Synthesis and structures of 10-hydroxy- and 10-acetoxy-6(5H)phenanthridinones

Treatment of 2,4,8,10-tetranitro-6(5H)-phenanthridinone with hexamethylphosphoric triamide leads to intermolecular nucleophilic substitution of the nitro group by a hydroxy group, the source of which is the water contained in the solvent, to give 10-hydroxy-2,4,8-trinitro-6(5H)-phenanthridinone. An intramolecular interaction with the participation of a proton of the aromatic ring and an oxygen atom of the hydroxy or acetoxy group of the 10-hydroxy- or 10-acetoxy-2,4,8,-trinitro-6(5H)-phenanthridinone, the properties of which are characteristic for an intramolecular hydrogen bond, was detected by x-ray diffraction analysis and PMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 314–319, March, 1987.     

Synthesis and structure of bromonitro-6(5H)-phenanthridinones

Treatment of 2-bromo-6(5H)-phenanthridone with nitrating mixture or fuming nitric acid results in nitration, debromination, and bromination in the 10-position. The brominating agent is apparently Br⁺, formed in the reaction mixture following replacement of the bromine in the 2-position by a nitro-group. Monocrystals of 2-bromo-1,4,8-trinitro-6(5H)-phenanthridinone and 10-bromo-2,4,8-trinitro-6(5H)-phenanthridinone have been subjected to x-ray diffraction examination. PMR has been used for structural identification.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 789–795, June, 1990.We thank A. N. Sobolev for assistance in calculating the structure of (III).     

6(5H)-phenanthridinones. III. halo-6(5H)phenanthridinones

Halogenation of 6(5H)-phenanthridinone or its 3,8-dihalo derivatives with N-bromo or N-chlorosuccinimide in dimethylformamide gives the corresponding 2-halophenanthridinones (I,V,XI-XIV). Further halogenation of 2-halo-6(5H)-phenanthridinone with the appropriate N-halosuccinimide, in the same medium, gives the corresponding 2,4-dihalo derivatives (II,VI). NXS/DMF is found to be a very convenient halogenating system in these preparations. 1,3,8-Trihalo-6(5H)-phenanthridinones (XIX,XX) are prepared from the 1-nitro derivatives which are obtained by a Schmidt rearrangement of 2,7-dihalo-4-nitro-9-oxofluorenes. Similarly, rearrangement and further reaction of 2-nitro-5-chloro-9-oxofluorene (XXI) leads to 3,10-dichloro-6(5H)-phenanthridinone (XXIV). UV absorptions as well as selected IR absorptions of these 6(5H)-phenanthridinones are described.     

Nitro derivatives of 1,3-dihydrobenzimidazol-2-one: II. Rearrangement of <Emphasis Type="Italic">N</Emphasis>-nitrobenzimidazol-2-ones

N-Nitrobenzimidazol-2-ones readily undergo rearrangement to C-nitro derivatives on heating in various solvents (ethyl acetate, butyl acetate, acetonitrile, acetone, dioxane, o-dichlorobenzene, anisole, acetic acid). This rearrangement was used to develop a procedure for the synthesis of 4,5,6,7-tetranitro-1,3-dihydrobenzimidazol-2-one in high yield (90–96%) by nitration of 1,3-dihydrobenzimidazol-2-one, as well as of 5,6-dinitro- and 4,5,6-trinitro-1,3-dihydrobenzimidazol-2-ones, with a small excess of concentrated nitric acid in a mixture with acetic anhydride and acetic acid at 50–60°C.     

Regioselective synthesis of amino- and nitroarenes based on [3+3] cyclocondensations of 1,3-bis(silyloxy)-1,3-butadienes

Functionalized amino- and nitro-substituted biaryls and dibenzo[b,d]pyrid-6-ones (6(5H)-phenanthridinones) were prepared by [3+3]cyclocondensation of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with nitro-substituted 1-aryl-1-silyloxy-1-en-3-ones and subsequent hydrogenation. 4-Nitro- and 4-aminophenols were prepared based on formal [3+3] cyclizations of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with 3-ethoxy-2-nitro-2-en-1-ones.     

3-(2喹啉基) 酚酮的卤代和硝化反应

本文首次报道了3-(2喹啉基) 酚酮的卤代和硝化反应在冰乙酸介质中,3-(2喹啉基) 酚酮与溴反应,在不同条件下分别得到单溴代产物和双溴代产物; 与硝酸反应得到单硝酸化产物,与过量硝酸反应,得到的硝化产物。     

Benzindoles. 21. Nitration of 3-formyl[4, 5]-and 3-formyl [6,7] benzindoles

It was established that products of monosubstitution of 4-nitro- and 7-nitro-3-formyl[4,5] benzindoles and products of disubstitution of 4,8-dinitro- and 7,8-dinitro-3-formyl [4,5] benzindoles are formed in low yields in the nitration of 3-formyl [4,5]benzindole with sodium nitrate in concentrated sulfuric acid. Similar nitration of 3-formyl [6,7] benzindole leads to 9-nitro- and 5, 6-dinitro-3-formyl [6,7]benzindoles. The 3-formylnitrobenzindoles obtained were converted to nitrovinyl derivatives by condensation with nitromethane.See [1] for Communication [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 949–955, July, 1980.     

2,6-Dithiodecahydro-1H,5H-Diimidazo[4,5,-b:4′,5′-e]Pyrazine and related dioxo- and diimino-decahydrodiimidazopyrazines

Thiourea condensed with 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine 2 in the presence of hydrochloric acid to give 2,6-dithiodecahydro-1 H,5H-diimidazo[4,5,-b:4′,5′-e]pyrazine 5 isolated as the dihydrochloride salt. The salt 5 . 2HCl was converted to the free base 5 by lithium hydroxide, to the dinitrate salt 5 . 2HNO₃ by silver nitrate, degraded to 2-thio-2,3,4,7-tetrahydro-1 H-imidazo[4,5-b]pyrazine 6 in a reaction with tert-butyl amine, and converted to 4,8-dihydro-4,8-dinitro-1H,5H-diimidazo[4,5-b:4′,5′-e]pyrazine-2,6- disulfonic acid 9 by nitric acid (100%) at −40°C. Denitration of the dinitramine 9 to give 4,8-dihydro-1H,5H-diimidazo[4,5-b:4′,5′-e]pyrazine 11 was brought about by methanolic hydrogen chloride in ether. In one run nitration without oxidation converted the salt 5 · 2HCl to the dinitrate salt of the 4,8-dinitro derivative 10 ; treatment with triethyl amine liberated the free base 10 from the salt. Degradation of 2,6-dioxo-1,3,4,5,7,8-hexanitrodecahydro-1H,5H-diimidazo[4,5-b:4′,5′-e]pyrazine 12 to 2-oxo-2,3-dihydro-1,3-dinitro-1H-imidazo[4,5-b] pyrazine 13 was brought about by hydrochloric acid. Treatment with lithium hydroxide also liberated 2,6-dioxodecahydro-1H,5H-diimidazo [4,5-b:4′,5′-e]pyrazine 3 from its dihydrochloride salt. Attempts to liberate 2,6-diiminodecahydro-1H, 5H-diimidazo[4,5-b:4′,5′-e]pyrazine 4 from its tetrahydrochloride salt led instead to intractable mixtures. The tetrahydrochloride salt 4 · 4HCl was converted to the dihydrochloride salt 4 · 2HCl in a reaction with tert-butyl amine.     

Synthesis of quinolines, 2-quinolones, phenanthridines, and 6(5h)-phenanthridinones via palladium[0]-mediated Ullmann cross-coupling of 1-bromo-2-nitroarenes with beta-halo-enals, -enones, or -esters

Palladium[0]-mediated Ullmann cross-coupling of 1-bromo-2-nitrobenzene (1 R = H) and its derivatives with a range of beta-halo-enals, -enones, or -esters readily affords the corresponding beta-aryl derivatives, which are converted into the corresponding quinolines, 2-quinolones, phenanthridines, or 6(5H)-phenanthridinones on reaction with dihydrogen in the presence of Pd on C or with TiCl(3) in aqueous acetone. [reaction: see text]     

Synthesis and reactions of trinitro-9,10-phenanthrenequinone derivatives

The reaction of 2,4,7-trinitro-9,10-phenanthrenequinone with CuCl in aqueous dimethylformamide or dimethyl sulfoxide at room temperature, followed by acidification, gave a stable red complex of 2,4,7-trinitro-9,10-dihydroxyphenanthrene with a solvent molecule. On heating in a polar aprotic solvent in the presence of CuCl or other metal salt, 2,4,7-trinitro-9,10-phenanthrenequinone underwent benzilic acid rearrangement with formation of 2,4,7-trinitrofluorenone. The nitration of 9,10-sulfuryldioxyphenanthrene and subsequent decomposition of cyclic sulfates afforded previously unknown 1,3,6-trinitro- and 1,8-dinitro-9,10-phenanthrenequinones.     

Magnetische Kernresonanz- und «Molecular Orbital»- untersuchungen über die struktur von MEISENHEIMER-komplexen 8. Mitteilung über nucleophile aromatische Substitutionsreaktionen [1]

(1) The NMR. spectra of the stable methoxide addition complexes of 2,4-dinitro-, 2,4,6-trinitro- and 2,4-dinitro-6-cyano-anisole, and the intramolecular (spiro) reaction product of 1-(2′-hydroxyethoxy)-2,4,6-trinitrobenzene demonstrate that these products are MEISENHEIMER (σ?) complexes (addition of base in position 1).     

Nitro derivatives of 1,3-dihydrobenzimidazol-2-one: I. Synthesis of <Emphasis Type="Italic">N</Emphasis>-nitrobenzimidazol-2-ones

1,3,5,6-Tetranitro-2,3-dihydro-1H-benzimidazol-2-one, 1,5,6-trinitro-2,3-dihydro-1H-benzimidazol-2-one, and 1,4,5,6-tetranitro-2,3-dihydro-1H-benzimidazol-2-one were synthesized for the first time by nitration of 5,6-di- and 4,5,6-trinitro-2,3-dihydro-1H-benzimidazol-2-ones with concentrated nitric acid in acetic anhydride.     

Synthesis of Some Halogen- and Nitro-substituted Nicotinic Acids and Their Fragmentation Under Electron Impact

Features of electrophilic and nucleophilic substitution under chlorination and nitration reactions conditions have been investigated for 6-hydroxy- and 6-methyl-substituted derivatives of 3-cyano-4-methyl-2(1H)-pyridones. The polychloro- and nitro-substituted 3-cyano-4-methylpyridines obtained were used as synthons in the synthesis of some polyhalo- and nitro-substituted nicotinic acids and their amides. The fragmentation pathways of the synthesized compounds under electron impact have been studied.     

Alteration of the aurophilic interactions in trimeric gold(I) compounds through charge transfer. Behavior of solvoluminescent Au(3)(MeN=COMe)(3) in the presence of electron acceptors.

The ability of the triangular gold(I) complex, Au(3)(MeN=COMe)(3), which as a solid displays the novel property of solvoluminescence (see: Vickery, J. C.; Olmstead, M. M.; Fung, E. Y.; Balch, A. L. Angew.Chem., Int. Ed. Engl. 1997, 36, 1179) to function as an electron donor has been demonstrated through spectroscopic studies and isolation of crystalline adducts with organic acceptor molecules. Four such adducts with nitro-9-fluorenones have been isolated and subject to single-crystal X-ray diffraction study. These are deep yellow [Au(3)(MeN=COMe)(3)].[2,4,7-trinitro-9-fluorenone], red [Au(3)(MeN=COMe)(3)].[2,4,5,7-tetranitro-9-fluorenone], red [Au(3)(MeN=COEt)(3)](2).[2,7-dinitro-9-fluorenone], and red [Au(3)(MeN=COEt)(3)](2).[2,4,7-trinitro-9-fluorenone]. The solid-state structures of [Au(3)(MeN=COMe)(3)].[2,4,7-trinitro-9-fluorenone] and [Au(3)(MeN=COMe)(3)].[2,4,5,7-tetranitro-9-fluorenone] consist of columns in which the planar gold(I) trimers and the nearly planar nitro-9-fluorenones are interleaved with the gold trimers making face-to-face contact with the nitroaromatic portion of the electron acceptor. Thus the organic acceptors disrupt the aurophilic interactions present in crystalline [Au(3)(MeN=COMe)(3)] itself. However, in [Au(3)(MeN=COEt)(3)](2).[2,7-dinitro-9-fluorenone] and [Au(3)(MeN=COEt)(3)](2).[2,4,7-trinitro-9-fluorenone], aurophilic interactions are found which produce dimers, [Au(3)(MeN=COEt)(3)](2), with nearly trigonal prismatic Au(6) cores. These dimers are interleaved with the nitro-9-fluorenone molecules to again form extended columns in which the components make face-to-face contact. Despite the fact that the gold atoms in [Au(3)(MeN=COMe)(3)] and [Au(3)(MeN=COEt)(3)] are in exposed sites and only two-coordinate, there is no evidence of additional coordination of the nitro-9-fluorenones with gold centers in the crystalline adducts.     

Nitration of 1,3-dihydro-2<Emphasis Type="Italic">H</Emphasis>-imidazo[4,5-<Emphasis Type="Italic">b</Emphasis>]pyridin-2-one derivatives

Nitration of 1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-one and its N-methyl derivatives at 0–5°C and 60°C gives 5-nitro-and 5,6-dinitro-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-ones, respectively. The latter can also be obtained by nitration of 5-mononitro derivatives under similar conditions. The nitration of 6-chloro-and 6-bromo-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-ones and their N-methyl-substituted analogs leads to the formation of the corresponding 6-chloro(bromo)-5-nitro compounds. The same products are formed in the nitration of 5,6-dichloro-and 5,6-dibromo-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-ones. In this case, the process involves replacement of the halogen atom in position 5 of the pyridine fragment by nitro group. The nitration of 6-bromo-5-methyl-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-one is accompanied by oxidation of the 5-methyl group to carboxy.     

Nitration of 2,3′-bithienyl

The nitration of 2,3′-bithienyl ( 1 ) with fuming nitric acid in acetic anhydride at 0° gives a mixture of 3-nitro- ( 2 ), 2′ -nitro- ( 3 ) and 5-nitro-2,3′-bithienyl ( 4 ) with relative percentages of 38.7%, 34.8% and 26.5%. When the nitration of 1 was carried out with fuming nitric acid in acetic acid at 20°, the same compounds 2, 3 and 4 were obtained, but with different relative percentages: 20.4%, 36.5% and 43.1% respectively. The results of the mononitration of 1 are compared with those obtained in other electrophilic substitutions and with the theoretical predictions. The further nitrations of 2, 3 and 4 with nitric acid in acetic anhydride at room temperature lead to the formation of five dinitro-2,3′-bithienyl isomers. Compound 2 gives a mixture of 2′,3-dinitro- ( 5 ) and 3,5′-dinitro-2,3′-bithienyl ( 6 ); compound 3 gives a mixture of 5 , 2′,5-dinitro- ( 7 ) and 2′,4-dinitro-2,3′-bithienyl ( 8 ); compound 4 gives 7 and 5,5′-dinitro-2,3′-bithienyl ( 9 ). The possible reasons of the formation of the various dinitro-2,3′-bithienyl isomers are discussed.     

Reactions of Quinazoline Alkaloids and their Derivatives with Electrophilic Reagents

Nitration of deoxypeganine (DOP), deoxyvasicinone (DOV), 2,3-tetramethylene-, 2,3-pentamethylene-, and 3,4-dihydroquinazol-4-ones and their 1,2-dihydro derivatives was studied. It was shown that the reaction pathway changed depending on the presence of a carbonyl on C-4 and an N=C bond in these compounds. Only the H atom on C-6 was subject to nitration if both functional groups were present, for example DOV and its homologs. Substitution of the H atom of either the 6-position (DOP, 1,2-dihydro-DOV, and their homologs) or the 6- and 8-positions simultaneously (DOP and its homologs) was enhanced if one of these functional groups was missing depending on the substrate:nitrating agent ratio. The bromination and nitration reactions of 1,2-dihydro-DOV and its analogs in a 1:2 ratio were accompanied by oxidation of the N¹H-CH bond with formation of 6,8-dibromo- and 6,8-nitro-DOV and their homologs. The difference in the behavior of these compounds was due to the different nucleophilicity of the benzene rings in them. The reaction of 1,2-dihydro-DOV and its homologs with isocyanates and p-nitro- and p-methylbenzoic acid chlorides was studied. 6-Nitro- and 6,8-dinitro-DOP and 6,8-dibromo- and 6,8-dinitro-DOV and their homologs and 6-bromo- and 6-nitro-1,2,3,4-tetrahydro-2,3-polymethylenequinazol-4-ones and their 1-alkyl(aryl)-carbamoyl and p-nitro(methyl)-benzoyl derivatives were synthesized. The molecular structures of 1-ethyl-and 1-(o-chlorophenyl)-carbamoyl-1,2-dihydrodeoxyvasicinones and 6,8-dinitro-2,3pentamethylene-3,4-dihydroquinazol-4-one were established. UDC 547.944/945 547.856.1 Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 387-393, July-August, 2008. Original article submitted May 5, 2008.     

Effect of Medium Basicity on the Coordination Kinetics of <Emphasis Type="Italic">meso</Emphasis>-Nitro-Substituted Derivatives of 5-Phenyl-β-Octaalkylporphine with Zinc Acetate

The kinetics of formation of zinc complexes of 10,15-dinitro-5-phenyl-2,3,7,8,12,13,17,18-octamethylporphine, 10,15,20-trinitro-5-phenyl-2,3,7,8,12,13,17,18-octamethylporphine, and 10,15,20-trinitro-5-(4-nitro-phenyl)-2,3,7,8,12,13,17,18-octamethylporphine were studied spectrophotometrically at 288–308 K in Zn(OAc)₂–acetonitrile and Zn(OAc)₂–1,8-diazabicyclo[5.4.0]-undec-7-en–acetonitrile solutions with different basicities. The compounds under study were identified by electronic absorption, IR and ¹H NMR spectroscopies. An analysis of the effect of nitro groups on the kinetics of coordination of Zn(II) with the studied ligands showed that the changes in complexing properties of nitro derivatives of 5-phenyl-β-octaalkylporphine are related to the electron-withdrawing effect of NO₂ groups, to structural effects of distortion of the planar structure of the macrocycle, and to alteration of basicity of the reaction medium.     

Dense energetic compounds of carbon,hydrogen, nitrogen,and oxygen atoms. V. 1,2,7,8-bisfuroxano-3,4,9,10-tetranitro-5, 11-dehydro-5H, 11H-benzotriazolo[2, 1-a]benzotriazole (BTBB)

A reaction between 2, 8-dichloro-4, 10-dinitro-5, 11-dehydro-5H, 11H-benzotriazolo[2, 1-a]-benzotriazole 8 and sodium azide in dimethyl sulfoxide produced 3, 9-diazido-4, 10-dinitro-5, 11-dehydro-5H, 11H-benzotriazolo [2, 1-a]benzotriazole 10 rather than the 2.8-diazido isomer 9 expected by direct displacement. Thermolytic elimination of nitrogen (2 moles) converted the dinitro diazide 10 to 3,4,9,10-bisfuroxano-5, 11-dehydro-5H, 11H-benzotriazolo[2, 1-a]benzotriazole 11 that was subsequently nitrated to give the 2,8-dinitro derivative 12 . Similar nitration converted the dinitro diazide 9 to the trinitro 15 and tetranitro 14 derivatives: thermolysis of the latter gave 1,2,7,8-bisfuroxano-4, 10-dinitro-5, 11-dehydro-5H, 11H-benzotriazolo[2, 1-a]-benzotriazole 16 . Nitration (100% HNO₃, CF₃SO₃H) converted compound 16 to the 3,4,10-trinitro derivative 17 , whereas a similar nitration (100% HNO₃, FSO₃H) gave the title compound BTBB, an insensitive high-energy, high-density (d 2.03 g/cc) molecule. © 1995 John Wiley & Sons, Inc.     

Luminescent nitro derivatives of benzotriazolo[2,1a]benzotriazole

Fluorescence was enhanced and laser activity introduced by substitution in 5,11-dehydro-5H,11H-benzotriazolo[2,1-a]benzotriazole 6 to give 2-nitro, 2,8-dinitro, 2,4,8-trinitro, and 2,4,8,10-tetranitro derivatives 9a–d . Luminescence for compounds 6 and 9a–d and the 2,8-dinitro-3,9-dimethyl and 2,3,8,9-tetramethyl-4,10-dinitro derivatives 11a,b was erratically solvent dependent when examined in ethyl acetate, acetonitrile, and acetone and was most efficient in the 2,8-dinitro derivative 9b [λ_f 479 nm (ethyl acetate) Φ 0.98, λ_f 501 nm (acetonitrile) Φ 0.58, and λ_f 494 nm (acetone) Φ 0.61] and in the tetranitro derivative 9d [λ_f 509 nm (acetonitrile) Φ 0.81 and λ_f 511 nm (acetone) Φ 0.66]. With laser activity at 560–590 nm (acetonitrile) the dye 9b was 30% as efficient as rhodamine 6G (ethanol) in power output. Luminescence was quenched by the reduction of nitro groups to give 2-amino and 2,8-diamino derivatives 9e,f and by the conversion of the tetranitro compound 9d to an unassigned diazido dinitro derivative 9g . Luminescence was not detected in 2,5-dimethyl-3,6-dinitro-1,3a-4,6a-tetraazapentalene 14 and ethyl 2,5-dimethyl-1,3a,4,6a-tetraazapentalene-3,6-dicarboxylate 15 . Azidoazobenzenes were obtained from 4-methyl- and 4,5-dimethyl-1,2-phenylene diamines via oxidation with lead dioxide to aminoazobenzene derivatives followed by treatment of the diazotized amines with sodium azide and thermolysis of azido intermediates to give 3,9-dimethyl and 2,3,8,9-tetramethyl derivatives 10a,b of the triazolotriazole 6 . Nitration converted the triazole 6 to the 2,4,8-trinitro derivative 9c and the alkyltriazoles to their dinitro derivatives 11a,b .