Synthèse des 2-hydroxy-7-〚benzimidazol-2-yl〛-méthyl-5-méthylpyrazolo〚1,5-a〛pyrimidines à partir de la 4-hydroxy-6-méthylpyran-2-one

Condensation of 3-amino-5-hydroxypyrazole 1 with triacetic acid lactone 2 in refluxed alcohols afforded 2-hydroxy-5,7-dimethylpyrazolo〚1,5-a〛pyrimidine 3 beside to 7-alkoxycarbonylmethyl-2-hydroxy-5- methylpyrazolo〚1,5-a〛pyrimidine 4. Action of hydrazine on compounds 4 yielded 7-hydrazinocarbonylmethyl-2-hydroxy-5-methylpyrazolo〚1,5-a〛pyrimidine 5. Condensation of o-phenylenediamines 6 with hydrazide 5 to melting reactants afforded 2-hydroxy-7-〚benzimidazol-2-yl〛methyl-5-methylpyrazolo〚1,5-a〛pyrimidines 7. Structures of the obtained products have been assigned by means of spectroscopic measurements.     

Synthèse et propriétés biologiques des pyrazolo〚4,3-c〛triazolo〚4,3-a〛〚1,5〛benzodiazépines

The addition of carbon disulfide to 3(5)-N-〚methyl (ethyl)-2-aminophenyl amino-5(3)-phenylpyrazole 3 (4) afforded 10-methyl (ethyl)-3-phenylpyrazolo〚4,3-c〛 〚1,5〛 benzodiazepine-4-thione 7 (8). These compounds reacted with alkyl halides and acetylhydrazide or benzoylhydrazide, to afford new heterocyclic systems: pyrazolo 〚4,3-c〛 triazolo〚4,3-a〛-1,5-benzodiazepines 15–18. Biological properties of compounds 8, 9, 16 and 17 have been evaluated.     

Cétonisation catalytique du méthyl-2-butène-3-ol-2 par des complexes du rhodium(III) ou du palladium(II)

A number of efficient catalytic procedures for the oxidation of acid-sensitive substrate such as 2-methyl-3-buten-2-ol to the corresponding ketone (2-methylbutan-2-ol-3-one) are compared. Reaction with dioxygen (or quinone) and a palladium precursor (PdCl₂ or [PdCl(NO₂)(CH₃CN)₂]) under mild conditions (⋍ 35°C), gave good conversions (⋍ 98%) and good selectivities (⋍ 90%).     

Analyse organique fonctionnelle : Combinaisons du dimédon (diméthyl-5,5 cyclohexa-nedione-1,3) avec les aldéhydes

The authors have traced and studied the thermolysis curves of dimedone and of the compounds it forms with 26 very different aldehydes. The purity of the aldehydes have been rigorously checked by infrared spectrography.     

Dédoublement et détermination des excès énantiomériques des complexes de ruthéniumII hexacoordinés 〚Ru(bpy)2ppy〛+ et 〚Ru(bpy)2Quo〛+ (bpy = bipyridine,ppy = phénylpyridine,Quo = 8-quinolate) utilisés comme templates dans la construction de réseaux anioniques tridimensionnels

The bimetallic networks coordinated with oxalate bridges {〚M^IIM^III(C₂O₄)₃〛^–C⁺〛}_n form an important family of molecular magnets. The role of the cation C⁺ is fundamental for the nature of the obtained network (bi- or tridimensional). Thus, tridimensional polymers can be obtained in optically active forms using monocationic resolved templates such as 〚Ru(bpy)₂ppy〛⁺ 1 and 〚Ru(bpy)₂Quo〛⁺ 2. These cations were synthesized and resolved. A ¹H NMR technique based on the formation of diastereomeric salts obtained with optically active anion 〚ΔTrisphat〛^– {Trisphat = tris(tetrachlorobenzenediolato)phosphate(V)} was used to measure the enantiomeric excesses. To cite this article: M. Brissard et al., C. R. Chimie 5 (2002) 53–58     

3-Äthyl-3-phenylpiperidindion-(2,4) und 3-Äthyl-3-phenylpyrrolidindion-(2,4) aus α-Phenylacetessigester

Zusammenfassung -Äthyl--phenylacetessigester (I) wurde bromiert, der resultierende -Bromacetylphenylbuttersäureester (II) mit NaBH₄ zum Bromhydrin (III) reduziert. Umsetzung mit KCN lieferte den -Cyan--hydroxy--phenyl--äthylbuttersäureester (IV), der in Gegenwart vonRaney-Ni zu den beiden stereoisomeren 3-Äthyl-3-phenyl-4-hydroxypiperidonen-(2) (Va) und (Vb) reduziert wurde. Oxydation von (Vb) mit CrO₃ lieferte das 3-Äthyl-3-phenylpiperidindion-(2,4) (VI).     

Synthesis and X-ray crystal structure of 〚VCl3((–)-sparteine)〛 and 〚FeCl2((–)-sparteine)〛

Novel complexes of vanadium(III), chromium(III) and iron(II) containing the alkaloid (–)-sparteine as a bidentate ligand have been prepared. Two of them, 〚VCl₃((–)-sparteine)〛 and 〚FeCl₂((–)-sparteine)〛, were characterised by X-ray diffraction. Known cobalt(III) and nickel(II) analogue complexes were prepared using the same procedure.     

Synthese des 1-Methyl-2-äthyl- und des 1-Äthyl-2-methylnaphthalins

Ohne Zusammenfassung     

Warfarin [3- (1-phenyl-2-acetyl) -?thyl-4-hydroxycumarin ]

Ohne Zusammenfassung     

2-?thyl-4-pyridinthions?ureamid

Ohne Zusammenfassung     

Chelatkomplexe von Eisen(II) und Kobalt(II) mit 2,6-Bis-(4-?thyl-2-pyridyl)-4-phenylpyridin

Ohne Zusammenfassung     

HYDROLYSE DE SPIROPHOSPHORANES I. Dérivés du Tétraoxa-1,4,6,9 Phospha V-5 Spiro (4–4) et de l'Heptaméthyl-2,2,4,7,7,8,8 Trioxa-1,6,9 aza 4 Phospha V-5 Spiro (4,4) Nonane

Abstract

L'hydrolyse de tétraoxaspirophosphoranes (1) et de trioxazaspirophosphoranes (2) conduit essentiellement soit [sgrave] des mono et des diesters phosphoniques (cas de 1) soit [sgrave] des monoesters phosphoniques (cas de 2). Le rôle de differents facteurs sur la réaction d'hydrolyse (solvant, température, groupements R extracycliques, nature du cycle) a été précisé. Un cas particulier de labilité de liaison P^v–C a été mis en évidence.

Tetraoxaspirophosphoranes (1) and trioxazaspirophosphoranes (2) hydrolysis lead mainly and respectively to phosphonic mono or diesters and to phosphonic monoesters. The effect of differents factors (solvent, temperature, extracyclic R groups, nature of the ring) has been examined. In one case the P^v–C bond has been found to be particularly labile.     

Phosphonates α-silylés (RO)2P(O)CR1R2SiR3R4R5 et α,α-disilylés (RO)2P(O)CR1[Si(CH3)3]2; preparation et propriétés

Phosphonoalkylation of trisubstituted chlorosilanes in the presence of excess i-Pr₂NLi has been examined to establish the steric acid and electrophilic properties of each silane. A similar sequence has been developed for the introduction of two Si(CH₃)₃ groups. The SiC bond cleavage clearly demonstrates the protecting effect of trisubstituted silyl groups; but the silyl groups do not influence the formation of vinylphosphonates in the Peterson reaction.     

配合物Nd(C7H7N2O2)3(H2O)3的合成及其晶体结构

用水热法合成了3,5-二氨基苯甲酸与Nd(Ⅲ)的配合物Nd(C7H7N2O2)3(H2O)3(1),其结构经IR,元素分析和X-射线单晶衍射仪表征。1为单核结构,属六方晶系,R3空间群,晶胞参数:a=1.887 29(18)nm,b=1.887 29(18)nm,c=0.603 53(12)nm,β=90,°γ=120°,V=1.861 7(4)nm3,Z=3,μ=2.154 mm-1,Dc=1.744 g.cm-3,R1=0.014 3,wR2=0.033 2。1中Nd(Ⅲ)与来自3个3,5-二氨基苯甲酸的6个氧原子及3个配位水的氧原子进行配位,形成9配位化合物。     

Etude par spectroscopie (IR et Raman) de l'éthylène diammonium bis dihydrogénomonophosphate NH3(CH2)2NH3(H2PO4)2

Infrared and Raman Spectra of single crystal and polycrystalline samples of NH₃(CH₂)₂NH₃(H₂PO₄)₂ and of its deuterated polycrystalline derivative have been recorded at 298 K. All the observed bands have been assigned using group theory. The IR and Raman spectra are consistent with the presence of strong OH⋯O hydrogen bonds.     

Synthesis of (7-polyfluoroalkyl)pyrazolo[1,5-a]pyrimidines based on lithium fluorine-containing β-diketonates

The reactions of Li enolates of fluorine-containing -diketones with 3-aminopyrazoles afforded (7-polyfluoroalkyl)pyrazolo[1,5-a]pyrimidines. The structure of 3-bromo-2-methyl-5-phenyl-7-trifluoromethylpyrazolo[1,5-a]pyrimidine was established by X-ray diffraction analysis.