Synthèse d'azido dithiényl-1,2 éthènes et éthanes

Two convenient preparations of azido-1,2-dithienylethenes are described. The synthesis of azido-1,2-dithienylethanes proceeds via metalation (n-Buli) and subsequent treatment by tosylazide of bromo-1,2-dithienyl-ethanes. The structures of the obtained derivatives were established on the basis of ¹H nmr, ir, and mass spectral data.     

Préparation de dithiényl-2-éthène-1,2, de dithiényl-2-pyrimidine-2,4 et de dithiényl-2-pyridazine-3,6

The condensation of 2-thienylmagnesium bromide with (Z)-1,2-dichloroethene 2,4-dichloropyrimidne, 3,6-dichloropyridazine and with a transition metal catalyst is described. The yields of these reactions are very good; 1,2-bis(2-thienyl)ethene and two new heterocyclic compounds 2,4-bis92-thientyl)pyrimidine and 3,6-bis(2-thienyl)pyridazine were obtained in one step from commercial products.     

Addition de la proline à quelques alcènes et alcynes électrophiles

Addition of proline in acetic anhydride to propiolic and pbenylpropiolic ester gave rise to two isomeric pyrroles 5 and 6 . Addition under the same conditions, to electrophilic alkenes pY-PhCH = C(X) (CN) led to a pyrroline-2 8 which eliminated HCN and produced pyrrole 9 . Addition of proline to fumarodinitrile is unusual, the reaction led to a new α-amino acid 10 and compound 11 . The structure of this product 11 was confirmed by X-ray measurements.     

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.     

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.     

Etude du mécanisme de la réaction de hantzsch des thiazoles. I. Mise en évidence et détermination des produits intermédiaires et de dégradation

The Hantzsch thiazole synthesis from α-haloketones and thioamides, proceeds via intermediates that can be isolated under certain conditions. These have been identified, mainly by nmr spectroscopy, as thioimidate derivatives. The chain or cyclic structures of these compounds depend upon the nature of the substituents. Their dehydration gives together with the expected thiazole, secondary products which have also been isolated and identified as α-mercaptoketones and α-ketothiolesters.     

Etude de la fragmentation par impact électronique en ions positifs et négatifs de dérivés nitrés de l'amino-2-benzothiazole

Study of Positive and Negative Ions Electron Impact Fragmentation of 2-Amino-benzothiazole Nitro Derivatives The positive and negative ions mass spectra of 2-amino-4,6-dinitrobenzothiazole ( 1 ), 2-amino-4-nitrobenzothiazole ( 2 ), 2-amino-6-nitrobenzothiazole ( 3 ) are reported and discussed. These compounds give an intense molecular ion and show interesting fragmentations in both positive and negative ions spectra. Specific ¹⁵N-labelling was used in order to confirm the fragmentation patterns.     

Sur la composition de l'arôme de thé

A gas-chromatographic investigation of black tea aroma has revealed, besides 19 known components, the presence of 4 new substances: 1-penten-3-ol, trans-2-hexen-1-ol, α-terpineol and β-ionone. The fragmentation pattern of 1-penten-3-ol has been determined by means of high resolution mass spectrography.     

Etude par Spectrométrie de Masse d'une Série de Phényl-1 Naphtalènes Substitués et des Dihydro-1,4 Naphtols-1 Correspondants

The 70 eV electron impact mass spectra of a series of substituted 1-phenylnaphthalenes and their corresponding 1,4-dihydro-1-naphthols have been studied. Plausible fragmentation modes which account for the formation of all the major ions are proposed. An interesting hydrogen transfer reaction, leading to major fragments through the elimination of methanol, seems to proceed via an 8-membered transition state mechanism.     

Etude par spectrométrie de masse des O-isopropylidène-1,2-thréo- et -érythro-furannoses et des quatre désoxy-5-O-isopropylidène-1,2-pentofurannoses

The mass spectra of the O-isopropylidene derivatives of threo- and erythro-furanose and those of the four C(4) methylated stereoisomers have been studied. Fragmentation modes based upon deuterium labelling, metastable peaks and high-resolution measurements are proposed. Each stereoisomer can be characterized by its low-resolution mass spectrum.     

Etude theorique des ruptures thermique et photochimique de la cyclopropanone

The primary processes involved in cyclopropanone reactivity have been investigated using a SCF-CI abinitio method. The C₂C₃ bond rupture has been found to be thermally favoured and the resulting oxyallyl could have a significant lifetime. By contrast, upon photonic excitation, C₁C₂ cleavage easily occurs, but does lead to stable intermediate. This constitutes the first step of CO extrusion. The results are discussed using simple MO and valence-state considerations, and compared with those of related compounds.     

Application de la réaction de Wittig à la synthèse de dérivés de bromoénosuloses et d'esters bromoénuroniques. Note de laboratoire

Use of the Wittig reaction for the synthesis of derivatives of bromoenosuloses and bromoenuronic esters Treatment of 3-O-benzyl (or 3-O-methyl)-1, 2-O-isopropylidene-α-D -xylo-pentodialdo-1, 4-furanoses ( 2 or 1 ) with acetylbromomethylidenetriphenylphosphorane ( 3 ), benzoylbromomethylidenetriphenylphosphorane ( 4 ) or bromoethoxycarbonylmethylidenetriphenylphosphorane ( 5 ) gave in good to excellent yields the expected enose ( 6--11 ). In all cases but one ( 8 where some 10% of the E-isomer was formed) the reaction led to the exclusive formation of the Z-isomer whose configuration was established by NMR.     

Évaluation ab initio de la couleur de diaryléthènes présentant un pont maléimide

We have investigated the visible spectra of closed-ring diarylethenes based on maleimide bridges. Our simulations have been performed with an ab initio time-dependent density functional theory approach that takes into account bulk environmental effects. The computed λ_max almost quantitatively agree with experimental data, with a mean absolute error limited to 13 nm for the 26 investigated photochroms.     

Sur la synthèse de quelques furochromènes,analogues pharmacochimiques de la xanthylétine et de la séseline

Some furochromenes substituted at the 2-position by an electron-attracting group were obtained starting from ortho-hydroxyformyl derivatives of 2,2-dimethyl-2H-chromene following various processes which are indicated. These new furochromenes are pharmacochemical analogues of some natural pyranocoumarins, and as such they are potential photosensitizers.     

Isolement de nouveaux complexes de zinc de dipyrrométhènes formés au cours de la synthèse de la méso-tétramésitylporphyrine par la réaction de Rothemund

Three new zinc bis(dipyrromethene) complexes have been isolated in the preparation of meso-tetramesitylporphyrin by the Rothemund zinc template based condensation process.     

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.     

Etude thermique de la N-methylmorpholine N-oxyde et de sa complexation avec l'eau

Résumé La N-méthylmorpholine N-oxyde (MMNO) a une température de fusion de 184.2°, une enthalpie de fusion de 160.5 J/g et une chaleur de décomposition de 1340 J/g. Son hydratation a été étudiée par analyse calorimétrique différentielle et par gravimétrie. A l'air et à la température ambiante, la quantité totale d'eau qui a diffusé dans la MMNO correspond à quatre molécules d'eau par molécule de MMNO. Plusieurs complexes MMNO-H₂O cristallins ont été mis en évidence par analyse calorimétrique differentielle: un complexe MMNO-2.5 H₂O (T _f =40.5°,H _f =143.4 J/g), un complexe MMNO-1 H₂O (T _f = 75.6°,H _f =160.5 J/g) et un complexe dont la quantité d'eau n'a pas été déterminée (T _f =102°,H _f =95 J/g).

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N-methylmorpholine N-oxide (MMNO) has a melting temperature of 184.2°, an enthalpy of fusion of 160.5 J/g and a heat of decomposition of 1340 J/g. Its hydration has been investigated by differential scanning calorimetry (DSC) and by gravimetry.In air and at room temperature, the total amount of water diffusing into MMNO corresponds to four molecules of H₂O per molecule of MMNO.Several MMNO-H₂O crystalline complexes have been studied by DSC: an MMNO-2.5 H₂O complex (T _f =40.5°,H _f =143.4 J/g), an MMNO-1 H₂O complex (T _f =75.6°,H _f =160.5 J/g) and a complex with an unknown amount of water (T _f =102°,H _f =95 J/g).

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Zusammenfassung Das N-Methylmorpholin N-Oxid (MMNO) hat eine Schmelztemperatur von 184.2°, eine Schmelzenthalpie von 160.5 J/g und eine Zersetzungswärme von 1340 J/g. Seine Hydratisierung wurde durch differentialkalorimetrische Analyse und durch Thermogravimetrie untersucht.In Luft und bei Raumtemperatur entspricht die gesamte, in das MMNO diffundierte Wassermenge 4 Wassermoleküle pro Molekül MMNO.Durch die differentialkalorimetrische Analyse wurden verschiedene kristalline MMNO-H₂O-Komplexe nachgewiesen: ein Komplex MMNO-2.5 H₂O (T _f =40.5°,H _f =143.4 J/g), ein Komplex MMNO-1 H₂O (T _f =75.6°,H _f =160.5 J/g) und ein Komplex, dessen Wassergehalt nicht bestimmt wurde (T _f =102°,H _f =95 J/g).

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N- -N- (MMNO) 184.2°, - 160.5 /, -1340 /. () MMNO. , MMNO , MMNO. MMNO ₂: MMNO · 2.5 ₂, _f =40.5°,H _f =143.4 /, MMNO · 1₂-T _f = 75.6°,H _f = 160.5 / , _f =102°,H _f =95 /.

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Nous tenons à remercier Monsieur H. Chanzy, Maître de Recherche au Centre de Recherches sur les Macromolécules Végétales (Grenoble), et son équipe de leur aide et de leurs conseils pour la préparation des produits.