Phenazine

Chembox new
Name = Phenazine
ImageFile = Phenazine.png ImageName = Phenazine
IUPACName = Phenazine
Section1 = Chembox Identifiers
CASNo = 92-82-0
SMILES = c12nc(C=CC=C3)#c3nc1cccc2
PubChem = 4757
Section2 = Chembox Properties
Formula = C₁₂H₈N₂
MolarMass = 180.18 g/mol
Density =
MeltingPtC = 177
BoilingPt =

Phenazine (C₁₂H₈N₂ or C₆H₄N₂C₆H₄), also called azophenylene, dibenzo-p-diazine, dibenzopyrazine, and acridizine, is a dibenzo annulated pyrazine and the parent substance of many dyestuffs, such as the eurhodines, toluylene red, indulines and safranines.

ynthesis

A classic method for the synthesis of phenazine is the reaction of nitrobenzene and aniline in the Wohl-Aue reaction (1901). Other methods are known, e.g.:

* by distilling the barium salt of azobenzoate
* by passing aniline vapor over lead oxide
* by the oxidation of dihydrophenazine, which is prepared by heating pyrocatechin with o-phenylenediamine.
* It is also formed when ortho-aminodiphenylamine is distilled over lead peroxide.

Phenazine crystallizes in yellow needles which melt at 174-177 °C, and are only sparingly soluble in alcohol. Sulfuric acid dissolves it, forming a deep-red solution.

Derivatives

* The more complex phenazines, such as the naphthophenazines, naphthazines and naphthotolazines, may be prepared by condensing ortho-diamines with ortho-quinones [OrgSynth | author = Alexander R. Surrey | title = Pyocyanine | collvol = 3 | collvolpages = 753 | year = 1955 | prep = cv3p0753] or by the oxidation of an ortho-diamine in the presence of α-naphthol, and by the decomposition of ortho-anilido-(-toluidido- et cetera)- azo compounds with dilute acids.
* If alkyl or aryl-ortho-diamines be used, azonium bases are obtained. The azines are mostly yellow in color, distill unchanged and are stable to oxidants. They add on alkyl iodides readily, forming alkyl azonium salts, anhydride formation also taking place between these hydroxylgroups. It dissolves in concentrated sulfuric acid with a yellowish-green fluorescence.
* The rhodamines, which are closely related to the phthaleins, are formed by the condensation of the alkyl metaaminophenols with phthalic anhydride in the presence of sulfuric acid. Their salts are fine red dyes. By the entrance of amino or hydroxyl groups into the molecule dyestuffs are formed. The mono-amino derivatives or eurhodines are obtained when the arylmonamines are condensed with orthoamino azo compounds; by condensing quinone dichlorimide or para-nitrosodimethyl aniline with monamines containing a free para position, or by oxidizing ortho-hydroxydiaminodipbenylamines. They are yellowish-red solids, which behave as weak bases, their salts undergoing hydrolytic dissociation in aqueous solution. When heated with concentrated hydrochloric acid the amino group is replaced by the hydroxyl group and the phenolic eurhodols are produced.

Diaminophenazine

.

Natural products

Many phenazine compounds are found in nature and are produced by bacteria such as "Pseudomonas" spp., "Streptomyces" spp., and "Pantoea agglomerans". These phenazine natural products have been implicated in the virulence and competitive fitness of producing organisms. For example, the phenazine pyocyanin produced by "Pseudomonas aeruginosa" contributes to its ability to colonise the lungs of cystic fibrosis patients. Similarly, phenazine-1-carboxylic acid, produced by a number of Pseudomonas, increases survival in soil environments and has been shown to be essential for the biological control activity of certain strains. [cite journal | author = Turner, J. M. and A. J. Messenger | year = 1986 | title = Occurrence, biochemistry, and physiology of phenazine pigment production | journal = Advances in Microbial Physiology | volume = 27 | pages = 211–275 | doi = 10.1016/S0065-2911(08)60306-9] [cite journal | author = McDonald, M., D. V. Mavrodi, et al. | year = 2001 | title = Phenazine biosynthesis in Pseudomonas fluorescens: Branchpoint from the primary shikimate biosynthetic pathway and role of phenazine-1,6-dicarboxylic acid | journal = J. Am. Chem. Soc. | volume = 123 | issue = 38 | pages = 9459–9460 | doi = 10.1021/ja011243+]

Biosynthesis

Phenazine biosynthesis branches off the shikimic acid pathway at a point subsequent to chorismic acid. Two molecules of this chorismate-derived intermediate are then brought together in a diagonally-symmetrical fashion to form the basic phenazine scaffold. Sequential modifications then lead to a variety of phenazine with differing biological activities.

References