Synthèse et réactivité de nitro indazoles

Synthese and nmr study of forty-four nitroindazoles in which twentry-three were never published have been carried out. The best way to obtain the halogenomethyl derivatives(halogenation before or after methylation) is shown. Relative reactivities of the different heterocyclic ring positions toward the electrophilic agent are discussed.     

Synthèse et réactivité de dihydrotriazines et de dihydrotriazolotriazines

Generally, 4,5-dihydro-3triazinones have been prepared by a basic hydrolysis of 3-methylmercapto-4,5-dihydrotriazines. Of the serveral methylation methods, namely, diazomethane, methyliodide, dimethyl sulfate all in the presence of sodium methylate or silver carbonate, only methyl bromide in the presence of phase transfer catalyst was sucessful in producing all of the N-2 and/or N-4 methylate compounds. Two unequivocal syntheses of dihydrotriazolo[4,3-b]triazine are reported.     

Synthèse de la diméthyl-4,4-dihydrofuranedione-2,3

4,4-Dimethyl-dihydro-2,3-furanedione ( 4 ), an intermediate in the synthesis of (+)-D -pantothenic acid, is obtained in good yield from readily available substances such as isopropyl chloride, diethyl oxalate and formaldehyde, without oxidative conditions.     

Synthèse d'analogues furanniques et nitro-2 furanniques du diméthyl-7,12 benzanthracène

A route to 1-formyl-2-hydroxy-9-methylanthracene and 1-formy 1-2-hydroxy-9,10-dimethylanthracene is desribed. These two aldehydes were further converted into mono- or dimethylanthra[2,1-b]furans, besides the corresponding acids and esters, by condensation with ethyl bromoacetate. The related mono- or dimethyl-2-nitroanthra[2,1-b]furans were also prepared by reaction between the above aldehydes and bromonitromethane, followaed by heating in toluene in the presence of p-toluene-sulfonic acid.     

Synthèse et réactivité des bromhydrines dérivées de la chromone

Bromohydroxylated derivatives of chromone are obtained by addition of N-bromosuccinimide in dimethylsulfoxide. The configuration and conformation of these compounds are confirmed by NMR spectroscopy. Alkaline alcoholates react with these bromohydrins to give a ring contraction into 2-formyl-3-benzofuranone.     

Etude en série triazénique. IV. Synthèse et réactivité d'aryl-3-(diméthyl-3,4-isoxazolyl-5)-1-triazènes et d'arylazo-4-diméthyl-3,4-isoxazolones-5

Synthesis and reactivity of 3-aryl-1-(3,4-dimethyl-5-isoxazolyl)-triazenes and 4-arylazo-3,4-dimethylisoxazol-5-ones According to the experimental conditions and the nature of the substituents on the aromatic ring, aryldiazonium salts react with 5-amino-3,4-dimethylisoxazole ( 3 ) leading to either 3-aryl-1 (3,4-dimethyl-5-isoxazolyl)-triazenes ( 1A ) or 4-arylazo-3,4-dimethylisoxazol-5-ones ( 4 ). Analyses of the products resulting from thermal decomposition of these triazenes in aromatic substrates and in DMSO and their behaviour in acidic medium show that it is essentially the arylazo form 1B which is reactive.     

Synthèse et réactivité d'un nouvel hydrure organostannique à “queue polaire”: le dibutyl-4,7,10-trioxaundécylstannane

A new tin hydride was prepared by reduction of the tin chloride obtained in the addition of hydrogenochlorodibutylstannane to the allyl methyl ether of diethyleneglycol. The efficiency of this compound in reductions and reductive additions to alkenes of alkyl halides was demonstrated as well as the easy separation of the organic products of reaction from the organotin compounds by liquid-solid chromatography over silica.     

Synthése,stéréochimie,et réactivité thermique de (N-méthylidenealkylamino)-2 aziridines

1-Alkyl-2-(N-methylidenealkylamino)aziridines are obtained by the reaction of primary amines with either α-chloroacraldehyde or α-chlorocrotonaldehyde. Structural assignments are made by nmr spectroscopy. The thermal rearrangement of 1-alkyl-2-(N-methylidenealkylamino)-3-methylaziridines to pyrroles is described.     

Synthèse de sucres aminès ramifiés II. Synthèse et réactions de spiro-aziridines. Communication préliminaire

Treatment of 3-C-cyano-1,2:5,6-di-O-isopropylidene-3-O-(toluene-p-sulfonyl)-α-D -allofurannose with AlLiH₄ or RMgX yields spiro-aziridines with two identical substituents on C(3′) (? H, ? CH₃, ? C₂H₅). Reactions of these products and their derivatives are briefly described. If the C(3′) substituents are protons, the aziridine ring is easily opened. In acidic media (HCl), an amino-sugar containing the branched chain ? CH₂Cl is produced; with hydrogenation, a ? CH₃ branched chain results. If the C(3′) substituents are methyl groups, the aziridine ring cannot be opened neither with HCl nor with hydrogen. The acetylated derivative of this latter compound rearranges to the corresponding allylamide with HCl. For both types of spiro-aziridine, the nitrous deamination leads to the corresponding alkene.     

Synthèse et Propriétés d'Alkylidénehydrazono-2 Méthyl-3 Dihydro-2,3 Benzothiazoles

The synthesis and the spectral properties of 2-alkylidenehydrazono-3-methyl-2,3-dihydrobenzothiazoles are reported. In the mass spectra of each of these compounds, the main fragmentation implies the breaking of the ?N? -N?bond of the azine.     

Synthèse de l'amino-4 formyl-3 méthyl-6 pyridazine

The 4-amino-3-formyl-6-methylpyridazine, a new reagent in the pyridazine series, has been synthesized by two different routes. For that purpose some new ortho-substituted compounds of pyridazine have also been prepared.     

Sels de N-alcoxyquinoléinium et d'isoquinoléinium porteurs d'une fonction cétone dans leur chaîne alcoxyle: Synthèse et réactivité vis-à-vis d'amines secondaires

Reaction of α-bromoisobutyrophenone on quinoline 1-oxide and isoquinoline 2-oxide in the presence of silver perchlorate leads to N-alkoxyquinolinium and isoquinolinium salts bearing a keto group in their alkoxyl chain. On treatment with secondary amines these salts are quantitatively converted to 2-benzoylquinoline and 1-benzoylisoquinoline. This conversion results from a decomposition analogous to the Katritzky mode A of the intermediate isoxazolo[2,3-a]quinolinium or isoquinolinium salts which are first formed by a Proton Abstraction Ring Closure sequence. These tricyclic intermediates have been isolated when 2,2,6,6-tetramethylpiperidine was used.     

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 transformations de pyridopyrimidopyrimidines

A convenient one-step synthesis of a pyridoprimidopyrimidine system by means of the chloride of 1,3-dimethy1-4amino-5-amino-5-(N,N-dimethyliminiumchloromethine)uracil and substituted pyridines is studied and the title compounds are described.     

Synthèse d'acétyl-6 et benzoyl-6 indoles

The synthesis of 6-acetyl and 6-benzoylindoles has been carried out via the Hemetsberger reaction. Some aspects of their chemical reactivity were investigated.     

Synthèse et tautoméric d'amino-3 et d'hydroxy-3 buténolide

The synthesis fo 3-amino- and 3-hydroxy-2-methyl-4,4-spiro-cyclohexane-2-butene-4-olide was achieved starting from isocyanate or an isocyanate precursor. The study and discussion of tautomeric structures were peformed using ir and nmr spectra functional groups reactivity.     

Pseudo-nucléosides dérivés des pyrrolo[2, 3-d]pyrimidines. Synthèse et activité biologique

A new series of pseudonucleosides has been obtained by condensation of various aminopentopyranoses on a 4,6-dichloro-5-acetonylpyrimidine. Cyclisation into pyrrolo[2,3-d] pyrimidine leads in one step to new tubercidin analogs. Some of them exhibit significant antiviral activity toward vaccinia virus and Sindbis virus.