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.     

Reactions of 9,10-phenanthrenequinone and its nitro derivatives with acetone in the presence of Al2O3

The addition of acetone to 9,10-phenanthrenequinone and 2-nitro-, 2,7-dinitro-, and 2,4,7-trinitro-9,10-phenanthrenequinones in the presence of Al₂O₃ affords mono- and bisadducts. The crystal structures of 10-hydroxy-10-(2-oxopropyl)-2-nitro-9,10-dihydrophenanthren-9-one and 9,10:10,9-bishemiketal of 9,10-dihydroxy-2-nitro-9,10-bis(2-oxopropyl)-9,10-dihydrophenanthrene were determined.     

X-ray structural and spectral study of 1:2 solvate of 2,7-dinitro-4-bromo-10,10-dihydroxyphenanthren-9-one with dimethylformamide

An x-ray structural study showed the total similarity of the behavior of 2,4,7-trinitro- and 2,7-dinitro-4-bromo-9,10-phenanthrenequinones dissolved in aqueous DMF: addition of a molecule of water at one of the two carbonyl groups with formation of the corresponding 10,10-dihydroxyphenanthren-9-ones takes place in both cases in soft conditions. These products of hydration exist as hydrogen-bonded solvates with molecules of the solvent whose crystals are isostructural to each other. The results of the x-ray structural study are in agreement with the data from the IR absorption and electron absorption spectra; their comparison suggests the existence of equilibrium between the starting compounds and the products of hydration, and the equilibrium position is a function of the polarity of the basic solvent.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow 117813. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 910–916, April, 1992.     

Effect of the solvent nature and the number of electrophilic substituents in the molecule on hydration of nitro derivatives of phenanthrene-9,10-quinone

Solvates (1⩺2) of 10,10-dihydroxy-2,4,7-trinitro-9,10-dihydrophenanthren-9-one with DMSO and of 10,10-dihydroxy-2,7-dinitro-9,10-dihydrophenanthren-9-one with HMPA were prepared. The crystal structure of 2,5-dinitrophenanthrene-9,10-quinone was established. The results of X-ray diffraction analysis and IR spectroscopy of a series of mono-, di-, and trinitro derivatives of phenanthrene-9,10-quinone demonstrated that the ability of carbonyl groups to participate in nucleophilic addition of water increases as the number of nitro groups in substituted phenanthrene-9,10-quinone increases. The nature of the solvent (HMPA, DMF, or DMSO) affects hydration of phenanthrenequinones primarily due to the difference in the strength of intermolecular hydrogen bonds stabilizing di- and tetrahydroxy-dihydrophenanetherenes. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 738–742, April. 1999.     

Spectrophotometric studies of CT complexes of poly(N-vinylhalogenocarbazole)s with 2,4,7-trinitrofluorenone

The effect of chlorine, bromine, and iodine at the 3 and 3,6 positions on a carbazole ring with thermodynamic properties, that is, enthalpy, entropy, and a stability constant of CT complex poly(N-vinylcarbazole–2,4,7-trinitrofluorenone), were studied in a temperature range of 268–323 K. The discussion of the results obtained, based on linear free-energy relationships, stressed the advantageous influence of the halogen substituent in the carbazole ring on the properties of the poly(N-vinylcarbazole)–2,4,7-trinitrofluorenone complex.     

Spectrophotometric studies of some CT complexes of 2,4,7-trinitrofluorenone with poly(vinyl halogenocarbazole)

The modified UV-Vis spectrophotometry has been applied to study of spectral and thermodynamic properties of charge-transfer complexes of poly-N -vinylhalogenocarbazole with 2,4,7-trinitrofluorenone. The application of numerical calculation allows for the separation of the absorption bands which result only from donor-acceptor interaction. The equilibrium constants, entropies, and enthalpies of complexing reaction studied in a wide range point out the beneficial influence of introduced chlorine, bromine, and iodine substituents in position 3 and 6 of carbazole ring over the complexing properties of poly-N-vinylhalogenocarbazole and properties of its complexes with 2,4,7-trinitrofluorenone.     

X-ray diffraction and spectral study of products of reaction between 2,7-dinitro and 2,4,7-trinitrophenanthrenequinone and nitromethane

The molecular and crystalline structures of three products of the reaction between 2,7-dinitro- and 2,4,7-trinitrophenanthrenequinone with nitromethane in an HMPTA solution were studied by x-ray diffraction. Two of these products are H-bonded 1:1 solvates.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Patrice Lumumba People's Friendship University, 117198 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1575–1584, July, 1992.     

Crystal and molecular structure of the benzene solvate of 2,4,7-trinitro-9,10-phenanthrenequinone

Conclusions An x-ray diffraction structural analysis established the molecular and crystal structure of the benzene solvate of 2,4,7-trinitro-9,10-phenanthrenequinone. The bond length distribution in this trinitrophenanthrenequinone indicates -electron localization at the periphery of the phenanthrenequinone system, whose significant distortion is due to steric and electronic factors.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1284–1290, June, 1986.     

Crystal and molecular structure of the solvate of 2,4,7-trinitro-9,9,10,10-tetrahydroxyphenanthrene with hexamethylphosphortriamide (I) and the solvate of 2,4,7-trinitro-10,10-dihydroxyphenanthren-9-one with dimethylformamide (II)

Two products of the addition reactions of H₂O at the carbonyl bonds of 2,4,7-trinitro-9,10-phenanthrenequinone, formed under mild conditions when it is dissolved in aqueous hexamethylphosphortriamide (HMPTA) and dimethylformamide (DMF), have been studied by x-ray diffraction. The crystalline solvates of 2,4,7-trinitro-9,9,10,10-tetrahydroxyphenanthrene (C₁₄H₉N₃O₁₀·3HMPTA) and 2,4,7-trinitro-10,10-dihydroxyphenanthren-9-one (C₁₄H₇N₃O₉·2DMF) are formed. In the first of these, all the molecules of the included solvent are disordered in complex fashion. Both crystal structures are stabilized by strong hydrogen bonds between the solvated and solvating molecules.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 575–580, March, 1990.     

Reaction of 5-nitrospiro[benzimidazole-2,1′-cyclohexane] 1,3-dioxide with electrophilic reagents: Bromine and nitric acid

Reactions of 5-nitrospiro[benzimidazole-2,1′-cyclohexane] 1,3-dioxide with bromine and nitric acid lead to the electrophilic substitution of the hydrogen atom in the meta-position with respect to the nitro group. At thebromination the primarily formed 4-bromo-6-nitrospiro[benzimidazole-2,1′-cyclohexane] 1,3-dioxide when kept in the solution loses an oxygen atom forming 4-bromo-6-nitrospiro[benzimidazole-2,1′-cyclohexane] 1-oxide and an isomerization product, 8-bromo-6-nitrospiro[3H-[2,1,4]benzoxadiazine-3,1′-cyclohexane] 4-oxide. The latter exposed to light turns into 4-bromo-6-nitrospiro[benzimidazole-2,1′-cyclohexane] 1,3-dioxide. The reaction of the initial 1,3-dioxide with nitric acid afforded 4,6-dinitrospiro[benzimidazole-2,1′-cyclohexan]-7-ol 1-oxide whose heating in o-dichlorobenzene resulted in 3,5-dinitro-1,8-diazatricyclo[7.5.0.0^2,7] tetradeca-2(7),3,5,8-tetraen-6-ol.     

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.     

3,6,9,10-tetrahalogenphenanthrene. A new cycliarylation reaction of DDT-derivatives

A simple synthesis of tetrachlorophenanthrene starting from DDT has been realized. 1,1,1,2-tetrachloro-2,2-bis-(4-chlorophenyl)-ethane (I) and its rearranged product 1,1,2,2-tetrachloro-1,2-bis-(4-chlorophenyl)-ethane (V) and other analogs substituted by halogen in the para-position undergo a cycliarylation yielding 3,6,9,10-tetrahalogenophenanthrenes. Partial dechlorination of this tetrachlorophenanthrene yields 3,6-dichlorophenanthrene. Oxidation gives 3,6-dichloro-9,10-phenanthrenequinone, and chlorosulfonation leads to 3,6,9,10-tetrachloro-2,7-bis-(chlorosulfonyl)-phenanthrene. The mechanism of this cyclization reaction in presence of LEWIS acids is discussed and compared with the cyclization of DDT derivatives to yield fluorenones.     

A re-entrant Col ho phase

The formation of a re-entrant columnar discotic hexagonal ordered phase (re-entrant Col ho phase) is reported for the asymmetrically substituted triphenylene 3,6,7,10,11-penta- pentyloxytriphenylene-2-yl pivaloate (pivaloate) and its structural and dynamic properties described. The re-entrant phase behaviour is strongly modified by doping the pivaloate with the electron acceptor 2,4,7-trinitrofluorenone (TNF).     

Flow-injection determination of 9,10-phenanthrenequinone with catalytic photometric detection

A catalytic photometric method with a flow-injection system is described for the determination of 9,10-phenanthrenequinone. It is based on the catalytic effect of 9,10-phenanthrenequinone on the redox reaction of 1,2-dinitrobenzene with formaldehyde under alkaline conditions. 9,10-Phenanthrenequinone at the 5.0 x 10(-8)-5.0 x 10(-6)M level can be determined at a rate of 20 samples/hr. The detection limit is 1.0 x 10(-8)M (40 pg in a 10-microl injection).     

Germylenes derived from pyridine-containing diols: reactions with diphenylphosphoryl azide and 9,10-phenanthrenequinone*

A study was carried out on the behavior of monomeric germylenes derived from pyridine-containing diols in reactions with diphenylphosphoryl azide and 9,10-phenanthrenequinone. It was found that the germanium atom increases its oxidation state to 4+ in these reactions. The structure of the product of the reaction with 9,10-phenanthrenequinone was confirmed by X-ray structural analysis, which showed a transannular germanium-nitrogen interaction in this product.     

A versatile synthesis for new 9,10-bis(4-alkoxyphenyl)-2,7-diiodophenanthrenes: useful precursors for conjugated polymers

A practical synthesis for 9,10-bis(alkoxyphenyl)-2,7-diiodophenanthrenes is described. 9,10-Bis(4-hexyloxyphenyl)-2,7-diiodophenanthrene was selectively obtained by a one-pot reaction of 10,10-bis-(4-hexyloxy-phenyl)-2,7-diiodo-10H-phenanthren-9-one with 1 equiv of triethylsilane in trifluoroacetic acid. The target molecular architecture was demonstrated to be a useful precursor for obtaining the corresponding poly(phenanthrene) and poly(phenanthrylene-vinylene).     

Palladium(II) 9,10-phenanthrenequinone N-substituted thiosemicarbazone/semicarbazone complexes as efficient catalysts for N-arylation of imidazole

A series of palladium complexes, [PdCl(L_1–4)] (1–4) (L₁ = 9,10-phenanthrenequinone thiosemicarbazone, L₂ = 9,10-phenanthrenequinone methylthiosemicarbazone, L₃ = 9,10-phenanthrenequinone phenylthiosemicarbazone, and L₄ = 9,10-phenanthrenequinone semicarbazone), have been synthesized and characterized by elemental analyses, UV–vis, FT-IR, ¹H and ¹³C NMR, and ESI-Mass spectroscopic methods. The catalytic efficiency of the synthesized complexes was examined against N-arylation of imidazole. The system works well with the electron-rich, -neutral, and -deficient aryl halides to afford the products in good to excellent yields. Sterically congested aryl halides and heteroaryl halides have also been used as substrates to provide N-arylated heterocycles. In addition, this methodology can be applicable to other substrates with N-containing heterocycles.     

3-Azabicyclo[3.3.1]nonane Derivatives: IV. Synthesis of Amino Acids with 3-Azabicyclo[3.3.1]nonane Fragment

A series of 1.5-dinitro-3-azabicyclo[3.3.1]non-6-enes was prepared by reduction of 1-R-2,4- and 1-R-3,5-dinitrobenzenes with potassium borohydride followed by Mannich reaction with formaldehyde and amino acids. The molecular structure of (6-bromo-1,5-dinitro-3-azabicyclo[3.3.1]non-6-en-3-yl)acetic acid was studied by X-ray diffraction analysis. The mechanism of decomposition under electron impact was determined for (7-methoxy-1,5-dinitro-3-azabicyclo[3.3.1]non-6-en-3-yl)acetic acid.     

Synthesis and Properties of 2-(2-Furyl)- and 2-(2-Thienyl)-1-methylphenanthro[9,10-d]imidazoles

Condensation of 9,10-phenanthrenequinone with 2-furaldehyde and 2-thiophenecarbaldehyde in glacial acetic acid in the presence of ammonium acetate gave 2-(2-furyl)- and 2-(2-thienyl)phenanthro[9,10-d]imidazoles which were converted into the corresponding 1-methyl derivatives. The furan and thiophene rings in the products lose their acidophobic properties. Depending on the conditions, electrophilic substitution reactions in 2-(2-furyl)- and 2-(2-thienyl)phenanthro[9,10-d]imidazoles occur both at the furan (thiophene) and phenanthrene moieties.     

Specific features of the photolytic transformations of the polynuclear quinone-aliphatic hydrocarbon systems

Dependence of the quantum yield of decomposition of quinone on the intensity of the absorbed irradiation in the compositions of 1,2-naphthoquinone, 9,10-phenanthrenequinone, and 4-nitro-9,10-phenathrenequinone with nonane has the extremal character.