Phenazine

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Phenazine
Phenazine 200.svg
Phenazine-3D-balls-B.png
Names
Preferred IUPAC name
Phenazine [1]
Other names
Dibenzopyrazine
9,10-Diazaanthracene
Azophenylene
acridizine
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.001.995 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C12H8N2/c1-2-6-10-9(5-1)13-11-7-3-4-8-12(11)14-10/h1-8H Yes check.svgY
    Key: PCNDJXKNXGMECE-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C12H8N2/c1-2-6-10-9(5-1)13-11-7-3-4-8-12(11)14-10/h1-8H
    Key: PCNDJXKNXGMECE-UHFFFAOYAM
  • n1c3c(nc2c1cccc2)cccc3
Properties
C12H8N2
Molar mass 180.21 g/mol
Appearanceyellow to brown crystalline powder
Density 1.25g/cm3
Melting point 174–177 °C (345–351 °F; 447–450 K)
Boiling point 357.2 °C (675.0 °F; 630.3 K) at 760 mmHg
insoluble in water
Hazards
Flash point 160.3 °C (320.5 °F; 433.4 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Phenazine is an organic compound with the formula (C6H4)2N2. It is a dibenzo annulated pyrazine, and the parent substance of many dyestuffs, such as the toluylene red, indulines, and safranines (and the closely related eurhodines). [2] Phenazine crystallizes in yellow needles, which are only sparingly soluble in alcohol. Sulfuric acid dissolves it, forming a deep-red solution.

Contents

Synthesis

Classically phenazine are prepared by the reaction of nitrobenzene and aniline in the Wohl–Aue reaction. Other methods include:

Derivatives

Aminophenazine

Neutral red Neutral red.png
Neutral red

Many aminophenazines are prominent dyes. Two of the first synthetic dyes are aminophenazines, these include induline and nigrosin. [2]

The symmetrical diaminophenazine is the parent substance of the important dyestuff neutral red (dimethyldiaminotoluphenazine). It is obtained by the oxidation of ortho-phenylenediamine with ferric chloride.

In a related process, oxidation of a cold mixture of para-aminodimethylaniline and meta-toluylenediamine gives toluylene blue. This indamine is formed as an intermediate product and passing into the red when boiled; and also by the oxidation of dimethylparaphenylene diatnine with metatoluylene diamine. It crystallizes in orange-red needles and its alcoholic solution fluoresces strongly. It dyes silk and mordanted cotton a fine scarlet. It is known commercially as neutral red. For the phenazonium salts, see safranine. Benzo[c]cinnoline is an isomer of phenazine, to which it bears the same relation that phenanthrene bears to anthracene.

Natural products

The known biological sources of phenazine compounds are mostly bacterial in nature. [4] Some of the genera known to produce phenazines include 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 Pseudomonads, increases survival in soil environments and has been shown to be essential for the biological control activity of certain strains. [5] [6] [7]

While bacterial phenazines are principally involved in secondary metabolisms, methanophenazine in methanogenic archaea (methanogens) is involved in primary metabolisms and are important electron carriers. [8] Methanophenazine acts as the functional equivalent of menaquinones and ubiquinones in other organisms. Methanophenazine is only known phenazine of non-bacterial origin and also is the only phenazine that engages in primary metabolisms. [9]

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. An example of phenazinic alkaloids are pyocyanin, saphenic acid and esmeraldins.

Pyocyanin Biosynthesis.png

Related Research Articles

<span class="mw-page-title-main">Amine</span> Chemical compounds and groups containing nitrogen with a lone pair (:N)

In chemistry, amines are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group. Important amines include amino acids, biogenic amines, trimethylamine, and aniline. Inorganic derivatives of ammonia are also called amines, such as monochloramine.

<span class="mw-page-title-main">Acridine</span> Chemical compound

Acridine is an organic compound and a nitrogen heterocycle with the formula C13H9N. Acridines are substituted derivatives of the parent ring. It is a planar molecule that is structurally related to anthracene with one of the central CH groups replaced by nitrogen. Like the related molecules pyridine and quinoline, acridine is mildly basic. It is an almost colorless solid, which crystallizes in needles. There are few commercial applications of acridines; at one time acridine dyes were popular, but they are now relegated to niche applications, such as with acridine orange. The name is a reference to the acrid odour and acrid skin-irritating effect of the compound.

<span class="mw-page-title-main">Aniline</span> Organic compound (C₆H₅NH₂); simplest aromatic amine

Aniline is an organic compound with the formula C6H5NH2. Consisting of a phenyl group attached to an amino group, aniline is the simplest aromatic amine. It is an industrially significant commodity chemical, as well as a versatile starting material for fine chemical synthesis. Its main use is in the manufacture of precursors to polyurethane, dyes, and other industrial chemicals. Like most volatile amines, it has the odor of rotten fish. It ignites readily, burning with a smoky flame characteristic of aromatic compounds. It is toxic to humans.

<span class="mw-page-title-main">Hydrazone</span> Organic compounds - Hydrazones

Hydrazones are a class of organic compounds with the structure R1R2C=N−NH2. They are related to ketones and aldehydes by the replacement of the oxygen =O with the =N−NH2 functional group. They are formed usually by the action of hydrazine on ketones or aldehydes.

<i>p</i>-Phenylenediamine Chemical compound

p-Phenylenediamine (PPD) is an organic compound with the formula C6H4(NH2)2. This derivative of aniline is a white solid, but samples can darken due to air oxidation. It is mainly used as a component of engineering polymers and composites like kevlar. It is also an ingredient in hair dyes and is occasionally used as a substitute for henna.

In organic chemistry, an aryl halide is an aromatic compound in which one or more hydrogen atoms, directly bonded to an aromatic ring are replaced by a halide. The haloarene are different from haloalkanes because they exhibit many differences in methods of preparation and properties. The most important members are the aryl chlorides, but the class of compounds is so broad that there are many derivatives and applications.

<span class="mw-page-title-main">Azo compound</span> Organic compounds with a diazenyl group (–N=N–)

Azo compounds are organic compounds bearing the functional group diazenyl.

<span class="mw-page-title-main">Safranin</span> Chemical compound

Safranin is a biological stain used in histology and cytology. Safranin is used as a counterstain in some staining protocols, colouring cell nuclei red. This is the classic counterstain in both Gram stains and endospore staining. It can also be used for the detection of cartilage, mucin and mast cell granules.

Organosulfur chemistry is the study of the properties and synthesis of organosulfur compounds, which are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur derivatives, e.g., saccharin. Nature is abound with organosulfur compounds—sulfur is vital for life. Of the 20 common amino acids, two are organosulfur compounds, and the antibiotics penicillin and sulfa drugs both contain sulfur. While sulfur-containing antibiotics save many lives, sulfur mustard is a deadly chemical warfare agent. Fossil fuels, coal, petroleum, and natural gas, which are derived from ancient organisms, necessarily contain organosulfur compounds, the removal of which is a major focus of oil refineries.

IARC group 3 substances, chemical mixtures and exposure circumstances are those that can not be classified in regard to their carcinogenicity to humans by the International Agency for Research on Cancer (IARC). This category is used most commonly for agents, mixtures and exposure circumstances for which the level of evidence of carcinogenicity is inadequate in humans and inadequate or limited in experimental animals. Exceptionally, agents (mixtures) for which the evidence of carcinogenicity is inadequate in humans, but sufficient in experimental animals may be placed in this category when there is strong evidence that the mechanism of carcinogenicity in experimental animals does not operate in humans. Agents, mixtures and exposure circumstances that do not fall into any other group are also placed in this category.

<i>o</i>-Phenylenediamine Chemical compound

o-Phenylenediamine (OPD) is an organic compound with the formula C6H4(NH2)2. This aromatic diamine is an important precursor to many heterocyclic compounds. OPD is a white compound although samples appear darker owing to oxidation by air. It is isomeric with m-phenylenediamine and p-phenylenediamine.

<span class="mw-page-title-main">Induline</span>

Induline is a dye of blue, bluish-red or black shades. Induline consists of a mixture of several intensely colored species, so the name is often indulines. It was one of the first synthetic dyes, discovered in 1863 by J. Dale and Heinrich Caro. The main components of induline are various substituted phenazines. Although induline no longer in use, the related dye nigrosin is still produced commercially.

<span class="mw-page-title-main">Diphenylamine</span> Chemical compound

Diphenylamine is an organic compound with the formula (C6H5)2NH. The compound is a derivative of aniline, consisting of an amine bound to two phenyl groups. The compound is a colorless solid, but commercial samples are often yellow due to oxidized impurities. Diphenylamine dissolves well in many common organic solvents, and is moderately soluble in water. It is used mainly for its antioxidant properties. Diphenylamine is widely used as an industrial antioxidant, dye mordant and reagent and is also employed in agriculture as a fungicide and antihelmintic.

Microbial metabolism is the means by which a microbe obtains the energy and nutrients it needs to live and reproduce. Microbes use many different types of metabolic strategies and species can often be differentiated from each other based on metabolic characteristics. The specific metabolic properties of a microbe are the major factors in determining that microbe's ecological niche, and often allow for that microbe to be useful in industrial processes or responsible for biogeochemical cycles.

<span class="mw-page-title-main">Nigrosin</span> Mixture of synthetic black dyes

In staining dyes, nigrosin is a mixture of black synthetic dyes made by heating a mixture of nitrobenzene, aniline, and hydrochloric acid in the presence of copper or iron. Related to induline, it is a mixture of phenazine-based compounds. Its main industrial uses are as a colorant for lacquers and varnishes and in marker pen inks. Sulfonation of nigrosin yields a water-soluble anionic dye, nigrosin WS.

<span class="mw-page-title-main">Pyocyanin</span> Chemical compound

Pyocyanin (PCN) is one of the many toxic compounds produced and secreted by the Gram negative bacterium Pseudomonas aeruginosa. Pyocyanin is a blue secondary metabolite, turning red below pH 4.9, with the ability to oxidise and reduce other molecules and therefore kill microbes competing against P. aeruginosa as well as mammalian cells of the lungs which P. aeruginosa has infected during cystic fibrosis. Since pyocyanin is a zwitterion at blood pH, it is easily able to cross the cell membrane. There are three different states in which pyocyanin can exist: oxidized (blue), monovalently reduced (colourless) or divalently reduced (red). Mitochondria play an important role in the cycling of pyocyanin between its redox states. Due to its redox-active properties, pyocyanin generates reactive oxygen species.

<span class="mw-page-title-main">2,5-Diaminotoluene</span> Chemical compound

2,5-Diaminotoluene is an organic compound with the formula C6H3(NH2)2CH3. It is one isomer of six with this formula. 2,5-Diaminotoluene is a colorless crystalline solid, although commercial samples are often colored owing to air oxidation. It is commonly used in hair coloring.

Methanophenazine, a phenazine derivative, is a strongly hydrophobic redox-active cofactor with a role in electron transport in some methanogens. This chromophore can be purified from membranes of methanogenic archaea such as Methanosarcina mazei. The enzyme methanosarcina-phenazine hydrogenase has the name methanophenazine hydrogenase as a synonym.

Electrophilic aromatic substitution is an organic reaction in which an atom that is attached to an aromatic system is replaced by an electrophile. Some of the most important electrophilic aromatic substitutions are aromatic nitration, aromatic halogenation, aromatic sulfonation, alkylation and acylation Friedel–Crafts reaction.

Azuline is a coal-tar blue dye that became popular for colouring silk in 1861. It was one of the first synthetic dyes. The name was a combination of "azure" and "aniline". A variant of the name was "Azurine". The word was introduced as a colour term about the same time as "mauve" and "magenta", but it has not survived in the English language.

References

  1. Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 211. doi:10.1039/9781849733069-FP001. ISBN   978-0-85404-182-4.
  2. 1 2 Horst Berneth (2012). "Azine Dyes". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a03_213.pub3. ISBN   978-3527306732.
  3. Alexander R. Surrey (1955). "Pyocyanine". Organic Syntheses ; Collected Volumes, vol. 3, p. 753.
  4. Pierson, Leland S.; Pierson, Elizabeth A. (2010). "Metabolism and function of phenazines in bacteria: impacts on the behavior of bacteria in the environment and biotechnological processes". Applied Microbiology and Biotechnology. 86 (6): 1659–1670. doi:10.1007/s00253-010-2509-3. ISSN   0175-7598. PMC   2858273 . PMID   20352425.
  5. Turner, J. M. & A. J. Messenger (1986). Occurrence, biochemistry, and physiology of phenazine pigment production. Advances in Microbial Physiology. Vol. 27. pp. 211–275. doi:10.1016/S0065-2911(08)60306-9. ISBN   978-0-12-027727-8. PMID   3532716.
  6. McDonald, M., D. V. Mavrodi; et al. (2001). "Phenazine biosynthesis in Pseudomonas fluorescens: Branchpoint from the primary shikimate biosynthetic pathway and role of phenazine-1,6-dicarboxylic acid". J. Am. Chem. Soc. 123 (38): 9459–9460. doi:10.1021/ja011243. PMID   11562236.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  7. Dietrich LE, Okegbe C, Price-Whelan A, Sakhtah H, Hunter RC, Newman DK (2013). "Bacterial community morphogenesis is intimately linked to the intracellular redox state" (PDF). Journal of Bacteriology . 195 (7): 1371–80. doi:10.1128/JB.02273-12. PMC   3624522 . PMID   23292774.
  8. Beifuss, Uwe; Tietze, Mario; Bäumer, Sebastian; Deppenmeier, Uwe (2000-07-17). "Methanophenazine: Structure, Total Synthesis, and Function of a New Cofactor from Methanogenic Archaea". Angewandte Chemie International Edition. 39 (14): 2470–2472. doi:10.1002/1521-3773(20000717)39:14<2470::aid-anie2470>3.0.co;2-r. ISSN   1433-7851. PMID   10941105.
  9. Beifuss, Uwe; Tietze, Mario (2005-01-26), Mulzer, Johann (ed.), "Methanophenazine and Other Natural Biologically Active Phenazines", Natural Products Synthesis II, vol. 244, Berlin, Heidelberg: Springer Berlin Heidelberg, pp. 77–113, doi:10.1007/b96889, ISBN   978-3-540-21124-2 , retrieved 2022-07-03

Wikisource-logo.svg This article incorporates text from a publication now in the public domain :  Chisholm, Hugh, ed. (1911). "Phenazine". Encyclopædia Britannica . Vol. 21 (11th ed.). Cambridge University Press. pp. 364–365.