Investigation of phenanthridone and dioxotetrahydrodiazapyrene. 3. Investigation of the nitration of 5H-phenanthridin-6-one and its derivatives

The nitration of 5H-phenanthridin-6-one (I), 5H-phenanthridin-6-one-10-carboxylic (II) and 5H-phenanthridin-6-one-1-carboxylic acids (III), 4H-cyclopenta[k,l,m]-phenanthridine-5,9-dione (IV), 4H-cyclopenta[k,l,m]phenanthridine-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 nitric acid (sp. gr. 1.42–1.51) and a nitrating mixture of 0–120 °C was investigated. The orientation and sequence of incorporation of nitro groups in I-VII are determined by the presence of a phenanthridone structure in them. Mono-, di-, tri-, and tetranitro-substituted I-VII were obtained and characterized.See [l] for Communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 388–393, 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.     

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.     

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.     

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.     

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.     

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.     

Efficient Synthesis of 3,5,6,7-Tetrahydro-4H-cyclopenta[4,5] thieno[2,3-d]Pyrimidin-4-ones

The title compounds 3,5,6,7-tetrahydro-4H-cyclopenta[4,5]thieno[2,3-d]pyrimidin-4-ones（6） were synthesized by base catalytic reactions of secondary amines with carbodiimides 4, which were obtained from the aza-Wittig reaction of iminophosphoranes（3） with aromatic isocyanates.     

Diversity-oriented synthesis of functionalized pyrrolo[3,2-d]pyrimidines with variation of the pyrimidine ring nitrogen substituents

Nine 2,4-dioxo-2,3,4,5-tetrahydro-1H-pyrrolo[3,2-d]pyrimidine-6-carboxylic acid benzyl esters 12 were synthesized in four steps from 4-oxo-N-(PhF)proline benzyl ester 7 by a general method in which elements of molecular diversity were readily added onto the pyrimidine nitrogens. Conversion of 4-oxoproline 7 into the corresponding aminopyrrole 8 using benzyl-, allyl-, and isopropylamine followed by treatment with phenyl, allyl, and ethyl isocyanate gave nine different ureas 9. 4-Ureido-1H-pyrrole-2-carboxylic acid benzyl esters 9 were then converted into the respective pyrrolo[3,2-d]pyrimidines 12 using trichloroacetyl chloride in acetonitrile followed by treatment with Cs(2)CO(3). Crystallization from toluene gave the desired deazapurines in 37-55% overall yield from proline 7.     

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.     

Reaction of organozinc reagents prepared from bromomalonic acid esters and zinc with 3-aryl-2-cyanopropenoic acid primary amides

Organozinc compounds prepared from bromomalonic acid esters and zinc react with 3-aryl-2-cyanopropenoic acid primary amides giving a single diastereomer of the corresponding 1-R′-4-aryl-2,6-dioxo-5-cyanopiperidine-3-carboxylic acid esters, or 3-R′-6-aryl-2,4-dioxo-5-cyano-3-azabicyclo[3.1.0]hexene-1-carboxylic acid esters.     

Remote stereocontrol in the Nazarov reaction: a new approach to the core of roseophilin

Three different procedures are compared to obtain properly substituted divinyl ketones in which one of the double bonds is embedded in a five-membered heterocyclic structure and therefore suitable to produce cyclopenta-fused pyrrole derivatives by the acid-catalyzed Nazarov reaction. These, on treatment with TFA, afforded 2,4-cis-disubstituted 2,3,4,5-tetrahydro-1H-cyclopenta[b]pyrrol-6-ones with high stereocontrol. One of these Nazarov products was oxidized to the corresponding 4,5-dihydro-1H-cyclopenta[b]pyrrol-6-one derivative, thus obtaining an enantiopure key intermediate in the total synthesis of roseophilin.     

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.     

Synthesis and cytotoxic properties of derivatives of the tert-butyl ester of 7-alkylidene-3-methyl-3-cepheme-4-carboxylic acid

Sulfones of the tert-butyl esters of 7-arylmethylene-and 7-(2-furyl)methylene-3-methyl-3-cepheme-4-carboxylic acid were obtained by the condensation of the tert-butyl ester of 3-methyl-7-oxo-3-cepheme-4-carboxylic acid with arylmethylene-and 2-furylidenetriphenylphosphoranes and subsequent oxidation of the intermediate products by meta-chloroperbenzoic acid. The combination of the tert-butyl esters of 7E-bromomethylene-and 7,7-dibromomethylene-3-methyl-1,1-dioxo-3-cepheme-4-carboxylic acids with trimethylsilylacetylene under conditions of the Sonogashira reaction gave the tert-butyl esters of 3-methyl-1,1-dioxo-7E-(3-trimethylsilyl-2-propynylidene)-3-cepheme-4-carboxylic acid and 3-methyl-1,1-dioxo-7-[1,5-bis(trimethylsilyl)-1,4-pentadiyn-3-ylidene]-3-cepheme-4-carboxylic acid. The Vilsmeier reagent was used to incorporate the dimethylaminomethylene group at C-2 of the 7Z-and 7E-isomers of the tert-butyl ester of 7-(4-chlorophenyl)methylene-3-methyl-1,1-dioxo-3-cepheme-4-carboxylic acid. The cytotoxic properties of the derivatives of the tert-butyl ester of 7-alkylidene-3-methyl-3-cepheme-4-carboxylic acid in regard to cancer and normal cells in vitro depends on the structure and 7Z-or 7E-isomerism of the substituent in the 7-alkylidene group as well as the presence of a dimethylaminomethylene group at C-2 of the 3-cepheme system.     

The photochemical synthesis of novel heterocyclic compounds from s-triazolo[4,3-b]pyridazine (II)

s-Triazolo[4,3-b Jpyridazine (I) photochemically reacted with dihydropyran; 2,3-dihydro-p-dioxin; 2,5-dihydrofuran; 2,5-dimethoxy-2,5-dihydrofuran; and 1,3-dioxep-5-ene to give a new series of substituted pyrrolo[1,2-b]-.s-triazoles (II-IX). In most reactions, two or more products were formed. The following compounds have been prepared from I: 9-methylene-4a,5,6,7,8a,9-hexahydropyrano[2,3 :4,5]pyrrolo[1,2-b]-s-triazole (Ha), the corresponding 9-cyanomethyl product (III), and 9-methylene-4a,7,8,8a-tetrahydro-6H,9H-pyrano[3′,2′:4,5]pyrrolo[1,2-b]-s-triazole (IIb) from dihydropyran; 9-methylene-4a,6,7,8a-tetrahydro-9H-p-dioxino[2′,3′:4,5]-pyrrolo[1,2-6]-s-triazole (IV) from 2,3-dihydro-p-dioxin; 8-methylene-4a,5,7a,8-tetrahydro-7H-furo[3′,4′:4,5]pyrrolo[1,2-b]-s-triazole (V) and the corresponding 8-cyanomethyl product (VI) from 2,5-dihydrofuran; 8-cyanomethyl-5,7-dimethoxy-4a,5,7a,8-tetrahydro-7H-furo[3′,4′:4,5]-pyrrolo[1,2-6]-s-lriazole (VII) from 2,5-dimethoxy-2,5-dihydrofuran; and 10-methylene-4a,5,9a,10-tetrahydro-9H-[1,3]dioxepino[5′,6′:4,5]pyrrolo[1,2-b]-s-triazole (VIII) and the corresponding 10-cyanomethyl product (IX) from 1,3-dioxep-5-ene. The addition of several other compounds (1,2,3,6-tetrahydropyridine, 1-acetylimidazole, 3-sulfolene, 2,3-dihydro-p-dithiin, and vinylene carbonate) was attempted, but no reactions were observed.     

Pyrimidines. 24. Analogues and derivatives of 2-amino-5-bromo-6-phenyl-4(3H)-pyrimidinone (ABPP)

Preparation of a number of derivatives of 2-amino-5-bromo-6-phenyl-4(3H)-pyrimidinone (ABPP) including the 2-dialkylaminoalkylamino-, 2-hydroxyalkylamino-, 2-ethoxycarbonylamino- and 2-alkylaminocarbonyl-amino- groups substituted on the pyrimidine ring as well as preparation of 1-(alkylaminoalkyl)-4,6-dioxo-8-phenyl-2,3,4,6-tetrahydro-1H-pyrimido[1,2-α]pyrimidines and 3,5-dioxo-7-phenyl-1,2,3,5-tetrahydroimidazo-[1,2-α]pyrimidines with or without the bromo-substitution are reported.     

Synthese von 2-Mercapto-thieno[2,3—d]pyrimidin-4(3H)-on-Derivaten

2-Mercapto-thieno[2.3-d]pyrimidine-4(3H)-one, 2-mercapto-5.6.7.8-tetrahydro-[1]benzothieno[2.3-d]pyrimidin-4(3H)-one and derivatives thereof were synthesized by cyclisation of esters or amides of the corresponding 2-amino-thiophene-3-carboxylic acids: either by direct reaction with thiourea or by reaction with methyl- or allyl-isothiocyanate via the corresponding N,N-disubstituted thioureas as intermediates.     

Benzofused tricycles based on 2-quinoxalinol

This paper describes our recent efforts to synthesize novel compound scaffolds integrating 2-quinoxalinol with privileged structures of 1,3-dihydro-benzoimidazol-2-one, 1,3-dihydro-benzoimidazole-2-thione, 3-hydroxy-1H-quinoxalin-2-one, 2H-benzo[1,4]oxazin-3-ol, 2H-benzo[1,4]thiazin-3-ol, and 1,3,4,5-tetrahydro-benzo[1,4]diazepin-2-one, respectively. Eight novel benzofused tricycles and their substituent diversity points were developed. These include pyrazino[2,3-g]quinoxaline-2,8-diol (I), 3-hydroxy-6,8,9,10-tetrahydro-1,4,6,10-tetraaza-cyclohepta[b]naphthalen-7-one (II), 6-hydroxy-4H-1-oxa-4,5,8-triaza-anthracen-3-one (III), 6-hydroxy-4H-1-thia-4,5,8-triaza-anthracen-3-one (IV), 6-hydroxy-1,1-dioxo-1,4-dihydro-2H-1lambda(6)-thia-4,5,8-triaza-anthracen-3-one (V), 6-hydroxy-1,3-dihydro-imidazo[4,5-g]quinoxalin-2-one (VI), 6-hydroxy-1,3-dihydro-imidazo[4,5-g]quinoxaline-2-thione (VII), and 7-hydroxy-1,4-dihydro-pyrazino[2,3-g]quinoxaline-2,3-dione (VIII). This strategy of integrating two benzofused privileged structures into one molecule may provide a greater chance for the discovery of novel lead compounds.