Synthesis of 1- and 2-Carbamoylalkyl-2,3-dihydro-1H-indole and 9-Carbamoylalkyl-2,3,4,4a,9,9a-hexahydro-1H-carbazole Derivatives

Treatment of 1,2,3,9a-tetrahydro-9H-imidazo- and 1,2,3,4,10,10a-hexahydropyrimido[1,2-a]indol-2-one derivatives with formic acid gave 1-carbamoylalkyl-2,3,3-trimethyl-2,3-dihydro-1H-indoles. 9-Carbamoylmethyl- and 9-(2-carbamoylethyl)-4a-methyl-2,3,4,4a,9,9a-hexahydro-1H-carbazoles were prepared from 5,6,7,7a-tetrahydro-1H,4H-imidazo- and 1,2,6,7,8,8a-hexahydro-5H-pyrimido[2,1-k]carbazolones in a similar manner. Synthesis of 2-(2-carbamoylpropyl)-2,3,3-trimethyl-2,3-dihydro-1H-indole was carried out by reduction of 1,3-dihydrospiro[2H-indolo-2,2'-piperidine] derivative with Zn in acetic acid solution.     

Condensation of 1-carbamoylmethyl-2,3,3-trimethyl-3H-indolium chloride with aromatic aldehydes

The reaction of 1-carbamoylmethyl-2,3,3-trimethyl-3H-indolium chloride with various aromatic aldehydes in acetic acid and the subsequent workup of the intermediate styrylic derivatives with strong bases yielded 9a-(2-arylethenyl)-1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-one derivatives. Condensation of the mentioned salt with salicylaldehyde in acidic or basic medium afforded the derivative of l-carbamoylmethylspiro[benzopyran-2,2-indole]. Alkylation of the latter compound with benzyl chloride in the presence of potassium hydroxide gave 9a-[2-(2-benzyloxyphenyl)ethenyl]-1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-one.Department of Organic Chemistry, Kaunas University of Technology, LT-3028 Kaunas, Lithuania Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 761–769, June, 2000.     

Transformation of indoline spiropyrans to bridged 1,3-benzoxazepino[3,2-<Emphasis Type="Italic">a</Emphasis>]indoles <Emphasis Type="Italic">via</Emphasis> carbanions stabilized by a cyano group

Condensation of 1-cyanomethyl-2,3,3-trimethyl-3H-indolium perchlorate with ortho-hydroxy-substituted aromatic aldehydes afforded 1-cyanomethylindoline spiropyrans. The latter underwent rearrangement to bridged 1,3-benzoxazepino[3,2-a]indoles on treatment with a base. The mechanism of the rearrangement includes generation of a carbanion stabilized by a cyano group. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1322–1328, September, 2007.     

Reaction of 2,3,3-trimethyl-3H-indole salts with acrylamide. Synthesis of 1,2,3,4,10,10a-hexahydropyrimido[1,2-a]indol-2-one derivatives

Methyl derivatives of pyrimido[1,2-a]indol-2-one were obtained by the reaction of 2,3,3-trimethyl-3H-indole salts with acrylamide in a proton-containing solvent. The products were condensed with aromatic aldehydes. The interconversion of pyrimido[1,2-a]indol-2-ones and 1-(2-carbamoylethyl)-3H-indolium salts under the influence of acids and bases was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1056–1059, August, 1986.     

Reactions of 4-methylidenedioxolan-2-ones with 2-methyltryptamines. Synthesis of core analogs of aurantioclavine

4-Hydroxy-4,5,5-trimethyl-3-[2-(2-methyl-7-R-1H-indol-3-yl)ethyl]-1,3-oxazolidin-2-ones (R = H or Alk), which were synthesized from 4-methylidene-1,3-dioxolan-2-one and substituted 2-methyltryptamines, undergo intramolecular amidoalkylation when treated with polyphosphoric acid. First representatives of a new heterocyclic system, viz., oxazolo[3",4":1,2]azepino[5,4,3-cd]indole, which are core analogs of aurantioclavine, were prepared.     

Reactions of N-(2-chloroacetyl)-α-amino acids with 3-cyanopyridine-2(1H)-thiones. New promising route to 3,4-dihydropyrido[3",2":4,5]thieno[3,2-e][1,4]diazepine-2(1H),5-diones

The reactions of N-(2-chloroacetyl)--amino acids with 3-cyanopyridine-2(1H)-thiones afforded N-(3-aminothieno[2,3-b]pyridin-2-ylcarbonyl)--amino acids. Heating of the latter smoothly produced 3,4-dihydropyrido[3",2":4,5]thieno[3,2-e][1,4]diazepine-2(1H),5-diones in high yields.     

Study of reaction of 2,3,3-trimethyl-3H-indole with haloacetic acid amides. Synthesis of 1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-ones

In the reaction of 2,3,3-trimethyl-3H-indole with -chloro- and -iodoacetamides, 1-carbamoylmethyl-2,3,3-trimethyl-3H-indolium salts are formed, which by the action of bases convert into imidazo[1,2-a]indol-2-one and 1-carbamoyl-2-methylene-2,3-dihydroindole. The latter compound can by cyclized into imidazo[1,2-a]indol-2-one by the action of acetic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 933–935, July, 1985.     

Synthesis and properties of (thieno[2,3-<Emphasis Type="Italic">b</Emphasis>]pyridin-3-yl)iminotriphenylphosphoranes. Molecular structure of (2-benzoyl-4-methoxymethyl-6-methylthieno[2,3-<Emphasis Type="Italic">b</Emphasis>]pyridin-3-yl)iminotriphenylphosphorane

Iminophosphoranes containing a thieno[2,3-b]pyridine fragment were obtained through a sequence of reactions: 1) alkylation of 3-cyano-2(1H)-pyridinethiones in alkaline medium by an -halocarbonyl compound with subsequent Thorpe-Ziegler cyclization of the resultant 2-thioalkylpyridines to give 3-aminothieno[2,3-b]pyridines, 2) diazotization of the amino group and nucleophilic substitution of the diazonium group by an azido group without isolation of the diazonium salts, and 3) reaction of the 3-azidothieno[2,3-b]pyridines with triphenylphosphine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1853–1862, December, 2004.     

Synthesis of 1,2,3,9a-tetrahydro-9H-imidazo[1,2-<Emphasis Type="Italic">a</Emphasis>]indole-2-thione and 1,5,6,10b-Tetrahydroimidazo[2,1-<Emphasis Type="Italic">a</Emphasis>]-isoquinoline-2(3H)-thione derivatives

Thionation of 1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-one derivative with Lawessons reagent in boiling toluene afforded 1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indole-2-thione derivative. Alkylation of the latter with ethyl iodide in DMF in the presence of a strong base gave 2-ethylthio-9,9,9a-trimethyl-9,9a-dihydro-3H-imidazo[1,2-a]indole. 1,5,6,10b-Tetrahydroimidazo[2,1-a]isoquinoline-2(3H)-thiones were synthesized by thionation of the corresponding carbonyl substrates.Published in Khimiya Geterotsiklicheskikh Soedinenii, No 11, pp. 1695–1700, November, 2004.     

Synthesis and Properties of Substituted Isoxazolo[3',4':4,5]thieno[2,3-b]pyridines

We synthesized derivatives of a novel heterocyclic system, isoxazolo[3',4':4,5]thieno[2,3-b]pyridine by sequential conversions in three steps: isomerization of 2-(2-R-ethylthio-2-oxo)-3-pyridyl cyanides obtained by alkylation from substituted 3-cyano-2(1H)-pyridinethiones by -halomethyl ketones in alkaline medium, to form 3-aminothieno[2,3-b]pyridines; diazotization of the amino group followed by nucleophilic substitution of the diazonium group by an azido group, bypassing the step of isolating the diazonium salts; and thermolysis of the azides formed.     

Acylation and Cyclodehydration of Benzofuran-, Benzothiophene-, and Indolyl-3-acetic Acid Arylamides. Synthesis of Novel Benzofuro[2,3-c]-, Benzothieno[2,3-c], and Indolo[2,3-c]pyrilium and Pyridine Derivatives

The acylation of benzo[b]furan-, benzo[b]thiophene, and indolyl-3-acetic acid arylamides using acetic anhydride in the presence of 70% perchloric acid occurs at the -position of the heterocycle to give 2-acetylbenzo[b]furan-, 2-acetylbenzo[b]thiophene, and 2-acetylindolyl-3-acetic acid arylamides. Depending on the amount of perchloric used in the reaction they undergo cyclodehydration to 3-arylamino-1-methylhetero[2,3-c]pyrilium salts and to N-aryl-1-methyl-3(2H)hetero[2,3-c]pyridones.     

Synthesis and reactions of 2-[3-(trifluoromethyl)phenyl]furo[3,2-<Emphasis Type="Italic">c</Emphasis>]pyridine

(E)-3-{5-[3-(Trifluoromethyl)phenyl]furan-2-yl}propenoic acid (I) was prepared from 5-[3-(tri-fluoromethyl)phenyl]furan-2-carbaldehyde under the Doebner’s conditions. The obtained acid was converted to the corresponding azide II, which was cyclized by heating in diphenyl ether to 2-[3-(trifluoromethyl)phenyl]-4,5-dihydrofuro[3,2-c]pyridin-4-one (III). This compound was aromatized with phosphorus oxychloride to chloroderivative IV which was reduced with H₂NNH₂-Pd/C to the title compound V. 2-[3-(Trifluoromethyl)phenyl]furo[3,2-c]pyridin-5-oxide (VI) was synthesized by reaction of V with 3-chloroperoxybenzoic acid in dichloromethane. On treatment of VI with benzoyl chloride and potassium cyanide (Reissert-Henze reaction), corresponding 2-[3-(trifluoromethyl)phenyl]furo[3,2-c]pyridine-1-carbonitrile (VII) resulted. 5-Amino-2-[3-(trifluoromethyl)phenyl]furo[3,2-c]pyridin-5-ium-4-methylbenzene sulfonate (VIII) was prepared by direct N-amination of the title compound V with 1-[(aminooxy)sulfonyl]-4-methylbenzene in dichloromethane. Then, VIII was transformed to a non-isolated zwitterionic N-imid IX which afforded the corresponding furo[3,2-c]pyrazolo[1,5-a]pyridine carboxylic acid esters X, XI by 1,3-dipolar cycloaddition reactions with dimethyl but-2-ynedionate (DBD) or ethyl propiolate. The structures of all compounds were confirmed by their IR and NMR spectra. Presented at the 1st International Conference “Applied Natural Sciences” on the occasion of 10th anniversary of the University of St. Cyril and Methodius, Trnava, 7–9 November 2007.     

Synthesis and Properties of Derivatives of the new Heterocyclic System Benz[4,5]imidazo[1,2-c]pyrido[3',2';4,5]thieno[2,3-e]pyrimidine

Derivatives of a new heterocyclic system - benz[4,5]imidazo[1,2-c]pyrido[3',2';4,5]thieno[2,3-e]pyrimidine have been obtained by successive reactions in three stages - alkylation of 3-cyanopyridine-2(1H)-thiones with 2-chloromethylbenzylimidazole to give 2-benzimidazolylmethylthio-3-cyanopyridines, closing the thiophene ring in the latter to form 3-amino-2-(benzimidazolyl-2)thieno[2,3-b]pyridines, and cyclization of the pyrimidine ring by acylation with carboxylic acid anhydrides or chlorides.     

Conformational peculiarities of a new heterocyclic dihydrothienothiopyranoisoxazole system

The crystalline and molecular structures of 3H-3a,4-dihydro-7-methylthieno[3,2:5,6]thiopyrano[4,3-c]isoxazole and 3H-3a,4-dihydro-3-isopropoxycarbonyl-3a,7-dimethylthieno[3,2:5,6]thiopyrano[4,3-c]isoxazole are determined by X-ray analysis. The effect of steric factors on intramolecular 1,3-dipolar cycloaddition is shown.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 302–304, February, 1995.This work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-18461).     

Diels-alder reaction with cyclic sulfones. 9.* Synthesis of 10-oxo-1h-tetrahydrofluo-reno[2,1-b]thiophene dioxides*2

The treatment of 5-aryl-4′,6′-dioxo-2,3,3a,4,5,6-hexahydrospiro-[benzothiophene-4,5′-1,3-dioxane] 1,1-dioxides with boron trifluoride etherate in dichloroethane leads to the formation of products of intramolecular acylation, namely, the corresponding 10-oxo-1H-5,5a,10a,10b-tetrahydrofluoreno-[2,1-b]thiophene dioxides. In all cases, 5-aryl-4-carboxyhexahydrobenzo[b]thiophene 1,1-dioxides were also isolated. The product ratio depends on the structure of the aromatic substituent at C(5) of the spiro- adducts. The structure of 4-carboxy-5-(2-methoxyphenyl)-7-methyl -2,3,3a,4,5,6-hexahydro-benzo[b]thiophene 1,1-dioxide was confirmed by X-ray diffraction structural analysis. ^*For Communication 9 see [1]. ^*2Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1503–1512, October, 2008.     

吲哚取代10H—吡啶并[1,2—a]吲哚盐的合成

通过2,3,3-三甲基-3H-吲哚高氯酸盐与吲哚取代查耳酮或芳基乙烯基酮在异戊醇介质中反应,合成了15种新的10H-吡啶并[1,2-a]吲哚高氯酸盐,其结构用各种波谱确定,从结构上进一步推理提出了反应历程,并讨论了~1H NMR谱中取代基对吡啶环质子化学位移的影响。     

Synthesis of new pyridazino[4′,3′:4,5]-thieno[3,2-d]-1,2,3-triazine and pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine derivatives

Summary 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (2), 3-substituted 8,9-diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-ones (3a–c), 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (4), 8-chloro-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (5), 8-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazines (6a–h) and 7-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-ones(7a–c) were synthesized from 5-amino-3,4-diphenylthieno[2,3-c]pyridazine-6-carboxamide (1).

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Synthese neuer Pyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-und Pyrimido[4,5:4,5]thieno[2,3-c]pyridazin-Derivate

Zusammenfassung Folgende Verbindungen wurden ausgehend von 5-Amino-3,4-diphenylthieno[2,3-c]pyridazin-6-carboxamid (1) synthetisiert: 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-on (2), 3-substituierte 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (3a–c), 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8[7H]-on (4), 8-Chlor-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin (5), 8-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (6a–h) und 7-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (7a–c).

     

On the Synthesis of Some 2-Arylhydrazono-3-oxothieno[2,3-<Emphasis Type="Italic">b</Emphasis>]pyridines by Reaction of Nitrilimines with 2-Mercaptonicotinic Acid

Summary. Nitrilimines prepared from N-arylhydrazono chlorides reacted with 2-mercaptonicotinic acid yielding the corresponding addition products, 2-[(2-oxo-1-arylhydrazonopropan-1-yl)mercapto] nicotinic acids, which were treated with 1,1-carbonyldiimidazole in THF affording by cyclocondensation the corresponding hitherto unknown 2-arylhydrazono-3-oxothieno[2,3-b]pyridines.     

Cyclocondensation of 2-Amino-1,3,4-thiadiazoles with β-Sulfonylvinyltrifluoromethyldiols

A series of CF₃-containing 6,7-dihydro-5H-[1,3,4]thiadiazolo[3,2-a]pyrimidin-7-ols was obtained by the interaction of 2-amino-1,3,4-thiadiazoles with -sulfonylvinyltrifluoromethyldiols and their stereochemistry was established. The structure of 5-(phenylsulfonyl)-7-(trifluoromethyl)-6,7-dihydro-5H-[1,3,4]thiadiazolo[3,2-a]pyrimidin-7-ol was confirmed by X-ray crystallography.     

Synthesis and molecular structure of 2,4,8a-triaryl-6-methylperhydro[1,3,2]dioxaborinino[5,4-c]pyridines

Condensation of arylboronic acids with 4-hydroxy-3-(-hydroxybenzyl)-1-methyl-4-phenylpiperidine afforded 2,4,8a-triarylperhydro[1,3,2]dioxaborinino[5,4-c]pyridines. The molecular structure of 6-methyl-2,4,8a-triphenylperhydro[1,3,2]dioxaborinino[5,4-c]pyridine was established by X-ray diffraction analysis.