68963-23-5

Usage

InChI:InChI=1/C15H10O3/c1-8-5-6-9-11(7-8)15(18)13-10(14(9)17)3-2-4-12(13)16/h2-7,16H,1H3

Upstream product

• 73451-87-3 trans-1-methoxy-3-methyl-1,3-butadiene 
• 5196-28-1 juglone acetate 
• 289666-79-1 1-methoxy-7-methylanthracene-9,10-dione 
• 116889-00-0 (1RS,2SR,3RS)-2,3-epoxy-1,2,3,4-tetrahydro-1,8-dihydroxy-2-methyl-9,10-anthraquinone 
• 116948-36-8 (1RS,2RS,3SR)-2,3-epoxy-1,2,3,4-tetrahydro-1,8-dihydroxy-2-methyl-9,10-anthraquinone 
• 481-39-0 5-hydroxynaphtho-1,4-quinone 
• 78-79-5 isoprene 
• 4923-61-9 5-methoxynaphthoquinone 
• 107-86-8 3,3-dimethyl acrylaldehyde 
• 497-03-0 2-methylbut-2-enal 
• 13061-96-6 dihydroxy-methyl-borane 
• 69008-03-3 2-bromo-5-hydroxy-[1,4]naphthoquinone 
• 83-56-7 1,5-dihydroxynaphthalene 
• 605-89-0 1,5-diacetoxynaphthalene 

Downstream Products

• 613-12-7 2-methylanthracene 

Relevant academic research and scientific papers

Regiocontrolled Diels-Alder Reactions of 9-Chloro-10-hydroxyanthracene-1,4-dione

The title compound reacts with isoprene in the presence of aluminium chloride or boron trifluoride-ether to give the 2-methyl derivative of 6-chloro-11-hydroxy-1,4,4a,12a-tetrahydronaphthacene-5,12-dione; in the presence of boron triacetate, the 3-methyl isomer is the major product.

Synthesis of Barleriaquinones-I & II

Synthesis of two naturally occurring anthraquinones, Barleriaquinone-I (BQ-I) and Barleriaquinone-II (BQ-II) is achieved from commercially available naphthalene-1,5-diol. The anthraquinone core is constructed by utilizing simultaneous Heck and cross coupling reaction as the key step.

Synthesis method of anthraquinone derivatives and tetracenedione derivatives through benzannulation reaction

The present invention relates to a method for synthesizing anthraquinone derivatives and tetracene dione derivatives through a benzannulation reaction, which presents a novel synthesis method, capable of processing synthesis easily, conveniently, and efficiently under mild conditions by an organic catalyst. The synthesis method uses an L-proline catalyst which is nontoxic, economical and easily available, compared to conventional production methods, thereby providing the anthraquinone derivatives and the tetracene dione derivatives through the one-pot benzannulation reaction of an α, β-unsaturated aldehyde compound, various 1,4-naphthoquinone compounds or 1,4-anthracenedione compounds. Various forms of anthraquinone derivatives or tetracene dione derivatives prepared by the synthesis method can be widely used for synthesis of natural products, dyes, and pharmaceutical products.COPYRIGHT KIPO 2017

Organocatalyzed benzannulation for the construction of diverse anthraquinones and tetracenediones

An efficient one-pot synthesis of anthraquinones and tetracenediones was achieved vial-proline catalyzed [4+2] cycloaddition of in situ generated azadiene from α,β-unsaturated aldehydes and 1,4-naphthoquinones or 1,4-anthracenedione in good to excellent yield. This protocol constitutes an unprecedented tandem benzannulation that allows one-pot construction of diverse anthraquinones and tetracenediones in the presence of organocatalysts. This methodology was applied successfully to the synthesis of naturally occurring molecules and photochemically interesting phenanthrenequinone derivatives.

Design, synthesis, biochemical studies, cellular characterization, and structure-based computational studies of small molecules targeting the urokinase receptor

The urokinase receptor (uPAR) serves as a docking site to the serine protease urokinase-type plasminogen activator (uPA) to promote extracellular matrix (ECM) degradation and tumor invasion and metastasis. Previously, we had reported a small molecule inhibitor of the uPAR·uPA interaction that emerged from structure-based virtual screening. Here, we measure the affinity of a large number of derivatives from commercial sources. Synthesis of additional compounds was carried out to probe the role of various groups on the parent compound. Extensive structure-based computational studies suggested a binding mode for these compounds that led to a structure-activity relationship study. Cellular studies in non-small cell lung cancer (NSCLC) cell lines that include A549, H460 and H1299 showed that compounds blocked invasion, migration and adhesion. The effects on invasion of active compounds were consistent with their inhibition of uPA and MMP proteolytic activity. These compounds showed weak cytotoxicity consistent with the confined role of uPAR to metastasis.

Highly strained dihydroanthraquinones: Oxidation versus elimination

The chemistry of strained dihydroanthraquinones was investigated for the purpose of developing syntheses for highly strained anthraquinones. The reaction of (1,4-dihydro-9,10-dioxo-anthracen-1-yl)-acetates with triethylamine under aerobic conditions was found to be dependent on the degree of substitution on the acetate. Dihydroanthraquinones bearing dimethylacetates underwent elimination of enolate exclusively, while those without acetate substitution dehydrogenated as expected. Furthermore, oxidation of the cyclohexadiene ring using iodine failed due to a competitive iodolactonization reaction. The desired strained anthraquinones could be prepared, in low yield, by treatment of the resulting lactones with acidic ethanol.

Asymmetric Diels-Alder Reactions. Part 6. Regio- and Stereo-selective Cycloadditions of 5-(2',3',4',6'-Tetra-O-acetyl-β-D-glucopyranosyloxy)-1,4-naphthoquinone

The title naphthoquinone 1d underwent reaction with cyclopentadiene to give a cycloadduct, established as (1R,4S,4aR,9aS)-1,4,4a,9a-tetrahydro-5-(2',3',4',6'-tetra-O-acetyl-β-D-glucopyranosyloxy)-1,4-methano-9,10-anthraquinone 9a by X-ray crystallographic analysis.Single cycloadducts, assigned the structures 4d, 4e and 17 were also isolated from the reactions of the naphthoquinone 1d with (E)-1-methoxy-3-trimethylsiloxybuta-1,3-diene 2b, (E)-3-methyl-1-trimethylsiloxybuta-1,3-diene 2f and (E)-2-methyl-1-trimethylsiloxybuta-1,3-diene 16.A 2:1 mixture of cycloadducts, formulated as the regioisomers 4g and 3f, arose in the reaction of the dienophile 1d with (E)-1-acetoxy-3-methylbuta-1,3-diene 2g. The sugar auxiliary was readily detached from the oxidation product of compound 9a, i.e. (1R,4S)-1,4-dihydro-5-(2',3',4',6'-tetra-O-acetyl-β-D-glucopyranosyloxy)-1,4-methano-9,10-anthraquinone 18b, by acidic hydrolysis to give the aglycone 18a. An X-ray crystallographic analysis of compound 1d revealed that the quinone ring adopts a boat-like geometry in which the carbonyl oxygen atoms shield the syn-face of the C(2)-C(3) double bond. endo-Addition of dienes to the anti-face provides an explanation for the high diastereofacial reactivity of the naphthoquinone 1d.

Regiospecific Addition of Monooxygenated Dienes to Halo Quinones

In spite of their decreased polarity with respect to previously studied electron-rich analogues, monooxygenated dienes also react regiospecifically with halo quinones.The corresponding adducts can easily be aromatized on silica gel to isomeric polysubstituted naphthoquinones of unambiguous structure and therefore provide ready access to substrates for subsequent regiospecific annulations.The scope of this approach is illustrated by advantageous syntheses of several natural products: chimaphilin, 6-methylalizarin, 6-methylxantopurpurin, and barleriaquinone.The adductscan also give rise to a series of products in which the oxygen function of the dienes is preserved as a hydroxyl group in the quinone.To this end adducts derived from 1-oxygenated dienes and halo quinones were oxidized effectively with Jones reagent while those obtained from the 2-oxygenated isomers responded better to manganese dioxide.Relative positions of substituens in the adducts were readily confirmed by comparison of some of the hydroxylated oxidation products with known compounds of unambiguous structure.The method is again illustrated by the ready synthesis of a number of natural products including plumbagin, soranjidiol, isochrysophanol and its 8-methyl ether, and isozyganein and its 5-methyl ether.

rac-Altersolanol A and Related Tetrahydroanthraquinones, Total Synthesis and Cytotoxic Properties

A key step in the first synthesis of racemic altersolanol A (1a) is the regioselective Diels-Alder reaction of 5-acetoxy-7-methoxy-1,4-naphthoquinone (12) with 2-methyl-1-(trimethylsiloxy)-1,3-butadiene (13) to afford the adduct 14.The structure of 14 has been confirmed by X-ray measurements.The hydroxy groups of ring A are introduced by epoxidation of 14 to 20, rearrangement to the allylic alcohol 26, epoxidation to 31, and opening of the oxirane to rac-altersolanol A (1a).Similar products were obtained starting from juglone (15).Many of the intermediate epoxidesand also compounds 42-44 show remarkable cytotoxicity in cell cultures but all compounds were too toxic to be useful as anticancer agents.

Regiochemical Control in the Diels-Alder Reaction of Substituted Naphthoquinones. The Directing Effects of C-6 Oxygen Substituents

The Diels-Alder reactions of 6-hydroxy, 6-methoxy-, and 6-acetoxynaphthoquinone with trans-1-methoxy-3-methyl-1,3-butadiene have been studied, and the regiochemistry of the adducts has been determined.The results are consistent with the hypothesis that th