1,4-Naphthoquinone

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Naphthoquinone [1]
1,4-Naphthoquinone.svg
Ball-and-stick model 1,4-Naphthoquinone-3D-balls.png
Ball-and-stick model
Names
Preferred IUPAC name
Naphthalene-1,4-dione
Other names
1,4-Naphthoquinone
Naphthoquinone
α-Naphthoquinone
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.004.526 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • 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
  • O=C1c2ccccc2C(=O)cc1
Properties
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
0.09 g/L
−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).
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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.

Contents

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 Naphthoquinone reaction with butadiene.tif
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. Juglone.png
Chemical structure of juglone, a compound produced by black walnut trees.

Synthetic 1,4-naphthoquinones

See also

References

  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.
  4. 1 2 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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