Successive electron transfer reaction of the lithium salt of 5-methyl-5,10-dihydrophenazine anion with 4-nitrophenethyl bromide via 4-nitrostyrene

The reaction of lithium salt of 5-methyl-5,10-dihydrophenazine anion with 4-nitrophenethyl bromide in 1,2-dimethoxyethane gave unexpected compounds, 1,2-bis[5-(10-methyl-5,10-dihydrophenazinyl)]-1-(4-nitrophenyl)ethane and 1,4-bis(4-nitrophenyl)-1,4-bis[5-(10-methyl-5,10-dihydrophenazinyl)]butane, while the reaction in dimethyl sulfoxide brought about the formation of 5-methyl-10-(4-nitrophenethyl)-5,10-dihydrophenazine. The successive electron transfer mechanism is proposed for the former reaction via 4-nitrostyrene.     

A stable radical-substituted radical cation with strongly ferromagnetic interaction: nitronyl nitroxide-substituted 5,10-diphenyl-5,10-dihydrophenazine radical cation

A stable radical-substituted radical ion with strongly ferromagnetic intramolecular interaction (J) between the radical and radical ion sites is an attractive spin building block of organic magnets. We prepared 2-nitronyl nitroxide-substituted 5,10-diphenyl-5,10-dihydrophenazine radical cation, 1+. The 1+ salt was stable under aerated conditions at room temperature and had a large J/kB value (>/=+700 K).     

Intramolecular hydrogen bonding in 1-nitro-5,10-dihydrophenazine derivatives

The formation of free radicals only for derivatives with a nitro group in the 1 position was observed in the oxidation of a number of 5-substituted 5,10-dihydrophenazines with lead dioxide. A long-wave absorption band was observed in the electronic spectra of the derivatives with a nitro group in the 1 position. The assumption of the formation of an intramolecular hydrogen bond in dihydrophenazines with a nitro group in the 1 position was confirmed by quantum-chemical modeling of the three structures of the 1,3-dinitro-5-phenyl-5,10-dihydrophenazine molecule. By comparison of the integral intensities of the bands of the stretching vibrations of the N-H bond in 5-substituted dihydrophenazines it was concluded that this bond is depolarized in derivatives with an intramolecular hydrogen bond.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 2, pp, 263–265, February, 1978.     

Synthesis of 5,10-dideazaminopterin

The synthesis of 5,10-dideazaaminopterin by two independent routes is described. Condensation of the piperidine enamine of 4-p-carbomethoxyphenylbutyraldehyde ( 4 ) with ethoxymethylenemalononitrile followed by treatment of the resultant arylethylenaminomalononitrile ( 5 ) with methanolic ammonia produced 2-amino-3-cyano-5-p-carbomethoxyphenethylpyridine ( 6 ). Cyclization of the aminocyanopyridine with guanidine afforded 4-amino-4-deoxy-5,10-dideazapteroic acid ( 8 ). Coupling of the pteroate intermediate with glutamate yielded the target 5,10-dideazaaminopterin ( 10 ). Alternatively, reduction of 2,4-diamino-6-formyl-5-deazapteridine ( 11 ) with sodium borohydride gave the 6-hydroxymethyl compound 12 . Conversion to the bromide was followed by alkylation of dimethyl homoterephthalate to afford methyl 4-amino-4-deoxy-10-carbomethoxy-5,10-dideazapteroate ( 14 ). Decarboxylation with ester cleavage (sodium cyanide in dimethyl sulfoxide at 180°) also gave the diaminopteroic acid ( 8 ). 5,10-dideazaaminopterin ( 10 ) was an effective growth inhibitorof folate dependent bacteria, S. faecium and L. casei.     

Syntheses of 10-Hydroxy-5,10-dihydrophenophosphazine 10-Oxide and Its Methyl Derivatives

Ph2NH and PCl3 interacted at a molar ratio of 1:1.05 and slow-elevated temperature and then at 210-220 ℃ for 6h.The brown solution obtained was treated with H2O to produce a very hard brown solid believed to be a mixture of 5,10-dihydrophenophosphazine 10-oxide(1a) and 10,10′(5H,5H′）-spirobipenophosphazinium chloride(1b).This brown solid was directly oxidized with peracetic acid in HOAc prior to the separation of them to give compound 10-hydroxy-5,10-dihydropheno-phosphazine 10-oxide(2) with a higher yield(45%) than that of the literature(27%).When treated with excess SOCl2.compound 2 could quantitatively be converted to the corresponding phosphinyl chloride and the latter could further be transformed into 10-methoxy-5,10-dihydrophenophosphazine 10-oxide in 70% as treated with NaOMe in methanol.Compound 2 could also be converted to a bisanion when treated with NaH in DMF.The resulted bisanion reacted with MeI to give 5-methyl-10-hydroxy-5,10-dihydrophenophosphzine 10-oxide in a 73% yield which would be converted to 5-methyl-10-methoxy-5,10-dihydrophenophosphazine 10-oxide.All these compounds obtained were identified by surveying their melting points.and spectra and elemental analysis.     

Study on the Methyl Migration of 10-Methoxy-5,10-dihydrophenophosphazine 10-oxide

The title compound (1) was treated with NaH at room temperature in anhydrous DMF to give a sodium salt (containing nitrogen anion)which could shift the methyl group from oxygen to nitrogen atom to form N-methyl phosphinic acid as the reaction temperature was increased to 120 ℃.Three nitro derivatives containing 5,10-dihydrophenophosphazine ring system were prepared for the investigation on the above reaction mechanism which would be possible regarded as a special inter-molecular substitution.viz.,the nucleophilic nitrogen anion from one molecule of 1 attacked the cabon atom of the O-methyl of another 1.In addition,the chemical structures of seven compounds containing 5,10-dihydrophenophosphazine ring system involved in the experiment were confirmed by IR,^1 H NMR,^31P NMR and mass spectroscopy.     

Reaction of 10-Methyl(phenyl)-5,10-dihydrophenarsazine 10-Oxides with Hydriodic Acid

We have studied the reaction of 10-methyl(phenyl)-5,10-dihydrophenarsazine 10-oxides with hydriodic acid and we have established the structure of the products by high-resolution mass spectrometry. We have shown that when the methyl group is replaced by a phenyl group in 5,10-dihydrophenarsazine 10-oxides, cleavage of the endocyclic arsenic–carbon bonds occurs.     

A Potential Iterative Approach to 1,4-Dihydro-N-Heteroacene Arrays

A new method for the synthesis of substituted 1,4-dihydrophenazines is reported and the structure of N-butyl-5-methyl-3-nitro-5,10-dihydrophenazine is proven by an X-ray single-crystal structure determination.     

2-氨基-10-羟基-5,10-二氢磷杂吖嗪-10-氧化物的合成、诱变性及应用

2-氨基-10-羟基-5;10-二氢磷杂吖嗪-10-氧化物的合成、诱变性及应用;二氢磷杂吖嗪; 吡唑啉酮; 合成; 结构鉴定; 诱变性     

Formyl substituted phenazine 5,10-dioxides

Two new formyl-substituted phenazine 5,10-dioxides were prepared, 2-formylphenazine 5,10-dioxide and 7-hydroxy-2-phenazinecarboxaldehyde 5,10-dioxide. Nitrones of these aldehydes were prepared as potential antibacterial agents but evaluation in vitro and in vivo did not disclose significant antibacterial activity.     

Äthinierungsreaktionen, 25. Mitt.: Äthinierung von 5,10-Dioxo-5,10-dihydro-benzo[g]chinolin (“1-Azaanthrachinon”)

Zusammenfassung 5,10-Dioxo-5,10-dihydro-benzo[g]chinolin bildet mit Alkaliacetyliden Mono- und Di-Anlagerungsprodukte, mit monosubstituierten Acetylenderivaten werden nur Mono-Anlagerungsprodukte in 10-Stellung erhalten.24. Mitt.:W. Ried undSt. Piesch, Mh. Chem.97, 57 (1966). R. Neumann, Teil der Staatsexamensarbeit, Univ. Frankfurt/M., 1966.     

Exchange interaction of 5,5'-(m- and p-phenylene)bis(10-phenyl-5,10-dihydrophenazine) dications and related analogues

[structures: see text] 5,5'-(m-Phenylene)bis[(10-aryl-5,10-dihydrophenazine) dications, 3a2+ and 3b2+, and their p-analogues 4a2+ and 4b2+, were prepared, and their exchange interaction was investigated. The EPR spectra of these dications at 123 K in a butyronitrile matrix showed the population of a triplet state. The temperature dependence of the EPR signal intensity (absolute value(delta m(s)) = 2) showed that these dications had singlet ground states with deltaE(ST)/k(B) = -27 to -21 K for the m-isomer 3(2+) and with deltaE(ST)/k(B) = -10 to -8 K for the p-isomer 4(2+). Theoretical calculation of the exchange interaction J for these dications at the orthogonal torsion angle geometries was carried out for 3a2+ and 4a2+ and for (m- and p-phenylene)bisphenothiazine dications 1(2+) and 2(2+) using the broken-symmetry approach for the singlet states. A good correlation was observed between the calculated J and a MO-energy term in the triplet state, deltaE(TMO) = absolute value(HOMO(alpha) - (HOMO - 1)(alpha)). The calculated J values were negative in the order of 10 K for the m-dications (J/k(B) = -14.7 K for 1(2+), -11.5 K for 3a(2+)), but much smaller negative values were found for the p-isomers (J/k(B) = -0.9 K for 2(2+), -0.8 K for 4a2+). The smaller absolute value(J) values for the p-dications are qualitatively consistent with the experimental deltaE(ST) (2J) values.     

Naphthoindoles. 10. Synthesis of 4,11-Dihydroxynaphtho[2,3-f]indole-5,10-dione and Some of Its Derivatives

4,11-Dihydroxynaphtho[2,3-f]indole-5,10-dione (pyrroloquinizarin), its 11-dehydroxy derivative, and Mannich base were synthesized by demethylation of previously obtained methoxynaphtho[2,3-f]indole-5,10-diones.     

2,8-二氨基-10-甲氧基-5,10-二氢磷杂吖嗪-10-氧化物的合成、诱变性及应用性能研究

10-羟基-5,10-二氢磷杂吖嗪-10-氧化物(1)经酰氯化、甲基化得到10-甲氧基-5,10-二氢磷杂吖嗪-10-氧化物(2),2经硝化得到10-甲氧基-2,8-二硝基,5,10-二氢磷杂吖嗪-10-氧化物(3.62％)．3在Pd／C(u=0．05)存在下,用氢气还原为2,8-二氨基-10-甲氧基-5,10-二氢磷杂吖嗪-10-氧化物(4.71％),考察了Bd／C(w=0．05)用量对氢化还原反应的影响．经过Salmonella／mammalian microsome assay测试,4表现为非诱变性,用4与乙酰J-酸作用得到新型双偶氮酸性染料(5)．5对羊毛和丝绸分别在2％与3％色度下浸染郜得到黑色染样,考察了5的上染曲线,并对染样进行了测色研究,发现该染料属于酸性蓝黑染料,其黑度优于目前市场上流行的酸性黑10B．     

Synthesis and Reactions of 1,6-Dibenzoyl-5H,10H-diimidazo[1,5-a;1',5'-d;]pyrazine-5,10-dione

5,10-Dioxo-5H,10H-diimidazo[1,5-a;1',5'-d]pyrazine-5,10-dicarboxylic acid dichloride in Friedel-Crafts reaction conditions formed with benzene the corresponding 1,6-dibenzoyl derivative 2, which reacted with alcohols and amines to give the keto esters and keto amides of 4(5)-benzoylimidazol-5(4)-carboxylic acids. The reaction of compound 2 with hydrazine gave substituted imidazo[4,5-f]pyridazine, and with o-phenylenediamine gave a derivative of imidazo[4,5-f]-1,4-benzodiazocine - a new heterocyclic system.     

A New Technique of Synthesizing 10—Hydroxy—5—methyl—5,10—dihydrophenophosphazine 10—Oxide

10-Hydroxy-5-methyl-5,10-dihydrophenophosphazine 10-oxide(1)was prepared by a new technique of treating 10-methoxy-5,10-dihydrophenophosphazine 10-oxide(2)with an equivalent of NaH in anhydrous DMF,and then at 120℃ for 3-4h,which not only avoided poisonous and expensive methyl iodide used in literature,but made the consumption of NaH greatly decrease as well.The possible reaction mechanism was also described.The chemical structure of 1 was confiremed by IR,NMR,and mass spectroscopy.     

Synthesis,molecular and crystal structure,and properties of 10‐propylthio‐5,10‐dihydrophenarsazine

10‐Propylthio‐5,10‐dihydrophenarsazine 2 was obtained by the reaction of 10‐chloro‐5,10‐dihydrophenarsazine 1 with propanethiol in the presence of triethylamine under mild conditions. The structure of 2 was established by X‐ray single crystal diffraction. The reaction of 2 with 2,4‐bis(ethylthio)‐1,3,2,4‐dithiadiphosphetane‐2,4‐disulfide 3 at room temperature affords a novel route to S‐10(5,10‐dihydrophenarsazine) S′‐ethyl‐S″‐propyltetrathiophosphate 4 . © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:287–291, 2000     

2-硝基-10-羟基-5,10-二氢磷杂吖嗪-10-氧化物的还原研究

10-羟基-5,10-二氢磷杂吖嗪-10-氧化物硝基衍生物的还原反应研究报道始见于1978年.尹志刚等进一步对2-硝基-10-羟基-5,10-二氢磷杂吖嗪-10-氧化物进行了催化加氢研究,结果发现,催化剂用量达到底物质量的7.5%以上,反应介质为中性或弱碱性,该化合物能够被顺利还原[1].该还原方法缺点是Pd/C催化剂不能够回收利用,还原成本高,需要较高氢气压力,危险性大,从而不利于该染料中间体工业化生产.     

Mass spectra of 5,10-dihydrophenarsazines, 5,10-dihydrophenarsazine and phenophosphazine oxides,and related heterocycles

The electron-impact-induced fragmentation of eight 5,10-dihydrophenarsazines and three 5,10-dihydrophenarsazine oxides proceeds by loss of the exocyclic arsenic substituents to give the stable ion (II) as the base peak followed by loss of arsenic to give a carbazole species (III). The fragmentation pattern is independent of substituents at either hetero-atom in the cases examined. Dihydrophenophosphazine oxides behave similarly but give as the base peak an ion in which the phosphoryl grouping is retained. 10,11-Dihydro-5-phenyl-5H-dibenzo[b, f][1,4]azarsepine and 2,3-dihydro-1,2-diphenyl-1H-benz [c]azarsole fragment by different pathways. It is suggested that the ability of arsenic and phosphorus to sustain a positive charge by dπ-pπ bonding is the dominating factor in these fragmentations.     

Heterocyclic analogs of 5,12-naphthacenequinone 7*. Synthesis of naphtho-[2,3-f]isatin-5,10-dione derivatives

On chlorination of 4,11-dimethoxynaphtho[2,3-f]indole-5,10-dione with sulfuryl chloride in chloroform, its mono-, di-, and trichloro derivatives are formed depending on the conditions. Hydrolysis of the di- and trichloro derivatives gives a new polycondensed derivative of isatin, 4,11-dimethoxynaphtho-[2,3-f]isatin-5,10-dione. Its demethylation occurs effectively on extended heating with HBr in acetic acid and leads to 4,11-dihydroxynaphtho[2,3-f]isatin-5,10-dione (4,11-di-hydroxynaphtho[2,3-f]indole-2,3,5,10-tetraone). *For Communication 6 see [1]. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1532–1536, October, 2008.