Higher reactivity of 3-pyridinium boronic acid compared with 3-pyridinium boronate ion toward 4-isopropyltropolone in acidic aqueous solution: Fundamental reaction analyses for an effective organoboron-based chemosensor

Satoshi Iwatsuki, Yuki Kanamitsu, Hidetaka Ohara, Eisuke Watanabe, Koji Ishihara

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The pK as of 3-pyridylboronic acid and its derivatives were determined spectrophotometrically. Most of them had two pK as assignable to the boron center and pyridine moiety. The pK a assignment performed by 11B nuclear magnetic resonance spectroscopy revealed that both boron centers in 3-pyridylboronic acid [3-PyB(OH) 2] and the N-methylated derivative [3-(N-Me)Py +B(OH) 2] have strong acidities (pK a = 4.4 for both). It was found that introduction of a substituent to pyridine-C atom in 3-pyridylboronic acid drastically increased the acidity of the pyridinium moiety, but decreased the acidity of the boron center, whereas the introduction to pyridine-N atom had no influence on the acidity of the boron center. Kinetic studies on the complexation reactions of 3-pyridinium boronic acid [3-HPy +B(OH) 2] with 4-isopropyltropolone (Hipt) carried out in strongly acidic aqueous solution indicated that the positive charge on the boronic acid influenced little on its reactivity; 3-HPy +B(OH) 2 reacts with Hipt and protonated H 2ipt +, and its reactivity was in line with those of a series of boronic acids. Kinetics in weakly acidic aqueous solution revealed that 3-HPy +B(OH) 2 reacts with Hipt faster than its conjugate boronate [3-HPy +B(OH) 3 -], which is consistent with our recent results. The reactivity of 3-(N-Me)Py +B(OH) 2 towards Hipt was also examined kinetically; the reactivities of 3-(N-Me)Py +B(OH) 2 and 3-(N-Me)Py +B(OH) 3 - are almost the same as those of their original 3-HPy +B(OH) 2 and 3-HPy +B(OH) 3 -, respectively.

Original languageEnglish
Pages (from-to)760-768
Number of pages9
JournalJournal of Physical Organic Chemistry
Volume25
Issue number9
DOIs
Publication statusPublished - 2012 Sep 1

Keywords

  • acid dissociation
  • boronate ion
  • boronic acid
  • kinetics
  • mechanism

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Fingerprint Dive into the research topics of 'Higher reactivity of 3-pyridinium boronic acid compared with 3-pyridinium boronate ion toward 4-isopropyltropolone in acidic aqueous solution: Fundamental reaction analyses for an effective organoboron-based chemosensor'. Together they form a unique fingerprint.

  • Cite this