Mild One-Step Synthesis of 4,6-Benzylideneglycopyranosides from Aromatic Aldehydes and Gelation Abilities of the Glucose Derivatives

Fumiyasu Ono, Osamu Hirata, Keiko Ichimaru, Koichiro Saruhashi, Hisayuki Watanabe, Seiji Shinkai

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

We report herein an efficient one-step synthesis of 4,6-benzylidene glycoside derivatives from aromatic aldehydes bearing electron-donating or -withdrawing groups as well as polymerisable monomer groups. Glucose, mannose and galactose derivatives could also be used successfully. Several of the glucose derivatives thus obtained acted as gelators for various solvents, including water. 4-(n-Butoxybenzylidene)glucose derivative 3a produced both a clear squalane gel and a hydrogel at 0.1 wt.-%. Furthermore, 3-(n-butoxybenzylidene)glucose derivative 3i produced a clear organogel and an opaque hydrogel. The critical gelation concentration (CGC) of 3i in squalane was determined to be 0.02 wt.-%, which is one of the lowest CGC values reported so far. The organogels, hydrogels and aqueous solution gels produced from 3a and 3d exhibited thixotropy. The strength and thixotropy of the organo- and hydrogel produced from 3a were estimated by a rheometer. The gel morphologies were observed by field-emission and wet-scanning electron microscopy, and the self-assembly modes were analysed by XRD. We have concluded that super-gelators can be created by this method. An efficient one-step synthesis of 4,6-benzylidene glycosides from aromatic aldehydes under mild conditions has been achieved. Some of the glucose derivatives synthesised by this method produced clear organo- and hydrogels with thixotropic properties. The critical gelation concentrations of the gels were below 0.1 wt.-%.

Original languageEnglish
Pages (from-to)6439-6447
Number of pages9
JournalEuropean Journal of Organic Chemistry
Volume2015
Issue number29
DOIs
Publication statusPublished - Sep 1 2015
Externally publishedYes

Fingerprint

gelation
Gelation
aldehydes
Aldehydes
glucose
Derivatives
Glucose
thixotropy
gels
Hydrogel
synthesis
Gels
glucosides
Hydrogels
Glycosides
Bearings (structural)
galactose
rheometers
Rheometers
self assembly

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Mild One-Step Synthesis of 4,6-Benzylideneglycopyranosides from Aromatic Aldehydes and Gelation Abilities of the Glucose Derivatives. / Ono, Fumiyasu; Hirata, Osamu; Ichimaru, Keiko; Saruhashi, Koichiro; Watanabe, Hisayuki; Shinkai, Seiji.

In: European Journal of Organic Chemistry, Vol. 2015, No. 29, 01.09.2015, p. 6439-6447.

Research output: Contribution to journalArticle

Ono, Fumiyasu ; Hirata, Osamu ; Ichimaru, Keiko ; Saruhashi, Koichiro ; Watanabe, Hisayuki ; Shinkai, Seiji. / Mild One-Step Synthesis of 4,6-Benzylideneglycopyranosides from Aromatic Aldehydes and Gelation Abilities of the Glucose Derivatives. In: European Journal of Organic Chemistry. 2015 ; Vol. 2015, No. 29. pp. 6439-6447.
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AB - We report herein an efficient one-step synthesis of 4,6-benzylidene glycoside derivatives from aromatic aldehydes bearing electron-donating or -withdrawing groups as well as polymerisable monomer groups. Glucose, mannose and galactose derivatives could also be used successfully. Several of the glucose derivatives thus obtained acted as gelators for various solvents, including water. 4-(n-Butoxybenzylidene)glucose derivative 3a produced both a clear squalane gel and a hydrogel at 0.1 wt.-%. Furthermore, 3-(n-butoxybenzylidene)glucose derivative 3i produced a clear organogel and an opaque hydrogel. The critical gelation concentration (CGC) of 3i in squalane was determined to be 0.02 wt.-%, which is one of the lowest CGC values reported so far. The organogels, hydrogels and aqueous solution gels produced from 3a and 3d exhibited thixotropy. The strength and thixotropy of the organo- and hydrogel produced from 3a were estimated by a rheometer. The gel morphologies were observed by field-emission and wet-scanning electron microscopy, and the self-assembly modes were analysed by XRD. We have concluded that super-gelators can be created by this method. An efficient one-step synthesis of 4,6-benzylidene glycosides from aromatic aldehydes under mild conditions has been achieved. Some of the glucose derivatives synthesised by this method produced clear organo- and hydrogels with thixotropic properties. The critical gelation concentrations of the gels were below 0.1 wt.-%.

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