Carbazole

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Carbazole
Carbazole.png
Carbazole-3D-vdW.png
Carbazole ball-and-stick.png
Names
Preferred IUPAC name
9H-Carbazole [1]
Other names
9-azafluorene
dibenzopyrrole
diphenylenimine
diphenyleneimide
USAF EK-600
Identifiers
3D model (JSmol)
3956
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.001.542 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 201-696-0
102490
KEGG
PubChem CID
RTECS number
  • FE3150000
UNII
  • InChI=1S/C12H9N/c1-3-7-11-9(5-1)10-6-2-4-8-12(10)13-11/h1-8,13H Yes check.svgY
    Key: UJOBWOGCFQCDNV-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C12H9N/c1-3-7-11-9(5-1)10-6-2-4-8-12(10)13-11/h1-8,13H
    Key: UJOBWOGCFQCDNV-UHFFFAOYAV
  • c1ccc2c(c1)c3ccccc3[nH]2
Properties
C12H9N
Molar mass 167.211 g·mol−1
Density 1.301 g cm−3
Melting point 246.3 °C (475.3 °F; 519.5 K) [2]
Boiling point 354.69 °C (670.44 °F; 627.84 K) [2]
−117.4 × 10−6 cm3 mol−1
Hazards
GHS labelling:
GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Warning
H341, H351, H400, H411, H413
P201, P202, P273, P281, P308+P313, P391, P405, P501
Flash point 220 °C (428 °F; 493 K) [2]
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 ?)

Carbazole is an aromatic heterocyclic organic compound. It has a tricyclic structure, consisting of two six-membered benzene rings fused on either side of a five-membered nitrogen-containing ring. The compound's structure is based on the indole structure, but in which a second benzene ring is fused onto the five-membered ring at the 2–3 position of indole (equivalent to the 9a–4a double bond in carbazole, respectively).

Contents

Carbazole is a constituent of tobacco smoke. [3]

History

Carl Graebe and Carl Glaser first isolated the compound from coal tar in 1872. [4]

Production

Few carbazole production methods are economically viable, due to limited demand. During coal tar distillation, carbazole concentrates in the anthracene distillate and must be removed before anthraquinone production; that waste product is the major industrial carbazole source. [4] [5] Polar compounds (e.g., ketones) selectively precipitate it from the anthracene; a more modern technique is simply selective crystallization from molten coal tar at high temperature [4] or low pressure (70 mmHg). [6]

A classic laboratory organic synthesis for carbazole is the Borsche–Drechsel cyclization. [7] [8]

Borsche-Drechsel synthesis Borsche-Drechsel cyclization.svg
Borsche–Drechsel synthesis

In the first step, phenylhydrazine is condensed with cyclohexanone to the corresponding imine. The second step is a hydrochloric acid-catalyzed rearrangement reaction and ring-closing reaction to tetrahydrocarbazole. In one modification, both steps are rolled into one by carrying out the reaction in acetic acid. [9] In the third step, this compound is oxidized by red lead to carbazole itself.

Another classic is the Bucherer carbazole synthesis, which uses a naphthol and an aryl hydrazine. [10]

Bucherer carbazole synthesis Bucherer Carbazole Synthesis Scheme.png
Bucherer carbazole synthesis

A third method for the synthesis of carbazole is the Graebe–Ullmann reaction.

Graebe-Ullmann reaction Reaccion de Graebe-Ullman.png
Graebe–Ullmann reaction

In the first step, an N-phenyl-1,2-diaminobenzene (N-phenyl-o-phenylenediamine) is converted into a diazonium salt which instantaneously forms a 1,2,3-triazole. The triazole is unstable and at elevated temperatures, nitrogen is released and the carbazole is formed. [11] [12]

Fluorescence of (9H-carbazol-9-yl)(2,4-dichlorophenyl) methanone DClPhCz kristall.jpg
Fluorescence of (9H-carbazol-9-yl)(2,4-dichlorophenyl) methanone

Diphenylamine derivatives, being electron rich, naturally oxidize to carbazoles when heated in air. [13] A similar reaction is the Mallory reaction:

StilScope7.png

Substituted carbazoles are most easily synthesized with transition metal coupling reactions. For applications that transition-metal impurities in the final product might inhibit, an alternative is nucleophilic aromatic substitution on dibenzothiophene dioxide. [14]

Natural Occurrence

Carbazoles occur naturally in carbazole alkaloids. Carbazole alkaloids with unsubstituted benzene rings occur rarely. Olivacin has been found in the bark of Aspidosperma olivaceum and ellipticin in Ochrosia elliptica . [15] Some carbazole alkaloids, especially glybomin B, have been isolated from Glycosmis pentaphylla . [16]

Applications

As carbazoles have a relatively rich UV-visible light spectrum, they see application as pigments [4] and photocatalysts. [17] The parent carbazole is used in Hydron Blue production [4] and aminoethylcarbazole is used in pigment violet 23 production. [18]

Pigment Violet 23 synthesis CI Pigment Violet 23 Synthesis.jpg
Pigment Violet 23 synthesis

Carbazoles stabilize triplet emitters in certain light-emitting diodes; [4] in general, they are electron photodonors (hole acceptors). [19]

Carbazole electrochemically oxidizes to a conductive polymer, which has not achieved substantial industrial use. [20] Polyvinylcarbazole is useful in the electrical and electronic industries, and certain carbazole novolaks are extremely heat resistant. [4]

In organic chemistry, carbazole proper is also an ingredient for several bioactive molecules. The insecticide Nirosan, [4] the cocaine overdose antidote Rimcazole, and the veterinary NSAID Carprofen are all made from carbazole. The topoisomerase II inhibitor ellipticine fuses carbazole to a pyridine ring.

See also

Related Research Articles

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Anthracene is a solid polycyclic aromatic hydrocarbon (PAH) of formula C14H10, consisting of three fused benzene rings. It is a component of coal tar. Anthracene is used in the production of the red dye alizarin and other dyes. Anthracene is colorless but exhibits a blue (400–500 nm peak) fluorescence under ultraviolet radiation.

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

Quinoline is a heterocyclic aromatic organic compound with the chemical formula C9H7N. It is a colorless hygroscopic liquid with a strong odor. Aged samples, especially if exposed to light, become yellow and later brown. Quinoline is only slightly soluble in cold water but dissolves readily in hot water and most organic solvents. Quinoline itself has few applications, but many of its derivatives are useful in diverse applications. A prominent example is quinine, an alkaloid found in plants. Over 200 biologically active quinoline and quinazoline alkaloids are identified. 4-Hydroxy-2-alkylquinolines (HAQs) are involved in antibiotic resistance.

<span class="mw-page-title-main">Benzofuran</span> Heterocyclic compound consisting of fused benzene and furan rings

Benzofuran is the heterocyclic compound consisting of fused benzene and furan rings. This colourless liquid is a component of coal tar. Benzofuran is the structural nucleus of many related compounds with more complex structures. For example, psoralen is a benzofuran derivative that occurs in several plants.

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

Norbornene or norbornylene or norcamphene is a highly strained bridged cyclic hydrocarbon. It is a white solid with a pungent sour odor. The molecule consists of a cyclohexene ring with a methylene bridge between carbons 1 and 4. The molecule carries a double bond which induces significant ring strain and significant reactivity.

Camphene is a bicyclic organic compound. It is one of the most pervasive monoterpenes. As with other terpenes, it is insoluble in water, flammable, colorless, and has a pungent smell. It is a minor constituent of many essential oils such as turpentine, cypress oil, camphor oil, citronella oil, neroli, ginger oil, valerian, and mango. It is produced industrially by isomerization of the more common alpha-pinene using a solid acid catalyst such as titanium dioxide.

Salicylic aldehyde (2-hydroxybenzaldehyde) is an organic compound with the formula C6H4OH(CHO). Along with 3-hydroxybenzaldehyde and 4-hydroxybenzaldehyde, it is one of the three isomers of hydroxybenzaldehyde. This colorless oily liquid has a bitter almond odor at higher concentration. Salicylaldehyde is a precursor to coumarin and a variety of chelating agents.

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

Methacrylic acid, abbreviated MAA, is an organic compound with the formula CH2=C(CH3)CO2H. This colorless, viscous liquid is a carboxylic acid with an acrid unpleasant odor. It is soluble in warm water and miscible with most organic solvents. Methacrylic acid is produced industrially on a large scale as a precursor to its esters, especially methyl methacrylate (MMA), and to poly(methyl methacrylate) (PMMA).

<span class="mw-page-title-main">Rhenium(VII) oxide</span> Chemical compound

Rhenium(VII) oxide is the inorganic compound with the formula Re2O7. This yellowish solid is the anhydride of HOReO3. Perrhenic acid, Re2O7·2H2O, is closely related to Re2O7. Re2O7 is the raw material for all rhenium compounds, being the volatile fraction obtained upon roasting the host ore.

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

Antimony trifluoride is the inorganic compound with the formula SbF3. Sometimes called Swarts' reagent, it is one of two principal fluorides of antimony, the other being SbF5. It appears as a white solid. As well as some industrial applications, it is used as a reagent in inorganic and organofluorine chemistry.

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

Dimethyl carbonate (DMC) is an organic compound with the formula OC(OCH3)2. It is a colourless, flammable liquid. It is classified as a carbonate ester. This compound has found use as a methylating agent and as a co-solvent in lithium-ion batteries. Notably, dimethyl carbonate is a weak methylating agent, and is not considered as a carcinogen. Instead, dimethyl carbonate is often considered to be a green reagent, and it is exempt from the restrictions placed on most volatile organic compounds (VOCs) in the United States.

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

Thiophosphoryl chloride is an inorganic compound with the chemical formula PSCl3. It is a colorless pungent smelling liquid that fumes in air. It is synthesized from phosphorus chloride and used to thiophosphorylate organic compounds, such as to produce insecticides.

The chloride process is used to separate titanium from its ores. The goal of the process is to win high purity titanium dioxide from ores such as ilmenite (FeTiO3) and rutile (TiO2). The strategy exploits the volatility of TiCl4, which is readily purified and converted to the dioxide. Millions of tons of TiO2 are produced annually by this process, mainly for use as white pigments. The chloride process has largely displaced the older sulfate process, which relies on hot sulfuric acid to extract iron and other impurities from ores.

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Indole is an organic compound with the formula C6H4CCNH3. Indole is classified as an aromatic heterocycle. It has a bicyclic structure, consisting of a six-membered benzene ring fused to a five-membered pyrrole ring. Indoles are derivatives of indole where one or more of the hydrogen atoms have been replaced by substituent groups. Indoles are widely distributed in nature, most notably as amino acid tryptophan and neurotransmitter serotonin.

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

Hexafluorobenzene, HFB, C
6F
6, or perfluorobenzene is an organofluorine compound. In this derivative of benzene, all hydrogen atoms have been replaced by fluorine atoms. The technical uses of the compound are limited, although it has some specialized uses in the laboratory owing to distinctive spectroscopic properties.

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

Buthalital sodium, or buthalitone sodium (BAN), is a barbiturate derivative which was under development as a short-acting anesthetic. However, development was discontinued, perhaps due to its extremely rapid elimination rate, and buthalital sodium was never marketed.

The diisopropylbenzenes(DIPB) are organic compounds with the formula C6H4(CH(CH3)2)2. Three isomers exist: 1,2- 1,3-, and 1,4-diisopropylbenzene. All are colorless liquids, immiscible in water, with similar boiling points. They are classified are aromatic hydrocarbons bearing a pair of isopropyl (CH(CH3)2) substituents. DIPB has been referred to as "a common diluent" alongside hexane.

<i>o</i>-Cymene Organic compound

o-Cymene is an organic compound classified as an aromatic hydrocarbon. Its structure consists of a benzene ring ortho-substituted with a methyl group and an isopropyl group. It is a flammable colorless liquid which is nearly insoluble in water but soluble in organic solvents.

<i>m</i>-Cymene Organic compound

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Geranylacetone is an organic compound with the formula CH3C(O)(CH2)2CH=C(CH3)(CH2)2CH=C(CH3)2. A colorless oil, it is the product of coupling geranyl and acetonyl groups. It is a precursor to synthetic squalene.

References

  1. ↑ International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 212. doi:10.1039/9781849733069. ISBN   978-0-85404-182-4.
  2. 1 2 3 Lide, David R. (2007). CRC Handbook of Chemistry and Physics, 88th Edition. CRC Press. pp. 3–86. ISBN   978-0-8493-0488-0.
  3. ↑ Talhout, Reinskje; Schulz, Thomas; Florek, Ewa; Van Benthem, Jan; Wester, Piet; Opperhuizen, Antoon (2011). "Hazardous Compounds in Tobacco Smoke". Int. J. Environ. Res. Public Health . 8 (12): 613–628. doi: 10.3390/ijerph8020613 . PMC   3084482 . PMID   21556207.
  4. 1 2 3 4 5 6 7 8 Collin, Gerd; Höke, Hartmut; Talbiersky, Jörg. "Carbazole". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a05_059.pub2. ISBN   978-3527306732.{{cite encyclopedia}}: CS1 maint: multiple names: authors list (link)
  5. ↑ Cofrancesco, A. J., "Anthraquinone", Kirk-Othmer Encyclopedia of Chemical Technology, New York: John Wiley, p. 5, doi:10.1002/0471238961.0114200803150618.a01, ISBN   9780471238966
  6. ↑ Betts, W. D., "Tar and Pitch", Kirk-Othmer Encyclopedia of Chemical Technology, New York: John Wiley, p. 5, doi:10.1002/0471238961.20011802052020.a01, ISBN   9780471238966
  7. ↑ W. Borsche (1908). "Ueber Tetra- und Hexahydrocarbazolverbindungen und eine neue Carbazolsynthese. (Mitbearbeitet von. A. Witte und W. Bothe.)". Justus Liebigs Ann. Chem. (in German). 359 (1–2): 49–80. doi:10.1002/jlac.19083590103.
  8. ↑ E. Drechsel (1888). "Ueber Elektrolyse des Phenols mit Wechselströmen". J. Prakt. Chem. (in German). 38 (1): 65–74. doi:10.1002/prac.18880380105.
  9. ↑ Rogers, Crosby U.; Corson, B. B. (1950). "1,2,3,4-Tetrahydrocarbazole (Carbazole, 1,2,3,4-tetrahydro-)". Organic Syntheses . 30: 90. doi:10.15227/orgsyn.030.0090 ; Collected Volumes, vol. 4, p. 884.
  10. ↑ Wang, Zerong (2010). "Bucherer Carbazole Synthesis". Comprehensive Organic Name Reactions and Reagents. pp. 549–552. doi:10.1002/9780470638859.conrr120. ISBN   9780470638859.
  11. ↑ Carl Graebe; Fritz Ullmann (1896). "Ueber eine neue Carbazolsynthese". Justus Liebigs Ann. Chem. (in German). 291 (1): 16–17. doi:10.1002/jlac.18962910104.
  12. ↑ O. Bremer (1934). "Über die Bedeutung der Graebe-Ullmannschen Carbazolsynthese und deren Übertragung auf N-substituierte Pyridino-triazole". Justus Liebigs Ann. Chem. (in German). 514 (1): 279–291. doi:10.1002/jlac.19345140116.
  13. ↑ Vogt, Peter F.; Gerulis, John J. "Amines, Aromatic". Ullmann's Encyclopedia of Industrial Chemistry . Vol. 2. Weinheim: Wiley-VCH. p. 703. doi:10.1002/14356007.a02_037. ISBN   978-3527306732.
  14. ↑ Bhanuchandra, M.; Yorimitsu Hideki. "Dibenzothiophene 5,5-dioxide". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rn02046.
  15. ↑ Eberhard Breitmaier (1997), Alkaloide, Wiesbaden: Springer Fachmedien, p. 49, ISBN   978-3-519-03542-8
  16. ↑
  17. ↑ Rizzo, Carmelo J. (2005). "N-Methylcarbazole". N -Methylcarbazole. Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rn00578. ISBN   0-471-93623-5.
  18. ↑ U.S. patent 4,345,074
  19. ↑ Ying Wang, "Photoconductive polymers", Kirk-Othmer Encyclopedia of Chemical Technology, New York: John Wiley, p. 15, doi:10.1002/0471238961.1608152023011407.a01, ISBN   9780471238966
  20. ↑ Naarmann, Herbert. "Polymers, Electrically conducting". Ullmann's Encyclopedia of Industrial Chemistry . Vol. 29. Weinheim: Wiley-VCH. p. 309. doi:10.1002/14356007.a21_429. ISBN   978-3527306732.
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