Synthesis of pyrazinyl compounds from glycerol and 1,2-propanediamine over Cu–TiO2 catalysts supported on γ-Al2O3

Li, Xue; Xu, Chenghua; Liu, Chuan-Qi; Chen, Yu; Liu, Jianying

doi:10.1016/j.cclet.2013.04.010

Cited by 5 publications

(5 citation statements)

References 10 publications

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“…The latter then undergoes self-condensation into bis(2-methylpyrazine)ether ( 62 ), and disproportionation of 62 into 2-methylpyrazine ( 24 ) and pyrazinaldehyde ( 63 ). Pyrazinaldehyde is then hydrogenated back into 61 (Scheme a). − For the preparation of 2,6-dimethylpyrazine ( 66 ) from glycerol and 1,2-propanediamine ( 64 ), another mechanism was proposed: it involved the dehydration of GL into hydroxyacetone ( 29 ), followed by the condensation of 29 and 64 , and a final dehydrogenation of intermediate 65 into 66 (Scheme b). − …”

Section: Upgrading Of Polyolsmentioning

confidence: 99%

“…Similarly, 66 was obtained from the gas-phase reaction between glycerol and 1,2-propanediamine ( 64 ), over CuO-CuCr 2 O 4 , , CuCr 2 O 4 , Zn/CuCr 2 O 4 , Cu-TiO 2 /Al 2 O 3 , and ZnO-ZnCr 2 O 4 catalysts, at high temperatures (350–380 °C) under atmospheric pressure. It was evidenced that catalysts possessing a high metallic Cu surface area, along with a combination of moderate Lewis acid sites and strong basic sites, were favorable for 2,6-dimethylpyrazine formation.…”

Section: Upgrading Of Polyolsmentioning

confidence: 99%

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Continuous Flow Upgrading of Selected C₂–C₆Platform Chemicals Derived from Biomass

et al. 2020

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The ever increasing industrial production of commodity and specialty chemicals inexorably depletes the finite primary fossil resources available on Earth. The forecast of population growth over the next 3 decades is a very strong incentive for the identification of alternative primary resources other than petro-based ones. In contrast with fossil resources, renewable biomass is a virtually inexhaustible reservoir of chemical building blocks. Shifting the current industrial paradigm from almost exclusively petro-based resources to alternative bio-based raw materials requires more than vibrant political messages; it requires a profound revision of the concepts and technologies on which industrial chemical processes rely. Only a small fraction of molecules extracted from biomass bears significant chemical and commercial potentials to be considered as ubiquitous chemical platforms upon which a new, bio-based industry can thrive. Owing to its inherent assets in terms of unique process experience, scalability, and reduced environmental footprint, flow chemistry arguably has a major role to play in this context. This review covers a selection of C2 to C6 bio-based chemical platforms with existing commercial markets including polyols (ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerol, 1,4-butanediol, xylitol, and sorbitol), furanoids (furfural and 5-hydroxymethylfurfural) and carboxylic acids (lactic acid, succinic acid, fumaric acid, malic acid, itaconic acid, and levulinic acid). The aim of this review is to illustrate the various aspects of upgrading bio-based platform molecules toward commodity or specialty chemicals using new process concepts that fall under the umbrella of continuous flow technology and that could change the future perspectives of biorefineries.

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Section: Upgrading Of Polyolsmentioning

confidence: 99%

Section: Upgrading Of Polyolsmentioning

confidence: 99%

Continuous Flow Upgrading of Selected C₂–C₆Platform Chemicals Derived from Biomass

et al. 2020

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“…Nowadays, direct transformation of polyols to N -containing compounds mainly relies on utilization of reactive acrolein and hydroxyacetone (HA) intermediates, which are usually generated from dehydration of glycerol at temperatures higher than 350 °C (Figure a). ,, A variety of N -containing compounds, such as acrylonitrile, , amines, pyridines, , quinolines , and pyrazines, − have been exploited via this dehydration-amination approach, but suffering from relatively low efficiency in glycerol’s carbon utilization. Compared with the dehydration route, the dehydrogenation route for polyols valorization seems more appealing, given that the transformation can smoothly occur at much lower temperature (<200 °C) to generate reactive pyruvaldehyde (PA) intermediate accompanied by an additional valuable hydrogen molecule.…”

Section: Introductionmentioning

confidence: 99%

Efficient Production of Valuable Aromatic N-Heterocycles from Bio-Polyols by Heterogeneous Catalysis via Controlling Unstable Intermediate Conversion

Xiao

2023

ACS Sustainable Chem. Eng.

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Efficient and controllable conversion of renewable polyols to valuable N-containing products by heterogeneous catalysis, especially under relativley mild conditions (<200 °C), remains a significant challenge. Here, we develop a method for one-step efficient production of 2-methylquinoxalines (2-MQs), a type of high-value aromatic N-heterocycles, directly from polyols in the presence of supported Pt dehydrogenation catalyst through controllably in situ trapping reactive pyruvaldehyde (PA) intermediate by aryl-1,2-diamine at the temperature of only 140 °C. The presence of aryl-1,2-diamine not only enabled the formation of 2-MQs, but also markedly enhanced the polyols’ carbon utilization to near-quantitative (>98 C%) level. More importantly, organic solvent-enabled kinetics control of competitive reactions associated with PA transformation, i.e., the condensation with aryl-1,2-diamine to produce 2-MQs and the Cannizzaro reaction to form lactic acid, allowed to access the desired 2-MQs in a controllable manner with yields ranging from 12 C% to 81 C%. The application of this approach to attain diverse 2-MQs and analogues of interest in pharmaceutical industry has been demonstrated.

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“…In the same way, a growing body of literature has recently started to examine the use of glycerol and glycerol derivatives as a carbon source to produce N-heterocycles. Some reports on pyridine synthesis that have been already mentioned [249][250][251][252], the oxazoline [279] and 3-methylindole [280] syntheses, processes to produce pyrazinyl compounds [281][282][283][284][285][286][287] [275,276].…”

Section: N-heterocyclesmentioning

confidence: 99%

“…Also, Venugopal's team worked with several MxOy-MCr2O4 systems to synthesize 2,6dimethylpyrazine from 1,2-propanediamine and glycerol, concluding that the system CuO-CuCr2O4 (Cu:Cr molar ratio equal to 2) was able to yield 68% of 2,6dimethylpyrazine at 350 ºC [283][284][285]. In addition, M-ZnO/Al2O3 (M: Zr, Ce, Ca, Mn, Mo) [282] and Cu-TiO2/Al2O3 [287] have been reported to achieve good yields of a mixture of pyrazine-type compounds at 380 ºC.…”

Section: Pyrazines: Applications and Synthesismentioning

confidence: 99%

Catalytic transformations of glycerol via hydroxyacetone into nitrogen heterocycles of industrial interest

Santa-Pau¹

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A lo largo de la lectura de la presente tesis, se le hará evidente al lector el hecho de que este trabajo se sustenta en el esfuerzo, dedicación y apoyo que otras muchas personas le han brindado al autor del mismo para que pudiera llevarlo a cabo de forma exitosa. Por ello, en estas líneas, me gustaría agradecer a todos aquellos que, de una u otra manera me han brindado a mí o a la presente tesis doctoral cualquier tipo de ayuda, personal o profesional, que haya quedado reflejada en mayor o menor medida en cualquiera de las líneas expuestas en el documento que se presenta a continuación. Pido disculpas de antemano por los muchos nombres que se me olvidarán, pero a todos, sabed que os estoy infinitamente agradecido.En primer lugar, debo dar las gracias a mi director de Tesis el Dr. Marcelo E. Domine por su apoyo y confianza desde nuestra primera reunión en septiembre de 2015, por haber visto en mí alguien en que merecía la pena apostar, y por seguir considerándolo así hasta el día de hoy. Por sus consejos, enseñanzas y, en especial, su paciencia conmigo durante todos estos años.En segundo lugar, a la Profesora Patricia Concepción y al doctor Yannick Mathieu.Gracias por toda vuestra ayuda y por todo el conocimiento que habéis volcado en mí.Siempre os voy a considerar referentes y espero teneros siempre cerca, para seguir aprendiendo y, lo más importante, disfrutando de vuestras opiniones, de vuestros consejos y de nuestras discusiones.A los doctores Pascual Oña-Burgos, Daniel Delgado y Luis Miguel Martínez-Prieto (aquí también debo incluir a Yannick). A lo largo de estos años son incontables los momentos que hemos compartido. Vuestro entusiasmo, vuestra pasión a la hora de entender esta profesión han sido, en muchos momentos, la verdadera fuerza motriz de esta Tesis Doctoral. Cada ratito con vosotros ha alimentado mi motivación, gracias además por vuestro cariño y apoyo. He tenido mucha suerte de encontrarme unos amigos tan buenos.A Silvia, una amiga excepcional, siempre dispuesta a escucharme, a apoyarme y a ayudarme. Uno de los grandes tesoros producidos, mejor dicho, descubiertos, en estos años.

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Synthesis of pyrazinyl compounds from glycerol and 1,2-propanediamine over Cu–TiO2 catalysts supported on γ-Al2O3

Cited by 5 publications

References 10 publications

Continuous Flow Upgrading of Selected C₂–C₆Platform Chemicals Derived from Biomass

Continuous Flow Upgrading of Selected C₂–C₆Platform Chemicals Derived from Biomass

Efficient Production of Valuable Aromatic N-Heterocycles from Bio-Polyols by Heterogeneous Catalysis via Controlling Unstable Intermediate Conversion

Catalytic transformations of glycerol via hydroxyacetone into nitrogen heterocycles of industrial interest

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Synthesis of pyrazinyl compounds from glycerol and 1,2-propanediamine over Cu–TiO2 catalysts supported on γ-Al2O3

Cited by 5 publications

References 10 publications

Continuous Flow Upgrading of Selected C2–C6Platform Chemicals Derived from Biomass

Continuous Flow Upgrading of Selected C2–C6Platform Chemicals Derived from Biomass

Efficient Production of Valuable Aromatic N-Heterocycles from Bio-Polyols by Heterogeneous Catalysis via Controlling Unstable Intermediate Conversion

Catalytic transformations of glycerol via hydroxyacetone into nitrogen heterocycles of industrial interest

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Product

Resources

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Continuous Flow Upgrading of Selected C₂–C₆Platform Chemicals Derived from Biomass

Continuous Flow Upgrading of Selected C₂–C₆Platform Chemicals Derived from Biomass