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A simple, efficient, and mild method for selective bromination of some activated aromatic compounds using potassium bromide in the presence of benzyltriphenylphosphonium peroxodisulfate in nonaqueous solution is reported. The results obtained revealed good to excellent selectivity between ortho and para positions of phenols and methoxyarenes. Copyright Taylor & Francis Group, LLC.

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Regioselective aromatic monobromination of alkyl phenyl ethers with NaClO2, NaBr, Mn(acac)3, and Montmorillonite K10 in dichloromethane

Regioselective and high-yielding nuclear monobromination of aromatic ethers can be accomplished with a combination of NaClO2, NaBr, and Mn(acac)3 catalyst in dilchloromethane under mild and neutral conditions with the aid of Montmorillonite K10.

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Alternative synthesis of 1,2,3,4-tetramethoxy-5-methylbenzene: A key intermediate for preparing coenzyme Q homologs and analogs

Preparation of 1,2,3,4-tetramethoxy-5-methylbenzene (1) through a new process from pyrogallol is described. In the preparation, a modified mild brominating agent was employed, and a simple introduction of methyl group into aromatic ring through chloromethylation of the corresponding substrate (4), followed by reductive dehalogenation, was achieved successfully with good yields. Copyright Taylor & Francis Group, LLC.

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Sequential Directed Ortho Metalation-Boronic Acid Cross-Coupling Reactions. A General Regiospecific Route to Oxygenated Dibenzopyran-6-ones Related to Ellagic Acid

A general regiospecific synthesis of dibenzopyran-6-one derivatives 1a,c and 8a-i related to ellagic acid is described (Scheme I, Table I).The sequence involves directed ortho metalation-boronation of benzamides 4 to give the arylboronic acids 5, which, upon palladium-catalyzed cross-coupling with alkoxybromobenzenes 6 leads to the biphenylamides 7.BBr3 demethylation followed by acid-catalyzed cyclization affords pyranone 8.In this manner, the naturally occurring dibenzopyranones 1a, autumnariol (1c), and the heterocyclic analogue 13 (Scheme III) were efficiently prepared.

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Ortho and remote metalation – cross coupling strategies. Total synthesis of the naturally occurring fluorenone dengibsinin and the azafluoranthene alkaloid imeluteine

The total synthesis of the naturally occurring fluorenone, dengibsinin (7a), and the azafluoranthene alkaloid, imeluteine (30e), is described. Using combined ortho metalation – cross coupling sequences that terminate in Friedel-Crafts (18b?6d) and remote metalation (21a,b?6c,d) reactions, the synthesis of fluorenone dimethyl ethers 6c and 6d is reported. 6c and 6d were shown not to be identical to dengibsinin dimethyl ether and dengibsin dimethyl ether, respectively, derived from the natural products. This work, together with synthetic and structural evidence from Sargent and Talapatra, led to the reassignment of structures for dengibsinin (7a) and dengibsin (7b). Using the metalation – cross coupling approach, the synthesis of the reassigned dengibsinin (7a) is presented. Two alternate unsuccessful approaches to imeluteine are briefly described (31+32 and 33+34). The successful approach incorporates the remote metalation – double cyclization, 43?44, as the key step.

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We developed the aerobic photooxidative bromination of aromatic compounds using carbon tetrabromide in the presence of anthraquinone-2-carboxylic acid under visible light irradiation.

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(Chemical Equation Presented) The scope of the palladium-catalyzed cross-coupling reaction of aryl bis(catechol) silicates has been extended to include the coupling of aryl bromides by employing microwave irradiation. This new set of coupling conditions is tolerant of electron-rich and -deficient aryl bromides. In addition, a variety of substituted aryl bis(catechol) silicates have been successfully cross-coupled.

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This invention relates to cyclobutane derivatives having the formula SPC1 Wherein R1 to R3, which may be the same or different, represent hydrogen atoms, halogen atoms, hydroxy, trifluoromethyl, benzyloxy, acyloxy groups, alkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 3 carbon atoms, phenyl, cyclohexyl, or 2 of the radicals R1 to R3 together represents a methylenedioxy group, R4 represents a hydrogen atom or an alkyl group with 1 or 2 carbon atoms, R5 represents a hydrogen atom or an alkyl group with 1 to 3 carbon atoms and R6 represents a phenyl group, which may be mono- or disubstituted by halogen atoms, trifluoromethyl, hydroxy, nitro, amino, benzyloxy, acyloxy groups, alkyl groups with 1 to 3 carbon atoms, alkoxy groups with 1 to 3 carbon atoms or alkylthio groups with 1 to 3 carbon atoms; or a pyridyl group, optionally substituted by a halogen atom, a hydroxy, nitro, amino, benzyloxy, acyloxy, carboxy group, a carbalkoxy group with 1 to 3 carbon atoms in the alkoxy, an alkyl group with 1 to 3 carbon atoms or an alkoxy group with 1 to 3 carbon atoms; To salts thereof with physiologically compatible inorganic or organic acids or bases as well as to processes for their preparation. The cyclobutane compounds of the above general formula show valuable pharmacological properties, especially a sedative and muscle relaxing activity.

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A new method for brief regioselective synthesis of anthraquinones via the reaction of anions of ethyl cyanoacetate or the anions of 2-(carbethoxyaryl)acetonitriles with arynes is described.

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A novel simple and efficient bromination protocol for activated arenes

An efficient, high yielding, and environmentally benign bromination using an alkali metal bromide as the bromine source is disclosed. Investigation of the protocol revealed that the method operates for activated arenes producing the corresponding monobrominated products in good to excellent yields.

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