Investigation of phenanthridone and dioxotetrahydrodiazapyrene. 4. Synthesis of amino-substituted phenanthridones and dioxotetrahydrodiazapyrenes

The corresponding mono-, di-, and triamino derivatives substituted in the 2, 4, and 8 positions of the phenanthridone ring were obtained by reduction of mono-, di-, and trinitro-substituted phenanthridone (I), phenanthridone-10-carboxylic acid (II), phenanthridone-1-carboxylic acid (III), 4H-cyclopenta[k,l,m]phenanthridine-5,9-dione (IV), 4H-cyclopenta[k,l,m]phenanthridin-5-one (V), 5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene (VI), and 5,9-dioxo-4,5,9,10-tetrahydro-4,10-diazapyrene (VII) with powdered iron in an electrolyte medium, with hydrogen in the presence of a nickel catalyst, or with stannous chloride. The 2,4,7,9-tetraamino derivative of VI was similarly obtained. 1-Amino-, 7-amino-, and 10-amino-phenanthridones were obtained by the Schmidt reaction from the corresponding carboxylic acids. 1,10-Diamino-, and 3,8-diaminophenanthridones were similarly obtained from the corresponding aminofluorenones.See [1] for Communication 3.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 394–397, March, 1981.     

Structures and reactivities of compounds that contain a phenanthridone grouping

The structures of 4H-cyclopenta[k,1,m]phenanthridine-5,9-dione, phenanthridone, and 5,10-dioxo-4,5,9,10-tetrahydro-5-aza-9-oxapyrene were refined by IR and electronic spectroscopy and quantum-chemical calculations, and the order of aromatic substitution of the lactam form of the first compound was evaluated. It is shown that all three compounds exist primarily in the form of lactam tautomers. The long-wave transition in their absorption spectra was interpreted.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1388–1392, October, 1982.     

Synthesis of nitro-substituted dioxotetrahydrodioxapyrenes and 6H-dibenzo[b,d]pyran-6-one

Methods for the synthesis of tri- and tetranitro-substituted 5,9-dioxo-4,5,9,10-tetrahydro-4,10-dioxapyrenes, 5,10-dioxo-4,5,9,10-tetrahydro-4,9-dioxapyrenes, and 6H-dibenzo[b,d]pyran-6-one were developed in a search for effective sensitizers for electrophotographic layers based on carbazole-containing polymers. The possibility of the production of nitro compounds that contain three vicinal nitro groups was demonstrated. Under severe nitration conditions 2,4,8-trinitro-6H-dibenzo[b,d]pyran-6-one is cleaved to give 2-hydroxy-2-carboxy-3,5,4-trinitro-biphenyl, which is resistant to cyclization to give the starting compound, evidently because of the existence of an intramolecular hydrogen bond between the hydroxy group and the nitro group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 463–467, April, 1985.     

Ring-chain isomerism and reactions of 2-(1-anthraquinonecarbonyl)-1,2,3,4-tetrahydrophthalazine

The ring isomer of the corresponding acyl derivative — 5,9-dioxo-17a-hydroxy-9,10,11,16-17,17a-hexahydro-5H-dibenzo[d,e,h]phthalazino[2,3-a]cinnoline — was obtained by acylation of 1,2,3,4-tetrahydrophthalazine with anthraquinone-1-carboxylic acid chloride. Treatment of the product with thionyl chloride or hydrogen chloride gave the deeply colored 5,9-dioxo-9,10,11,16-tetrahydro-5H-dibenzo[d,e,h]phthalazino[2,3-a]cinnolinium chloride. The possibility of charge transfer between the chloride anion and the phthalazinium cation is examined as a reason for the deep coloration. This compound very readily undergoes hydrolytic oxidative cleavage at the C-N bond to give 2-(2-formylbenzyl)-3,7-dioxo-2,3-dihydro-7H-dibenzo[d,e,h]cinnoline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1411–1415, October, 1977.     

Research on phenanthridone and tetrahydrodiazapyrene

The synthesis of 2, 7-diamino-5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene (Ia) and its 4,9-dihydroxy derivative (IIa) from diphenic acid (III) is described. 4,4,6,6-Tetranitrodiphenic acid (IV) was obtained by nitration of III. Reduction of IV with iron or with hydrogen over Raney nickel gave Ia, while reduction with stannous chloride gave IIa. Diacetyl and tetraacetyl derivatives of Ia and IIa were obtained. The amino groups in Ia and IIa were replaced by H, Cl, Br, I, CN, N0², and OH through diazotization. It is shown that II and its derivatives can be reduced with iron or with hydrogen over a nickel catalyst to compounds of the 5,10-dioxo-4,5,9, 10-tetrahydro-4,9-diazapyrene series.See [4] for communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1672–1677, December, 1979Original article submitted August 31, 1978; revision submitted June 27, 1979.     

Design and synthesis of novel tricycles based on 4H-benzo[1,4]thiazin-3-one and 1,1-dioxo-1,4-dihydro-2H-1lambda6-benzo[1,4]thiazin-3-one

This paper reports our recent efforts to develop novel tricycles based on 4H-benzo[1,4]thiazin-3-one ( 2) and 1,1-dioxo-1,4-dihydro-2H-1lambda(6)-benzo[1,4]thiazin-3-one (3) using 1,5-difluoro-2,4-dinitrobenzene (1). All of these tricycles integrate two privileged structures into one skeleton, including 3,8-dihydro-5-thia-1,3,8-triaza-cyclopenta[b]naphthalene-7-one (4, 10, 12), 5,5-dioxo-3,5,6,8-tetrahydro-5lambda(6)-thia-1,3,8-triaza-cyclopenta[b]naphthalene-7-one (5, 11), 3,8-dihydro-5-thia-1,2,3,8-tetraaza-cyclopenta[b]naphthalene-7-one (6), 5,5-dioxo-3,5,6,8-tetrahydro-5lambda(6)-thia-1,2,3,8-tetraaza-cyclopenta[b]naphthalene-7-one (7), 3,8-dihydro-1H-5-thia-1,3,8-triaza-cyclopenta[b]naphthalene-2,7-dione (8), and 5,5-dioxo-3,5,6,8-tetrahydro-1H-5lambda(6)-thia-1,3,8-triaza-cyclopenta[b]naphthalene-2,7-dione (9). A typical library of scaffold 5 was synthesized in a parallel solution-phase manner and analyzed by HPLC-UV-MS or HPLC-UV-ELSD method.     

Synthesis of dihydro-1,3-thiazine derivatives. II

1-Oxo-3-thioxo-5-hydroxy-2-acyl-2,3-dihydro-1H-1,3-thiazino[6,5-c]quinolines were obtained for the first time by condensation of 2-hydroxy-3-mercaptoquinoline-4-carboxylic acid with acyl isothiocyanates. Alkyl and acyl isothiocyanates react with 1-methyl-2-oxo-3-mercapto-1, 2-dihydroquinoline-4-carboxylic acid to give 1,5-dioxo-3-thioxo-2-alkyl (acyl)6-methyl-2, 3,5,6-tetrahydro-1H-1,3-thiazino [6,5-c] quinolines.See [1] for communication I.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 641–643, May, 1973.     

Spectral characteristics and acid-base equilibria of 4,9-dihydroxy-5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene and its 2,7-derivatives

The IR and electronic spectra of 2,7-disubstituted 4,9-dihydroxy-5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene (R = H, I, NH₂, NO₂, OH) are studied. Analysis of the IR bands shows that, in crystalline form and in neutral and basic solutions, the compounds exist predominantly in the hydroxamic form. It is established that in sulfuric acid solutions the oxygen atoms of the C=O groups are protonated. The spectral characteristics of the neutral and ionized forms of the compounds are determined. The acid ionization constants are measured by potentiometric titration.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 94–99, January, 1993.     

Decarboxylation in proton acceptor solvents

Heating 3,8-dinitro-10-carboxy-6H-dibenzo[b,d]pyran-6-one in DMSO, DMF, or HMPTA leads to decarboxylation and the replacement of the carboxyl group by a hydroxy group with the formation of 3,8-dinitro-6H-dibenzo[b,d]pyran-6-one and 3,8-dinitro-10-hydroxy-6H-dibenzo [b,d]pyran-6-one. The decarboxylation of 2,7-dinitro-5,10-dioxo-4,5,9,10-tetrahydro-4,9-dioxapyrene in HMPTA is preceded by opening of the two lactone rings and the formation of a 1:4 molecular complex of 4,4-dinitro-6,6-dihydroxy-2,2-dicarboxybiphenyl with HMPTA, whose structure was established by x-ray diffraction structural analysis.Translated from Khimiya Geterotsiklicheskik Soedinenii, No. 2, pp. 164–170, February, 1989.     

Synthesis and properties of (4-hydroxy-5-methoxycarbonylthieno)-tetrathiafulvalenes

6-Hydroxy-5-methoxycarbonylthieno[2,3-d]-1,3-dithiol-2-thione, -2-one, and 2-selenone were prepared by intramolecular cyclocondensation of 4-methoxycarbonylmethylthio-1,3-dithiol-2-thione-, 2-one-, and 2-selenone-5-carboxylic acid methyl ester. 2,6(7)-Di(methoxycarbonylmethylthio)-3,7(6)-di(methoxycarbonyl)tetra-thiafulvalene, 2-methoxycarbonylmethylthio-3-methoxycarbonyl-6,7-ethylenedithiotetrathiafulvalene, and the corresponding thieno-condensed tetrafulvalene derivatives were synthesized from them. The electrochemical oxidation potentials of the new tetrafulvalene derivatives were determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 761–768, June, 1993.     

Copper(II), iron(III), and chromium(III) complexes with 5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene derivatives

Six copper(II), iron(III), and chromium(III) complexes with 5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene derivatives (H₂L¹-H₂L³) have been synthesized and studied by physical methods (IR and electronic absorption spectroscopy, quantum-chemical calculations). The composition of the complexes has been determined and their stability constants in aqueous dimethylformamide solutions have been calculated. The energy characteristics, electronic structure and geometry of isolated diazapyrenes and their tautomeric forms have been calculated by the PM6 method, and their complexes have been modeled.     

Condensed isoquinolines. 9. Alkylation of 7,12-dihydro-5H-isoquino[2,3-a]quinazolin-5-ones

The alkylation of 7,12-dihydro-5H-isoquino[2,3-a]quinazolin-5-one proceeds at N₍₆₎ or C_(–) depending on the type of alkylating agent and reaction conditions. C_(–)-Alkylation occurs in the presence of base. The secondary alkylation of the 7-alkyl derivatives occurs at the same position under these conditions. Depending on the conditions, the reaction with o-xylylene dibromide leads to spiro[5H-isoquino[2,3-a]quinazolin-7(12H).2-indane]-5-one or 11-oxo-4b,5,10,16-tetrahydro-11H-10a-azonia-15b-azadibenz[a,e]pleiadene bromide, which are derivatives of new heterocyclic systems.Communication 8, see ref. [1].See also Letter to Editor [2].Taras Shevchenko Kiev University, 252017 Kiev, Ukraine. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 643–652, May, 2000.     

Synthesis of imidazo[4,5-e][1,4]diazepine-8-one

We have developed a method for synthesis of 1-methyl-4,5,7, 8-tetrahydro-6H-imidazo[4,5-e][1,4]diazepin-8-one. We have shown that in intramolecular cyclization of N-(2-hydroxyethyl)- or N-(2-chloroethyl)amides of 1-methyl-4-aminoimidazolyl-5-carboxylic acids it is not the corresponding tetrahydroimidazo[4,5-e][1,4]diazepin-8-ones which are formed but rather the isomeric 4-amino-5-(oxazolin-2-yl)imidazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1203–1206, September, 1993.     

Reactivity of 4,9-diazapyrene

Heating 5,10-dimethyl-4,9-diazapyrene with nitric acid to 200°C does not bring about disruption of the heteroring but leads to the formation of nitro derivatives of 5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene. 4,9-Diazapyrene is a weak base that forms quaternary salts only under severe conditions. Piperidine replaces two chlorine atoms in 5,10-dichloro-4,9-diazapyrene, whereas only monosubstitution occurs in the case of 1,6-dibromo-5,10-dimethyl-4,9-diazapyrene. Calculations by the Hückel MO method, in agreement with the experimental data, characterize 4,9-diazapyrene as a strong electron acceptor and indicate that the effect of conjugation is propagated primarily along the periphery of the molecule rather than between the heterorings.     

Selective reductive dimerization of homocubane series oximes

The mixture of di- and monoethylene ketals obtained by the reaction of 1,9-dibromopentacyc lo[5.4.0.0^2,6.0^3,10.0^5,9]-undeca-8,11-dione followed by hydrolysis and ring contraction by Faworsky method was converted into a mixture of ethylene ketals of 7-bromopentacyclo[5.3.0.0^2,5.0^3,9.0^4,8]decan-6-one-4- and 5-bromopentacyclo[5.3.0.0^2,5.0^3,9.0^4,8]decan-6-one-8-carboxylic acid where the carboxy group was replaced by bromine along the procedure of Hunsdiecker-Borodine-Cristol. 6-Ethylene ketal of the pentacyclo[5.3.0.0^2,5.0^3,9.0^4,8] decan-6-one obtained by the debromination of ethylene ketals of 4,7- and 5,8-dibromopentacyclo[5.3.0.0^2,5.0^3,9.0^4,8] decan-6-one was hydrolyzed to ketone whose oxime was selectively reduced on a platinum catalyst into the di-6-pentacyclo[5.3.0.0^2,5.0^3,9.0^4,8]decylamine. The reaction of reductive dimerization was also characteristic of pentacyclo[4.3.0.0^2,5.0^3,8.0^4,7]-nonan-9-one and pentacyclo[6.3.0.0^2,6.0^3,10.0^5,9]undecan-4-one oximes, whereas the composition of the reduction products of pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecan-8-one oxime depended on the amount of the catalyst.     

Photochemical reactions of 7-aminocoumarins. 2. [2 + 2]-cycloadducts with styrene

The photocycloaddition of styrene to 4-methyl-7-aminocoumarin, 4-methyl-7-diethylaminocoumarin, 7-(N-morpholino) coumarin, 3-ethoxycarbonylmethyl-4-methyl-7-diethylaminocoumarin, and coumarin-102 (2,3,6,7-tetrahydro-9-methyl-1H, 5H,11H-[l]-benzopyrano[6,7,8-ij] quinolizin-11-one) was investigated. Adducts of regio- and stereospecific [2 + 2]-cycloaddition to the 3–4 bond were isolated. It was established by means of x-ray diffraction analysis that the phenyl group in the cycloadducts occupies the 1-endo position. The participation of the singlet excited states of the 7-aminocoumarin molecules in [2 + 2]-cycloaddition was demonstrated.See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1176–1184, September, 1988.     

Synthesis of 11-bromo-9-methyl-6-methylene-3-methylthio-5,6,9,10-tetrahydro-8H-[1,2,4]triazolo[3′,4′;3,4]pyrazino[1,2-c]pyrimidine-8,10-dione from 4-allyl-1-(3-methyl-2,4-dioxo-1,2,3,4-tetrahydro-6-pyrimidinylcarbonyl)thiosemicarbazide

4-Allyl-1-(3-methyl-2,4-dioxo-1,2,3,4-tetrahydro-6-pyrimidinylcarbonyl)thiosemicarbazide is cyclized in alkaline medium into 4-allyl-3-(3-methyl-2,4-dioxo-1,2,3,4-tetrahydro-6-pyrimidinyl)-1,2,4-triazoline-3-thione, which is converted on alkylation with iodomethane into the methylthio derivative. Reaction of the latter with bromine occurs with formation of 3-(5-bromo-3-methyl-2,4-dioxo-1,2,3,4-tetrahydro-6-pyrimidinyl)-4-(2,3-dibromopropyl)-5-methylthio-1,2,4-triazole, dehydrobromination of which with potassium carbonate leads to formation of the first representative of a new heterocyclic system, viz. 11-bromo-9-methyl-6-methylene-3-methylthio-5,6,9,10-tetrahydro-8H-[1,2,4]triazolo[3,4:3,4]pyrazino[1,2-c]pyrimidine-8,10-dione.Vilnius University, Vilnius 2734, Lithuania. e-mail: sigitas.tumkevicius@chf.vu.lt. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 67–70, January, 1999.     

Polycyclic nitrogen compounds. Part II. Tricyclic quinoxalinones and their 4- or 6-aza analogues

1,2,3,3a-Tetrahydro-9-nitropyrrolo[1,2-α]quinoxalin-4-one and 7,8,9,10-tetrahydro-3-nitropyrido[1,2-α]quin-oxalin-6-one (V-VI) were reduced and deaminated to give new parent tricyclic quinoxalinone skeletons I-II. The latter compounds were identical with the tricycles obtained by an unambiguous independent synthesis. New 6-aza-1,2,3,3a-tetrahydropyrrolo[1,2-α]quinoxalin-4-one (III) and 4-aza-7,8,9,10-tetrahydropyrido[1,2-α]-quinoxalin-6-one (IV) were prepared by selective hydrogen transfer reductive cyclisation of esters of N-(2-nitro-3-pyridyl)pyrrolidine-2-carboxylic acid and N-(2-nitro-3-pyridyl)piperidine-2-carboxylic acid (Xb and XIb) respectively.     

Study of Nitrogen- and Sulfur-Containing Heterocycles. 57. Synthesis and Conversion of 4′-Substituted 5-(5-Amino-6-Pyrimidylthio)-2,2-Dimethyl-4,6-Dioxo-1,3-Dioxanes

By reaction of 4-substituted 5-amino-6-mercaptopyrimidines with 5-bromo-2,2-dimethyl-4,6-dioxo-1,3-dioxane, we have obtained 4′-substituted 5-(5-amino-6-pyrimidylthio)-2,2-dimethyl-4,6-dioxo-1,3-dioxanes. We have studied diazotization of these compounds by isoamyl nitrite. In the case of 4′-methoxy- and 4′-dimethylamino-substituted derivatives, we have obtained derivatives of novel heterocyclic systems: pyrimido[5,4-e][1,3,4]thiadiazine and pyrimido[5,4-e][1,3,4]thiadiazine-7-spiro-5′-1,3-dioxane, and in the case of the 4′-isopropylamino-substituted derivative we obtained 4-isopropyl-7-(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)-1,2,3-triazolo[5,4-d]pyrimidin-7-ylidene.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 613–623, April, 2005.     

Investigation of naphthyridines. 16. Synthesis of derivatives of 2,5-dioxo-1,2,5,6,7,8-hexahydro-1,6-naphthyridine-3-carboxylic acids from anilides (hydrazides) of 6-oxo-2-styrylnicotinic acids

Heating anilides (hydrazides) of 5-cyano-6-oxo-2-styrylnicotinic acids in polyphosphoric acid (PPA) leads to amides of 7-aryl-2,5-dioxo-6-phenyl(amino)-1,2,5,6,7,8-hexahydro-1,6-naphthyridine-3-carboxylic acids, which on heating with perchloric acid in acetic acid give the corresponding acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1809–1812, December, 2004.For Part 15 see [1].