2-Methyl-1,4-Naphthoquinon

Sandur, S.K. et ah, Plumbagin (5-hydroxy-2-methyl-1,4-naphthoquinone) suppresses NF-kappa B activation and NF-kappa B-regulated gene products through modulation of p65 and I-kappa-B-alpha kinase activation, leading to potentiation of apoptosis induced by cytokine and chemotherapeutic agent, J. Biol. Chem., 281, 17023, 2006. 

Thor, H., Smith, M.T., Hartzell, P., Bellomo, G., Jewell, S.A. and Orrenius, S. (1982). The metabolism of menadione (2-methyl-1,4-naphthoquinone) by isolated hepatocytes. A study of the impact of oxidative stress in the intact cell. J. Biol. Chem. 257, 12419-12425. 

Many quinones (including anthracyclines considered above) are well-known prooxidants that makes them potential DNA damaging agents. It has been shown that menadione (2-methyl-1,4-naphthoquinone), a redox cycling quinone, induced single- and double-strand... 

Figure 12.10 Active forms of vitamin K. Although 2-methyl-1,4-naphthoquinone has vitamin K activity, the more important compounds have an isoprene chain at position 3.

Compounds showing vitamin K activity are substituted naphthoquinones. The parent compound, 2-methyl-1,4-naphthoquinone, does show some biological activity as do other similar but synthetic compounds. The production of the complete naturally active forms is thought to depend upon the addition of an isoprene chain at position 3 on the aromatic ring. Differences in this side chain produce the various K vitamins (Figure 12.10). A most important physiological role of vitamin K is in the synthesis of the blood clotting factors, II (prothrombin), VII, IX and X. 

The same method described in Procedure 2 (Section 12.1.2) was used for preparative-scale biotransformation of 150 mg of 2-methyl-1,4-naphthoquinone, except that reactions were incubated for only 72 h before being combined, centrifuged, extracted and chromatographically purified to give 50 % yield (92 mg) of product. 

Further reduction of quinones - acquisition of four or more hydrogens per molecule - was achieved with lithium aluminum hydride which reduced, in yields lower than 10%, 2-methyl-1,4-naphthoquinone to 1,2,3,4-tetrahydro-l,4-dihydroxy-2-methylnaphthalene and to l,2,3,4-tetrahydro-4-hydroxy-l-keto-2-methylnaphthalene [931]. Lithium aluminum hydride [931], sodium borohydride, lithium trie thy Iborohydride and 9-borabicyclo[3.3.1Jnomine [100] converted anthraquinone to 9,10-dihydro-9,10-dihydroxyanthracene in respective yields of 67, 65, 77 and 79%. 

C11H9NO3 3-Hy droxy-2-methyl-1,4-naphthoquinone 4-oxime Photometric It, Rh 93... 

Aromatic compounds are oxidized to quinones by bis(triorganosilyl) peroxides in the presence of a metal acid catalyst. Thus, 2-methylnaphthalene was oxidized with BTSP in the presence of Re207 and BU3PO in the presence of CHCI3, to a mixture of 59% 2-methyl-1,4-naphthoquinone and 8% 6-methy 1-1,4-naphthoquinone. ... 

Peroxo Fe(ni), Mn(III) and Ti(IV) porphyrins were reacted with a variety of electron-poor organic substrates in order to compare their activity with that of different metalloper-oxide complexes. Epoxidation of 2-cyclohexen-l-one and 2-methyl-1,4-naphthoquinone was observed, in 25 and 75% yield respectively, with the extremely nucleophilic Fe(III) complex . These results opened new perspectives in the oxidation mechanisms of some enzymatic reactions. 

However, attempts by Kiefer and Carlson59 to prohibit undesired bi-molecular reactions by irradiating 2,3,3-trimethyl-l-penten-4-one adsorbed onto silica gel were unsuccessful (due probably to steric inhibition of adsorption) the product composition was the same as that previously obtained in solution. Werbin and Strom80 attempted to restrain the freedom of movement of the radicals formed from the photolysis of vitamin K3 (2-methyl-1,4-naphthoquinone) by adsorption onto silica gel, but obtained the same mixture of dimers as that obtained from the irradiation in acetone solution, viz., syn and anticyclobutanes, an oxetane dimer, and a binaphthoquinone dimer. Photolysis of the solid substrate, however, produced only the syn isomer of cyclobutane, in this case no migration of radicals is possible, hence only one product. 

Vitamin K3 (2-methyl-1,4-naphthoquinone, Menadione, Menaphthone) [58-27-5] M 172.2, m 105-106°, 105-107°. Recrystd from 95% EtOH, or MeOH after filtration. Bright yellow crystals which are decomposed by light. Solubility in EtOH is 1.7% and in C Hg it is 10%. It IRRITATES the mucous membranes and skin. [Fieser JBC 133 391 1940]. 

VITAMIN K. Sometimes referred to as the antihemmorhagic vitamin, and. earlier in its development, the prothrombin factor or Koagulations-vitamin, vitamin Kis a substituted derivative of naphthoquinone and occurs in several forms. The designationphylloquinone. or Ki, refers to 2-methyl-3-phytyl-l,4 naphthoquinone the designations famoquinone and prertyl-menaquinone, or K2, refer to 2-difarnesyl-3-methyl-1, 4-naphthoquinone. Menadione, sometimes called oil-soluble vitamin K3, is 2-methyl-1,4-naphthoquinone. The structure of phylloquinone is ... 

An assay for the determination of vitamin K3 (2-methyl-1,4-naphthoquinone) by a combination of both constant-potential and constant-current cou-lometry has been reported [13]. The assay requires the two-electron reduction of the compound to the corresponding hydroquinone at a mercury pool electrode (E = -0.60 V vs. SCE) in acetate buffer, pH 5.9, followed by the coulometric titration of the reduction product with electrogenerated Ce(VI). This method is preferable to the standard method requiring preliminary reduction to the hydroquinone by zinc dust in acid medium, followed by titration with standard Ce(IV) solution. It is capable of low-level determination (1-2 mg) of this vitamin in pharmaceuticals, biological fluids, and foods. 

In a basic medium, structures 2-4 exist. The fluorescence maxima of 1-naphthol shift from 306 (excitation) and 362 nm (emission) in acidic or neutral solution to 338 (excitation) and 462 nm (emission) in base [29]. The increase in wavelength is attributed to the naphthoquinone structures of the ionized forms. These structures are supported by the fact that other stable naphthoquinone compounds exhibit, in neutral solution, almost identical fluorescence spectra as 1-naphthol in basic media. Menadione (2-methyl-1,4-naphthoquinone), for example, has excitation and emission maxima at 335 and 480 nm, respectively, in 95% ethanol [30]. 

Reaction of 2-methyl-1,4-naphthoquinone with the ylide derived from phenacylpyridinium bromide in acetonitrile gives 2-methyl-3-phenacyl-1,4-naphthoquinone in 82% yield. Under the same conditions, but using 2-phenoxymethyl-1,4-naphthoquinone instead of the 2-methyl derivative, the product was 3 -pheny 1-1 ff-naphtho[2,3-c]pyran-5,10-dione (97%). 

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Decarroz C, Wagner JR, van Lier JE, Krishna CM, Riesz P, Cadet J (1986) Sensitized photo-oxidation of thymidine by 2-methyl-1,4-naphthoquinone. Characterization of the stable photoproducts. Int J Radiat Biol 50 491-505... 

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