One-Pot Synthesis of Methyl-Substituted Benzenes and Methyl-Substituted Naphthalenes from Acetone and Calcium Carbide

Wang, Dong; Liu, Zhenyu; Liu, Qingya

doi:10.1021/acs.iecr.9b00175

Cited by 22 publications

(11 citation statements)

References 39 publications

(62 reference statements)

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“…They could also be prepared by p -isopropyltoluene or benzene/xylene hydroxylation. − However, some strong acids, such as H 2 SO 4 , may be involved in these methods, thus leading to high cost and causing damage to the environment. In addition, MPs could be produced by isophorone transformation, which also has low MPs yield with mesitylene as the main byproduct . Therefore, it is urgent to find a new way to produce MPs efficiently.…”

Section: Introductionmentioning

confidence: 99%

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Facile Preparation of Methyl Phenols from Ethanol over Lamellar Ce(OH)SO₄·xH₂O

Guo

Feng

et al. 2021

ACS Catal.

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Ethanol transformation with high product selectivity is a great challenge, especially for high weight molecules. Here, we show a combination study of kinetic, thermodynamic, and in situ spectroscopy measurements to probe the selective upgrading of ethanol over lamellar Ce(OH)SO 4 •xH 2 O catalysts, with 60− 70% Ce 3+ preserved during the catalysis. High methyl phenols (MPs) selectivity at ∼80% within condensation products was achieved at ∼50% condensation yield (3.0 kPa C 2 H 5 OH, 15 kPa H 2 , Ar balanced, 693 K, 1 atm, gas hourly space velocity (GHSV) ∼5.4 min −1 ), with acetaldehyde, acetone, 4-heptanone, and 2pentanone as the key reaction intermediates. Kinetic measurements with the assistance of isotope labeling proved that MPs generated from the kinetically relevant step (KRS) of C−C bond coupling of enolate nucleophilically attacks surface C 2 H 4 O following a Langmuir−Hinshelwood model. Low ethanol and water pressures and high acetaldehyde and hydrogen pressures were proved to be favored for MPs generation rather than dehydration, in which hydrogen could reduce the amount of lattice oxygen and facilitate the preparation of MPs while water and ethanol both compete with acetaldehyde for active sites during catalysis. On the basis of in situ X-ray diffraction (XRD), quasi-in situ X-ray photoelectron spectroscopy (XPS), and Raman characterizations, the Ce(OH)SO 4 crystal structure was proved to be maintained along with ethanol activation, and the Ce 3+ −OH Lewis acid−base pair was proved to be the active species for the selective C−C bond coupling. The KRS assumption was also supported by the apparent activation energy assessment within the reaction network on dehydration, dehydrogenation, aldol condensation, and cyclization and a series of negligible kinetic isotope effects (KIEs). This system can be easily extended to some other systems related to C−C bond coupling and is attracting attention on converting oxygenate platform molecules over lanthanide species.

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Section: Introductionmentioning

confidence: 99%

“…In addition, MPs could be produced by isophorone transformation, which also has low MPs yield with mesitylene as the main byproduct. 17 Therefore, it is urgent to find a new way to produce MPs efficiently.…”

Section: Introductionmentioning

confidence: 99%

Facile Preparation of Methyl Phenols from Ethanol over Lamellar Ce(OH)SO₄·xH₂O

Guo

Feng

et al. 2021

ACS Catal.

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“…[ 24 ] Interestingly, the reaction of acetone with calcium carbide in the presence of a base at 200–300 °C affords aromatic hydrocarbons and phenols instead of propargylic alcohols. [ 25 ]…”

Section: A Map Of Calcium Carbide Synthetic Transformationsmentioning

confidence: 99%

Calcium Carbide: Versatile Synthetic Applications, Green Methodology and Sustainability

et al. 2020

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Acetylene is a key building block for organic chemistry and potentially can be involved in a diverse range of synthetic transformations. However, critical analysis of practical considerations showed that application of gaseous acetylene in regular synthetic labs encounters a number of difficulties. Safety limitations due to flammable and explosive nature of gaseous acetylene and requirements for specialized high‐pressure equipment impose serious drawbacks. Typical reaction conditions involve excess of gaseous reactant, which is simply released to the atmosphere at the end of the reaction, thus generating waste and causing contamination. Calcium carbide brings a new green and sustainable wave into powerful alkyne transformations and significantly expands the repertoire of traditional acetylene chemistry. The novel trend of using calcium carbide instead of gaseous acetylene is synthetically beneficial and opens a novel reactivity for the C≡C unit. This review highlights recent advances in carbide chemistry, demonstrates its advantages and prospects in term of green synthetic approach.

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“…Acetone can be transformed into products with higher molecular weights by acid or base catalysts. 14–20 Typically, basic catalysts can catalyze the production of phorone 17 and acid catalysts can catalyze the production of mesitylene. 14 Both products are nine carbon-containing products.…”

mentioning

confidence: 99%

“…21 Various catalysts such as hydrotalcite, mixed metal oxides, Nb 2 O 5 , and zeolites are active for the conversion of acetone to mesitylene. 14–20 However, the mesitylene yield over these catalysts is normally less than 60%, which is a great challenge for the practical conversion of acetone to biofuels.…”

mentioning

confidence: 99%