Abstract
Preparation of quaternary ammonium compounds from various tertiary amines and the (environmentally friendly) alkylating agent dimethyl carbonate (DMC) under conditions within the bounds of industrial production has been carried out. After unsuccessful attempts to catalyze and entrain the process, the reaction has been accelerated by using a 10-fold excess of alkylating agent. The recovered DMC and solvent have been recycled in up to five subsequent batches without loss of rate or yield. The expected steric hindrance effects on the rate were evidenced by comparison of the half-lives of dihydrogenatedtallowmethylamine (1 h), tributylamine (4 h), and the ester quat (7.5h). The product methyl carbonate quaternaries have been shown to be noncorrosive to 316 stainless steel for extended periods at elevated temperatures.
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Abbreviations
- DHTMA:
-
dihydrogenatedtallowmethylamine
- DMC:
-
dimethyl carbonate
- FT:
-
Fourier transform
- GC:
-
gas chromatography
- IR:
-
infrared
- MS:
-
mass spectrometry
- NMR:
-
nuclear magnetic resonance
- PMC:
-
phenylmethyl carbonate
References
Friedli, F.F., R. Keys, C.J. Toney, O. Portwood, D. Whittlinger, and M. Doeri, Ester Quaternaries for Improved Benefits in Rinse Cycle Fabric Solfteners, J. Surfact. Deterg. 4:401 (2001).
Menschutkin, N., Beiträgen zur Kenntnis der Affinitätskoeffizienten der Alkylhaloide und der organischen Amine, Z. phys. Chem. 5:589 (1890) and über die Affinitätskoeffizienten der Alkylhaloide und der Amine, Z. Phys. Chem. 6:41 (1890).
Walden, I., Organic Solvent and Ionizing Agents, Part X:Solvent Power and Dielectric Constant, Z. Phys. Chem. 55:698 (1906).
Abraham, M.H., Solvent Effects on Transition States and Reaction Rates, Prob. Phys. Org. Chem. 11:1 (1974).
Abraham, M.H., and P.L. Grellier, Substitution at Saturated Carbon. Part XX. The Effect of 39 Solvents on the Free Energy of Triethylamine, Ethyl Iodide and the Triethyl-Ethyl Iodide Transition State Comparisons, J. Chem. Soc., Perkin Trans. 2:1735 (1976).
Abraham, M.H., Substitution at Saturated Carbon. Part XIV. Solvent Effects on the Free Energies of Ions, Ion-pairs, Non-electrolytes, and Transition States in Some SN and SE Reactions, J. Chem. Soc., Perkin Trans. 2:1343 (1972).
Abraham, M.H., Substitution at Saturated Carbon, Part VIII. Solvent Effects on the Free Energy of Trimethyl Amine, the Nitrobenzyl Chloride and the Trimethyl Amine-Nitrobenzyl Chloride Transition States, J. Chem. Soc. B:299 (1971).
Abraham, M.H., Solvent Effects on the Free Energies of the Reactants and Transition States in the Menschutkin Reaction of Trimethylamine with Alkyl Halides, Chem. Commun.:1307 (1969).
Abraham, M.H., Ionic Entropy of Transfer from Water to Nonaqueous Solvents: Can Primary Alkyl Halides Hydrolyze by the Ion-Pain Mechanism? J. Chem. Soc., Faraday Trans. 1:1375 (1973).
Earl, G., Imidazoline Surfactants, in Cationic Surfactants, edited by J. Richmond, Marcel Dekker, New York, 1990, Surfactant Science Series Vol. 34, p. 107.
Werntz, J.H., Monoquaternay Ammonium Carbonates, U.S. Patent 2,635,100 (1953).
Romano, U., and P. Zani, Quaternization with Methyl Carbonate, Italian Patent Appl. 21878 A/82 (1982).
Mauri, M., U. Romano, and F. Rivetti, Dimethyl Carbonate: A New Building Block for Organic Chemicals Production, Ing. Chim. Ital. 21:6 (1985).
Rivetti, F., and U. Romano, Alcohol Carbonylation with Palladium(II) Complexes, J. Organometal. Chem. 174:221 (1979).
Tundo, P., and M. Selva, The Chemistry of Dimethyl Carbonate, Acc. Chem. Res. 35:706 (2002).
Mori, S., I. Ida, M. Ue, and U. Makoto, Process for Producing Quaternary Salts, U.S. Patent 4,892,944 (1990).
Cross, J.T.D., R. Hunter, and V.R. Stimson, The Thermal Decomposition of Simple Carbonate Esters, Aust. J. Chem. 29:1477 (1976).
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Earl, G.W., Weisshaar, D.E., Paulson, D. et al. Quaternary methyl carbonates: Novel agents for fabric conditioning. J Surfact Deterg 8, 325–329 (2005). https://doi.org/10.1007/s11743-005-0363-1
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DOI: https://doi.org/10.1007/s11743-005-0363-1