Bromodecarbonylation and Bromodecarboxylation of Electron-Rich Benzaldehydes and Benzoic Acids With Oxone® and Sodium Bromide

Koo, Bon-Suk; Kim, Eun-Hoo; Lee, Kee‐Jung

doi:10.1081/scc-120005997

Cited by 21 publications

(4 citation statements)

References 38 publications

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Section: Additional Methods For the Halodecarboxylation Of Aromatic Cmentioning

confidence: 99%

“…The reaction is based on the application of a strong oxidizer, potassium hydrogen persulfate (KHSO 5 , commercially available as Oxone), in combination with NaBr and Na 2 CO 3 base (Scheme 56). 267 Unfortunately, the reaction worked only for benzoic acids bearing MeO-or AcNH-electron-donating substituents at the ortho-and para-positions. Moreover, it was accompanied by a side process of aromatic electrophilic bromination.…”

Section: Additional Methods For the Halodecarboxylation Of Aromatic C...mentioning

confidence: 99%

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Decarboxylative Halogenation of Organic Compounds

2020

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Decarboxylative halogenation, or halodecarboxylation, represents one of the fundamental key methods for the synthesis of ubiquitous organic halides. The method is based on conversion of carboxylic acids to the corresponding organic halides via selective cleavage of a carbon–carbon bond between the skeleton of the molecule and the carboxylic group and the liberation of carbon dioxide. In this review, we discuss and analyze major approaches for the conversion of alkanoic, alkenoic, acetylenic, and (hetero)aromatic acids to the corresponding alkyl, alkenyl, alkynyl, and (hetero)aryl halides. These methods include the preparation of families of valuable organic iodides, bromides, chlorides, and fluorides. The historic and modern methods for halodecarboxylation reactions are broadly discussed, including analysis of their advantages and drawbacks. We critically address the features, reaction selectivity, substrate scopes, and limitations of the approaches. In the available cases, mechanistic details of the reactions are presented, and the generality and uniqueness of the different mechanistic pathways are highlighted. The challenges, opportunities, and future directions in the field of decarboxylative halogenation are provided.

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Section: Additional Methods For the Halodecarboxylation Of Aromatic Cmentioning

confidence: 99%

Section: Additional Methods For the Halodecarboxylation Of Aromatic C...mentioning

confidence: 99%

Decarboxylative Halogenation of Organic Compounds

2020

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“…9d : 1 H NMR (200 MHz, CDCl 3 ) δ ppm: 3.97 (s, 3H), 7.08 (dd, 1H, J = 8.8 Hz and J = 2.5 Hz), 7.20 (d, 1H, J = 8.8 Hz), 7.36 (d, 1H, J = 2.5 Hz, 1H). 20 : , 1 H NMR (200 MHz, CDCl 3 ) δ ppm: 3.97 (s, 3H), 7.00 (dd, 1H, J = 8.9 Hz and J = 2.5 Hz), 7.92 (d, 1H, J = 8.8 Hz), 7.94 (d, 1H, J = 2.5 Hz, 1H).…”

Section: Methodsmentioning

confidence: 99%

First General, Direct, and Regioselective Synthesis of Substituted Methoxybenzoic Acids by Ortho Metalation

et al. 2007

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New general methodology of value in aromatic chemistry based on ortho-metalation sites in o-, m-, and p-anisic acids (1-3) (Scheme 1) is described. The metalation can be selectively directed to either of the ortho positions by varying the base, metalation temperature, and exposure times. Metalation of o-anisic acid (1) with s-BuLi/TMEDA in THF at -78 degrees C occurs exclusively in the position adjacente to the carboxylate. On the other hand, a reversal of regioselectivity is observed with n-BuLi/t-BuOK. With LTMP at 0 degrees C, the two directors of m-anisic acid (2) function in concert to direct introduction of the metal between them while n-BuLi/t-BuOK removes preferentially the proton located ortho to the methoxy and para to the carboxylate (H-4). s-BuLi/TMEDA reacts with p-anisic acid (3) exclusively in the vicinity of the carboxylate. According to these methodologies, routes to very simple methoxybenzoic acids with a variety of functionalities that are not easily accessible by other means have been developed (Table 1).

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“…3. Replacement of a carboxyl group by the action of bromine on the salts of carboxylic acids (29) or by treatment with sodium bromide in the presence of Oxone (DuPont Chemical Solutions Enterprise, Wilmington, DE) (30).…”

Section: Preparation and Productionmentioning

confidence: 99%

Bromine, Organic Compounds

Ioffe

Kampf²

2011

Kirk-Othmer Encyclopedia of Chemical Technology

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This article focuses on organic bromine compounds with industrial application. The organic bromine compounds are prepared and produced either by substitutive or additive bromination. Organic bromine compounds, in which the bromine atom is retained in the final molecular structure, and where its presence contributes to the properties of the desired products, are the largest segment in terms of consumed volumes. This segment includes mainly flame retardants (50%), biocides (mostly for water treatment), gasoline additives, halons, bromobutyl rubber, pharmaceuticals, and dyes. New process developments resulted in new applications in ultraviolet (UV) sunscreens, high‐performance polymers, and others.

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Bromodecarbonylation and Bromodecarboxylation of Electron-Rich Benzaldehydes and Benzoic Acids With Oxone® and Sodium Bromide

Cited by 21 publications

References 38 publications

Decarboxylative Halogenation of Organic Compounds

Decarboxylative Halogenation of Organic Compounds

First General, Direct, and Regioselective Synthesis of Substituted Methoxybenzoic Acids by Ortho Metalation

Bromine, Organic Compounds

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