• Journal of Integrative Natural Science
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• v.10 no.4
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• pp.175-191
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• 2017

In organic chemistry amide synthesis is performed through condensation of a carboxylic acid and an amine with releasing one equivalent of water via the corresponding ammonium carboxylate salt. This method is suffering from tedious processes and poor atom-economy due to the adverse thermodynamics of the equilibrium and the high activation barrier for direct coupling of a carboxylic acid and an amine. Most of the chemical approaches to amides formations have been therefore being developed, they are mainly focused on secondary amides. Direct carbonylations of tertiary amines to amides have been an exotic field unresolved, in particular direct carbonylation of trimethylamine in lack of commercial need has been attracted much interests due to the versatile product of N,N-dimethylacetamide in chemical industries and the activation of robust N-C($sp^3$) bond in tertiary amine academically. This review is focused mainly on carbonylation of trimethylamine as one of the typical tertiary amines by transition metals of cobalt, rhodium, platinum, and palladium including the role of methyl iodide as a promoter, the intermediate formation of acyl iodide, the coordination ability of trimethylamine to transition metal catalysts, and any possibility of CO insertion into the bond of Me-N in trimethylamine. In addition reactions of acyl halides as an activated form of acetic acid with amines are reviewed in brief since acyl iodide is suggested as a critical intermediate in those carbonylations of trimethylamine.

• Clean Technology
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• v.22 no.3
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• pp.196-202
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• 2016

In this study, ceria- based catalysts were prepared for dimethyl carbonate (DMC) synthesis and reaction conditions were evaluated for finding the optimal reaction route. In order to find optimal catalysts for DMC synthesis, calcination temperature and Cu(II) impregnation amount were evaluated. The oxidative carbonylation using methanol, carbon monoxide and oxygen and the direct synthesis using methanol and carbon dioxide were introduced for producing DMC. Following the law of Le Chatelier, the dehydration reaction was applied for enhancing the reactivity (methanol conversion) as removing water during the reaction. 2-cyanopyridine, as a chemical dehydration agent, was used. In the case of the oxidative carbonylation, methanol conversion rate increased from 15.1% to 38.7% and the DMC selectivity increased from 0% to 98.8%. In the case of the direct synthesis, methanol conversion rate increased from 1.0% to 77.8% and the DMC selectivity increased from 41.2% to 100.0%.

• Korean Chemical Engineering Research
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• v.50 no.3
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• pp.417-420
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• 2012

This study is about reduction reaction making 2, 4-dinitrotoluene (2, 4-DNT) to 2, 4-toluene diisocyanate (2,4-TDI) with Pd/$SiO_2$. Catalytic systems based on Pd/$SiO_2$ at about $200^{\circ}C$ and under 100 bars of carbon monoxide. We studied the effect of pyridine on the yield of the TDI. TDI was not created without pyridine, but created with pyridine, at the reaction result. According to research, homogeneous synthesis of TDI with direct carbonylation, palladium and pyridine complexion is known to catalyze. When adding pyridine the reason of TDI synthesis is palladium leaching, ICP-AES was performed to confirm it. As a result, the proportion of Pd loaded in $SiO_2$ was decreased 52% than before, after the reaction by adding 20 vol% pyridine. Generating TDI by adding pyridine might be the effect of the complex ion, which is composed of leached palladium and pyridine.

• Clean Technology
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• v.14 no.3
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• pp.160-165
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• 2008

The synthesis of dimethyl carbonate (DMC) with Cu catalysts was investigated in a semi-batch high-pressure reactor. DMC was synthesized via the direct oxidative carbonylation of carbon monoxide with oxygen in methanol. The corrosion rate was evaluated fie the weight change for SUS test pieces which had been added into the reactor. In order to reduce the corrosion rate without significantly losing DMC yield, various additives such as amines, olefins, and other metal salts were used. When 1-methylimidazole was used as an additive, 18.6% of DMC yield could be obtained without corrosion. If the amount of 1-methylimidazole was decreased, a high DMC yield (33.2%) could be obtained with a low corrosion rate (0.5%).