3958-82-5

Usage

Synthesis Reference(s)

Tetrahedron Letters, 35, p. 1335, 1994 DOI: 10.1016/S0040-4039(00)76211-3

Upstream product

• 583-69-7 2-bromobenzene-1,4-diol 
• 5273-61-0 5,6-dibromo-cyclohex-2-ene-1,4-dione 
• 615-36-1 2-bromoaniline 
• 106-51-4 p-benzoquinone 
• 95-56-7 2-hydroxybromobenzene 
• 7664-93-9 sulfuric acid 
• 107125-57-5 3-bromo-4-(2,4-dibromophenyl)imino-1,4-benzoquinone 
• 64-19-7 acetic acid 
• 123-31-9 hydroquinone 
• 17332-11-5 2-bromo-4-methoxyphenol 
• 62-53-3 aniline 
• 25245-34-5 1-bromo-2,5-dimethoxybenzene 
• 591-19-5 m-Bromoaniline 
• 98-83-9 isopropenylbenzene 

Downstream Products

• 98434-23-2 2-aziridin-1-yl-5-bromo-[1,4]benzoquinone 
• 15516-58-2 2-bromo-4-nitroso-phenol 
• 3333-25-3 2,6-dibromohydroquinone 
• 14753-51-6 2,5-dibromohydroquinone 
• 143144-59-6 2-Bromo-4-(5,6-dihydro-4H-pyran-2-yl)-4-hydroxy-cyclohexa-2,5-dienone 
• 108046-83-9 5-Bromo-2-methyl-1,3-diphenyl-2H-isoindole-4,7-dione 
• 3490-49-1 2-phenoxy-1,4-benzoquinone 
• 17863-80-8 1,4-bis(trimethylsilyloxy)-2-trimethylsilylbenzene 
• 387401-16-3 (Z)-4-(2,5-Dihydroxy-phenyl)-but-3-enoic acid methyl ester 
• 387400-88-6 (E)-4-(2,5-Dihydroxy-phenyl)-but-3-enoic acid methyl ester 
• 134153-39-2 4'-(4-Benzoyl-phenyl)-bicyclohexyl-3,6-diene-2,5-dione 

Relevant academic research and scientific papers

Hetero Diels-Alder reactions of 1-acetylamino- and 1-dimethylamino-1- azadienes with benzoquinones

Treatment of bromobenzoquinone with 2 equiv. of a 1-dimethylamino-1- azadiene afforded mixtures of the corresponding 1,8-diaza-9,10-anthraquinone and 1,5-diaza-9,10-anthraquinone. Double hetero Diels-Alder reactions between 1-dimethylamino-1-azadienes and

Synthesis of bromo-conduritol-B and bromo-conduritol-C as glycosidase inhibitors

For the synthesis of bromo-conduritol-B skeleton, bromo-1,4-benzoquinone was subjected to bromination followed by the reduction of the carbonyl groups with NaBH4. Substitution of bromides bonded to sp3-hybridized carbon atoms with AgOAc gave the bromo-conduritol-B tetraacetate in high yield. For the construction of bromo-conduritol-C skeleton, 2,2-dimethyl-3a,7a-dihydro-1,3-benzodioxole was used as the starting material. Photooxygenation of the diene unit gave an unsaturated bicyclic endoperoxide. Bromine was incorporated into the molecule by the addition of bromine to the double bond. Opening of the peroxide linkage followed by HBr elimination and reduction of the carbonyl group provided the conduritol-C structure in good yield. Bromo-conduritol-B exhibited strong enzyme-specific inhibition against α-glycosidase.

Oxidative Dearomatization of Phenols and Polycyclic Aromatics with Hydrogen Peroxide Triggered by Heterogeneous Sulfonic Acids

We report herein a method for the oxidative dearomatization of phenols and bare polycyclic arenes into the corresponding quinoid derivatives using hydrogen peroxide. The reaction is catalyzed by sulfonic acids and best results were achieved using heterogenized species. The best results using phenols were achieved using a hybrid material, namely a perfluorinated polymer functionalized with sulfonic acid groups supported on silica. The dearomatization of polycyclic aromatic hydrocarbons performed better using the polymeric acid catalyst. These methods operate under mild conditions, using mild and benign oxidants and thus minimizing the formation of waste.

Strategies towards potent trypanocidal drugs: Application of Rh-catalyzed [2?+?2?+?2] cycloadditions, sulfonyl phthalide annulation and nitroalkene reactions for the synthesis of substituted quinones and their evaluation against Trypanosoma cruzi

Rhodium-catalyzed [2 + 2 + 2] cycloadditions, sulfonyl phthalide annulations and nitroalkene reactions have been employed for the synthesis of 56 quinone-based compounds. These were evaluated against Trypanosoma cruzi, the parasite that causes Chagas disease. The reactions described here are part of a program that aims to utilize modern, versatile and efficient synthetic methods for the one or two step preparation of trypanocidal compounds. We have identified 9 compounds with potent activity against the parasite; 3 of these were 30-fold more potent than benznidazole (Bz), a drug used for the treatment of Chagas disease. This article provides a comprehensive outline of reactions involving over 120 compounds aimed at the discovery of new quinone-based frameworks with activity against T. cruzi.

Activated Carbon-Promoted Dehydrogenation of Hydroquinones to Benzoquinones, Naphthoquinones, and Anthraquinones under Molecular Oxygen Atmosphere

We found that the activated carbon-molecular oxygen system promotes the conversion of hydroquinones to benzoquinones, naphthoquinones, and anthraquinones, which are often found in natural products and pharmaceuticals. In particular, the one-pot synthesis of naphthoquinones and anthraquinones involving a Diels-Alder reaction is a useful protocol for this purpose.

The impact of an isoreticular expansion strategy on the performance of iodine catalysts supported in multivariate zirconium and aluminum metal-organic frameworks

Iodine functionalized variants of DUT-5 (Al) and UiO-67 (Zr) were prepared as expanded-pore analogues of MIL-53 (Al) and UiO-67 (Zr). They were prepared using a combination of multivariate and isorecticular expansion strategies. Multivariate MOFs with a 25% iodine-containing linker was chosen to achieve an ideal balance between a high density of catalytic sites and sufficient space for efficient diffusion. Changes to the oxidation potential of the catalyst as a result of the pore-expansion strategy led to a decrease in activity with electron rich substrates. On the other hand, these larger frameworks proved to be more efficient catalysts for substrates with higher oxidation potentials. Recyclability tests for these larger MOFs showed sustained catalytic activity over multiple recycles.

Unusual Chemistry in an Uncatalyzed Bromate-Aniline Oscillator: Ring-Contraction Oxidation of Aniline with Pulsative CO2 Production

The bromate-aniline oscillatory reaction was discovered 4 decades ago, but neither the detailed mechanism nor the key products or intermediates of the reaction were described. We report herein a detailed study of this reaction, which yielded new insights. We found that oscillatory oxidation of aniline by acidic bromate proceeds, to a significant extent, via a novel reaction pathway with the periodic release of carbon dioxide. Several products were isolated, and their structures, not described so far, were justified on the basis of MS and NMR. One of the main products of the reaction associated with the CO2 release route can be assigned to 2,2-dibromo-5-(phenylimino)cyclopent-3-en-1-one. A number of known compounds produced in the studied reaction, including unexpected brominated 1-phenylpyrroles and 1-phenylmaleimides, were identified by comparison with standards. A mechanism is suggested to explain the appearance of the detected compounds, based on coupling of the anilino radical with the produced 1,4-benzoquinone. We assume that the radical adduct reacts with bromine to form a cyclopropanone intermediate that undergoes a Favorskii-type rearrangement. Further oxidation and bromination steps including decarboxylation lead to the found brominated phenyliminocyclopentenones. The detected derivatives of 1-phenylpyrrole could be produced by a one-electron oxidation of a proposed intermediate 2-phenylamino-5-bromocyclopenta-1,3-dien-1-ol followed by β-scission with the abstraction of carbon monoxide. Such a mechanism is known from the combustion chemistry of cyclopentadiene. The proposed mechanism of this reaction provides a framework for understanding the observed oscillatory kinetics.

Rhodium-catalyzed C-H bond activation for the synthesis of quinonoid compounds: Significant Anti-Trypanosoma cruzi activities and electrochemical studies of functionalized quinones

Thirty four halogen and selenium-containing quinones, synthesized by rhodium-catalyzed C-H bond activation and palladium-catalyzed cross-coupling reactions, were evaluated against bloodstream trypomastigotes of T.?cruzi. We have identified fifteen compounds with IC50/24?h values of less than 2?μM. Electrochemical studies on A-ring functionalized naphthoquinones were also performed aiming to correlate redox properties with trypanocidal activity. For instance, (E)-5-styryl-1,4-naphthoquinone 59 and 5,8-diiodo-1,4-naphthoquinone 3, which are around fifty fold more active than the standard drug benznidazole, are potential derivatives for further investigation. These compounds represent powerful new agents useful in Chagas disease therapy.

Rh-Catalyzed Reactions of 1,4-Benzoquinones with Electrophiles: C-H Iodination, Bromination, and Phenylselenation

Under Rh-catalyzed conditions, typically electrophilic 1,4-benzoquinones exhibit nucleophilic reactivity, such that exposure to appropriate electrophiles generates products of C-H iodination, bromination, and phenylselenation. This provides a mild and general method for direct halofunctionalization, and the first method that can achieve direct C-H phenylselenation of this compound class. The scope and limitations of the new protocols are outlined, and representative derivatizations are highlighted.

Functional models of nonheme diiron enzymes: Kinetic and computational evidence for the formation of oxoiron(IV) species from peroxo-diiron(III) complexes, and their reactIVity towards phenols and H2O2

The reactivity of the previously reported peroxo adducts [Fe2(μ-O2)(L1)4(CH3CN)2]2+, and [Fe2(μ-O2)(L2)4(CH3CN)2]2+, (L1 = 2-(2′-pyridyl)benzimidazole and L2 = 2-(2′-pyridyl)-N-methylbenzimidazole) towards H2O2 as catalase mimics, and towards various phenols as functional RNR-R2 mimics, is described. Kinetic, mechanistic and computational studies gave direct evidence for the involvement of the (μ-1,2-peroxo)diiron(iii) intermediate in the O-H activation process via formation of low-spin oxoiron(iv) species.