Phenazine derivatives

CgHeNj. Brown-yellow crystals m.p. 103-104 C, b.p. 256 258°C. Its solutions reduce Ag ions and it is used as a photographic developer. It is also used as a dye-precursor, for the synthesis of phenazine derivatives and for characterizing inter alia) a-diketones. 

Phenazine-l-carboxamide (137) is known as oxychlororaphine and has been isolated from cultures of Pseudomonas chlororaphisit has some limited inhibitory properties, but the inhibitory action of phenazines is generally disappointing. Some phenazine derivatives have insecticidal properties thus, phenazine itself has been found to be toxic to the clothes moth, the Hawaiian beet webworm, the rice weevil and larva of the codling moth, but under trial conditions its toxicity to plant material, as evidenced by severe burning of foliage, was found to be too high to make it of practical value. 

Phenazines — These are dibenzopyrazine derivatives with fnnctional groups (hydroxy-, carboxy-) at C, and Cg and an oxygen or methyl gronp at Nj and N,o. There are also more complex structures, substituted phenazines, terpenoidal, and carbohydrate-containing phenazines and phenazines derived from saphenic acid. ... 

Watanabe T, T Hirayama, S Fukui (1989) Phenazine derivatives as the mutagenic reaction product from o- or m-phenylenediamine derivatives with hydrogen peroxide. Mutation Res 227 135-145. 

Azaquinone structures possessing two adjacent carbonyl groups provided phenazine derivatives, e.g., 58 and 59, when reacted with o-pheny-lenediamine (Scheme 16) [63JOC260 72JCS(P 1)977]. 

A naturally occurring phenazine of nonbacterial origin is the methano-phenazine (MP) (10) which has been isolated from the cytoplasmic membrane of Methanosarcina (Ms.) mazei Gol archaea. The structure, synthesis, properties, and function of this natural product will be discussed in detail since it is not only the first and so far the sole phenazine derivative from archaea, but also the first one that is acting as an electron carrier in a respiratory chain - a biologic function equivalent to that of ubiquinones in mitochondria and bacteria. 

The more recently discovered and most unusual structures include the dimeric phenazine derivatives esmeraldin A (52) and esmeraldin B (53), which are produced by Streptomyces antibioticus Tii 2706 together with 49 [54]. Esmeraldins exhibit no antibacterial activity but 53 is effective against tumor cells. Much effort has been directed to the elucidation of the biosynthesis of the esmeraldins [55]. Some rare L-quinovose esters (55a-d) of saphenic acid have... 

Dynamic quenching of the MLCT excited state of [Ru(phen)2(dppz)] " " by H" " transfer in MeCN solution occurs for proton donors with pAa values in the range 4.7-15.7. Comparisons of the quenching have been made in the presence and absence of DNA. " The addition of Cu " " to DNA-bound [Ru(bpy)2L] " " (L is the phenazine derivative (167)) leads to luminescence quenching. This is explained in terms of complexation of Cu " " with the vacant coordination site of L in [Ru(bpy)2L] " ". Formation of the [Ru(bpy)2L] " "/Cu " " complex in the presence of DNA is proposed to place one metal center in the major groove and one in the minor groove. " ... 

Pusecker, K., Laatsch, H., Helmke, E., and Weyland, H., Dihydrophencomycin methyl ester, a new phenazine derivative from a marine Streptomycete, J. Antibiot., 50, 479, 1997. 

The nitro group can take part in the formation of heterocyclic nitrogen-containing rings. For example, one of the well known methods for the preparation of phenazine derivatives consists in heating derivatives of 2-nitro-2 -aminodiphenyl-arnine at high temperature (Kehrmann et al. [11]) ... 

The synthesis of phenazine derivatives and phenazine oxide based on the condensation of aromatic nitro compounds with aromatic amines in an alkaline medium (sodium hydroxide), reported for the first time by Wohl [12] in 1901, was of similar character ... 

The accumulation of phenazine-1,6-dicarboxylic acid (154) by mutants of Pseudomonas phenazinium148 which normally produce hydroxy-phenazine derivatives supports a role for (154) in phenazine biosynthesis. In further studies143 with Ps. phenazinium the sequence of hydroxylative steps leading to the various phenazines has been deduced143 148 to be that illustrated in Scheme 15 the biosynthesis deduced for iodinin (156) is in agreement with earlier conclusions about its formation in cultures of another organism (Brevibacterium iodinum ).146... 

JA13474>. A trypanocidal phenazine derived from p-lapachone was found to be active against Trypanosoma cruzi, the microorganism that causes Chagas disease, and its structure was determined in part by X-ray crystallography <02JMC2112>. 

The BINAP/Pd- and DPPF/Pd-catalyst systems have been used by numerous groups to react aryl bromides with arylamines. Ward and Farina as well as Willoughby and Chapman performed the arylation reaction with arylamines and resin-bound aryl bromides [31,32]. Snieckus reported the use of the Pd-cat-alyzed C-N bond forming reaction to prepare several acridone derivatives, Eq. (81) [92]. Kamikawa et al. prepared phenazine derivatives via an initial C-N bond coupling and subsequent cyclization, Eq. (82) [93]. 

X-ray structure analysis shows that phenazine is a planar molecule of symmetry. Its crystalline form is holohedral with a unit cell of two molecules. Interatomic distances, bond angles and bond orders of phenazine are presented in Table 1. X-ray bond data are also available for substituted phenazine derivatives and phenazine A -oxides. ... 

Reductive cyclization of 2,2 -dinitrodiphenylamines 1 under mild reduction conditions in alkaline media affords phenazine derivatives 2 in good yields." ... 

The condensation of A, A -dimethyl-4-nitrosoaniline hydrochloride with aromatic mono-and diamines in ethanolic solution affords phenazine derivatives, exhibiting dye character (see Houben-Weyl, Vol. 10/1, p 1086). 

The oxidation of substituted aromatic amines with silver(l) carbonate on Celite has been shown to yield symmetrically substituted phenazines, albeit in poor yields. 2,7-Dimethoxy-hexafluorophenazine has been obtained upon electrolysis of solutions of 4-methoxytetrafluoro-aniline, and oxidative coupling of benzene-1,4-diamine with aniline or substituted anilines also gives phenazine derivatives. ... 

Several phenazine derivatives, e.g. phenazin-2-ol, phenazine-l-carboxylic acid, 2-hydroxy-phenazine-1-carboxylic acid, phenazine-2,3-diol, and 2,3-dihydroxyphenazine-l-carboxylic acid have been isolated from Pseudomonas aureofaciens. 

Shikimic acid, an intermediate in the biosynthesis of phenazine derivatives (e.g., iodinine, pyocyanin) can act as the sole carbon source in the formation of the phenazine skeleton. 

The electronic absorption, fluorescence emission, photoinduced intramolecular charge transfer, and electrochemical behavior of another phenazine derived tetrathiafulvalene (TTF)-fused dipyrido[3,2- 2, 3 -f]phenazine (dppz) compound were studied <2007GEJ3804>. 

A special kind of condensation reaction occurs as a side reaction during the reduction of o-nitroaniline [120,137] A phenazine derivative is formed. In the reaction (Chapter 18), a double Michael addition of o-phenylenediamine to the intermediate o-quinonedi-imine takes place other nucleophiles might under suitable conditions attack the diimine. 

Reduction of o-dinitrobenzene in alkaline solution at the potential of the first polaro-graphic wave (—0.7V) also yields o-nitrophenylhydroxylamine [151]. In slightly acid solution, some phenazine derivatives may be formed [137]. 

The dyestuffs eoming under this classifieation contain four nitrogen atoms. Unlike the previous azine dyestuffs they contaiu at least three hydrocarbon chains. Although their behaviour shows them to be phenazine derivatives, they differ in many respects from those previously described. Especially noticeable is their strong basic character, which in many respects resembles that of the quaternary ammonium bases, and the characteristic bitter taste of the latter compounds is also present in the saffra-nines. Another point of difference from the rest of the azine dyestuffs is that the free base has the same colour as the monoacid salts. 

The redox-active natural product (+)-methanophenazine (MP) is the first phenazine to be isolated from archea. This compound is able to mediate the electron transport between membrane-bound enzymes and was characterized as the first phenazine derivative involved in the electron transport of biological systems. The research team of U. Beifuss prepared this natural product by using the Williamson ether synthesis in the last step of the synthetic sequence. The etherification was conducted under phase-transfer conditions in a THF/water system in the presence of methyltrioctyl-ammonium chloride and using potassium hydroxide as a base. 

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