1,4-Naphthoquinone

Naphthoquinone^[1]
	Ball-and-stick model
Names
	Preferred IUPAC name Naphthalene-1,4-dione
	Other names 1,4-Naphthoquinone; Naphthoquinone; α-Naphthoquinone
Identifiers
CAS Number	130-15-4 ;
3D model (JSmol)	Interactive image;
ChEMBL	ChEMBL55934 ;
ChemSpider	8215;
ECHA InfoCard	100.004.526
PubChem CID	8530;
UNII	RBF5ZU7R7K ;
CompTox Dashboard (EPA)	DTXSID5040704 ;
	InChI InChI=1S/C10H6O2/c11-9-5-6-10(12)8-4-2-1-3-7(8)9/h1-6H Key: FRASJONUBLZVQX-UHFFFAOYSA-N; InChI=1/C10H6O2/c11-9-5-6-10(12)8-4-2-1-3-7(8)9/h1-6H Key: FRASJONUBLZVQX-UHFFFAOYAK;
	SMILES O=C1c2ccccc2C(=O)cc1;
Properties
Chemical formula	C10H6O2
Molar mass	158.15 g/mol
Density	1.422 g/cm3
Melting point	126 °C (259 °F; 399 K)
Boiling point	Begins to sublime at 100 °C
Solubility in water	0.09 g/L
Magnetic susceptibility (χ)	−73.5·10−6 cm3/mol
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

1,4-Naphthoquinone or para-naphthoquinone is a quinone derived from naphthalene. It forms volatile yellow triclinic crystals and has a sharp odor similar to benzoquinone. It is almost insoluble in cold water, slightly soluble in petroleum ether, and more soluble in polar organic solvents. In alkaline solutions it produces a reddish-brown color.

Natural vitamin K is a derivative of 1,4-naphthoquinone. It is a planar molecule with one aromatic ring fused to a quinone subunit.^[2] 1,4-naphathoquinone itself has some vitamin K activity.^[3]

It is an isomer of 1,2-naphthoquinone.

Preparation

The industrial synthesis involves aerobic oxidation of naphthalene over a vanadium oxide catalyst:^[4]

C₁₀H₈ + 3/2 O₂ → C₁₀H₆O₂ + H₂O

In the laboratory, naphthoquinone can be produced by the oxidation of a variety of naphthalene compounds. An inexpensive route involves oxidation of naphthalene with chromium trioxide.^[5]

Reactions

1,4-Naphthoquinone acts as strong dienophile in Diels-Alder reaction. Its adduct with 1,3-butadiene can be prepared by two methods: 1) long (45 days) exposure of naphthoquinone in neat liquid butadiene taken in huge excess at room temperature in a thick-wall glass tube or 2) fast catalyzed cycloaddition at low temperature in the presence of 1 equivalent of tin(IV) chloride:^[6]

Diels-Alder reaction of 1,4-naphthoquinone with 1,3-butadiene

Reduction of 1,4-naphthoquinone with dithionite gives 1,4-dihydroxynaphthalene. The reaction is reversible: oxidation of the diol give back the quinone.^[7]

Uses

1,4-Naphthoquinone is mainly used as a precursor to anthraquinone by reaction with butadiene followed by oxidation. Nitration gives 5-nitro-1,4-naphthalenedione, precursor to an aminoanthroquinone that is used as a dye precursor.^[4]

Naphthoquinone functions as a ligand through its electrophilic carbon-carbon double bonds.^[8]

Derivatives

Naphthoquinone forms the central chemical structure of many natural compounds, most notably the K vitamins. 2-Methyl-1,4-naphthoquinone, called menadione, is a more effective coagulant than vitamin K. Some naphthoquinone derivatives are cytotoxic, they have significant antibacterial, antifungal, antiviral, insecticidal, anti-inflammatory, and antipyretic properties. Plants with naphthoquinone content are widely used in China and the countries of South America, where they are used to treat malignant and parasitic diseases.^[9]

Natural 1,4-naphthoquinones

Chemical structure of juglone, a compound produced by black walnut trees.

Alkannin, commercial red-brown dye from Alkanna tinctoria
Dichlone, a chlorinated derivative of 1,4-naphthoquinone, a fungicide.
Droserone, found in plants of the genus Plumbago
Hexahydroxy-1,4-naphthalenedione
Juglone, growth-stunting exudate of black walnut trees
Lapachol, yellow irritant from lapacho tree
Lawsone, dye in henna
Menatetrenone, a polyhydroxylated 1,4-naphthoquinone found in some sea urchins
2-Methoxy-1,4-naphthoquinone, a compound found in Impatiens species
Nigrosporin B, lightly studied compound found in the fungus Nigrospora sp
Plumbagin, yellow toxin found in plants of the genus Plumbago
Spinochrome B, a marine pigment
Spinochrome D, a marine pigment
Vitamin K and related compounds
- Phylloquinone
- Vitamin K2
- Menadione (2-Methyl-1,4-naphthoquinone)
Naphthazarin, red solid that occurs naturally and is earily prepared

Synthetic 1,4-naphthoquinones

Atovaquone, a drug
Buparvaquone, an antiprotozoal drug used in veterinary medicine

References

^ Merck Index, 11th Edition, 6315.
^ Gaultier, J.; Hauw, C. (1965). "Structure de l'α-Naphtoquinone". Acta Crystallographica. 18 (2): 179–183. Bibcode:1965AcCry..18..179G. doi:10.1107/S0365110X65000439.
^ Fernholz, Erhard; Ansbacher, S.; MacPhillamy, H. B. (February 1940). "The Vitamin K Activity of Naphthoquinones". Journal of the American Chemical Society. 62 (2): 430–432. doi:10.1021/ja01859a052.
^ ^a ^b Grolig, J.; Wagner, R. "Naphthoquinones". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a17_067. ISBN 978-3-527-30673-2.
^ Braude, E. A.; Fawcett, J. S. (1953). "1,4-Naphthoquinone". Organic Syntheses. 33: 50. doi:10.15227/orgsyn.033.0050.
^ M.A. Filatov; S. Baluschev; I.Z. Ilieva; V. Enkelmann; T. Miteva; K. Landfester; S.E. Aleshchenkov; A.V. Cheprakov (2012). "Tetraaryltetraanthra[2,3]porphyrins: Synthesis, Structure, and Optical Properties". J. Org. Chem. 77 (24): 11119–11131. doi:10.1021/jo302135q. PMID 23205621.
^ Booth, Gerald (2000). "Naphthalene Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a17_009. ISBN 978-3-527-30385-4.
^ Kündig, E. P.; Lomberget, T.; Bragg, R.; Poulard, C.; Bernardinelli, G. (2004). "Desymmetrization of a meso-Diol Complex Derived from [Cr(CO)₃(η⁶-5,8-Naphthoquinone)]: Use of New Diamine Acylation Catalysts". Chemical Communications. 2004 (13): 1548–1549. doi:10.1039/b404006f. PMID 15216374.
^ Babula, P.; Adam, V.; Havel, L.; Kizek, R. (2007). "Naphthoquinones and their Pharmacological Properties". Ceská a Slovenská Farmacie (in Czech). 56 (3): 114–120. PMID 17867522.

[1] Merck Index, 11th Edition, 6315.

[2] Gaultier, J.; Hauw, C. (1965). "Structure de l'α-Naphtoquinone". Acta Crystallographica. 18 (2): 179–183. Bibcode:1965AcCry..18..179G. doi:10.1107/S0365110X65000439.

[3] Fernholz, Erhard; Ansbacher, S.; MacPhillamy, H. B. (February 1940). "The Vitamin K Activity of Naphthoquinones". Journal of the American Chemical Society. 62 (2): 430–432. doi:10.1021/ja01859a052.

[Ullmann-4] Grolig, J.; Wagner, R. "Naphthoquinones". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a17_067. ISBN 978-3-527-30673-2.

[5] Braude, E. A.; Fawcett, J. S. (1953). "1,4-Naphthoquinone". Organic Syntheses. 33: 50. doi:10.15227/orgsyn.033.0050.

[6] M.A. Filatov; S. Baluschev; I.Z. Ilieva; V. Enkelmann; T. Miteva; K. Landfester; S.E. Aleshchenkov; A.V. Cheprakov (2012). "Tetraaryltetraanthra[2,3]porphyrins: Synthesis, Structure, and Optical Properties". J. Org. Chem. 77 (24): 11119–11131. doi:10.1021/jo302135q. PMID 23205621.

[7] Booth, Gerald (2000). "Naphthalene Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a17_009. ISBN 978-3-527-30385-4.

[8] Kündig, E. P.; Lomberget, T.; Bragg, R.; Poulard, C.; Bernardinelli, G. (2004). "Desymmetrization of a meso-Diol Complex Derived from [Cr(CO)₃(η⁶-5,8-Naphthoquinone)]: Use of New Diamine Acylation Catalysts". Chemical Communications. 2004 (13): 1548–1549. doi:10.1039/b404006f. PMID 15216374.

[9] Babula, P.; Adam, V.; Havel, L.; Kizek, R. (2007). "Naphthoquinones and their Pharmacological Properties". Ceská a Slovenská Farmacie (in Czech). 56 (3): 114–120. PMID 17867522.

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