Practical and regioselective brominations of aromatic compounds using tetrabutylammonium peroxydisulfate

Simple and Regioselective Bromination of 5,6-Disubstituted-indan-1-ones with Br2 Under Acidic and Basic Conditions

“…The reactions of indan-1-one (10), synthesized from 1 by a reported method [23], with Br 2 under acidic and basic conditions at room temperature gave the α-brominated product 2-bromoindan-1-one (11) in 84% yield and the α,α-dibrominated product 2,2-dibromoindan-1-one (12) in 67% yield, respectively (entry XVII). The reaction of 5,6-difluoroindan-1-one (13) with Br 2 in acetic acid yielded 2-bromo-5,6-difluoroindan-1-one (14) in 65% yield and with Br 2 in KOH it yielded 2,2-dibromo-5,6-difluoroindan-1-one (15) regioselectively in 84% yield (entry XVIII).…”

“…The reaction mixture was stirred 1 hr at room temperature and worked up as described for 1.8 to yield 2-bromo-5,6-difluoroindan-1-one (14) …”

“…Recently, bromoarenes have assumed increasing importance in organic synthesis as useful reagents for functionalization through carbon-carbon bond formation of diarenes, ethylenic, or acetylenic condensation via metal catalyzed cross coupling reactions such as the Suzuki, Negishi, and Sonogashira reactions [2]. Various reagents and reaction conditions have been developed and reported for the bromination of aromatic systems using different brominating agents, including Br 2 /SbF 3 /HF [3], NBS/H 2 SO 4 /CF 3 COOH [4], NBS/NaOH [5], NBS/ FeCl 3 [6], HBr/tert-BuOOH, HBr/H 2 O 2 , and HBr/DMSO [7], NH 4 Br/H 2 O 2 /CH 3 COOH [8], CuBr/tertBuONO [9], Br 2 /SO 2 Cl 2 over microporous catalyst [10], 3-methylimidazolium tribromide [11], NaBr/Oxone ® , KBr/Oxone ® , and KBr/H 2 O 2 /Oxone ® [12], Br 2 /tetrabutylammonium peroxydisulfate [13], quaternary ammonium tribromide [14] and quinolinium bromochromate in glacial acetic acid [15]. On the other hand, selective α-bromination of carbonyl compounds is another important transformation, as the resulting α-brominated products are also versatile synthetic intermediates.…”

Highly Efficient Halogenation of Organic Compounds with Halides Catalyzed by Cerium(III) Chloride Heptahydrate Using Hydrogen Peroxide as the Terminal Oxidant in Water

“…However, a number of articles describing the application of peroxo compounds for the oxidative iodination and bromination of arenes has been recently appeared in the literature; Ce(OH) 3 OH/SDS-H 2 O, [12] NH 4 I/oxone/MeOH, [45] KI/oxone/MeOH, [46] KI/ben-A C H T U N G T R E N N U N G zyltriphenylphosphonium peroxomonosulfate/ MeCN, [47] [50] [52] NaS 2 O 8 / MeCN [53] and NaI/H 2 O 2 /organotelluride catalyst at pH 6 buffer in Et 2 O-H 2 O, [54] KBr/benzyltriphenylphosphonium peroxodisulfate/MeCN, [55] Br 2 or LiBr/ tetrabutylammonium peroxydisulfate/MeCN or CH 2 Cl 2 [56] and I 2 /poly(4-vinylpyridine)-supported peroxodisulfate/MeCN. [57] All the above-mentioned reactions proceed in organic solvents except for one in which Ce(OH) 3 OOH is used in SDS micellar solution.…”

A Novel Synthesis of Bromobenzenes Using Molecular Bromine

“…The manufacture of a wide range of bulk and fine chemicals, including flame retardants, disinfectants and antibacterial and antiviral drugs, involves bromination reactions [1]. Aryl bromides are often used in the syntheses of aryl esters, aryl olefins and other useful classes of compounds, consequently, numerous methods for the bromination of aromatics have been reported in the literature [2][3][4][5][6][7][8][9][10][11][12][13][14]. Some of the drawbacks of classical direct bromination of aromatic systems using elemental bromine as the reagent are the waste of bromine and the difficulties in selectively achieving monobromination (especially in the case of electron-rich compounds).…”