Activity and selectivity of different base catalysts in synthesis of guaifenesin from guaiacol and glycidol of biomass origin

Bhanawase, Shivaji L.; Yadav, Ganapati D.

doi:10.1016/j.cattod.2016.12.008

Cited by 12 publications

(5 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Guaiafenesin and mephenesin represent two interesting examples of MAGEs useful as drugs which was synthesized by glycidol ring-opening with phenols (guaiacol and o-cresol). Yadav et al reported the guaiafenesin (selectivity 86 % at guaiacol conversion of 92%) synthesis in the presence of calcined hydrotalcite at 120°C in 4 h [65]. Recently, bio-glycidol conversion to surfactants has been reported through glycidol etherification with long-chain alcohols (n-octanol, ndecanol and n-dodecanol) catalyzed by Al(OTf) 3 reaching initial turnover frequency up to 2633 h -1 in the case of octanol [66].…”

Section: Monoalkyl Glyceryl Ethers (Mages)mentioning

confidence: 99%

Glycidol syntheses and valorizations: Boosting the glycerol biorefinery

Prete

Cespi

Passarini

et al. 2022

Current Opinion in Green and Sustainable Chemistry

View full text Add to dashboard Cite

Section: Monoalkyl Glyceryl Ethers (Mages)mentioning

confidence: 99%

Glycidol syntheses and valorizations: Boosting the glycerol biorefinery

Prete

Cespi

Passarini

et al. 2022

Current Opinion in Green and Sustainable Chemistry

View full text Add to dashboard Cite

“…Noteworthily, the synthesis of MPP analogues is mainly performed by using glycidol or epichlorohydrin, which are toxic and carcinogenic compounds, while DPP is only produced by the phenolysis reaction of phenyl glycidyl ether (i.e., the phenoxy ether of glycidol) in the presence of a catalyst (e.g., homogeneous or supported bases or Lewis acids like bismuth triflate) or by the use of the carcinogenic epychlorohydrin. − However, despite both the flourishing interest in finding new applications to versatile, bio-based compounds like GlyC and the importance of β-aryloxy alcohols, only few works have been published on the potential applications of GlyC as an alkylating agent for phenolic compounds. In 2013, Truscello et al investigated the synthesis of β-aryloxy alcohols through the reaction between glycerol, diethyl carbonate (DEC), and phenol (or derivatives) in basic catalysis via GlyC in situ production.…”

Section: Introductionmentioning

confidence: 99%

Glycerol Carbonate as a Versatile Alkylating Agent for the Synthesis of β-Aryloxy Alcohols

Galletti

Prete

Vanzini

et al. 2022

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

The possibility to use glycerol carbonate (GlyC) as an innovative alkylating agent for phenolic compounds in solventless conditions and in the presence of a catalytic amount of both homogeneous and heterogeneous bases is herein described. In particular, the peculiar, polyfunctional structure of GlyC allows one to obtain the formation not only of the mono-phenoxy-1,2propanediol (MPP) analogue but also of 1,3-diphenoxy-2-propanol (DPP), the latter being elusive using the more traditional, toxic, and carcinogenic reagents such as glycidol and/or 3-chloro-1,2propandiol. The production of DPP is indeed possible due to the in situ formation of a reactive intermediate, 4-(phenoxy)methyl-1,3-dioxolane-2-one (PhOGlyC), which may undergo a consecutive nucleophilic attack of a phenolate, leading to the selective formation of the disubstituted product. This reaction is nonetheless in competition with PhOGlyC decarboxylation that finally limits DPP yield up to 20%, with an MPP yield up to roughly 60% in the optimized conditions (atmospheric pressure, 140 °C, 5 h using Cs 2 CO 3 as the basic catalyst) starting directly from a GlyC/phenolic mixture. For this reason, a multistep synthetic strategy has also been developed, first by obtaining the quantitative formation and isolation of the PhOGlyC intermediate and then by promoting the consecutive reaction with phenol, in this way obtaining a DPP yield of 66% after only 1 h of reaction at 170 °C. The obtained phenyl glyceryl ethers are interesting drugs scaffolds (i.e., guaifenesin, mephenesin), intermediates in the preparation of active pharmaceutical ingredients (e.g., chlorphenesin carbamate, methocarbamol), and hydrotropic solvents; preliminary evaluations of MPP and DPP biodegradability and use as alternative surfactants have also been described in this paper.

show abstract

“…Two kinetic models, that is, the power‐law and Langmuir–Hinshelwood–Hougen–Watson (LHHW), were developed for guaiacol HDO. Bhanawase et al developed a LHHW model for guaiacol HDO over a hydrotalcite catalyst, and Leiva et al reported a similar LHHW model when the HDO reaction occurred over Re‐based catalysts . In addition, Nie and Resasco presented LHHW kinetics for the conversion of a similar model compound (m‐cresol) over the Pt/SiO 2 catalyst .…”

Section: Introductionmentioning

confidence: 99%

“…Excellent reviews of laboratory reactors for kinetic measurements have been published in the literature . Note that for the above investigations on kinetic modeling of guaiacol HDO, only two studies used a differential reactor, while others employed the integral mode …”

Section: Introductionmentioning

confidence: 99%

“…[24][25][26] Note that for the above investigations on kinetic modeling of guaiacol HDO, only two studies used a differential reactor, 17,18 while others employed the integral mode. 13,15,16,[19][20][21] Using guaiacol as a model compound of bio-oil, 27,28 our prior study presents that Pt/AC is an efficient catalyst for guaiacol HDO reaction, providing superior deoxygenation activity at relatively low operating temperature (less than 300 C) and atmospheric pressure. 29 Following this, under integral operating conditions, the reaction kinetics study was carried out, and kinetic parameters such as rate constants and activation energies were obtained for the various reaction steps (see Figure 1).…”

mentioning

confidence: 99%

See 1 more Smart Citation

Refinement of the kinetic model for guaiacol hydrodeoxygenation over platinum catalysts

et al. 2020

View full text Add to dashboard Cite

In our prior work (Ind Eng Chem Res, 2015, 54, 10638‐10644), hydrodeoxygenation (HDO) kinetics of guaiacol, a well‐known model compound of bio‐oil, over Pt/AC (activated carbon) catalysts were investigated under integral operating conditions. It was found that the pseudo‐homogeneous plug‐flow model utilizing these kinetics describes the experimental observations well (with normalized RMS error = 7.6%). In the present work, under differential operating conditions instead, we refine the kinetic model for the same reaction network over the same catalyst. We show that among the five reaction steps in the network, the reaction order of one step differs from our prior work, while the orders remain unchanged for the other four steps. The activation energies of two steps differ from our prior values by 10–15 kJ/mol, and for the other three steps remain essentially consistent with our prior work. The kinetic parameters from the present work are used to predict fixed‐bed reactor performance under integral operating conditions as well. The comparison between experimental and predicted values for both the prior and new sets of data is excellent and even better than our prior model (with reduced normalized RMS error = 4.2%). The kinetic analysis additionally proposed that the direct and indirect pathways of phenol formation from guaiacol HDO depend on guaiacol conversion values. The present work demonstrates that kinetic expressions and parameters obtained from a gradientless differential reactor are more reliable and can be used to successfully predict integral reactor performance data.

show abstract

Activity and selectivity of different base catalysts in synthesis of guaifenesin from guaiacol and glycidol of biomass origin

Cited by 12 publications

References 30 publications

Glycidol syntheses and valorizations: Boosting the glycerol biorefinery

Glycidol syntheses and valorizations: Boosting the glycerol biorefinery

Glycerol Carbonate as a Versatile Alkylating Agent for the Synthesis of β-Aryloxy Alcohols

Refinement of the kinetic model for guaiacol hydrodeoxygenation over platinum catalysts

Contact Info

Product

Resources

About