Abstract

Glycerol is a non-toxic, non-hazardous, non-volatile, biodegradable, and recyclable liquid that is generated as a byproduct in the manufacture of biodiesel fuel from vegetable oils. Due to its easy availability, along with its unique combination of physical and chemical properties, glycerol has recently emerged as an economically appealing and safe solvent for organic synthesis. Recent works have also demonstrated that glycerol can be used as a hydrogen source in metal-catalyzed transfer hydrogenation of organic compounds, such as aldehydes, ketones, olefins and nitroarenes. Herein, the advances reached in this emerging field are reviewed. The utility of glycerol as solvent and reducing agent for the generation of metal nanoparticles is also briefly discussed.

Highlights

  • The impressive and fast development of the biodiesel industries has led to a large surplus of glycerol since about 100 kg of this byproduct are formed per ton of biodiesel (Scheme 1)

  • According to recent estimates [1], world-wide production of glycerol could have reached 2 million tons in 2010 and it is expected to grow in the near future due to the increasing demand for biodiesel, as well as the emergence of other large-scale processes based on the conversion of cellulose and lignocelluloses in which glycerol is a byproduct

  • The current body of work in the field is still very limited, from the studies published in the last three years it becomes apparent that this waste generated by the biodiesel industry can be a reliable alternative to replace 2-propanol in the near future

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Summary

Introduction

The impressive and fast development of the biodiesel industries has led to a large surplus of glycerol since about 100 kg of this byproduct are formed per ton of biodiesel (Scheme 1). Its renewable origin and unique combination of physicochemical properties, such as high polarity, low toxicity and flammability, high boiling point, ability to form strong hydrogen bonds and to dissolve both organic and inorganic compounds (salts, acids, bases and transition metal complexes), make glycerol a good candidate to be employed as green reaction medium for synthetic chemistry [28] This innovative way to revalorize glycerol has been very well received by the chemical community and a wide variety of organic reactions and synthetic methodologies have been successfully developed in this medium in recent years [29,30,31,32,33].

Transfer Hydrogenation of Carbonyl Compounds in Glycerol
Transfer Hydrogenation of Olefins in Glycerol
Transfer Hydrogenation of Nitroarenes in Glycerol
Transfer Hydrogenation of Other Organic Molecules in Glycerol
Glycerol as Solvent and Reductant for the Formation of Metal Nanoparticles
Findings
Conclusions and Perspectives
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