The preparation of methylpyridines by catalytic methods

Cullinane, N. M.; Chard, S. J.; Meatyard, R.

doi:10.1002/jctb.5000670405

Cited by 23 publications

(11 citation statements)

References 4 publications

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“…More than sixty years ago, Cullinane et al mentioned the formation of pyridine and derivatives by reacting ammonia, urea or ammonia salts with glycerol for about 10 hours, but the selectivity and yield of pyridine were too low to be applied in industry. 19 Acrolein is an important intermediate in the production of pyridines from formaldehyde and acetaldehyde. Many literature papers have reported that acrolein could be produced from glycerol via a catalytic gas phase dehydration process.…”

Section: Introductionmentioning

confidence: 99%

Towards the sustainable production of pyridines via thermo-catalytic conversion of glycerol with ammonia over zeolite catalysts

Han

Yao

et al. 2015

Green Chem.

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In this study, renewable pyridines could be directly produced from glycerol and ammonia via a thermocatalytic conversion process with zeolites. The major factors, including catalyst, temperature, weight hourly space velocity (WHSV) of glycerol to catalyst, and the molar ratio of ammonia to glycerol, which may affect the pyridine production, were investigated systematically. The optimal conditions for producing pyridines from glycerol were achieved with HZSM-5 (Si/Al = 25) at 550°C with a WHSV of glycerol to catalyst of 1 h −1 and an ammonia to glycerol molar ratio of 12 : 1. The carbon yield of pyridines was up to 35.6%. The addition of water to the feed decreased the pyridine yield, because water competed with glycerol on the acid sites of the catalyst and therefore impacted the acidity of the catalyst. After five reaction/ regeneration cycles, a slight deactivation of the catalyst was observed. The catalysts were investigated by N 2 adsorption/desorption, XRD, XRF and NH 3 -TPD and the results indicated that the deactivation could be due to the structure changes and the acid site loss of the catalyst. The reaction pathway from glycerol to pyridines was studied and the main pathway should be that glycerol was initially dehydrated to form acrolein and some by-products such as acetaldehyde, acetol, acetone, etc., and then acrolein, a mixture of acrolein and acetaldehyde, or other by-products reacted with ammonia to form imines and finally pyridines.

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Section: Introductionmentioning

confidence: 99%

Towards the sustainable production of pyridines via thermo-catalytic conversion of glycerol with ammonia over zeolite catalysts

Han

Yao

et al. 2015

Green Chem.

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“…(mp 133°, lit.6 mp 134°) and Ie (mp 87°, lit.6 mp 85-87°) were prepared by the same procedure as used by de la Mare and co-workers. 5 Reaction of Aniline with .-A side-arm test tube, equipped with thermometer and nitrogen line, was charged with 15 ml of aniline and 2.70 g (10 mmoles) of . The tube was heated in an oil bath maintained at 110°.…”

Section: Nphmentioning

confidence: 99%

The Reaction of Aniline with 1,2,3,4-Tetrachloro-1,2,3,4-tetrahydronaphthalene

Ecke¹,

Zitelli²

1966

J. Org. Chem.

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“…As the previous study showed, using glycerol as feedstock could form many aldehydes that are also the raw materials for the production of pyridines, such as acrolein, acetol, formaldehyde, and acetaldehyde. ,− Thus, it is possible to convert glycerol to synthesis pyridine. Cullinane et al reported the formation of pyridine rings by reacting ammonia with glycerol . Xu et al conducted several experiments to confirm the catalytic activity of HZSM-5, which is a one step process expanding the yield of pyridines, which exhibits an extraordinary application potential for using glycerol to synthesize pyridines. , It was suggested that the dehydration of glycerol, the amination of oxidation products, and the polymerization of imine substances occurred during the pyridine synthesis process.…”

Section: Introductionmentioning

confidence: 99%

“…Cullinane et al reported the formation of pyridine rings by reacting ammonia with glycerol. 30 Xu et al conducted several experiments to confirm the catalytic activity of HZSM-5, which is a one step process expanding the yield of pyridines, which exhibits an extraordinary application potential for using glycerol to synthesize pyridines. 31,32 It was suggested that the dehydration of glycerol, the amination of oxidation products, and the polymerization of imine substances occurred during the pyridine synthesis process.…”

Section: ■ Introductionmentioning

confidence: 99%

Insight into the Mechanism of Glycerol Dehydration and Subsequent Pyridine Synthesis

Jiang

Wang

et al. 2021

ACS Sustainable Chem. Eng.

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In the present study, glycerol was exploited as the feedstock to synthesize pyridine with ammonia gas as a carrier and reactant through thermal conversion. A density functional theory (DFT) at the M06-2X method was applied to understand the mechanism of glycerol dehydration, the ammonization of oxygenated compounds, and the condensation of imines. The results confirmed that glycerol could be directly converted into pyridine in ammonia atmosphere at 550 °C. The overall view of the thermal conversion mechanism of glycerol was compared with the previous experimental data and the proposed mechanisms, which indicated that the neutral glycerol dehydration process should mainly produce acrolein, acetaldehyde, formaldehyde, and acetol. The produced oxygenated compounds (acrolein and acetaldehyde) can react with ammonia to form imine, which would further undergo Michael addition, a Diels-Alder reaction, deammonization, and dehydrogenation to form pyridine. In a catalytic condition, ZSM-5 not only plays a shape-selective effect on the conversion of glycerol to pyridine but also changes the path of the reaction. The structure of ZSM-5 limits the formation of multisubstituted pyridine products, which is beneficial to the formation of pyridine and monosubstituted pyridine. Protonated vinylamine intermediates may be a critical step limiting pyridine yield and selectivity. The kinetic analysis that is based on transition state theory was consistent with product contribution in experiments. The present study confirmed the selectivity and the conversion route of glycerol to pyridine.

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The preparation of methylpyridines by catalytic methods

Cited by 23 publications

References 4 publications

Towards the sustainable production of pyridines via thermo-catalytic conversion of glycerol with ammonia over zeolite catalysts

Towards the sustainable production of pyridines via thermo-catalytic conversion of glycerol with ammonia over zeolite catalysts

The Reaction of Aniline with 1,2,3,4-Tetrachloro-1,2,3,4-tetrahydronaphthalene

Insight into the Mechanism of Glycerol Dehydration and Subsequent Pyridine Synthesis

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