Substituted pyridines. Syntheses based on 2, 5-dimethyl-4-phenyl (β-phenylethyl)pyridine

Condensation of the methyl groups of 2, 5-dimethyl-4-phenylpyridine and 2, 5-dimethyl-4--phenylethylpyridine with some aromatic aldehydes is investigated. The cyclization of 2, 5-dimethyl-4-phenylpyridine to 3-methyl-2-azafluorene and some derivatives of the latter is effected.     

7-Azaindole derivatives

The Bischler-Napiralski reaction is used to synthesize 1-phenyl-3, 9-dimethyl-5, 6-dihydro-12-aza--carboline, and its 5-methyl and 5-ethyl derivatives, from 1-phenyl-4-methyl-3-aminoalkyl-T-azaindoles. 5, 6-Dihydro-12-aza--carbolines prepared by sodium borohydride reduction are converted into 1-phenyl-3, 9-dimethyl-3, 4, 5, 6-tetrahydro-12-aza--carboline and its 5-methyl and 5-ethyl derivatives. 1-Phenyl-9-methyl-12-azaharman is synthesized by palladium dehydrogenation of 1-phenyl-3, 9-dimethyl-5, 6-dihydro-12-aza--carboline.For Part XVII see [1].     

Synthesis of Some New Thiazoles and Pyrazolo[1,5-a]pyrimidines Containing an Antipyrine Moiety

Ethyl 2-{2-[4-(2,3-dimethyl-5-oxo-1-phenyl-3-(pyrazolin-4-yl)]-2-cyano-1-(phenylamino)vinylthio}-acetate, 2-[4-(2,3-dimethyl-5-oxo-1-phenyl-(3-pyrazolin-4-yl))(1,3-thiazol-2-yl)]2-(4-oxo-3-phenyl-(1,3-thiazoilidin-2-ylidene))ethanenitrile, 2-[4-(2,3-dimethyl-5-oxo-1-phenyl(3-pyrazolin-4-yl))(1,3-thiazol-2-yl)]-2-(4-methyl-3-phenyl(1,3-thiazolin-2-ylidene))ethanenitrile, 2-(5-acetyl-4-methyl-3-phenyl(1,3-thiazolin-2-ylidene))-2-[4-(2,3-dimethyl-5-oxo-1-phenyl(3-pyrazolin-4-yl))(1,3-thiazol-2-yl)]ethanenitrile, and ethyl 2-(cyano(4-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)thiazol-2-yl)methylene)-2,3-dihydro-4-methyl-3-phenylthiazole-5-carboxylate were synthesized by treatment of 2-(4-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)thiazol-2-yl)-3-mercapto-3-(phenylamino)-acrylonitrile with appropriate halo ketones or halo esters. Also, 4-{2-[5,7-dimethyl-2-(phenylamino)(7a-hydropyrazolo[1,5-a]pyrimidin-3-yl](1,-thiazol-4-yl)}-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one derivatives were synthesized via reaction of 4-{2-[5-amino-3-(phenylamino)pyrazolin-4-yl](1,3-thiazol-2-yl)}-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one with β-diketone or β-keto ester. All synthesized compound were established by elemental analysis, spectral data, and alternative synthesis whenever possible.     

7-Azaindole derivatives

A study is made of new synthetic routes, based on accessible 3-formyl-7-azaindoles, to 3-substituted 7-azaindole. 2-Phenyl-4-(1-phenyl-4-methyl-7-azaindolyl-3-rnethylene)-1, 3-oxazol-5-one is synthesized, and it is converted to 1-phenyl-4-methyl-7-azatryptophane, 1-phenyl-4-methyl-7-azaindolyl-3-acetic acid,1-phenyl-3-(,-dihydroxypropyl)-4-methyl-7-azaindole, and 1-phenyl-4-methyl-7-azaindolyl-3-pyrotartaric acid.For Part XVIII see [1].     

Reaction of ethylene oxide with n-phenylated isomers of 1,2,4-triazoline-3-thione and 1-phenyltetrazoline-5-thione

It is demonstrated that ethylene oxide forms N--hydroxyethyl derivatives of the corresponding triazolin-3-ones in the reaction with 1-phenyl- and 4-phenyl-1,2,4-triazolin-3-thiones and with 3--hydroxyethylthio derivatives of 1-phenyl- and 4-phenyl-1,2,4-triazole in acetic acid. 1-Phenyltetrazolin-5-thione reacts similarly with ethylene oxide. Under the influence of ethylene oxide, 2-methyl-4-phenyl-1,2,4-triazolin-3-thione is converted to 2-methyl-4-phenyl-1,2,4-triazolin-3-one.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 700–703, May, 1971.     

α-phenylisocinchomeronic and 4-azafluorenone 3-carboxylic acids

3,6-Dimethyl-6-phenylpyridine, obtained on phenylation of 2,5-lutidine, has been used in the synthesis of -phenylisocinchomeronic acid, derivatives of it, and also for the preparation of 4-azafluorenone 3-carboxylic acid. It was established that 4-hydroxy-3,6-dimethyl-2-phenylpyridine was formed on phenylation of 2,5-lutidine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 645–648, May, 1986.     

Ring — chain tautomerism and reactions of 4-aryl-4-hydroxy-2,3-dimethyl-3,4-dihydrophthalazinones

It has been established by IR spectroscopy that the N,N-dimethylhydrazides of 2-aroylbenzoic and benzil-o-carboxylic acids, with the exception of 2-mesitoylbenzoic acid, have the ring structure of 4-aryl- or 4-benzoyl-4-hydroxy-2,3-dimethyl-3,4-dihydrophthalazinones. The action of electrophilic agents on 4-hydroxy-2,3-dimethyl-4-phenyl-3,4-dihydrophthal-azinone under mild conditions leads to N₍₃₎-demethylation with the formation of 2-methyl-4-phenylphthalazinone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1124–1126, August, 1973.     

Indole derivatives

A new method for the synthesis of alkyl-substituted tetrahydro--carbolines has been developed which involves the cyclodehydration of 2-(2'-aminoisobutyl)indole and 2-(2 aminoethyl)indole with various aldehydes and ketones. The reduction with amalgamated zinc in hydrochloric acid of 2, 2-dimethyl-, 4, 4-dimethyl-, and 2, 2-dimethyl-4-phenyl-1, 2, 3, 4-tetrahydro--carbolines has been studied. The structure of the compounds obtained on reduction has been demonstrated.For part XXV, see [2].     

Synthesis of new polydentate tweezers ligands of amido-amine type

A series of new tweezers amido-amine ligands containing pyrrole, bipyrrole, and dipyrrolylmethane fragments were synthesized by reaction of 2-thioxothiazolidin-3-yl derivatives of α-pyrrolecarboxylic acids {5-[1-(5-carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl)-1-methylethyl]-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid, 5-[(5-carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl)phenylmethyl]-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid, 5-(5-carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl)-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid, and 3,4-dimethyl-pyrrole-2,5-dicarboxylic acid} with o-phenylenediamine. All compounds obtained were characterized by elemental analysis, NMR and mass spectra.     

Synthesis of substituted 2-pyridones and 4-aza-3-fluoridones

Substituted N-methyl-2-pyridones and N-methyl-4-aza-3-fluoridones, a previously unknown group of heterocyclic compounds, were obtained by oxidation of 3-methyl-2-phenylpyridine, 3-methyl-2-phenyl-5-(3-methyl-2-phenylpyridin-6-yl)pyridine iodomethylates, as well as of 4-aza-fluorenes substituted at the 9-position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 939–942, July, 1986.     

Synthesis of 4H-pyrazolo- and 4H-pyrrolophenothiazin-4-one derivatives

5-Methyl- and 6-methyl-2-phenyl-2H-indazole-4,7-diones were condensed with 2-aminobenzenethiol or 6-substituted-3-aminopyridine-2(1H)thiones 4 to produce a new type of 5-methyl-2-phenyl-4H-pyrazolophenothiazin-4-ones or 8-substituted-7-aza-5-methyl-2-phenyl-4H-pyrazolophenothiazin-4-one derivatives. From 6-bromo-2,5-dimethyl-1,3-diphenyl-2H-isoindole-4,7-dione and 4 8-substituted-7-aza-2,5-dimethyl-1,3-diphenyl-4H-pyrrolophenothiazin-4-one derivatives were also prepared.     

Tetrahydro- and octahydropyrido[1,2-a]pyrimidin-4-ones

The catalytic hydrogenation of 2-methyl-, 1 2,8-dimethyl-, 2 , 2,9-dimethyl-, 3 , 9-methyl-2-propyl-, 4 , 2,3,9-trimethyl-, 5 , 9-methyl-2-phenyl-, 6 , 9-hydroxy-2-methyl-, 7 , 9-acetoxy-2-methyl, 8 , 9-carboxy-2-methyl-, 16 , 9-carboethoxy-2-methyl-, 17 , 9-carbomethoxy-2-methyl-, 18 , and several 9-carboxamido-2-methyl-, 19, 20 , and 21 , derivatives of the pyrido[1,2-a]pyrimidin-4-one heterocycle has led to a series of novel 6,7,8,9-tetrahydro- and fully saturated, octahydro analogs. In deuteriochloroform or DMSO-d₆ solution, the pmr spectra of the tetrahydro derivatives derived from 1-7 revealed only the 6,7,8,9-tetrahydro structures. In the pmr spectra of 16-21 , there was evidence of a facile 1,3-prototropic shift of the proton from position-9 to position-1, resulting in equilibria between tautomeric species, i.e., . The ratio of tautomers present at equilibrium, with the esters, favored the enamine conformation, whereas, with both the carboxylic acid and the amides, the imine structure predominated. Supportive evidence for the enamine structure with the esters was derived also from the ir spectra. Alkylation of the anion derived from the tetrahydro 9-carbomethoxy derivative with sodium hydride led exclusively to derivatives of 6,7,8,9-tetrahydro system.     

Synergistic extraction of uranium(VI) with 1-phenyl-3-methyl-4-acylpyrazolone-5 and neutral extractants

The synergistic extraction of uranium(VI) from hydrochloric acid solution with five chelating agents: 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (PMBP), 1-phenyl-3-methyl-4-acetylpyrazolone-5 (PMAP), 1-phenyl-3-methyl-4-(2-chlorobenzoyl)pyrazolone-5 (PMCBP), 1-phenyl-3-methyl-4-(p-nitrobenzoyl)pyrazolone-5 (PMNBP) and 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5 (PMTFP) plus the neutral extractants tributylphosphate (TBP), dioctyl sulfoxide (DOSO) and trioctylphosphine oxide (TOPO) in chloroform has been investigated. The extraction coefficients have been found to be greater for such mixtures than the individual component. The formulas of the extracted species have been determined to be UO₂A₂B (where HA = chelating agent, B = neutral extractant). Extraction power of these chelating agents increases as follows: PMCBP>PMNBP>PMTFP=PMBP>PMAP. Synergistic extraction power of the neutral extractants increases as follows: TOPO>DOSO>TBP. The extraction equilibrium constants have been calculated. The mechanism of the synergistic extraction and possible structure of the extracted species are discussed.     

Synthesis of azoxindoles

Heating N-substituted 2-methyl-3-phenyl-5-nitroindoles in methanol with excess base yields the corresponding azoxindoles. Under the same conditions 2-methyl-5-nitroindole is converted to bis(2-methyl-5-nitroindol-3-yl)methane. Reaction of 1,2-dimethyl-3-formyl-5-nitroindole with benzyl cyanide gives 1,2-dimethyl-3-(-cyano--phenyl)vinyl-5-nitroindole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 622–624, May, 1990.     

Nitropyrazoles: XII. Transformations of the 4-Methyl Group in 1,4-Dimethyl-3,5-dinitropyrazole and Cyclization of the Transformation Products

A preparative procedure for the synthesis of 1,4-dimethyl-3,5-dinitropyrazole by nitration of 1,4-dimethylpyrazole was developed. The reaction of 1,4-dimethyl-3,5-dinitropyrazole with dimethoxymethyl- (dimethyl)amine (N,N-dimethylformamide dimethyl acetal) gave (E)-N,N-dimethyl-2-(1-methyl-3,5-dinitropyrazol- 4-yl)ethenylamine. Acid hydrolysis of the latter afforded (1-methyl-3,5-dinitropyrazol-4-yl)acetaldehyde, and the reaction with sodium nitrite in hydrochloric acid led to formation of 2-hydroxymino-2-(1-methyl- 3,5-dinitropyrazol-4-yl)acetaldehyde. The corresponding O-methyloxime and phenylhydrazone reacted with K₂CO₃ to give 6-methyl-4-nitropyrazolo[4,3-d]isoxazole-3-carbaldehyde O-methyloxime and 1-methyl-3-nitro-4-(2-phenyl-2H-1,2,3-triazol-4-yl)pyrazol-5-ol, respectively. Treatment of (1-methyl-3,5-dinitropyrazol-4-yl)-acetaldehyde with benzenediazonium chloride gave (1-methyl-3,5-dinitropyrazol-4-yl)acetaldehyde phenylhydrazone which underwent intramolecular cyclization with replacement of the 5-nitro group by the action of K₂CO₃ in acetonitrile; in the reaction with K₂CO₃ in ethanol, the 5-nitro group was replaced by ethoxy.     

Reaction ofβ,β -dimethyldivinyl ketone with 2,5-dimethyl- and 1,2,5-trimethyl-4-piperidones

1-(3-Oxo-5-methyl-4-hexen-1-yl)-2,5-dimethyl-4-piperidone, 5-(3-oxo-5-methyl-4-hexen-1-yl)-2, 5-dimethyl-4-piperidone, and 5-(3-oxo-5-methyl-4-hexen-1-yl)-1,2,5-trimethyl-4-piperidone were synthesized. In the absence of a catalyst,-dimethyldivinyl ketone adds to 2,5-dimethyl-4-piperidone at the 1-position, while in the presence of alkali it adds at the 5-position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 350–351, March, 1971.     

Synthese der isomeren 3, 4-Dimethyl-4-phenyl-3, 4-dihydro-carbostyrile

Cyclisation of 2-methyl-3-phenyl-but-3-en-anilide (III) with polyphosphoric acid gave cis-3, 4-dimethyl-4-phenyl-3, 4-dihydro-carbostyril (VII) in 61% yield together with a small amount of 2, 3-dimethylindenone (VIII), whereas with AlCl₃ a phenyl group was split off to give 3, 4-dimethylcarbostyril (VI). The anilide III isomerises to cis- and trans-2, 3-dimethyl-cinnam-anilide (IV resp. V) under basic conditions. The anilides IV and V gave only small yields of the dihydrocarbostyril VII with polyphosphoric acid. Chlorination of VII in position 3 using PCl₅ yielded IX which, on splitting out HCl, gave 3-methylene-4-methyl-4-phenyl-3, 4-dihydro-carbostyril (X). X was converted to trans-3, 4-dimethyl-4-phenyl-3, 4-dihydro-carbostyril (XI) by catalytic hydrogenation.     

Pyrimidines

The reaction of substituted 3-methyl-5-pyrazolones with arylidenebisureas has been studied. Substituted spiro[pyrazole-4, 5-pyrimidines] have been obtained from 1-phenyl- and 1-benzyl-3-methyl-5-pyrazolones. When only one hydrogen atom was present in the ring of the 3-methyl-5-pyrazolone, the corresponding -ureidobenzyl derivative was obtained.For communication XI see [1].     

Synthesis of unsaturated derivatives of 2,5-dimethyl-4-phenylpyridine and 3-methyl-2-azafluorene

A substituted butadiene — 1-phenyl-4-(5-methyl-4-phenyl-2-pyridyl)buta-1,3-diene with a trans, trans configuration — was obtained by condensation of 2,5-dimethyl-4-phenylpyridine with cinnamaldehyde. Two 3-methyl-9-cinnamylidene-2-azafluorene isomers are formed as a result of condensation of the same aldehyde with 3-methyl-2-azafluorene. Data from the PMR and IR spectra were used to prove the configuration of the compounds obtained. It was established that the condensation of 3-methyl-2-azafluorene with salicylaldehyde gives 3-methyl-9-(2-hydroxybenzylidene)-2-azafluorene, which has a zwitterionic structure, and 1,2-bis(3-methyl-2-aza-9-fluorenylidene)ethane. Ideas regarding the chemical mechanism of the formation of the latter are presented. The preparation of an unsaturated alcohol — 3-methyl-9-allyl-2-aza-9-fluorenol — is described.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 82–86, January, 1978.     

N-allylation and N-benzylation of 2-phenylindole and its condensation with carbonyl compounds

By allylation and benzylation of 2-phenyl- and 2-phenyl-3-formylindole, N-allyl- and benzyl-substituted indoles have been obtained. By condensation of 2-phenylindole with 2-formylfluorene, and also with 4-aza- or 3-methyl-2-azafluorenone, compounds containing fragments of the indole, fluorene, and azafluorenone systems have been synthesized. In the interaction of 2-phenylindole or indole with formaldehyde and 2,5-dimethylpiperidin-4-one, depending on the temperature, bis(2-phenylindol-3-yl)methane, (2,5-dimethyl-4-oxopiperidino)-(1-indolyl)methane, and bis(indol-3-yl)methane are formed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 29, No. 5, pp. 648–650, May, 1993.