Synthèse,réduction chimique et électrochimique de benzopyranno[1][4,3-e] et [3,4-e]pyrimido[1,2-b]-as-triazinones

From 9H-amino [l]benzopyranno-as-triazines 2 and 3 , [l]ben-zopyranno[4,3-e] or [3,4-e]pyrimido[l,2-b]-as-triazinones have been prepared by reaction with β-ketoesters. Chemical reduction of the compounds gives tetrahydro derivatives. By electrochemical reduction the dihydro compounds 14 and 15 were from-ed. The same dihydro derivatives were obtained with Grignard reagents.     

Synthèse de nouveaux alkyl-2 et -3 tétrahydrofurannes et -pyrannes

New 2- and 3-alkyltetrahydrofurans or -pyrans were synthesized by various methods which can be extended to a larger series. These compounds include tertiary and quaternary α carbon substituted heterocycles, a very few of which were already known.     

Synthèse de L'hydroxy-9 pyrimido[1,6-a]pyrimidine one-4 et dérivés

Condensation of 5-alkoxy-4-aminopyrimidines with diethyl ethoxy-methylenemalonate and with isopropylidene methoxymethylenemalon-ate, followed by thermal cyclization of the resulting enaminoesters intermediates yielded 9-alkoxypyrimido[l,6-a]pyrimidin-4-ones which were substituted in the 3 position by an ethoxycarbonyl group in the first case. Subsequent hydrogenolysis of the corresponding benzylic ethers afforded new heterocyclic phenols 9-hydroxypyrimido[l,2-a]pyrimidin-4-one and its 3-ethoxycarbonyl derivative.     

Synthèse partielle et propriétés oncostatiques des pseudo-tubulosines,analogues de l'émétine et de la tubulosine

Partial Synthesis and Oncostatic Properties of Pseudotubulosines, Analogues of Emetine and Tubulosine Pseudotubulosines, structural analogues of emetine and tubulosine, have been synthesized by either Pictet-Spengler or Bischler-Napieralski condensation from dihydrocorynantheal or corynantheidal. Spectral data, cytotoxic and oncostatic properties of these new alkaloids are described.     

Synthèse et propriétés des aroylhydrazones du benzoate d'éthyle. Synthèses d'hétéroscycles azotes

The aroylhydrazones of ethyl benzoate have been prepared in fair yield by the action of aroylhydrazines on ethyl benzimidate hydrochloride. These products give rise, quantitatively, at their melting point, to 5-aryl-2-phenyl-1,3,4-oxadiazoles, and, in the presence of hydrazine hydrate, in boiling 1-propanol to 4-amino-5-aryl-3-phenyl(4H)-1,2,4-triazoles (Yields 50%). The addition of methylmagnesium iodide to these products give aroylhydrazones of acetophenone.     

Chimie et pharmacologie de l'apiose III. Synthèse et propriétés de l'hydrate de l'O-isopropylidène-1, 2-tétrosulo-3-furannose

Ruthenium tetroxide oxidation of 1, 2-O-isopropylidene-β-D -threofuranose affords, besides the known 1, 2-O-isopropylidene-α-L -glycero-tetros-3-ulofuranose, a lactone. The tetrosulose is easily hydrated to the corresponding gem-diol whose dehydration on molecular sieves leads to a branched-chain dimer. Lead tetraacetate oxidation of 1, 2-O-isopropylidene-α-L -glycero-tetros-3-ulofuranose p-nitrophenylhydrazone leads quantitatively, to a gem-azoacetate, a new synthetic intermediate in carbohydrate chemistry. The 3-O-acetyl-1, 2-O-isopropylidene-α-L -glycero-tetr-3-enofuranose is easily obtained from the gem-diol. A highly stereoselective procedure is described to prepare the 3-O-acetyl-1, 2-O-isopropylidene-α-L -3, 4-exo-D₂-erythrofuranose.     

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

3-Benzyl-2-quinoxalinones were obtained by condensation of o-phenyl-enediamine with phenylpyruvic acids. These quinoxalinones were easily substituted in position 2 and which permitted the preparation of many derivatives, however, cyclisation of these compounds into 12H-[1]benzopyrano[2,3-b]quinoxalines failed. This new heterocycle might be synthesized from ethyl 2-phenoxy-3-quinoxalinecarboxylate.     

Synthèses de 1,2,4-triazolo[4,3-d][1,4]diazépines et de 1,2,4-oxadiazolo[4,5-d][1,4]diazépines par cycloaddition dipolaire-1,3

We report here a one-step synthesis of the 4,5,6,7-tetrahydro-1H- 1,2,4,-triazolo[4,3-d][1,4]diazepine, 4-6, and 1,2,4-oxadiazolo[4,5-d][1,4]-diazepine, 7-10, by 1,3-dipolar cycloaddition of nitrile imines and nitrile oxides with 2,3-dihydro-H-1,4-diazepine, 1. In all cases these cycloaddition are peri- and regioselectives (the C ? N bond is sole affected) and occures with high yields. Structure and conformations of cycloadducts have been assigned by means of nmr analysis     

Synthèse de l'oxo-7 7H cyclohepta[b] pyridine et de quelques dérivés

This communication describes the synthesis of 7-one (7H) cyclohepta[b]pyridine and some derivatives (6,8-dimethyl; 8-methyl; 8-ethyl….). These compounds have been obtained by condensation of ketones with 2,3-diformylpyridine.     

Un nouvel hétérocycle telluré: le benzisotellurazole-1,2. I. Synthèse et propriétés

Two different synthetic methods for 1,2-benzisotellurazole are described. The properties of this new heterocyclic system are compared with the analogous sulfur and selenium heterocycles.     

Synthése de la pyrido[4,3-e]-as-triazine

This communication describes the synthesis of a new heterocycle, pyrido[4,3-c]-as-triazine, its 3-methyl derivative, and their nmr spectral data.     

Synthèse et désamination enzymatique des C-hydroxyméthyl-3′- et C-méthyl-3′-β-D-xylofurannosyl-9-adénines

Synthesis and enzymatic deamination of 3′-C-hydroxymethyl- and 3′-C-methyl-β-D -xylofuranosyl-9-adenines The title compounds have been prepared by classical synthetic steps after having optimized the nature of the blocking groups. Both nucleosides were found to be substrates of adenosine aminohydrolase which proved that C(3′)-branched-chain sugar nucleosides can be deaminated when the branched-chain is exo (trans relative to the base) if a suitably disposed hydroxy group is available on the endo side of the furanose ring.     

Synthèse et étude conformationnelle de dioxa-1,3 aza-9 spiro[5,5]undecanes

Synthesis of the new l,3-dioxa-9-azaspiro[5.5]undecane ring, was realized by the scheme represented in Figure 2. Butyro-phenones 6 posses neuroleptic activity similar to that of halo-peridol. The pharmacological activity was reported in another publication (2). Conformational study of l,3-dioxa-9-azaspiro-[5.5]undecanes shows the existence of four conformations A, B, C and D, which are shown in Figure 4. The existence of these conformations depends on the nature of the substituents R and R' on the dioxane ring. Thus, in the compounds where R ≠ H, R' = H, the four conformations are possible with a preponderance of A and B. If R and R' are different from H only the conformation A is present in 99% concentration. Lastly, when R = R' = H, the four conformations are possible with equal population for the couple A, B and the couple C, D; the first couple predominating. The presence of a fluorophenylbutyric moiety on the piperidine nitrogen does not seem to stereochemically modify the heterocyclic group.     

Synthèse et stéréochimie de perhydrocyclopenta[b]furannones-3-cis et perhydrocyclopenta[b]furannols-3-cis

Synthetic route to new cis-perhydrocyclopenta[b]furan-3-ones and cis-perhydrocyclopenta[b]furan-3-ols is described. Their configurations and conformations were inferred by ¹H and ¹³C nmr spectroscopy. A certain rigidity is associated with the bond common to the two fused ring. The conformation of tetrahydrofuran-3-one ring appears to be a composite of the C, and C₂ forms depending on the C-2 substitution.     

Synthèse de dérivés de la benzo[c] quinolizine

The introduction of polar groups in planar polycyclic systems, for the purpose of studying their intercalating action, has been realized in the benzo[c]quinolizinium series. A functionalizing synthesis has been developed from 2-picolyl-and quinaldyllithium. Intermediate ketones or imines were cyclized by a quaternization reaction involving a concerted process. Structure and physico-chemical features of the compounds prepared were studied.     

Synthesis of spiro[3H-indole-3,2′-tetrahydro-1,3-thiazine]-2,4′(1H)-diones

The title compounds have been prepared by the cyclocondensation of 3-mercaptopropanoic acid with isat-in-3-imines. The 1-benzyl derivatives have been synthesized by simultaneously reacting 1-benzylisatin, substituted anilines and 3-mercaptopropanoic acid. Mannich condensation of the spiro thiazanones with secondary amines gave the corresponding 1-aminomethyl derivatives.     

Synthéses de bitriazoles-3(-5),1′ méthylés en position 1 ou 4 et de bitriazoles-4,4′

The synthesis of bitriazoles linked by C₃₍₅₎-N₁ or N₄-N₄′ bonds is reported and discussed. Two reactions have been investigated: a nucleophilic substitution of the halotriazole halogen by the triazole anion itself and a desulfurization reaction of the bis-s-triazolothiadiazines by the Raney Nickel. The determination of the structure of these bitriazoles is demonstrated by nmr spectroscopy. Their uv spectra are also reported.