2-Methyl-l, 4-naphthoquinone

Quinones of various degrees of complexity have antibiotic, antimicrobial, and anticancer activities, eg, a2iddinornitosene [80954-63-8] (36), (-)-2-methyl-l,4-naphthoquinone 2,3-epoxide [61840-91 -3] (37), and doxombicin [23214-92-8] (adriamycin) (38) (see Antibiotics Chemotherapeutics, anticancer), ah of these natural and synthetic materials have stimulated extensive research in synthetic chemistry. 

In order to circumvent this problem, there has been significant activity directed toward the search for a less environmentally toxic and more selective oxidizing agent than chromium. For example, Hoechst has patented a process which uses organorhenium compounds. At a 75% conversion, a mixture of 86% of 2-methyl-l,4-naphthoquinone and 14% 6-methyl-l,4-naphthoquinone was obtained (60). Ceric sulfate (61) and electrochemistry (62,63) have also been used. 

Vitamin K3 (2-methyl-l,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 C6H6 it is 10%. It IRRITATES the mucous membranes and skin. [Fieser J Biol Chem 133 391 1940.]... 

Methyl-l,4-naphthoquinone [ 1,4 -Naphthalenedione, 2-methyl-] Cyclopropanecarboxylie [Cyclopropan ecarboxylic acid] 2 -Cyclopropyl -3 -methyl [ 1,4-Naphthalenedione, 2-cyclopropyl-3-methyl-] 37 3... 

Monney, L., Ohvier, R., Otter, 1., Jansen, B., Poirier, GG., and Bomer, C., 1998, Role ofan acidic compartment in tumor-necrosis-factor-a-induced production of ceramide, activation of caspase-3 and apoptosis. Eur. J. Biochem. 251 295-303 Morrison, H., Jemstrom, B., Nordenskjdld, M., Thor, H., and Orrenius, S., 1984, Induction of DNA damage by menadione (2-methyl-l,4-naphthoquinone) in primary cultures of rat hepatocytes. Biochem. Pharmacol. 33 1763-1769 Neuzil, J., Svensson, 1., Weber, T, Weber, C., and Brunk, U.T., 1999, alpha-tocopheryl succinate-induced apoptosis in Jurkat T cells involves caspase-3 activation, and both lysosomal and mitochondrial destabilisation. FEES Lett. 445 295-300 Ngo, E.O., Nutter, L.M., Sura, T., and Gutierrez, P. L., 1998, Induction ofp53 by the... 

Chemical/Physical. An aqueous solution containing chlorine dioxide in the dark for 3.5 d at room temperature oxidized 2-methylnaphthalene into the following l-chloro-2-methylnaphtha-lene, 3-chloro-2-methylnaphthalene, l,3-dichloro-2-methylnaphthalene, 3-hydroxymethylnaphtha-lene, 2-naphthaldehyde, 2-naphthoic acid, and 2-methyl-l,4-naphthoquinone (Taymaz et al., 1979). 

Silver(I) catalyzed oxidative decarboxylation using peroxydisulfate is well studied . Decarboxylated carbon radicals can form a C—C bond with 1,4-benzoquinone or 1,4-naphthoquinone (equation 17) . In the case of 1,4-benzoquinone and phenylacetic acid the yield is 87%, whereas in the case of 2-methyl-l,4-naphthoquinone and cyclopropanecar-boxylic acid the yield is as low as 37%. 

Menaquinone. The incorporation of [2- C]mevalonate and [2- C]-2-methyl-l,4-naphthoquinone into MK-4, normally considered a bacterial quinone, has been demonstrated in marine invertebrates such as crabs and starfish." Incorporation into 2,3-epoxy-MK-4 (163) was also observed. Cell-free extracts have been prepared from Escherichia coli which catalyse the conversion of o-succinylbenzoic acid (164) into l,4-dihydroxy-2-naphthoic acid (165) and menaquinones. In the presence of farnesyl pyrophosphate the major menaquinone produced was MK-3. Genetic studies with mutants of E. coli K12 that require (164) offer support for the generally accepted pathway for MK biosynthesis via (164) and (165)." The enzyme system that catalyses the attachment of the polyprenyl side-chain to 1,4-dihydroxy-2-naphthoic acid to form demethylmenaquinone-9 (166) has been isolated from E. colU ... 

The structure of vitamin Kj has been established by degradation and by synthesis. Surprisingly, the long alkyl side chain of vitamin K, is not necessary for its action in aiding blood clotting because 2-methyl-l,4-naphthoquinone is almost equally active on a molar basis. 

The 2-naphthalenesulfonic acid, l,2,3,4-tetrahydro-2-methyl-l,4-dioxo-, sodium salt, trihydrate can be prepared by mixing the 2-methyl-l,4-naphthoquinone with the bisulphite salt in the presence of water. Ordinarily gentle warming of the aqueous mixture is preferred to facilitate solution. The mixture of 2-methyl-l,4-naphthoquinone (250 mg 1 molar equivalent) sodium bisulphite (149 mg 1 molar equivalent) distilled water (250 ml) or 2-methyl-1,4-naphthoquinone (250 mg 1 molar equivalent) potassium bisulphate (349 mg 2 molar equivalent) distilled water 250 ml may be used. These examples representing preferred ratios of ingredients are merely illustrative and are not to be interpreted as limiting. 

The bisulphite addition compounds have a vitamin K activity equal to that of the 2-methyl-l,4-naphthoquinone contained in the molecule. The compounds, although suitable for oral administration, are particularly adaptable in aqueous solution for parenteral administration in the treatment of hemorrhagic conditions. 

Polyprenylation of quinones. Trimethylstannyllithium converts polyprenyl halides (e.g., geranyl chloride, phytyl chloride) into polyprenyltrimethylstannyl compounds in high yield with retention of stereochemistry of the allylic double bond. In the presence of a Lewis acid (BF3 etherate) these tin compounds couple regio- and stereoselectively with 2-methyl-l,4-naphthoquinone. The reaction to form vitamin K (2) is typical (equation I). ... 

Fig. 14-10. A t) curves observed at 380nm in the photoreduction of 2-methyl-l,4-naphthoquinone (MNQ) in as SDS micellar solution at room temperature under Bo=331 mT with and without a microwave pulse (a) without a microwave pulse, (b) with a short microwave pulse (tD=300ns, /lfMw=15ns, and Si=l 0.1mT), (c) with a long microwave pulse (fD=-40ns, zltMw=5 J.s, and Si=2 0.3mT). (Reproduced from Ref. [21] by permission from Elsevier Science B. V.)...

Vitamin K is the name of a group of compounds, all of which contain the 2-methyl-l,4-naphthoquinone moiety. Common nomenclature is ... 

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