6,7-dimethoxy-l,2,3,4-tetrahydroisoquinoline (II), 8,13-diaza-2,3-dimethoxygona-l,3,5(10)trien-12-one (VI) and 8,13-diaza-2,3-dimethoxygona-l,3,5(10)triene (VII) were obtained in good yield. The oxidation of VI and VII with mercuric acetate was examined.     

Détermination de la Conformation et de la Configuration de Sulfoxydes à Sept Chainons,Intermédiaires de Synthèse d'un Analogue de la Biotine

The conformation of the two isomeric 8,10-diaza-8,10-dibenzyl-4-thiabicyclo[5.3.0]decan-9-one 4-oxides has been studied by NMR. The vicinal coupling constants show that these two sulfoxides exist in a highly preferred chair conformation where the S→O bond is axial.     

Spectrographie de Masse de Diazastéroïdes Possédant le Motif Tétrahydroisoquinoléique

We have determined the characteristic fragmentations in a series of 3,4-dihydroisoquinoline and of 8,13 diazaestrones, with the aid of metastable ions, ‘simili’ mass analysed ion kinetic energy spectra (E/V² constant) and some deuterated compounds. In the diazasteroidal series, we could distinguish three essential types of fragmentation, as well as preferential abstraction of the hydrogen situated on the 14-carbon.     

Synthesis in the diazasteroid group. III . Syntheses of the 8,16- and 8,17-diazasteroid systems

By using 3-pyrrolidone derivatives as a source of the D ring, the following five diazasteroids were synthesized: 8,16-diaza-2,3-dimethoxy-15,15,16-trimethylgona-1,3,5(10),13-tetraen-12-one (VII), 8,16-diaza-2,3-dimethoxy-16-acetylgona-1,3,5(10),13-tetraen-12-one (X), 8,17-diaza-2,3-dimethoxy-17-acetylgona-1,3,5(10),13-tetracn-12-one (XI), 8,16-diaza-16-acetylgona-1,3,5(10), 13-tetraen-12-one (XII), and 8,17-diaza-17-acetylgona-1,3,5(10),13-tetraen-12-one (XIII).     

Tordanone,un stéroïde replié avec une jonction de cycle A/B β-cis (5β) et B/C α-cis(8α)

Tordanone, a Twice Bent Steroid Structure with Ring A/B β-cis(5β)- and Ring B/C α-cis(8α)-Fused The 3β, 14α, 25-trihydroxy-5β, 8α-cholestan-6-one ( = tordanone; 4 ) has been prepared by stereospecific hydrogenation of 3β, 14α, 25-trihydroxy-5β-cholesta-7,22ξ-dien-6-one ( 5 ). This is the first stereospecific synthesis of a B/C cis-fused steroid belonging to the 5β, 8α -cholestane group with a H-atom at positions 5β (A/B cis-fused) and 8α. The resulting twice bent structure shows a particularly strong steric hindrance of the β-face where CH₃(18) at the C/D ring junction and H_β? C(7) of the B ring are very close to each other. Structural features and mechanistic aspects of the hydrogenation are discussed.     

Réarrangement de thiénobenzothiépinones en thiénoisothiazolinone et benzoisothiazolinone

Under the conditions of the Schmidt reaction the thienobenzothiepinones 1 , 2 and 13 involve a rearrangement respectively in N-benzythieno[2,3-d]isothiazolin-3-one ( 5 ) and benzoisthiazolin-3-one ( 6 ). A mechanism for this rearrangement is proposed.     

Identification de stérols à chaîne latérale oxygénée dans une éponge de l'espèce Hyrtios

Thirty-two sterols are identified in the sponge Hyrtios sp. In addition to fourteen monohydroxylated compounds, the sterol fraction contains eight functionalized sidechain sterols, three of them new: 3 β-hydroxy-24-norchol-5-en-23-al (19) , (22-trans)-3 β-hydroxycholest-5, 22-dien-24-one (20) and (22R, 23R, 24S) or (22S, 23S, 24S)- 22,23-epoxy-24-methylchoest-5-en-3 β-ol (24). The probable biological origin, rather than artifact production, of these undescribed components is discussed.     

Etude par spectrométrie de masse du diaza-2,5 dioxa-1,6 thia-6a λ IV pentalègne et de ses analogues séléniés et tellurés

The mass spectra of 2,5-diaza-1,6-dioxa-6a-λ-IV-pentalenes and of its selenium and tellurium analogs are recorded. The spectra show strong stability of these compounds under electronic impact and a rather good reproductibility for their fragmentations independently of thenature of the heteroatom (s, Se or Te).     

Propriétés de la benzopyranno[1][2,3-b]quinoxalinone-12

Under basic conditions. [1]benzopyrano[2,3-b]quioxakin-12-one leads to 3-(i-hydroxybenzoy1)-1H-quinoxalin-2-one. This ketone reacts with hydroxylamine and phenylhydrazine to give the expected derivatives or those of [1]benzopyrano92,3-b]quinoxalin-12-one. The reduction of [1]benzopyrano[2,3-b]quinoxalin-12-one was unsucessful by chemical means. However, electrochemical reduction leads to a dihydropyrazine nucleus.     

New Diterpenoids from Coleus forskohlii

Two new diterpenoids, forskolin G and H were isolated from the chloroform extract of the roots of Coleus forskohlii, and based on spectroscopic data,their structures were identified as 1α-hydroxy-6β,7β-diacetoxy-8,13-epoxylabd-14-ene-11-one(1),and 1α，6β-diacetoxy-8,13-epoxy labd-14-ene-11-one (2),respectively.     

Investigation of the products of the ozonolysis of larixol

On the ozonization of larixol in methanol followed by treatment with ammonium chloride, the main reaction products were 15,16,20-trisnorlabd-6-ene-8,13-dione and 6-hydroxy-8,13;8,14-diepoxy-15,20-bisnorlabd-14-one. When ozonization was performed in methanol in the presence of dimethyl sulfide or in methylene chloride in the presence of pyridine, 6,14-dihydroxy-8,13;8,14-diepoxy-15,20-bisnorlabdane and 6-hydroxy-14,50,20-trisnorlabd-8,13-dione predominated in the reaction products.     

Synthesis of polynuclear heterocyclic quinone imines — Derivatives of 4a,9-diazahydrofluoren-6-ones

When derivatives of 4a-9-diaza-1,2,4a,9a-tetrahydrofluorene are oxidized by treatment with MnO₂, the corresponding derivatives of 4a,9-diaza-1,2,4a,9a-tetrahydrofluoren-6-one are obtained. In a number of cases the reaction is accompanied by dehydrogenation of the side chains as well as the diazahydrofluorene fragment.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 793–798, June, 1988.     

Etudes sur les composés organométalliques partie XX Sélectivité de l'addition 1,4 de composés benzyliques du titane IV avec la benzylidéneacétone

Studies of Organometallic Compounds, XX. Selectivity of 1,4-Addition of Benzyltitanium Compounds with Benzylildenacetone Tetrabenzyltitanium and dialkoxydibenzyltitanium compounds give essentially 1,4- addition with trans-4-phenyl-3-buten-2-one.     

Synthesis and structure of 9,10,11,12-Dibenz[a,c]-7,14-diaza-1,4-dioxacyclohexadecane-8,13-dione

The reaction of diphenic acid dioxatriethylenediimide with a methanolic solution of amines leads to splitting of the imide heterocyclic ring by methanol with the formation of the corresponding amidoester of diphenic acid. Amines catalyze this reaction. 9,10,11,12-Dibenz[a,c]-7,14-diaza-1,4-dioxahexadecane-8,13-dione was obtained from diphenoyl dichloride and the corresponding diamine. An x-ray diffraction study has been carried outTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 974–978, July, 1992.     

Etude de l'oxydation de tétrahydroisoquinoléinols-4 diméthoxylés en 6,7 ou 7,8, et sur la réactivité du carbonyle de la tétrahydroisoquinolone-4 diméthoxylée en 6,7

Preparation of the tetrahydroisoquinolin-4-ols indicated in the title and their oxidation by different reagents (chromic anhydride, NBA, dimethylsulfoxide, Oppenauer oxidation) is reported. Only the last reaction led to the title compounds, while the other reagents (except NBA) yielded 1,2,3-trioxotetrahydroisoquinoline. Furthermore, the reactivity of 6,7-dimethoxytetrahydroisoquinolin-4-one was examined towards different carbonyl reagents.     

Investigation of the products of the ozonolysis of larixol

On the ozonization of larixol in methanol followed by treatment with ammonium chloride, the main reaction products were 15,16,20-trisnorlabd-6-ene-8,13-dione and 6-hydroxy-8,13;8,14-diepoxy-15,20-bisnorlabd-14-one. When ozonization was performed in methanol in the presence of dimethyl sulfide or in methylene chloride in the presence of pyridine, 6,14-dihydroxy-8,13;8,14-diepoxy-15,20-bisnorlabdane and 6-hydroxy-14,50,20-trisnorlabd-8,13-dione predominated in the reaction products.Institute of Chemistry of the MSSR Academy of Sciences, Kishinev, and Institute of Organic Chemistry of the Bashkir Branch of the USSR Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 577–584, September–October, 1986.     

Synthèses d'indoles par cyclisation réductrice. II Nouvelle mélhode de synthèse des indole carboxamides-3, donnant accés aux dérivés de la gramine

A new synthetic method for 3-indolecarboxamides, in two steps from 2-halogenonitrobenzenes, is reported. These benzene derivatives, reacting with sodium salts of cyanoacetamides in N,N-dimethylformamide, give 2-(2-nitrophenyl)cyanoacetamides. Catalytic hydrogenation of the nitro derivatives, at 80°, leads directly to 3-indolecarboxamides. Reduction of the amides by lithium aluminium hydride gives finally 3-aminomethylindoles (gramine and its derivatives), so obtained by a new synthetic route.     

Synthèse de l'ériodermine

Synthesis of Eriodermin The total synthesis of eriodermin (=2,7-dichloro-4-formyl 3-hydroxy-8-methoxy-1,6-dimethyl-11H-dibenzo[b,e] [1,4]dioxepin-11-one) is described.     

Synthèse de sucres aminés ramifiés. IV Synthèse de quelques dérivés nouveaux par l'intermédiaire d'une hexose-spiro-aziridine

Treatment of 3-C-cyano-1,2:5,6-di-O-isopropylidene-3-O-(toluene-p-sulfonyl)-α-D -allofurannose with AlLiH₄ yields a sugar-spiro-aziridine and a branched chain sulfonamide. Reaction mechanisms are briefly discussed and the configurations of the products obtained are proved by chemical reactions. With hydrogenation, the spiro compound is opened to a branched chain amino sugar with the same tertiary carbon as in vancosamine. Several derivatives of this new compound are described: the 6-deoxy sugars in series L and D and the pentose resulting from its oxidation by periodic acid. The conformation around C(4)–C(5) bond is deduced for three compounds from NMR. data.     

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.