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.     

Synthesis of some phenanthridone derivatives

The alkylation of phenanthridone and some nuclear-substituted phenanthridones using sodium hydride in DMF/benzene is reported. Various 5-cyanoalkylphenanthridones were converted to further derivatives by either hydrolysis or reduction.     

Synthesis and structure of azido-and amino-substituted dibenzoxazepinones

1,3-Dinitro[b, f][1,4]dibenzoxazepin-11(10H)-one enters nucleophilic substitution reactions with N-nucleophiles, azide ion preferably replacing the nitro group in position 3, whereas amines the one in position 1. Structures of the substitution products were confirmed by X-ray diffraction and ¹H NMR NOE spectroscopy. The selectivity observed in the reaction with amines was supposed to be caused by the stabilization of the intermediate σ-complex with the NH…O intramolecular hydrogen bond. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2018–2022, October, 2007.     

Synthesis of some amino-substituted furanopyrimidines and styrylpyrimidines

5-p-Chlorophenyl-6,6-dimethyl-5,6-dihydro-3H-furano[2,3-d]pyrimidine-4-one is readily converted to 4,6-dichloro-5-β-β-dimethyl-α- (p-chlorostyryl)pyrimidine by warming in phosphorus oxychloride and acetic acid, behavior which is in strong contrast to that of the analogous 5-phenyl derivative. The reaction provides a convenient source of 4-amino-6-chloro-5β,β-dimethyl-α- (p-chlorostyryl)pyrimidines and 4,6-diamino-5-β,β-dimethyl-α- (p-chlorostyryl)pyrimidines, compounds of potential biological interest.     

Synthesis of diacylals of amino-substituted aldehydes

Russian Journal of General Chemistry -     

Synthesis of amino-substituted indoles using the Bartoli reaction

We report herein the concise preparation of a range of functionalised aminoindoles via a new application of the Bartoli reaction. Scope and limitations of the methodology have been extensively studied to reveal the importance of protecting groups and substitution patterns. The use of amino substituted nitroanilines for the Bartoli reaction is to our knowledge unprecedented. Our work thus represents a novel entry into substituted aminoindoles which are relevant building blocks for both the fine chemical and pharmaceutical industry.     

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 phenanthridones using Diels-Alder reactions of 4-substituted 2(1H)-quinolones acting as dienophiles

Diels-Alder reactions of 2(1H)-quinolones having an electron-withdrawing group at the 4-position with 1,3-butadiene derivatives were carried out to give the phenanthridones richly functionalized under the conditions of atmospheric and high pressure. Furthermore, the reactivities of 4-substituted 2(1H)-quinolones acting as a dienophile were examined using MO calculation.     

Synthesis, characterization and photodynamic activity of amino-substituted hypocrellin derivatives

Three new hypocrellin derivatives, amino- or amino acid-substituted on the side ring of hypocrellin B (HB), were synthesized by the reactions of HB with 3-methoxypropylamine, 6-aminohexanoic acid and gamma-amino-n-butyric acid, respectively. The structures of these compounds were characterized with proton nuclear magnetic resonance spectra, infrared spectra and mass spectra. The UV-visible absorption spectra, singlet oxygen-generating quantum yield and amphiphilicities of hypocrellin derivatives were measured and compared with HB, the parent compound. These derivatives showed strong absorption in the domain of the phototherapeutic window (600-900 nm) and improved amphiphilicity. HB and the derivatives were preliminarily tested for their photodynamic effects on human oral cavity epithelial carcinoma KB cell line in vitro. Two amino acid-substituted hypocrellins showed phototoxicity to the KB cell line. At an inhibitory dosage of 50% killing only 0.51 mumol L-1 compound 3 (or 0.88 mumol L-1 compound 2) and 0.5 J cm-2 irradiation were required. The hypocrellins exhibited some dark toxicity to the KB cell line. HB and amino acid-substituted hypocrellins showed lower dark toxicity to the KB cell line than amino-substituted hypocrellins in the assessment of cell survival.     

Synthesis and reactivity of amino-substituted BEDT-TTF donors as building blocks for bifunctional materials

The first two amino-substituted BEDT-TTF derivatives, aminomethyl-ET (AMET) and aminoethyl-ET (AEET), have been prepared; the critical step in both cases was a hetero Diels-Alder reaction with 1,3-dithiole-2,4,5-trithione. AEET shows expected reactivity towards electrophiles whereas AMET will not react with aryl acid chlorides or sulfonyl chlorides, but amides of AMET can be produced by DCC coupling and mixed anhydride methods.     

Synthesis of some members of the hydroxylated phenanthridone subclass of the Amaryllidaceae alkaloid family

The total synthesis of several members of the hydroxylated phenanthridone subclass of the Amaryllidaceae alkaloid family has been carried out. (+/-)-Lycoricidine and (+/-)-7-deoxypancratistatin were assembled through a one-pot Stille/intramolecular Diels-Alder cycloaddition cascade to construct the core skeleton. The initially formed [4+2]-cycloadduct undergoes nitrogen-assisted ring opening followed by a deprotonation/reprotonation of the resulting zwitterion to give a rearranged hexahydroindolinone on further heating at 160 degrees C. The stereochemical outcome of the IMDAF cycloaddition has the side arm of the tethered vinyl group oriented exo with respect to the oxygen bridge. The resulting cycloadduct was used for the stereocontrolled installation of the remaining functionality present in the C-ring of the target molecules. Key features of the synthetic strategy include (1) a lithium hydroxide induced tandem hydrolysis/decarboxylation/elimination sequence to introduce the required pi-bond in the C-ring of (+/-)-lycoricidine, and (2) conversion of the initially formed Diels-Alder adduct into an aldehyde intermediate which then undergoes a stereospecific decarbonylation reaction mediated by Wilkinson's catalyst to set the trans-B-C ring junction of (+/-)-7-deoxypancratistatin.     

Synthesis of Polysubstituted 1,4-Diazacycloheptan-5-ones. 1. Synthesis and Conformational Investigation of Polysubstituted 4-Piperidones

A series of tri- and tetrasubstituted 4-piperidones and their bicyclic analogs has been synthesized. It was established by ¹H NMR spectroscopy that all the piperidones obtained have the chair conformation in solution with equatorially disposed substituents.     

Synthesis of amino-substituted 2-methylcoumarins,chromans, and benzoxepanes and their N-(alkylaminoacyl) derivatives

The isomeric compositions of the products of nitration of 2-methylcoumaran and chroman with acetyl nitrate were determined. More convenient methods for the synthesis of 7-amino-2-methylcoumaran and 8-aminochroman were developed, and 9-amino-1-benzoxepane was obtained for the first time. Alkylaminoacylamino-substituted 2-methylcoumarans, chromans, and 1-benzoxepanes were synthesized. A method for the synthesis of 2-bromocaproyl chloride from caproic acid was developed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 320–324, March, 1987.     

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 amino-substituted 1,3-bis(tert-butyl-NNO-azoxy)benzenes 2.* 2-amino and 2,4-diamino derivatives

Oxidation of one of the amino groups of 2-bromo-4,6-dichloro-1,3-phenylenediamine to the nitroso group followed by its conversion into thetert-butyl-NNO-azoxy group afforded a derivative ofm-(tert-butyl-NNO-azoxy)aniline,viz., 2-bromo-3-(tert-butyl-NNO-azoxyl)-4,6-dichloroaniline. Analogously, the second amino group was converted into thetert-butyl-NNO-azoxy group to form a derivative of 1,3-bis(tert-butyl-NNO-azoxy)benzene,viz., 3-bromo-2,4-bis(tert-butyl-NNO-azoxyl)-1,5-dichlorobenzene The reaction of the latter with ammonia yielded 2-amino- and 2,4-diamino-substituted 1,3-bis-(tert-butyl-NNO-azoxyl)benzenes. For Part 1, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2126–2130, November, 1999.     

Spectral characteristics,structure, and properties of phenanthridone derivatives

On the basis of IR and electronic spectra and quantum-chemical calculations, a conclusion has been drawn regarding the structure of phenanthridone and its derivatives: It has been confirmed that in the crystalline state and in solutions, phenanthridones exist primarily in the lactam form. An interpretation is given for the longwave bands in the electronic absorption spectra. Certain spectral criteria are proposed for determining the positions of substituents in the phenyl rings of phenanthridones, and the direction of aromatic substitution of the lactim and cationic forms of phenanthridone have been evaluated. Acid association constants of phenanthridone and its derivatives have been determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1361–1368, October, 1992.     

The site of protonation in amino-substituted pteridines

SCF -LCAO -MO -CI calculations made on 2- and 4-amino-, and 2,4-diaminopteridines indicate that the most favorable site where the protonation can take place is N-1.