Kinetic study of the reaction of dimethyl carbonate with trialkylamines

Duane E. Weisshaar; Gary W. Earl; Eric M. Villa; Jessica L. Zierke; Christopher J. Fry; Kara L. Becvar; Shik Ki Li; Matthew C. Schafer

doi:10.1002/kin.20476

Kinetic study of the reaction of dimethyl carbonate with trialkylamines

Duane E. Weisshaar, Gary W. Earl, Eric M. Villa, Jessica L. Zierke, Christopher J. Fry, Kara L. Becvar, Shik Ki Li, Matthew C. Schafer

Research output: Contribution to journal › Article

8 Scopus citations

Abstract

Quaternary ammonium compounds are produced worldwide in hundreds of millions of pound volume annually for a plethora of end-uses from fabric-care formulations to asphalt emulsifiers, typically from nongreen alkylating reagents. The kinetics of a reaction employing dimethyl carbonate (DMC) as a green alkylating agent was investigated using three trialkylamines (tributylamine, trihexylamine, and trioctylamine) at several temperatures. Arrhenius and Eyring analysis of the data showed that values of Ea (79 kJ/mol), ΔH‡ (75 kJ/mol), and ΔS‡ (220 J/(mol K)) were the same for all three amine reactants, consistent with a report that E _a is independent of alkyl chain length when the chain length is greater than three carbons. Although rates are significantly slower with DMC than with other alkylating reagents, the resulting methyl carbonate anion has advantages for clean anion metathesis, which is important for some applications, especially those involving ionic liquids.

Original language	English (US)
Pages (from-to)	221-225
Number of pages	5
Journal	International Journal of Chemical Kinetics
Volume	42
Issue number	4
DOIs	https://doi.org/10.1002/kin.20476
State	Published - Apr 1 2010
Externally published	Yes

All Science Journal Classification (ASJC) codes

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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Weisshaar, D. E., Earl, G. W., Villa, E. M., Zierke, J. L., Fry, C. J., Becvar, K. L., Li, S. K., & Schafer, M. C. (2010). Kinetic study of the reaction of dimethyl carbonate with trialkylamines. International Journal of Chemical Kinetics, 42(4), 221-225. https://doi.org/10.1002/kin.20476

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title = "Kinetic study of the reaction of dimethyl carbonate with trialkylamines",

abstract = "Quaternary ammonium compounds are produced worldwide in hundreds of millions of pound volume annually for a plethora of end-uses from fabric-care formulations to asphalt emulsifiers, typically from nongreen alkylating reagents. The kinetics of a reaction employing dimethyl carbonate (DMC) as a green alkylating agent was investigated using three trialkylamines (tributylamine, trihexylamine, and trioctylamine) at several temperatures. Arrhenius and Eyring analysis of the data showed that values of Ea (79 kJ/mol), ΔH‡ (75 kJ/mol), and ΔS‡ (220 J/(mol K)) were the same for all three amine reactants, consistent with a report that E a is independent of alkyl chain length when the chain length is greater than three carbons. Although rates are significantly slower with DMC than with other alkylating reagents, the resulting methyl carbonate anion has advantages for clean anion metathesis, which is important for some applications, especially those involving ionic liquids.",

author = "Weisshaar, {Duane E.} and Earl, {Gary W.} and Villa, {Eric M.} and Zierke, {Jessica L.} and Fry, {Christopher J.} and Becvar, {Kara L.} and Li, {Shik Ki} and Schafer, {Matthew C.}",

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T1 - Kinetic study of the reaction of dimethyl carbonate with trialkylamines

AU - Weisshaar, Duane E.

AU - Earl, Gary W.

AU - Villa, Eric M.

AU - Zierke, Jessica L.

AU - Fry, Christopher J.

AU - Becvar, Kara L.

AU - Li, Shik Ki

AU - Schafer, Matthew C.

PY - 2010/4/1

Y1 - 2010/4/1

N2 - Quaternary ammonium compounds are produced worldwide in hundreds of millions of pound volume annually for a plethora of end-uses from fabric-care formulations to asphalt emulsifiers, typically from nongreen alkylating reagents. The kinetics of a reaction employing dimethyl carbonate (DMC) as a green alkylating agent was investigated using three trialkylamines (tributylamine, trihexylamine, and trioctylamine) at several temperatures. Arrhenius and Eyring analysis of the data showed that values of Ea (79 kJ/mol), ΔH‡ (75 kJ/mol), and ΔS‡ (220 J/(mol K)) were the same for all three amine reactants, consistent with a report that E a is independent of alkyl chain length when the chain length is greater than three carbons. Although rates are significantly slower with DMC than with other alkylating reagents, the resulting methyl carbonate anion has advantages for clean anion metathesis, which is important for some applications, especially those involving ionic liquids.

AB - Quaternary ammonium compounds are produced worldwide in hundreds of millions of pound volume annually for a plethora of end-uses from fabric-care formulations to asphalt emulsifiers, typically from nongreen alkylating reagents. The kinetics of a reaction employing dimethyl carbonate (DMC) as a green alkylating agent was investigated using three trialkylamines (tributylamine, trihexylamine, and trioctylamine) at several temperatures. Arrhenius and Eyring analysis of the data showed that values of Ea (79 kJ/mol), ΔH‡ (75 kJ/mol), and ΔS‡ (220 J/(mol K)) were the same for all three amine reactants, consistent with a report that E a is independent of alkyl chain length when the chain length is greater than three carbons. Although rates are significantly slower with DMC than with other alkylating reagents, the resulting methyl carbonate anion has advantages for clean anion metathesis, which is important for some applications, especially those involving ionic liquids.

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