Spectres ir de quelques dérivés 3-acyl de la coumarine

The IR spectra of sixty-nine coumarin-3-acyl derivatives have been recorded and analysed in the region 4000-660 cm⁻¹ and 4000-400 cm⁻¹.

Band assignments are proposed as far as possible. Some absorption bands are characteristic for the examined coumarins and can be used in recognizing and differentiating a coumarin structure in an unknown compound.     

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.     

Equilibres conformationnels de dérivés de sucres à insaturation terminale

The conformation in solution of several unsatured sugars of the general type XHC?CH—glycosyl has been studied by NMR. In the trans series, the population of the sterically permitted gauche conformer increases with the M-ability of X. In the cis series, the population of the trans conformer increases with the space requirements of X. These phenomena are discussed.     

Synthèse de dérivés indoliques substitués in 7

The synthesis and some aspects of the chemical reactivity of 7-acetyl-, 7-benzoyl- and 7-bromoindoles are described.     

Dérivés C-glycosyliques XXIII. Radicaux libres stables dérivés de sucre Communication préliminaire

Treated with 2,3-dimethyl-2,3-bis-(hydroxylamino)-butane, aldehydo-dialdofuranoses ( 1 ) gave a mixture of two compounds: a 1,3-dihydroxyimidazolidine ( 2 ) and a 1-hydroxyimidazoline ( 3 ). Oxidation (PbO₂) of compounds 3 gave stable free radicals having the structure of 2-C-Glycosyl-4,4,5,5-tetramethylimidazolines 1-oxyl ( 4 ), whereas 2-C-Glycosyl-4,4,5,5-tetramethylimidazolines 3-oxide 1-oxyl ( 5 ) were formed by oxidation of 2 . The ESR. spectra of compounds 4 and 5 establish the structure of the imidazoline part of these radicals and provide informations on the sugar moiety.     

Ylides du soufre dérivés de sucres Communication préliminaire

S-Methylation of 6-S-benzyl-6-deoxy-1,2-O-isopropylidene-3-O-methyl-α-D-xylo-6-thiohexofuranos-5-ulose ( 1 ) gave the expected sulfonium salt 2 which on alcaline treatment yielded the stable sulfur ylide 3 . This compound constitutes an useful synthetic intermediate in carbohydrate chemistry. On heating in 1,2-dimethoxyethane, it underwent a Stevens rearrangement which led to an extension of the carbon chain of the sugar and, reacted with Michael acceptors, it gave cyclopropanation reactions.     

Synthèse de l'acide décarboxythamnolique

Synthesis of Decarboxythamnolic Acid The total synthesis of the meta-depside decarboxythamnolic ( = 3-[(3-formyl-2-4-dihydroxy-6-methyl-phenyl)oxy]-2-hydroxy-6-methoxy-4-methylbenzoic acid; 25 ) by the biomimetic condensation of the substituted β-orcinol units 9 and 22 is described.     

Dérivés de l'hydroxyméthyl-5 furfural. I. Synthése de dérivés du di- et terfuranne

Addition of α, β-unsaturated sulfones or ketones to 5-hydroxmethyl-furaldehyde or related furanaldehydes in the presence of a thiazolium salt gives di or tetraketonic furan compounds. Dehydrative cyclizationled to di- and terfuryl derivatives.     

Nouveaux dérivés tricycliques du benzimidazole

A general acid catalysed reaction of heterocyclization of 1-(hydroxyethyl)-2-ketobenzimidazole with an alcohol or a thiol is described. The methods used to prepare new derivatives of tricyclic benzimidazoles, bearing alkylamine side chains were accomplished.     

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.     

Etude de la fragmentation par impact électronique de dérivés du benzothiazole

Study of Electron-Impact Fragmentation of Benzothiazole Derivatives The mass spectra of eighteen substituted benzothiazoles are reported and discussed. All these compounds are thermodynamically stable and give an intense molecular ion, which undergoes different types of fragmentation depending on the nature of the substituent which is rarely eliminated directly. β-Cleavage with respect to the heterocyclic double bond is often observed. Specific ²H-, ¹³C-, ¹⁵N- and ³⁴S-labelling have been used in order to confirm the fragmentation patterns.     

Radicaux libres dérivés de sucres. Partie. VII. Analogues de nucléosides marqués par un spin. Communication préliminaire

Sugar Free Radicals. VIII. Spin-Labeled Nucleosides Analogs A series of 5′-deoxy-5′-hydroxylamino derivatives of adenosine and uridine have been prepared by reduction of the corresponding oxime or nitrone. ‘Second generation’ 3′-deoxy-3′-N-aryl(or N-alkyl) hydroxylamino-β-D -xylofuranosyluracils have also been synthesized by a one-pot reaction including the following elementary steps: deblocking of the starting material, reduction of the 3′-deoxy-3′-oximinouridine, condensation of the resulting hydroxylamine with an aldehyde, reduction of the nitrone formed. The deoxy-hydroxylaminonucleosides oxidized spontaneously in the air (or in presence of traces of PbO₂) to give the corresponding nitroxide free radicals, ESR spectra of which furnished useful informations on their structures. Some of these modified nucleosides bore notable cytotoxic or antiviral activities.     

Nouveaux Élastomères de polyuréthanes dérivés d'aminoacides

Synthesis and characterization of new polyurethane elastomers with rigid blocks derived from aminoacids have been achieved by polycondensation using poly(tetramethylene oxide) (PTMO) as a soft segment. Aminotelechelic oligopeptides or pseudopeptides were used in the hard block, eventually in association with lysine diisocyanate (ethyl 2, 6-diisocyanatohexanoate, LDI). Physicochemical characteristics of the so obtained materials, especially good filmmaking properties, allow their use as biomaterials of reduced toxicity.     

Stéréochimie de β-diols et de leurs dérivés cycliques—VII. Calcul empirique des déplacements chimiques en série dioxannique. Application a l'analyse conformationnelle de dérivés alkyles

The empirical calculation of chemical shifts of methyl-1,3-dioxans leads to consistent results. Deviations from the experimental value are correlated with ring deformation. This method is applied to 4 or 6-ethyl, -isopropyl and tertiary butyl-1,3-dioxans. With no substituent at C5, the 4-tertiary butyl group causes no more deformation than at the 2 or 5 position. Interactions of this group with one or two methyl groups at C5 are examined.