Eight out of eight: A detailed kinetic study on the reactivities of the eight hydroxyl groups of sucrose with phenyl isocyanate

Lajos Nagy, Bence Vadkerti, G. Batta, Péter Pál Fehér, M. Zsuga, S. Kéki

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

In this paper a detailed kinetic study between sucrose (S) and phenyl isocyanate (PI) in dimethylsulfoxide is reported for the first-time. In order to obtain monosubstituted sucrose derivatives overwhelmingly, i.e., when only one phenyl isocyanate molecule is attached to sucrose, sucrose was applied in a high molar excess to isocyanate (the molar ratio of S/PI was 16/1). Such an experimental setup indeed resulted in the formation of eight different sucrose derivatives which were separated and detected by high performance liquid chromatography combined with UV spectroscopy and mass spectrometry (HPLC-UV/MS). Under these experimental conditions, the disubstituted sucrose derivatives formed could be detected only in a few percent (ca. 2% with respect to the monosubstituted sucrose derivatives). Furthermore, by means of HPLC-UV/MS, HPLC-UV/MS/MS and NMR methods such as 1H-, 13C-NMR and 2D-NMR the reactivity of each of the eight OH groups of sucrose was determined. It was found that the most reactive moieties of sucrose are the three primary OH groups (hydroxymethyl) and the reactivity of the sucrose's OH groups decreases in the order of k(OH)6′(1) > k(OH)6(0.84) > k(OH)1′(0.31) > k(OH)3(0.25) > k(OH)4(0.23) > k(OH)2(0.13) > k(OH)4′(0.11) > k(OH)3′(0.09), where the numbers in subscript and in brackets represent the OH position in sucrose and the relative reactivity with respect to that of the highest one. The reactivity order is in line with the Mulliken charges of the OH groups of sucrose calculated by density functional theory (DFT) and also with those expected according to the theory of chromatographic separation. The dependences of the relative reactivities on temperature were also investigated and the differences between the corresponding activation parameters were also determined and discussed.

Original languageEnglish
Pages (from-to)15316-15325
Number of pages10
JournalNew Journal of Chemistry
Volume43
Issue number38
DOIs
Publication statusPublished - Jan 1 2019

Fingerprint

Sugar (sucrose)
Hydroxyl Radical
Sucrose
Kinetics
High performance liquid chromatography
Ultraviolet spectroscopy
Derivatives
Mass spectrometry
Nuclear magnetic resonance
phenyl isocyanate
Isocyanates
Dimethyl Sulfoxide
Density functional theory
Chemical activation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

Cite this

Eight out of eight : A detailed kinetic study on the reactivities of the eight hydroxyl groups of sucrose with phenyl isocyanate. / Nagy, Lajos; Vadkerti, Bence; Batta, G.; Fehér, Péter Pál; Zsuga, M.; Kéki, S.

In: New Journal of Chemistry, Vol. 43, No. 38, 01.01.2019, p. 15316-15325.

Research output: Contribution to journalArticle

@article{b5673ad09e444eceb68cf39977d37566,
title = "Eight out of eight: A detailed kinetic study on the reactivities of the eight hydroxyl groups of sucrose with phenyl isocyanate",
abstract = "In this paper a detailed kinetic study between sucrose (S) and phenyl isocyanate (PI) in dimethylsulfoxide is reported for the first-time. In order to obtain monosubstituted sucrose derivatives overwhelmingly, i.e., when only one phenyl isocyanate molecule is attached to sucrose, sucrose was applied in a high molar excess to isocyanate (the molar ratio of S/PI was 16/1). Such an experimental setup indeed resulted in the formation of eight different sucrose derivatives which were separated and detected by high performance liquid chromatography combined with UV spectroscopy and mass spectrometry (HPLC-UV/MS). Under these experimental conditions, the disubstituted sucrose derivatives formed could be detected only in a few percent (ca. 2{\%} with respect to the monosubstituted sucrose derivatives). Furthermore, by means of HPLC-UV/MS, HPLC-UV/MS/MS and NMR methods such as 1H-, 13C-NMR and 2D-NMR the reactivity of each of the eight OH groups of sucrose was determined. It was found that the most reactive moieties of sucrose are the three primary OH groups (hydroxymethyl) and the reactivity of the sucrose's OH groups decreases in the order of k(OH)6′(1) > k(OH)6(0.84) > k(OH)1′(0.31) > k(OH)3(0.25) > k(OH)4(0.23) > k(OH)2(0.13) > k(OH)4′(0.11) > k(OH)3′(0.09), where the numbers in subscript and in brackets represent the OH position in sucrose and the relative reactivity with respect to that of the highest one. The reactivity order is in line with the Mulliken charges of the OH groups of sucrose calculated by density functional theory (DFT) and also with those expected according to the theory of chromatographic separation. The dependences of the relative reactivities on temperature were also investigated and the differences between the corresponding activation parameters were also determined and discussed.",
author = "Lajos Nagy and Bence Vadkerti and G. Batta and Feh{\'e}r, {P{\'e}ter P{\'a}l} and M. Zsuga and S. K{\'e}ki",
year = "2019",
month = "1",
day = "1",
doi = "10.1039/c9nj03569a",
language = "English",
volume = "43",
pages = "15316--15325",
journal = "New Journal of Chemistry",
issn = "1144-0546",
publisher = "Royal Society of Chemistry",
number = "38",

}

TY - JOUR

T1 - Eight out of eight

T2 - A detailed kinetic study on the reactivities of the eight hydroxyl groups of sucrose with phenyl isocyanate

AU - Nagy, Lajos

AU - Vadkerti, Bence

AU - Batta, G.

AU - Fehér, Péter Pál

AU - Zsuga, M.

AU - Kéki, S.

PY - 2019/1/1

Y1 - 2019/1/1

N2 - In this paper a detailed kinetic study between sucrose (S) and phenyl isocyanate (PI) in dimethylsulfoxide is reported for the first-time. In order to obtain monosubstituted sucrose derivatives overwhelmingly, i.e., when only one phenyl isocyanate molecule is attached to sucrose, sucrose was applied in a high molar excess to isocyanate (the molar ratio of S/PI was 16/1). Such an experimental setup indeed resulted in the formation of eight different sucrose derivatives which were separated and detected by high performance liquid chromatography combined with UV spectroscopy and mass spectrometry (HPLC-UV/MS). Under these experimental conditions, the disubstituted sucrose derivatives formed could be detected only in a few percent (ca. 2% with respect to the monosubstituted sucrose derivatives). Furthermore, by means of HPLC-UV/MS, HPLC-UV/MS/MS and NMR methods such as 1H-, 13C-NMR and 2D-NMR the reactivity of each of the eight OH groups of sucrose was determined. It was found that the most reactive moieties of sucrose are the three primary OH groups (hydroxymethyl) and the reactivity of the sucrose's OH groups decreases in the order of k(OH)6′(1) > k(OH)6(0.84) > k(OH)1′(0.31) > k(OH)3(0.25) > k(OH)4(0.23) > k(OH)2(0.13) > k(OH)4′(0.11) > k(OH)3′(0.09), where the numbers in subscript and in brackets represent the OH position in sucrose and the relative reactivity with respect to that of the highest one. The reactivity order is in line with the Mulliken charges of the OH groups of sucrose calculated by density functional theory (DFT) and also with those expected according to the theory of chromatographic separation. The dependences of the relative reactivities on temperature were also investigated and the differences between the corresponding activation parameters were also determined and discussed.

AB - In this paper a detailed kinetic study between sucrose (S) and phenyl isocyanate (PI) in dimethylsulfoxide is reported for the first-time. In order to obtain monosubstituted sucrose derivatives overwhelmingly, i.e., when only one phenyl isocyanate molecule is attached to sucrose, sucrose was applied in a high molar excess to isocyanate (the molar ratio of S/PI was 16/1). Such an experimental setup indeed resulted in the formation of eight different sucrose derivatives which were separated and detected by high performance liquid chromatography combined with UV spectroscopy and mass spectrometry (HPLC-UV/MS). Under these experimental conditions, the disubstituted sucrose derivatives formed could be detected only in a few percent (ca. 2% with respect to the monosubstituted sucrose derivatives). Furthermore, by means of HPLC-UV/MS, HPLC-UV/MS/MS and NMR methods such as 1H-, 13C-NMR and 2D-NMR the reactivity of each of the eight OH groups of sucrose was determined. It was found that the most reactive moieties of sucrose are the three primary OH groups (hydroxymethyl) and the reactivity of the sucrose's OH groups decreases in the order of k(OH)6′(1) > k(OH)6(0.84) > k(OH)1′(0.31) > k(OH)3(0.25) > k(OH)4(0.23) > k(OH)2(0.13) > k(OH)4′(0.11) > k(OH)3′(0.09), where the numbers in subscript and in brackets represent the OH position in sucrose and the relative reactivity with respect to that of the highest one. The reactivity order is in line with the Mulliken charges of the OH groups of sucrose calculated by density functional theory (DFT) and also with those expected according to the theory of chromatographic separation. The dependences of the relative reactivities on temperature were also investigated and the differences between the corresponding activation parameters were also determined and discussed.

UR - http://www.scopus.com/inward/record.url?scp=85072823438&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85072823438&partnerID=8YFLogxK

U2 - 10.1039/c9nj03569a

DO - 10.1039/c9nj03569a

M3 - Article

AN - SCOPUS:85072823438

VL - 43

SP - 15316

EP - 15325

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 38

ER -