Highly selective methoxycarbonylation of aliphatic diamines with methyl phenyl carbonate to the corresponding methyl N-alkyl dicarbamates

Yoshida, Tsutomu; Sasaki, M; Hirata, Fumiaki; Kawamani, Yukio; Inazu, Koji; Ishikawa, Akio; Murai, Kazuhito; Echizen, Tsuneo; Baba, Toshihide

doi:10.1016/j.apcata.2005.04.049

Cited by 9 publications

(4 citation statements)

References 5 publications

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“…Aniline did not react with dimethyl carbonate towards methyl N-phenylcarbamate without a catalyst. This is in accordance with the studies and results presented by other research groups [23,[25][26][27]. Margetić and co-workers found that aromatic amines such as aniline did not react with dimethyl carbonate at room temperature (800 MPa) for 24 hours [23].…”

Section: The Carbamoylation Reactions Of Various Amines With Dmcsupporting

confidence: 80%

“…Aniline did not react with MPC under such conditions. Methoxycarbonylation did not proceed in the absence of catalyst even at a reaction temperature of 180°C [25]. Zhang and co-workers have investigated the reaction of aniline with DMC catalyzed by acid-base bifunctional ionic liquids at 160°C for 4 hours and obtained methyl N-phenyl carbamate with a yield of 8% and methyl N-methyl-Nphenyl carbamate with a yield of 72%.…”

Section: The Carbamoylation Reactions Of Various Amines With Dmcmentioning

confidence: 99%

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Carbamoylation of primary, secondary and aromatic amines by dimethyl carbonate in a flow system over solid catalysts

Litwinowicz

Kijeński

2015

sustain chem process

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Background: Carbamate esters represent an important class of organic compounds which find wide application in chemical industry. Classical procedures for the preparation of carbamates are based on the reaction with a very risky compound -phosgene or phosgene derivatives. Results: A phosgene-free flow-system synthesis of eight carbamates in the reaction of various amines with dimethyl carbonate has been presented. The influence of amine order and structure on their activity in the carbamoylation process was studied. Fe 2 O 3 , Fe 2 O 3 /SiO 2 , Fe 2 O 3 /CoO/NiO/SiO 2 , TZC-3/1 and T-4419 were used as catalysts for the process.

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Section: The Carbamoylation Reactions Of Various Amines With Dmcsupporting

confidence: 80%

Section: The Carbamoylation Reactions Of Various Amines With Dmcmentioning

confidence: 99%

Carbamoylation of primary, secondary and aromatic amines by dimethyl carbonate in a flow system over solid catalysts

Litwinowicz

Kijeński

2015

sustain chem process

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“…To enhance the yield of HDC, the methoxycarbonylation of HDA was also carried out using a Dean-Stark apparatus in the presence of excess of DMC (HDA/DMC/H 2 O = 1/10/ 6 or 1/10/0). The reaction was performed at 25 8C for 2 h and then at a reflux temperature for an additional 2 h with a continuous withdrawal of the co-product CH 3 OH as an azeotrope with DMC from the reaction system.…”

Section: Catalysismentioning

confidence: 99%

Methoxycarbonylation of Aliphatic Diamines with Dimethyl Carbonate Promoted by in situ Generated Hydroxide Ion: A Mechanistic Consideration

et al. 2010

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Abstract:The methoxycarbonylation reactions of aliphatic diamines with dimethyl carbonate are accelerated greatly in the presence of water. Theoretical investigations on the mechanistic aspects of the methoxycarbonylation of 1,6-hexanediamine strongly suggest that the hydroxide ion, generated in situ from the interaction of 1,6-hexanediamine with water, is an active catalytic species and plays a pivotal role in the rate-determining hydrogen abstraction step from the amino group.

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“…The amine carbonylation reaction requires a suitable carbonyl source. Compared with other carbonyl sources like CO, CO 2 , and DMC, alkyl carbamates as carbonyl sources have obvious advantages, such as low toxicity, safety, high reactivity, relatively low price, and difficulty in forming azeotropes with methanol. , In this work, methyl carbamate (MC) was used as a green carbonyl source. The reaction formula of PDA and MC to synthesize PDC is shown in Scheme , and ammonia gas is produced during the reaction.…”

Section: Introductionmentioning

confidence: 99%

Well-Defined CeO₂ as Efficient Catalysts for the Green Synthesis of Pentamethylene Dicarbamate via Carbonylation of 1,5-Pentanediamine with Methyl Carbamate

Wei,

Wang,

Zhang

et al. 2024

Ind. Eng. Chem. Res.

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Bio-based pentamethylene dicarbamate (PDC) belongs to N-substituted carbamates, which are important fine chemicals and organic intermediates. In this work, well-defined CeO 2 rods, cubes, and octahedrons were successfully prepared to catalyze the synthesis of PDC by carbonylation of 1,5-pentanediamine (PDA) with methyl carbamate (MC). Among them, CeO 2 rods with higher amounts of acid−base sites and abundant oxygen vacancies showed superior intrinsic activity in the PDA carbonylation reaction. In situ FTIR results showed that intermediate polyureas were readily formed in the reaction, and then, CeO 2 rods promoted the alcoholysis of polyureas to PDC. In situ DRIFTS results indicated that the surface of CeO 2 rods is more favorable for the adsorption and activation of the reactants. CeO 2 rods can also be used for the efficient synthesis of a series of N-substituted carbamates. We believe that this work will contribute to the efficient, green, and sustainable production of N-substituted carbamates.

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Highly selective methoxycarbonylation of aliphatic diamines with methyl phenyl carbonate to the corresponding methyl N-alkyl dicarbamates

Cited by 9 publications

References 5 publications

Carbamoylation of primary, secondary and aromatic amines by dimethyl carbonate in a flow system over solid catalysts

Carbamoylation of primary, secondary and aromatic amines by dimethyl carbonate in a flow system over solid catalysts

Methoxycarbonylation of Aliphatic Diamines with Dimethyl Carbonate Promoted by in situ Generated Hydroxide Ion: A Mechanistic Consideration

Well-Defined CeO₂ as Efficient Catalysts for the Green Synthesis of Pentamethylene Dicarbamate via Carbonylation of 1,5-Pentanediamine with Methyl Carbamate

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Highly selective methoxycarbonylation of aliphatic diamines with methyl phenyl carbonate to the corresponding methyl N-alkyl dicarbamates

Cited by 9 publications

References 5 publications

Carbamoylation of primary, secondary and aromatic amines by dimethyl carbonate in a flow system over solid catalysts

Carbamoylation of primary, secondary and aromatic amines by dimethyl carbonate in a flow system over solid catalysts

Methoxycarbonylation of Aliphatic Diamines with Dimethyl Carbonate Promoted by in situ Generated Hydroxide Ion: A Mechanistic Consideration

Well-Defined CeO2 as Efficient Catalysts for the Green Synthesis of Pentamethylene Dicarbamate via Carbonylation of 1,5-Pentanediamine with Methyl Carbamate

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Product

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Well-Defined CeO₂ as Efficient Catalysts for the Green Synthesis of Pentamethylene Dicarbamate via Carbonylation of 1,5-Pentanediamine with Methyl Carbamate