A Convenient Synthesis of Quaternary Ammonium Gemini Surfactants from Long-Chain Alkyldimethylamines and Epichlorohydrin

Abstract

Aqueous micellar systems proved to be an excellent reaction medium for the selective synthesis of bis-quaternary ammonium salts 5a-c from epichlorohydrin 2 and long-chain alkyldimethylamines 1a-c, in the presence of the corresponding amine chlorohydrates 3a-c as functional surfactants. Unlike alcohol or alcohol-water mixtures as reaction medium, mono-quaternary ammonium salts 4a-c were formed, if any, in very small amounts under micellar conditions, allowing a more direct and rapid access to these quaternary ammonium gemini surfactants.

gemini surfactants - bis-quaternary ammonium compounds - epichlorohydrin - quaternization - micellar system

References and Notes

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8

Compounds 4a-c and 5a-c have been isolated in a pure analytical form and their spectral data (¹H NMR and ¹³C NMR) were consistent with the structure. Spectral data for 4b and 5b are in full agreement with those previously reported in ref. [5] Isolated yields were slightly lower (6-8%) than those obtained by the combined technique based on the combined HPLC and colorimetric methods described in ref. [9]

9a

Simultaneous determination of mono- and bis-quaternary salts 4a-c and 5a-c from crudes of reaction by ion-exchange HPLC was not successful due to the unacceptable reproducibility. We overcame these difficulties by combining reversed-phase ion-pair HPLC using sodium p-toluen-sulfonate as UV-absorbing ion-pair reagent, and UV quantification of quaternary ammonium-bromophenol blue complexes extracted with chloroform from a mixture of a suitable aliquot of the reaction mixture in alkaline solution (10% sodium carbonate) and bromophenol blue (0.001 N). After comparison with standard mixtures, the experimental error was found to be about 2-3%.

9b The HPLC method was based on that of: Dowle CJ. Campbell WC. Analyst  1989,  114:  883 

9c The colorimetric determination method was based on that of: van Steveninck J. Maas M. In Cationic Surfactants, Surfactant Science Series   Vol. 4:  Jungermann E. Marcel Dekker, Inc.; New York: 1970.  Chap. 13.

10

A typical procedure was as follows. A stirred solution of N,N-dimethyloctylamine(1a) (1.26 g, 8 mmol) and N,N-dimethyloctylamine hydrochloride (3a, 0.78g, 4 mmol) in of ethanol-water (80:20, 5 mL) mixture was heated until complete dissolution at 50 °C. The epichlorohydrin (2, 0.37g, 4 mmol) was then added under vigorous agitation. After being stirred for 8-10 hours, the reaction mixture was immediately cooled and the solvent was removed under vacuum at room temperature. The residue was washed with acetone, and the quaternary ammonium salts were isolated by recrystallization from acetone. It afforded the mono-quaternary ammonium salt 4a (0.96 g, 84% isolated yield, 90% analytical yield). The bis-quaternary ammonium salt 5a (1.53 g, 87% isolated yield, 92% analytical yield), was obtained by performing the reaction with the same amount of reagents and solvent, at 80 °C.

11

A typical procedure was as follows. A stirred solution of N,N-dimethyloctylamine hydrochloride (3a, 2.36 g, 12.4 mmol) in water (5 mL) was heated until complete dissolution at 50 °C. A mixture of N,N-dimethyloctylamine (1a, 1.26 g 8 mmol) and epichlorohydrin (2, 0.37 g, 4 mmol) was then added at once under vigorous agitation, with spontaneous micellization. The solution was stirred for 6-8 hours. After evaporation of the solvent under vacuum at room temperature, the residue was washed with acetone and the quaternary ammonium salts were isolated by recrystallization from acetone. It afforded the bis-quaternary ammonium salt 5a (1.48 g, 84% isolated yield, 88% analytical yield), instead of the mono-quaternary ammonium salt 4a, as described in ref. [9] There was no problem to separate the surfactants 5a-c from the excess of 3a-c because these amine hydrochlorides are soluble in cold acetone, while the bis-quaternary ammonium salts are insoluble ones.

12 Hartley GS. Q. Rev. (London)  1948,  2:  152 

13 McKelvey JB. Benerito RR. Ward TL. I and EC Product Research and Development  1967,  6:  115