Nitroazines. 8. Reactions of 6-nitroazolo[1,5-a]pyrimidines with pyrroles

The reactions of 6-nitroazolo[1,5-a]pyrimidines with pyrroles have been examined, and the influence of substitution in the azole moiety of the substrate on the course of the reaction studied. The formation of two isomeric sigma-adducts has been established by spectroscopy.For Communication 7, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1251–1255, September, 1988.     

Benzo[b] thiophene derivatives. XXII. Synthesis of the isomeric 5-methyl-6-methoxy- and 5-methoxy-6-methylbenzo[b] thiophene-2-carboxylic acids

The two isomeric benzo[b] thiophene-2-carboxylie acids having methyl and methoxy groups at positions 5 and 6 have been prepared and characterized. Both acids have been decarboxylated to the corresponding isomeric 5,6-disubstituted benzo[b]thophenes, and esterified to their methyl esters. The intermediate rhodanines, α-mercaptocinnamic acids and corresponding disulfides are described. An unusual by-product in the oxidative cyclization of β-3-methyl-4-methoxyphenyl-α-mercaptoacrylic acid with iodine is shown to be trans-3-methyl-4-methoxycinnamic acid, which can also be formed directly from the mercaptoacrylic acid by reduction with hydrogen iodide.     

Ion Complexation Properties of Calix[6]Arene Derivatives: I. 1,4-Calix[6]Crown-4 Derivatives

Abstract

A series of 1,4-p-tert-butyl-calix[6]crown-4 tetraesters, tetraamides, tetraacids with defined conformation have been synthesized, and their complexation properties towards metal ions and alkyl ammonium ions were investigated systematically. It was found that 1,4-p-tert-butyl-calix[6]crown-4 tetraethylester (3a) and 1,4-p-tert-butyl-calix[6]benzocrown-4 tetramethyl-ester (4b) show high selectivity towards Na⁺, Li⁺, respectively and all of them exhibit high complexation abilities towards Et₂NH₂ ⁺ cation.     

Recent developments in the chemistry of bicyclic 6-6 systems: Chemistry of pyrido[1,2-c]pyrimidines

The present review provides a study on the structural features, reactions, and synthetic methodologies of pyrido[1,2-c]pyrimidines. The maximum deviation from the mean plane of the pyridopyrimidine skeleton of 4-(pyridin-2-yl)-1H-pyrido[1,2-c]pyrimidine-1,3(2H)-dione indicated a reasonably planar system. The aim of this review is to give an overview of the diverse methodologies that have been reported on the chemistry of pyrido[1,2-c]pyrimidines. The different synthetic routes have been grouped according to the way the pyrido[1,2-c]pyrimidine moiety has been created. Thus, pyrido[1,2-c]pyrimidine compounds were obtained by the formation of one bond α to the bridgehead nitrogen atom [6+0(β)] and formation of two bonds from ([3+3], [4+2], and [5+1]) atom fragments. The mechanistic pathways of the reactions are discussed.     

Photochemical reactions of 6-alkylamino- and 6-alkylanilino-5H-benzo[a]phenothiazin-5-ones

Photochemical reactions of 6-alkylamino- and 6-alkylanilino-5H-benzo[a]phenothiazin-5-ones have been investigated. 6-Ethylamino- and 6-isopropylamino-5H-benzo[a]phenothiazin-5-ones and 6-methylanilino- and 6-ethylanilino-5H-benzo[a]phenothiazin-5-ones gave 6-amino-5H-benzo[a]phenothiazin-5-one and 6-anilino-5H-benzo[a]phenothiazin-5-one, respectively, on irradiation.     

Condensed Pyridopyrimidines. 6. Synthesis of Novel Pyrano[3',4':6,7]pyrido[2,3-d]pyrimidines

The previously unreported pyrano[3',4':6,7]pyrido[2,3-d]pyrimidines have been synthesized from 2-ethyl-2-methyltetrahydropyran-4-one.     

Studies on the chemistry of thienoanellated O,N- and S,N-containing heterocycles. 6. Synthesis of some thienoanellated [1,4]benzoxazepines

Substituted thieno[2,3-b][1,4]benzoxazepine derivatives as well as thieno[3,2-b][1,4]benzoxazepine deriva- tives have been synthesized. They are thienoanalogues of loxapine, a potent antipsychotic drug. Research activities concentrate on the preparation of structurally modified compounds of loxapine to minimize its undesirable extrapyramidal symptoms.     

Elektronentransfer und Ionenpaar-Bildung. 46. Mitteilung. Titrationen von Tetracyanethen mit Alkali- und Erdalkalimetallen in aprotischen Lösungen

Electron Transfer and Ion-Pair Formation: Titrations of Tetracyanoethene by Alkaline and Alkaline Earth Metals in Aprotic Solution For alkaline and earth alkaline metal ‘titrations’ of the π-acceptor tetracyanoethene in aprotic (c(H^⊕) < 0.1 ppm) solution, UV/VIS and ESR spectra have been measured in a sealed glas apparatus. Isosbestic points prove uniform but differing metal-mirror reduction processes for [Li]_x, [Na]_x, and [K]_x vs. [Cs]_x. The formation of solvent-shared or solvent-separated contact ion pairs detected is supported by subsequent crystallization and structure determination. For the tetracyanoethene radical anion, semiempirical PM3 calculations with limited configuration interaction allow to reproduce the structural data as well as the long-wavelength charge transfer excitation.     

Über die Synthese von 1-Aryl-und 1-Alkyl-2, 3-dimethyl-chinoxalinium-perchloraten. 2. Mitteilung. Synthese und 1H-NMR.-Spektren von 2,3-Dimethyl-1-phenyl-6-X-chinoxalinium-perchloraten

On the Synthesis of 1-Aryl- and-1-Alkyl-2, 3-dimethyl-quinoxalinium Perchlorates. 2nd Communication

1 1. Mitt.: [1].

. Synthesis and ¹ H-NMR. Spectra of 2, 3-Dimethyl-1-phenyl-6-X-quinoxlinium Perchlorates The synthesis of the title compounds ( 5 ) which have been useful as precursors for a lot of conventional and new-type dyes [2-8] has yet been limited to examples with X?H [2] [3] [11] [15] and with electron-donating [4] [12] or at best slightly electron-accepting [1] [6] substituents X and R. We now describe a method suitable even for compounds 5 with strongly electron-accepting substituents: N-monosubstituted o-phenylendiamines 4 , were condensed with 2, 3-butanedione and perchloric acid in mixed solvents containing an excess of diethyl ether. The products - mostly substituted at position 6 of the quinoxalinium ring - are chracterized by ¹H-NMR. spectra, elemental analyses and in most cases by isolation of the corresponding bases 6 . Correlations of chemical shifts with Hammett's σ_p [18] are given by equations (1)-(5).     

Research in the field of furopyridines. 2. Synthesis and steric structure of 6-methyl-1-hetarylidene-3,4-dioxo[3,4-c]pyridines

By condensation of 6-methyl-3,4-dioxo-1H-furo[3,4-c]pyridine with heteroaromatic aldehydes, furfurylidene- and thenylidenefuropyridinediones have been obtained. By means of ¹H NMR spectrometry using the nuclear Overhauser effect, it has been established that these compounds have the cis-s-cis and cis-s-trans conformations, respectively.For Communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 29, No. 5, pp. 633–638, May, 1993.     

Studies of polyazapentalenes. I. The preparation of 6-dehydroindazolo[1,2-a]benzotriazole

The photolysis of 1-(o-azidophenyl)-1H-indazole (IV) has been found to give a mix ture of 6-dehydroindazolo[1,2-a]benzolriazole (VI) and 2,2′-di(1-indazolyl)azobenzene (VII). On the other hand, 1-(o-nilrophenyl)-1H-indazole (1) was reduced with triethyl phosphite, affording VI and dibenzo[a,i] indazolo[1,2,′3-cd] indazolo[3,2,1-fg]-3,3a,5a,6,8a,8b-hexaaza-as-indacene (XIa).     

Synthesis of 6-phenyl and 6-styrylthiazolo[3,2-b] [1,2,4]triazoles

Thiazole rings have been often encountered in the structure of antibiotic or antitumor drugs. An easy synthesis of them has revealed itself necessary in order to elucidate the mechanism of action of these naturally occurring substances. A method of preparation of conjugated b-ethylenic thiazole[3,2-b] [1,2,4]triazoles by heating a 3-thio substituted [1,2,4]triazole in the presence of polyphosphoric acid is reported here, giving the expected product in a 60% yield.     

Benzo[b]thiophene derivatives. XXVII. 5-methoxy-6-halo-3-β-acetamidoethylbenzo[b]thiophenes,blocked analogs of melatonin

The preparation of the 6-fluoro and 6-chloro analogs of the title compound is described, in a seven-step synthesis giving 30-40% overall yields. All intermediates have been isolated and characterized, including important by-products, such as the corresponding benzo[b]thienyl-3-acetic acids, and 3-methylbenzo[b]thiophenes. Cyclization of the 3-halo-4-methoxyphenylthioacetoacetic esters gave more ortho-cyclization in the chlorine case than was observed for the fluorine derivative. The title compounds were shown to have weak antiovulatory action, with the fluoro analog most active.     

Mass spectrometric studies of 6-chloro-6H-dibenz[c,e] [1,2]oxaphosphorine-6-sulphide and its derivatives

The electron-impact induced fragmentation of 6-chloro-6H-dibenz[c,e] [1,2]oxaphosphorine-6-sulphide and its 6-ethoxy and 6-hydroxy derivatives has been studied and it has been found that formation of the dibenz[c,e] [1,2]oxaphosphorin system and elimination of HCP are common features. β-Hydrogen rearrangement, in the case of the ethoxy derivative, is comparable to ethers with a P? O? CH₂? CH₃ linkage.     

Chemistry of heterocycles 6—13C NMR study of 7,8-dihydro-6H-3-methyl-5,7-diarylisoxazolo-[4,5-B]azepines

The ¹³C NMR data of six 7,8-hydro-6H-3-methyl-5,7-diarylisoxazolo[4,5-b]-azepines have been studied. The studies have been confirmed by a new technique called the ‘attached proton test’.     

A 6-bromocoumarin analog of chloramphenicol

dl-threo-2-Dichloroacetamidol-1-[3-(6-bromocoumarinyl)]propane-1,3-diol ( 7 ) was synthesized according to Sorm's method. The fragmentation of dichloroacetamidomethyl 3-(6-bromocoumarinyl)ketone ( 4 ) under electron impact is reported. The results of in vitro antibacterial screening of the newly synthesized compounds have been presented.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 6. Naphthothienonaphthyridines

Five novel polycyclic heterocyclic ring systems are reported via photocyclization. The specific final products in these ring systems are: naphtho[1′,2′:4,5]thieno[2,3-c][1,8]naphthyridin-6(5H)-one ( 5 ), naphtho-[1′,2′:4,5]thieno[2,3-c][1,6]naphthyridin-6(5H)-one ( 6 ), naphtho[1′,2′:4,5]thieno[2,3-c]-1,5-naphthyridine ( 9 ), naphtho[1′,2′:4,5]thieno[2,3-c][1,2,4]triazolo[4,3-a]-1,5-naphthyridine ( 12 ), and naphtho[2′,1′:4,5]thieno[2,3-c]-1,5-naphthyridine ( 17 ). The direction of photocyclization to produce 9 was established from a zero quantum two-dimensional nmr spectroscopy experiment (ZQCOSY) using 6-chloronaphtho[1′,2′:4,5]thieno[2,3-c]-1,5-naphthyridine ( 8 ) as the model compound.     

A facile approach to 6-amino-2H-pyrano[2,3-g]isoquinolin-2-ones via a sequential Sonogashira coupling of 6-cyanoumbelliferone triflate and annulations with amines

Palladium-catalyzed synthesis of 2H-pyrano[2,3-g]isoquinolinones have been described from easily accessible precursor 6-cyanoumbelliferone triflate via sequential of Sonogashira coupling and the following annulations with several primary alkylamines under basic conditions The so obtained 6-propargylamino-2H-pyrano[2,3-g]isoquinolinones were involved in the CuAAC reaction with 2-azidobenzoic acid for obtaining 2H-pyrano[2,3-g]isoquinoline-benzoic acid hybrid compounds containing a 1,2,3-triazole linker.     

A new one-step synthesis of 2,3-dihydro-5H-thiazolo[2,3-b]quinazolin-5-one and 3,4-dihydro-2h,6h[1,3]thiazino[2,3-b] quinazolin-6-one

2,3-Dihydro-5H-thiazolo[2,3-b]quinazolin-5-one and 3,4-dihydro-2H,6H[1,3] thiazino[2,3-b]-quinazolin-6-one have been synthesized in one step by the reaction of methyl anthranilate with ehloroalkyl isothiocyanates.     

Reaction of nitrenes with strained olefins. Preparation and reactions of some 6-azabicyclo[3.1.0]hexanes

A number of examples of the 6-azabicycIo[3.1.0]hexane ring system have been prepared by the oxidation of N-aminophthalimide or 3-amino-2-methyl-4-quinazoIone with lead tetraacetate in the presence of variously substituted cyclopentenes. Thus, 6-phthalimidyl-6-azabicyclo[3.1.0]hexane, dimethy 1–6-phthalimidyl-6-azabicyclo[3.1.0]-hexane-1,5-dicarboxylate, 2,3-benzo-6-phthalimidyl-6-azabicycIo[3.1.0]hexane and N-3-(2-methyl-4-quinazolyl)-6-azabicyclo [3.1.0]hexane were prepared for the first time. All of the new compounds were found to be stable in refluxing carbon tetrachloride and chlorobenzene. Refluxing 6-phthalimidyl-6-azabieyclo[3,1.0]hexane in acetic acid for 24 hours resulted in quantitative rearrangement to a phthalohydrazide, 8 .