Elevated reaction order of 1,3,5-tri-tert-butylbenzene bromination as evidence of a clustered polybromide transition state: a combined kinetic and computational study

文献情報

出版日 2019-03-20

DOI 10.1039/C9OB00607A

インパクトファクター 3.876

著者

Alexander M. Genaev, Vyacheslav G. Shubin, Henry S. Rzepa

原文を見る

要旨

The kinetics and mechanism of concurrent bromo-de-protonation and bromo-de-tert-butylation of 1,3,5-tri-tert-butylbenzene at different bromine concentrations were studied experimentally and theoretically. Both reactions have high order in bromine (experimental kinetic orders ∼5 and ∼7, respectively). According to quantum chemical DFT calculations, such high reaction orders are caused by participation of clustered polybromide anions Br2n−1– in transition states. Bromo-de-tert-butylation has a higher order due to its bigger reaction center demanding clusters of extended size. A significant primary deuterium kinetic isotope effect (KIE) for bromo-de-protonation is measured indicating proton removal is rate limiting, as confirmed by computed DFT models. The latter predict a larger value for the KIE than measured and possible explanations for this are discussed.

掲載誌

Organic & Biomolecular Chemistry

CiteScore: 3.4

自己引用率: 10.3%

年間論文数: 1041

Organic & Biomolecular Chemistry (OBC) publishes original and high impact research and reviews in organic chemistry. We welcome research that shows new or significantly improved protocols or methodologies in total synthesis, synthetic methodology or physical and theoretical organic chemistry as well as research that shows a significant advance in the organic chemistry or molecular design aspects of chemical biology, catalysis, supramolecular and macromolecular chemistry, theoretical chemistry, mechanism-oriented physical organic chemistry, medicinal chemistry or natural products. Articles published in the journal should report new work which makes a highly-significant impact in the field. Routine and incremental work is generally not suitable for publication in the journal. More details about key areas of our scope are below. In all cases authors should include in their article clear rationale for why their research has been carried out.

Elevated reaction order of 1,3,5-tri-tert-butylbenzene bromination as evidence of a clustered polybromide transition state: a combined kinetic and computational study

文献情報

おすすめジャーナル

関連文献

Computational design of faster rotating second-generation light-driven molecular motors by control of steric effects

Finite pulse effects in CPMG pulse trains on paramagnetic materials

A near field optical image of a gold surface: a luminescence study

DFT studies of the bonding mechanism of 8-hydroxyquinoline and derivatives on the (111) aluminum surface

Al atom on MoO3(010) surface: adsorption and penetration using density functional theory

Two-bit memory and quantized storage phenomenon in conventional MOS structures with double-stacked Pt-NCs in an HfAlO matrix

Tunable conduction type of solution-processed germanium nanoparticle based field effect transistors and their inverter integration

A general view on the reactivity of the oxygen-functionalized graphene basal plane

A novel synthetic strategy for magnetite-type compounds. A combined experimental and DFT-computational study

Fundamental aspects in surface self-assembly: theoretical implications of molecular polarity and shape

こちらもおすすめ

2,5-二羧基氟苯の市場動向や研究トレンドはどうですか？

8-甲基-2-噻吩-2-基-喹啉-4-羧酸を含む廃棄物はどのように処理すべきですか？

2,4-二氯-6-甲基5-嘧啶甲醛の主な用途は何ですか？

レターメビールとは何ですか？

2-(1,3-二氧杂烷-2-基)噻唑の物理化学的性質は何ですか？

L-beta-高酪氨酸塩酸塩は安全ですか？

睡茄灯笼草素Cはどのように合成されますか？

4-(嘧啶-2-基)哌嗪-1-羧酸叔丁酯はどのように保存すればよいですか？

NBI-74330の主な用途は何ですか？

6-トリフルオロメチル-2-クロロピリジン-4-ボリリック酸はどのように合成されますか？

掲載誌

Organic & Biomolecular Chemistry

おすすめ化合物

1,1'-(9-ethyl-9H-carbazole-3,6-diyl)diethanone

4-[(1-Methyl-1H-pyrrol-2-yl)methylene]-1,3(2H,4H)-isoquinolinedione

5-Amino-1-(2,4-difluorophenyl)-3-methyl-1H-pyrazole-4-carbonitrile

(2E)-3-(5-Nitro-2-furyl)acrylaldehyde

9H-Fluoren-9-ylmethyl [(2S)-1-hydroxy-3-(1H-indol-3-yl)-2-propanyl]carbamate

おすすめサプライヤー