Quinazolines et benzodiazépines-1,4. LX Imidazo[5,1-c]benzodiazépines-1,4

Upon treatment with oxalyl chloride followed by reaction with the appropriate nucleophile, the 3-carbamoyl-benzodiazepines 6 , 7 and 8 were converted stereospecifically to the tricyclic compounds 12, 13, 14, 16 and 19 . Epimerization of 19 in presence of p-toluenesulfonic acid led to 21 . The stereochemistry of these tricyclic compounds and of some of their N(2)-alkyl derivatives ( 22-31 ) has been established by NMR. spectroscopy. Under proper reaction conditions, attack by bases on the tricyclic esters 13 and 26 was shown to cause an inversion of the chiral center C(11a) and to yield stereospecifically rearranged products, e.g. 23 from 26 and 33 from 13 .     

Furannes et pyrroles disubstitués en 2,3. XVI synthèse de furo[3,2-c]pyranones-4 et nouvelle voie d'accès aux furo[3,2-c]pyridines

Treatment of 4-hydroxy-6-methylpyran-2-one with chloracetalhyde in basic aqueous medium gave 6-methylfuro[3,2-c]pyran-4-one. This compound reacted with ammonium hydroxide and some primary amines to form the corresponding N-substituted furo[3,2-c]pyrid-4-ones which may also be obtained from 4-hydroxy-α-pyridones. Furo[3,2-c]pyran-4-one was acylated at the 2 position and 4-chloro-6-methylfuro[3,2-c]pyridine easily gave 4-substituted derivatives by displacement of the halogen atom.     

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.     

Synthèse des pyrido[2,3-d] el [3,2-d] -s-triazolo[3,4-f] pyrimidines el de (pyrazolyl-1')-4 pyrido[2,3-d] et [3,2-d] pyrimidines

The synthesis of two new heterocycles is described: pyrido-[2,3-d]-.s-triazolo[ 3,4-f] pyrimidine and pyrido[3,2-d]-.s-triayzolo-[3,4-f] pyrimidine. 4-[I'-Pyrazolyl]pyrido[2,3-d]pyrimidines and 4-[1′-pyrazoly1] pyrido[ 3,2-d] pyrimidine are obtained by the action of 4-hydrazinopyrido[2,3-d]pyrimidine and 4-hydrazinopyrido-[3,2-d]pyrimidine with several β-diketones.     

Selenium heterocycles. XXXIX. Synthesis of thieno[3, 4-d]thiazole,thieno[3, 4-d]selenazole,selenolo[3, 4-d]thiazole and selenolo[3, 4-d]selenazole

Starting from readily available methyl 2-substituted4-methyl-5-thiazolyl ketone and methyl 4-methyl-2-phenyl-5-selenazolyl ketone, thieno[3, 4-d]thiazole, thieno[3, 4-d]selenazole, selenolo[3, 4-d]thiazole and selenolo[3, 4-d]selenazole were prepared. The structures of all compounds were confirmed by analytical and spectroscopic methods.     

Cyclisations intramoléculaires: Accés aux 9-oxo-4H,9H-pyrrolo[1,2-a]thieno[2,3-d]pyridine et 4-oxo-4H,9H-pyrrolo[1,2-a]thieno[2,3-d]pyridine. Synthèse des pyrrolo[1,2-a]thieno[3,2-e][1,4]diazepine et pyrrolo[1,2-a]thieno[2,3-e][1,4]diazepine

Synthesis of 1-(2- or 3-thienylmethyl)methyl)pyrrole and some derivatives are described from halogenomethylthiophenes. The intramolecular cyclisation of carboxylic acid 19 and 20 leads to pyrrolothienopyridines 22 and 23. On the other hand azide-aldehydes 29 and 30 in aqueous acid mixture gave the pyrrolo[1,2a]thieno[2,3-e][1,4]diazepine.     

Sur l'amino-5-benzoyl-4-méthyl-3-isoxazole: synthèse et transformation en dihydro-6,8-diméthyl-3,8-phényl-4-7H-isoxazolo[5,4-e]diazépin-1,4-one-7

On treatment with ammonia and benzaldehyde the benzalisoxazolone 3 does not give the aminoketone 7 as assumed by Speroni [ 1 ] but a product which has been shown to be identical with the enamine 8 prepared by Ried & Czack [4] from ethyl oximinoacetoacetate and benziminoethyl ether. Authentic aminoketone 7 was synthesized in a three-step procedure starting from the aminonitrile 19 . Conversion of 7 into the bromacetyl derivative 23 and subsequent treatment with hexamethylene-tetramine yielded the isoxazolodiazepine 24 . Methylation of 24 with diazomethane produced predominantly the N-methyl derivative 1 along with a small amount of the O-methyl compound 25 .     

5-丁基-9-苯基-4, 5, 6, 9-四氢苯并[d, e]恶唑[5, 4-g]-异喹啉-4, 6-二酮的合成

本文给出了一条较好的制备5-丁基-9-苯基-4, 5, 6, 9-四氢苯并[d, e]恶唑[5, 4-g]-异喹啉-4, 6-二酮的反应路线, 即: 先由4-溴-1, 8-萘酐经亚胺化、硝化、水解和还原等反应制得N-丁基-3-硝基-4-羟基-1, 8萘酰亚胺, 再在硼酸的存在下, 将亚胺与苯甲酰氯反应可得到目标化合物。文中给出了该化合物的质谱、核磁共振、红外、紫外和荧光等光谱数据。     

Recherches en série azabenzodiazépine VII. Synthése de pyrazolo[3,4-b]diazépines-1,4

Condensation of ethyl acetoacetate or acetylacetone with 4,5-diaminopyrazoles are reported and discussed. They gave new pyrazolo[3,4-b]-1,4-diazepines or intermediates which can be cyclised.     

Sur l'arǒme de viande de bœuf grillée III. Pyrrolo [1,2-a]pyrazines,identification et synthèse

Synthesis of alkylpyrrolo[1,2-a]pyrazines, roasted meat flavor constituents Seven alkylpyrrolo[1,2-a]pyrazines have been identified for the first time in a roasted meat aroma obtained by thermolysis of the hydrosoluble flavor precursors of raw meat. Identification of individual components was done by capillary gas chromatography/mass spectroscopy coupling. The structure of these nitrogen heterocyclic compounds was for some time in doubt because of the similarity of the MS. with those of other diazaindene and diazanaphthalene derivatives such as benzimidazoles, indazoles, cyclopenta [b]pyrazines and dihydroquinoxalines. The structure of these new flavor components was completely elucidated in some cases by interpretation of NMR. spectra, the others being deduced by analogy. Hypotheses are formulated concerning the formation of this skeleton by a non-enzymatic browning reaction between carbohydrates and amino acids. Four different schemes have been adopted to synthesize substituted isomers selectively.     

Sur la synthèse d'alkoxy-2 nitro-3 2H-chroménes

2-Alkoxy-3-nitro-2H-chromenes have been obtained by the reaction of β-nitroacetaldehyde dialkyl acetals with some salicylic aldehydes in the presence of triethylamine p-toluene sulfonate.     

Nouvelle synthèse des pyrido[4,3-b]quinoléines substituées sur leur sommet 1

A three step synthesis of pyrido[4,3-b]quinolines is reported. Thus, treatment of 2-hydroxy-4-arylaminopyridines under Vilsmeir-Haack conditions directly afforded 1-oxo-1,2-dihydropyrido[4,3-b]quinolines. Chlorination of these compounds gave the corresponding 1-chlorinated derivatives which were then substituted by various primary and secondary amines.     

Réductions chimique et électrochimique de 5H-benzopyranno[4,3-d]pyrimidines

The chemical reduction of 5H-[1]benzopyranno[4,3-d]pyrimidines with lithium aluminum hydrrde leads to 3,4-dihydro derivations. The electro-chemical reducation in acidic medium shows two monoelectronic cathodic waves. In netural or basic medium, substituted compounds in 2 position show a single bielectronic wave while two bielectronic waves are observed for unsubstituted compounds In all cases, preparative electrolysis lead to a hydrodimer in the 4,4′-positiom.