Diazabicycloalkanes with nitrogen atoms in the nodal positions. 21. Heteroatom-promoted lithiation of benzo[b]-1,4-diazabicyclo[2.2.2]octene and introduction of substituents into the annelated benzene ring

The action of n-butyllithium on benzo[b]-1,4-diazabicyclo[2.2.2]octene leads to lithiation in the 3 position of the aromatic ring. The reaction of this lithium derivative with electrophilic reagents was used to synthesize 3- and 3,6-substituted derivatives of benzo[b]-1,4-diazabicyclo[2.2.2]octene.See [1] for Communication 20.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 798–803, June, 1991.     

Synthesis of 1,4-diazabicyclo[2.2.2]octane

Double intramolecular cyclization of N,N-bis(2-chloroethyl)-N-N-bis(2-cyanoethyl)ethylenediamine leads to 1,4-bis(2-cyanoethyl)-1,4-diazoniabicyclo[2.2.2]octane dichloride, which undergoes decyanoethylation to 1,4-diazabicyclo[2.2.2]octane when it is heated. The structures of the compounds were confirmed by their IR and PMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 548–550, April, 1978.     

Diazabicycloalkanes with nitrogen atoms in nodal positions. 14. Synthesis of dibenzo[1′,2′-b,e]-1,4-diazabicyclo[2.2.2]octadienes containing a tertiary amino group in the aromatic ring

The corresponding 2-amino derivatives of phenazinium salts were obtained by the action of dimethylamine and morpholine on N-(2-hydroxyethyl)phenazinium chloride. The subsequent exchange of the hydroxyl group for chlorine and the reductive cyclization of 2-amino derivatives of N-(2-chloroethyl)phenazinium salts leads to 4-aminodibenzo[1,2-b,e]-1,4-diazabicyclo[2.2.2]octadienes, together with unsubstituted dibenzo-[b,e]-1,4-diazabicyclo[2.2.2]octadiene and the corresponding 2-aminophenazines.For Communication 13, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1658–1661, December, 1986.     

Diazabicycloalkanes with nitrogen atoms in the nodal positions. 6. Synthesis and some properties of benzo[f]-1,5-diazabicyclo[3.2.2]nonene and benzo[g]-1,6-diazabicyclo[4.2.2]decene

The reaction of N-acetyl derivatives of N,N-trimethylene- and N,N-tetramethylene-o-phenylenediamines with ethylene oxide gave the corresponding N-(-hydroxyethyl)-N-acetyl derivatives, the cyclization of which in refluxing hydrobromic acid leads to benzo[f]-1,5-diazabicyclo[3.2.2]nonene and benzo[g]-1,6-diazabicyclo[4.2.2.]decene.See [1] for Communication 5.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1538–1542, November, 1981.     

Indolobenzo[b]furans. 3. Synthesis of unsubstituted indolo[7′,6′∶2,3]- and indolo[6′,7′∶2,3]benzo[b]pyrans

Indolo[7,62,3]- and indolo[6,72,3]benzo[b]furans have been synthesized with the aid of the Fischer reaction. The physicochemical characteristics of the compounds synthesized are considered.For communication 2, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 631–634, May, 1985.     

1, 4-Diazabicyclo [2.2.2] octanes

1,4-Diazabicyclo[2.2.2]octane hydrochloride methylchloride was obtained from N-benzoylpiperazine through 1-(2-hydroxyethyl)-4-benzoylpiperazine, 1-(2-acetoxyethyl)-4-benzoylpiperazine methyltosylate, 1-(2-hydroxyethyl)piperazine methylchloride, and 1-(2-chloroethyl)piperazine methylchloride.See [1] for communication I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 845–847, June, 1976.     

Diazabicycloalkanes with bridgehead nitrogen atoms. 19. Reactions of monoquaternary salts of dibenzo[b,e]-1,4-diazabicyclo[2.2.2]octadiene with nucleophilic reagents

The monoquaternary salt of dibenzo[b,e]-1,4-diazabicyclo[2.2.2]octadiene reacts with piperidine, 1,3-propylenediamine and sodium p-nitrophenolate with the formation of N,N-disubstituted dihydrophenazines. In its degree of reactivity level, the compound studied is comparable with a typical alkylating agent, such as methyl iodide.For Communication 18, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1106–1108, August, 1989.     

Über Tetrahydrospiro [cyclohexan-1,4′(1′H)-chinazolin]-2′(3′H)-one

Zusammenfassung Cyclohexanon bzw. Cyclopentanon sowie ihre durch Aldolreaktion entstehenden Dimeren reagieren mit Harnstoff im sauren Medium zu 5,6,7,8-Tetrahydrospiro[cyclohexan-1,4(1H)-chinazolin]-3(2H)-onen (2) bzw. zum Dihydrospiro-(cyclopentan-1,4(1H)-5H-cyclopenta[d]pyrimidin)-2(3H)-on (10). Substituierte Harnsotoffe geben Gemische der isomeren 5,6,7,8-Tetrahydro- und 4a,5,6,7-Tetrahydroverbindungen (2, 3) bzw. 6,7-Dihydro-tH- und 5,6-Dihydro-4aH-verbindungen (10, 11). Charakteristisch für2 (3),10 (11) ist die Reaktivität der Kernstellen 8 bzw. 7 gegenüber elektrophilen Agentien (2f-v, 3f-j, 9 a-i, 10 d-f). Äthylmalonsäurebis-trichlorphenylester bzw. Formaldehyd und prim. Amine führen2 in ein partiell hydriertes 1H-Pyrido[3,2,1-ij]chinazolintrion (6) bzw. 1H-Pyrimido[5,6,1-ij]chinazolinon (7) über. Die 1-Alkylverbindungen (2) geben mit Formaldehyd und primären Aminen Hexahydro-8a-hydroxy-4a,8-propanospiro-(cyclohexan-1,4(1H)-pyrido[4,3-d]pyrimidin)-2(3H)-one (8).

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Heterocycles, XXV: tetrahydrospiro [cyclohexane-1,4(1H)-quinazoline]-2(3H)-ones

Cyclohexanone and cyclopentanone, resp., as well as their dimers (formed by aldol reaction) react with urea in the presence of acids to 5,6,7,8-tetrahydrospiro[cyclohexane-1,4-(1H)-quinazoline]-3(2H)-ones (2) and to the dihydrospiro-(cyclopentane-1,4(2H)-5H-cyclopenta[d]pyrimidine)-2(3H)-one (10), resp. Substituted ureas give the isomeric 5,6,7,8-tetrahydro- and 4a,5,6,7-tetrahydro compounds (2, 3), and 6,7-dihydro-5H- and 5,6-dihydro-4aH-compounds (10, 11), resp. Characteristic for2 (3),10 (11) is the reactivity of the nuclear places 8 and 7 with electrophilic agents (2f-v, 3f-j, 9a-i, 10d-f). Ethylmalonic acid bistrichlorophenylester resp. formaldehyde and primary amines react with2 to the partially-hydrogenated 1H-pyrido[3,2,1-ij]-quinazolinetrione (6) and 1H-pyrimido[5,6,1-ij]-quinazolinone (7), resp. The 1-alkyl compounds (2) give with formaldehyde and primary amines hexahydro-8a-hydroxy-4a, 8-propanospiro(cyclohexane-1,4-(1H)-pyrido[4,3-d]pyrimidine)-2(3H)-ones (8).

     

Peculiarities of the reaction of cycloalka[b]thiopyrylium salts and their hetero analogs with bases

The reaction of aryl-substituted cycloalka[b]thiopyrylium salts, as well as their O and N analogs, with bases (pyridine, NaOH, NaHCO₃) was studied. The formation of 6,6,7,7-tetrahydro-2,2,4,4-tetraarylbis(5H-1-benzothiopyrans) through the intermediate anhydro bases was established for the cyclohexa[b]thiopyrylium salts, while the formation of 2,4-diphenyl-7-(2,4-diphenyl-8-cyclopenta[b]thiopyranyl)-_7,8-cyclopenta[b]thiopyran was established for 2,4-diphenylcydopenta[b]thiopyrylium perchlorate. The peculiarities of the behavior of the O and N analogs of the cycloalka[b]thiopyrylium salts in reactions with bases were ascertained. The investigation was carried out using electronic, IR, and PMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 26–31, January, 1992.     

2-Amino-4-[2-(5-nitro-furyl)vinyl]thiazole and its derivatives

The reactions of 4-bromo-1-(5-nitro-2-furyl)but-1-en-3-one and its 2-methyl and 2-chloro derivatives with thiourea and its N-allyl and N-phenyl derivatives have yielded 2-amino-4-[-5-nitro-2-furyl)-vinyl]thiazole and its - and N-substituted derivatives. 2-Amino-4-[-(5-nitro-2-furyl)vinyl]thiazole and its -methyl derivative have also been prepared by the direct reaction of the corresponding , -unsaturated ketones with bromine and an excess of thiourea in chloroform, as was shown by a comparison of UV spectra. A series of N-acyl derivatives of the aminothiazoles has been obtained. UV and IR spectra are given.     

Redox properties of 2,4-diaryl-substituted cyclohexa[b]thiopyrylium salts

Ascheme for formation of 6,6,7,7-tetrahydro-2,2,4,4-tetraaryl-8,8-bis(5H-1-benzothiopyranyls) through intermediate radicals and cation radicals was substantiated as a result of a study of the electrochemical behavior of 2,4-diarylcylohexa[b]thiopyrylium tetrafluoroborates and 2,4-diaryl-4H-cyclohexa[b]thiopyrans and comparison with the results of their oxidative dimerization. The formation of 2,4-diarylcyclohexa[b]thiopyranyl radicals is also confirmed by EPR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 349–354, March, 1992.     

First representative of macroheterocyclic ligands of the dibenzo-[c,m]dipyrazolo[3,4-f:4′,3′-j][1,2,5,8,912]hexaazacyclotetradecene class

The first representative of macroheterocyclic ligands of the dibenzo[c,m]dipyrazolo[3,4-f:4,3-j][1,2,5,8,9,12]hexaazacyclotetradecene class was obtained by nontemplate cyclization of 4,4-azobis(5-chloro-2,3-dimethyl-1-phenyl-1H-pyrazolium) bis(methylsulfate) with 2,2-diaminoazobenzene in an aprotic solvent in the presence of potassium carbonate or magnesium oxide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 239–243, February, 1984.     

Reaction of steroido[16α,17α-d]-4′h-1′,2′-oxazoles with methyl fluosulfonate

Conclusions The methylation of steroido[16,17-d]-4H-1,2'-oxazoles with methyl fluosulfonate leads to N-methyl-3-hydroxysteroido[16,17-d]tetrahydro-1,2-oxazoles, which when treated with POC1₃ are converted to steroidal 16-(2-glyoxyl)17-lactones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1924–1926, August, 1977.     

Direct nitration and acetylation of the furan nucleus of 1-alkyl-2-[Β -(2′-furyl) vinyl]-benzimidazoles

The direct nitration and acetylation of 1-methyl-, 1-ethyl-, and 1-benzyl-2-[-(2-furyl)vinyl]benzimidazoles has given the corresponding 1-alkyl- and 1-benzyl-2-[-(5-nitro-2-furyl)vinyl]benzimidazoles and 1-alkyl- and 1-benzyl-2-[-(5-acetyl-2-furyl)vinyl]benzimidazoles. The UV spectra of these compounds have been recorded and their ionization constants have been determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 832–834, June, 1970.     

Synthesis and alkylation of 4,6-diphenyl-3-thiocarbamoyl-3,4,5,6-tetrahydropyridine-2(1H)-one and 4,6-diphenyl-3-thiocarbamoyl-3,4-dihydropyridine-2(1H)-one

Alkylation of 3-thiocarbamoyl-3,4,5,6-tetrahydropyridine-2(1H)-one with methyl iodide has given 5-methylthio-2,6-diazabicyclo[2.2.2]oct-5-en-3-one and 3-methyl-thiocarbonyl-3,4-dihydropyridine-2(1H)-one. Alkylation of 3-thiocarbamoyl-3,4-dihydridine-2(1H)-one with iodoacetamide affords 3-(1-amino-1-carbamoyl-3,4-methyl-thiomethylene)-1,4-dihydropyridine-2-one, which in acidic media is converted into 3-(4-oxo-3,5-dihydro-1,3-thiazol-2-ylidene)-1,4-dihydropyridine-2-one.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 787–794, June, 1989.     

Study of lactams. VI. Synthesis of 6-substituted purino [8, 9-11, 22]isoindol1nes

It is shown with 1-ethoxyisoindolenine that the reaction of lactim ethers with -amino--cyanoacetamide also extends to partly aromatized lactim ethers, although these react much less readily. Condensation of 1-ethoxyisoindolenine with -amino-cyanoacetamide gives 4-carbamido-5-aminoimidazo[1, 2-1, 2]isoindoline, from which a new series of purinoisoindioline derivatives is synthesized.For part V see [2].     

Dibenzo[f,j]-5.12-dihydrodipyrazolo[4, 5-c: 5′.4′-m],-[1,2,5,8,9,12]hexaazatetradecyne — The first representative of a new macroheterocyclic system

The first representative of a 14-membered macroheterocyclic system — dibenzodipyrazolo-5,12-dihydro[1,2.5,8,9,12]hexaazatetradecyne — was obtained by template cyclization of 5,5-dichloro-3,3-dimethyl-1.1-diphenyl-4.4-azopyrazole with 2.2-diaminoazobenzene in aprotic solvents in the presence of nickel(II) acetate and potassium carbonate.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 968–971, July, 1976.     

Synthesis of 2-[β-(5′-halogenofur-2′-yl)vikyl]benzimidazoles

2-[-(5-halogenofur-2-yl)vinyl]benzimidazoles (I) have been synthesized by the condensation of o-phenylenediamine with 5-halogeno-fur-2-ylacroleins or of 2-methylbenzimidazole with 5-halogenofurfurals. The methiodides of the 1-methyl-substituted derivatives ofI readily react with secondary amines (piperidine, dimethylamine)giving methiodides of 2-[-(5-dialkylaminofur-2-yl)vinyl]-1-methylbenzimidazoles.     

Preparation and stereochemical characterization of some N-acyl-[1]benzopyrano[3,4-c]pyrazole derivatives from rotenoids

Summary Several new N-acyl derivatives of 1-(4-hydroxy-2,3-dihydrobenzofuran-5-yl)-7,8-di methoxy-1,9 b,2,3,3 a,4-hexahydro-[1]benzopyrano[3,4-c]pyrazole-1-ene have been prepared by appropriate chemical transformation of isohydrazones of rotenone and amorphigenin. A study of their¹H- and¹³C-NMR spectra confirmed the presence of the twocis 3a, 9b, 2 and 3a, 9b, 2 diastereomers in the parent isohydrazones and revealed the strong predominance of the conformers withendo orientation of the 3-NAc group. The conformations due to rotation about the 1,5-bond between rings C and D in the 4-OH and 4-O-substituted compounds were also determined by taking into account the anisotropic effect of aromatic rings A and D, and the hydrogen bond between 4-OH and the 2-N atom, as well as by inspecting the Dreiding models.

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Darstellung und stereochemische Charakterisierung einiger N-Acyl-[1]benzopyrano[3,4-c]pyrazol-Derivate von Rotenoiden

Zusammenfassung Mittels geeigneter chemischer Transformationen von Isohydrazonen von Rotenon und Amorphigenin wurden einige neue N-Acyl-Derivate von 1-(4-Hydroxy-2,3-dihydrobenzofuran-5-yl)-7,8-dimethoxy-1,9 b,2,3,3 a,4-hexahydro-[1]benzopyrano[3,4-c]pyrazol-1-en hergestellt. Eine Untersuchung ihrer¹H und¹³C-NMR-Spektren zeigt die Gegenwart von zweicis 3a, 9b, 2- und 3a, 9b, 2-Diastereomeren in den Ausgangs-Isohydrazonen und eine starke Bevorzugung der Konformeren mitendo-Orientierung der 3-NAc-Gruppe. Die Konformationen bezüglich der Rotation um die 1,5-Bindung zwischen Ring C und D werden für die 4-OH und 4-O-substituierten Verbindungen unter Berücksichtigung von Anisotropie-Effekten der aromatischen A- und D-Ringe, der Wasserstoffbrücken zwischen 4-OH und dem 2-N Atom und auch der Betrachtung der entspechenden Dreiding-Modelle diskutiert.

     

Preparation of 8-(5-oxoindeno [3,2-b]-4-pyridyl)-1-naphthoic acids

The condensation of 1-(1,3-indanedion-2-ylidene)-2-acenaphthenone with imines of -dicarbonyl compounds gave 2,5-dioxospiro 1,4,acenaphthene-1,4-dihydroindeno-[3,2-b]pyridines. Oxidation of the pyridines with air oxygen at room temperature without catalysts brings about cleavage of the C-C bond to give 8-(5-oxoindeno[3,2-b]-4-pyridyl)-1-naphthoic acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 210–212, February, 1972.