Etude dans la série des radicaux hétérocycliques: partie XIV. Radicaux diméthyl-3, 4-isoxazolyl-5. Réactivité en série aromatique et hétéroaromatique: nouvelle voie d'accès à des diméthyl-3, 4-isoxazoles subsitués en C(5) par des groupements aryle et hétéroaryle

The aprotic decomposition of 5-amino-3, 4-dimethyl-isoxazole with excess isoamyl nitrite in aromatic solvents (alkylbenzenes, polyalkylbenzenes, anisole etc.) and in heteroaromatic solvents (thiophene, 2, 4-dimethylthiazole, pyridine, 4-alkylpyridines, dimethyl- and trimethyl-pyridines) leads to 5-aryl- and 5-heteroaryl-isoxazoles in yields of about 40%. This method provides a new way of obtaining 5-iodo-3, 4-dimethyl-isoxazole by the aprotic decomposition of the corresponding amine in the presence of iodine (yield: 30%). The relative reactivity of the 3,4-dimethylisoxazol-5-yl radical in alkyl benzenes, in anisole and in alkylpyridines is very similar to that of other heteroaromatic radicals with the radical site next to a sulfur or an oxygen atom. The radical shows electrophilic character because of the inductive effect of the oxygen atom. In the pyridine series an abnormally high percentage of 2-substitution occurs. This may be explained by a solvatation effect. The characteristic GLC., NMR. and MS. data are reported for most of the compounds studied.     

Réduction alkylante de quelques composés hétéroaromatiques polyazotés

The reduction-aldylation of quinoxaline, phthalazine and pyrido[2,3-b] pyrazine by potassium borohydride in a carboxylic acid medium is described. Formic, acetic, chloroacetic and propinic acids were used. The diazine ring of the molecule was reduced and alkylated into an N,N¹-dialkyltetrahydro compound. With quinoxaline and formic acid, N-formylation may be an important factor. Sodium borodeuteride allows one to prepare an hexadeuterated compound.     

Synthèse photochimique de biaryles et hétérobiaryles à partir d'aryl-et hétéroarylamines,d'un nitrite d'alkyle et d'un substrat aromatique ou hétéroaromatique

Photochemical synthesis of biaryls and heterobiaryls from aryl and heteroarylamines, alkylnitrite and aromatic or heteromatic substrates The photochemical reaction of aromatic and heteroaromatic amines with excess t-butyl nitrite in aromatic solvents (benzene, p-xylene, mesitylene) and in hetero-aromatic solvents (furan, thiophene) leads to biaryls or heterobiaryls. t-Butyl nitrite is more convenient than isopentyl nitrite which gives by-products. This new method has been used to synthesize 28 compounds in 17 to 60% yield.     

Une synthèse générale des tétraazamacrocycles mono-C-fonctionnalisés

A General Synthesis for Mono-C-Functionalized Tetrazamacrocycles A new synthesis, under usual conditions of concentration, medium, and temperature, of a series of mono-C-functionalized tetraazamacrocycles is given. The method may easily be generalized. The new procedure allows the modification of the length of the side-chain or the size of the cavity by choosing fitted staring materials. The key intermediate has a tosylated linear side-chain susceptible to be transformed into a large variety of functional groups.     

Propriétés chimiques du benzisosélénazole-1,2

The nitration and the bromination of 1,2-benzisoselenazole give mono derivatives at 5- or 7-position. With potassium amide 3-amino-1,2-benzisoselenazole is obtained from the unsubstituted ring. We observe a ring opening by action of organolithium compounds. We describe also the synthesis of functional derivatives at the 3-position from 3-styryl-1,2-benzisoselenazole and selenonaphthenequinone.     

Constantes d'acidité de quelques bihétérocycles

The pKa₁ and pKa₂ of 19 biheterocycles A-(CH₂)-n B(in which A and B represent pyrazole, imidazole, or pyridine rings, and n=0 or 1) were determined in water at 25° using poterntiometry and UV spectroscopy methods.     

Synthèse d'hétérocycles dérivés du (+)-camphre

Diamines react with 3-dimercaptomethylenecamphor giving either a bis-oxothioamide or a heterocyclic compound via in oxoaminothioamide intermediate. In this last reaction, there is cleavage of both C? S bonds. Similarly, diamines react with β-oxothioamides to produce the same heterocyclic derivatives. In these reactions, a transamination is involved and the carbonyl group of camphor is preserved. A distinctly different reaction occurs when the same camphor derivatives are treated with hydrazine; thioxo- alcoylamino- or arylaminoindazoles are then obtained. Ring closure occurs on the carbonyl carbon of the camphor molecule.     

Diénamines hétérocycliques. III. Réexamen de la réaction de la base de Fischer avec le tétracyanoéthylène

Heterocyclic dienamines III. A re-examination of the reaction of Fischer's base on tetracyanoethylene Depending on the order of addition, Fischer's base 5 (1,3,3-trimethyl-2-methylidene-indoline) reacts 1:1 with tetracyanoethylene to give either the tricyanovinylation product 6 or the spiro compound 7 . A skeletal rearrangement of a zwitterionic intermediate can explain the formation of the spiro compound. The latter undergoes a thermal isomerization yielding by ring expansion the tetrahydroquinoléine 8 . On reaction with LiAlH₄ or CH₃ONa 7 and 8 lead both to triazatetracycles. All structures are assigned on the basis of spectral data.     

Sur les orthoamino formyl quinoléines,nouveaux synthons hétérocycliques

The four o-aminoformylquinolines substituted on the pyridine ring were synthesized from the corresponding aminoquinoline-carboxylic acids. This convenient method was to used to prepare the four isomers and among them the 2-formyl-3-aminoquinoline which is not very stable. These new compounds provide new nitrogen-containing heterocyles having potential pharmaceutical properties.     

Diazo-, azo- et azidoazoles. III. Tautoméric azido/tétrazole dans des nouveaux azidoazoles

Some derivatives of 2-azidoimidazole and 3(5)azido-s-triazole were prepared to investigate the possibility of an azido/tetrazole equilibrium in these compounds. An explanation for observed differences in azido/tetrazole equilibrium between azole series and azine or thiazole series is suggested.     

Transposition de neber en série tétrahydropyrannone

The Neber rearrangement applied to the oxime tosylates of the 4- and 3-tetrahydropyranones gives the α-aminoacetals 5 and 20 , as well as 3-amino-4,4-diethoxy and 2-amino-3,3-diethoxy-tetrahydropyranes. The hydrolysis of the former gives the pyrazine 6 and the latter gives the aminoketone 21. On the other hand the aminoacetal 5 allows one to obtain the 4-acetoxy-3-trimethylammonium tetrahydropyran iodide ( 12 ) with a preferential cis axial acetoxy equatorial trimethylammonium conformation. The oxime tosylate of the 3-tetrahydropyranone readily undergoes the Beckman rearrangement into lactam 18 whose open chain product is the (3-aminopropoxy)acetic acid ( 19 ).     

Réactivité d'analogues bihétérocycliques du phénanthrène,vis-à-vis des agents d'acétylation et de lithiation

The influence of annelaction and of the heteroatom upon the reactity of some haterocyclic analogus of phenanthrene with a pyrrole nucleos was tested toward acetylation and lithiation. If methy-l[1]benzofuro-[3,2-b]pyrrole was acetylated only in the 2-position, the sulfer and selenious analogues with [3,2-b] and [2,3-b] annelarion were acetylated in the -2 and -3 position. No reaction at all or only with poor yield (in the oxygenated series) was observed with butyllithium except on the case of l-methyl[1]benzoselenono[2,3-b]pyrrole, where the opening of the selenophene nucleos gives, after carbonation and action of diazomethane, l-methyl-2-methoxycarbony 1-3-(o-methylselenophenyl) pyrrole.     

Synthèse de (3-aminopropyl)arylsilanes,comportant un ou deux motifs hétérocycliques,fongicides potentials

Synthesis of (3-Aminopropyl)arylsilanes, Including One or Two Heterocyclic Patterns, Potential Fungicides Flusilazole is an effective silylated fungicide used on a large scale for plant protection. We synthesized several flusilazole analogs and also copied the tebuconazole design, an other very efficient fungicide, which has four atoms between the aromatic group and the heterocyclic moiety. In contrast to flusilazole, we obtained dissymetric structures around the Si-atom by using successively two different Grignard reagents. In another way, the 1H-1,2,4-triazole moiety was exchanged in several cases by other N-heterocycles such as 1H-imidazole, piperidine, and 2,6-dimethylmorpholine, already present in other fungicidal compounds. Finally, several compounds having two N-heterocycles of the same or different nature were prepared.     

Synthèse de composés comportant deux hétérocycles oxygénés accoles au noyau benzénique, éthers du résorcinol

We wish to report the preparation of new bisheterocyclic compounds derived from resoreinol. We tried to sue methods during this investigation which would be selective and afford only tricyclic linear compounds. The starting material was resorcinol or the monomethylether of resorcinol. By reaction with chloroacetonitrile, acrylonitrile or ethyl chlorobutanoate, we obtained the intermediate compounds which were then cyclized by reaction with sodium acetate or polyphosphoric acid; either a catalytic reduction or treatment with zinc in presence of hydrochloric acid furnished the heterocyclic base. Another condensation followed by a cyclization and a reduction gave the desired compounds.     

β-Dicéto énamines hététrocycliques: 1. Indanediones-1,3 substituées en 2 par un hétérocycle azoté

The condensation of methylated N-heterocycles and espically monomethyl- and polymethylpyridinets on phthalic enhydrides leads to 2-ary1-1,3-indanediones. The 3alklidenylphthalides formed in an intermediary state have been isloated. The influence of solvents and temperature on the velocity and yeild of formation of 2-(2- and 4-pyridyl)-1,3-indandiobnes has been studies. The ir and nmr spectra confirm taht these compunds exist under a β-diketoenamine form resonating witj a betaine form.     

Photolyse stéréosélective des [α-tétrahydropyrannyloxy] -2 tétrahydropyrones-3

The photochemical irradiation of the 2-[sα-tetrahydropyrannyl-oxy]-3-tetrahydropyrones (3) gives the -3-tetrahydropyrone (6)and the α-valerolactone (7). the structures (S*, R*) or (S*, S*) which were determined by mmr and by comparison with the 2-[α-tetrahydropyrannyloxy]-2tetrahydropyrannes (5) (S*, R*) and (S*, S*) influence the rate of the photolysis     

Hétérocyclisations intramoléculaires par réaction d'oxymercuration. I — synthèse et configurations des hétérocycles

We have accomplished the intramolecular oxymercuration of γ-δ ethylenic alcohols, with different mercuric salts under different conditions. By “in situ” reduction, or by direct reduction of isolated mercuric compounds, we obtain, in some cases, diastereoisomers with different relative yields.     

Synthèse d'analogues bihétérocycliques du phénanthrène: Les méthyl-1-[1]benzothinéo,benzoséléno[2,3-b ]pyrroles,et méthyl-1-[1]benzofuro,benzothiéno et benzoséléno[3,2-b ]pyrroles

The condensation of ethyl sarcosinate on 2- or 3-halogeno 3- or 2-formyl[1]benzofuran. benzothiophene or benzoselenophene, and on the related 2h-[1]-3-benzoheteroyclanones is described. In the last instances the resulting compounds were formylated in teh 2-position with subsequent. After hydrolysis and decarboxylation, the I1methy][1]benzothieno-, benzoseleno [2,3-b]pyrroles were were thus obtained.     

Additions radicalaires du tétrahydrothiophène à des dérivés éthyléniques: Préparation de tétrahydrothiophènes substitués en 2

Di-t-butyl peroxide induces a free radical addition of tetrahydrothiophene to ethylenic compounds. The main products arise from an α-attack of the substrate. This reaction seems to be an interesting synthesis of these heterocycles.     

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.