DOI: 10.1002/slct.

201900240 Full Papers

1
2 z Organic & Supramolecular Chemistry
3
4
5
Synthesis of Imidazolium Derivatives Comprising a Fatty
6 Acid Methyl Ester Structure
7
8 Sebastian Walther and Veronika Strehmel*[a]
9
10
11 The synthesis of new imidazolium derivatives is discussed in imidazole substituent using benzyl bromide was carried out on
12 this work that are substituted with a fatty acid methyl ester the other hand. Halide exchange by bis(trifluoromethylsulfonyl)
13 structure. These new compounds were made from methyl imide resulted in two new imidazolium compounds comprising
14 oleate. The synthetic way started with epoxidation of methyl a fatty acid methyl ester structure. These new imidazolium
15 oleate followed by epoxy ring opening reaction using compounds exhibit low glass transition temperatures that are
16 imidazole. 4-Iodomethyl styrene was used for quaternization of typical for ionic liquids. They may be interesting as surfactants,
17 the resulting imidazole substituent bound at the fatty acid as starting materials for polyelectrolyte manufacturing, as
18 methyl ester on the one hand. Reaction of the hydroxy group barrier materials for coatings, and as source for N-heterocyclic
19 with methacrylic anhydride followed by quaternization of the carbenes.
20
21
22 Introduction Results and Discussion
23
Oleic acid is one of the most abundant fatty acids available in Oleic acid is converted in methyl oleate by esterification with
24
many vegetable oils. It is a cis-configurated olefin, which allows methanol.[12,6] Further conversion of methyl oleate is epoxida-
25
the application of known chemical reactions, such as epoxida- tion of the double bond.[1,2,6] Although esterification of oleic
26
tion, hydrogenation, and ozonolysis.[1–5] In the previous work, acid and epoxidation of the resulting methyl oleate followed
27
we used epoxidation followed by epoxy ring opening reaction by epoxy ring opening reaction with (meth)acrylic acid are well
28
with (meth)acrylic acid to receive functionalized methyl described in the literature, the reaction of the internal epoxy
29
oleates.[6] group with imidazole has received only less attention.[1,2,6,10,12]
30
Although the ring opening reaction of terminal epoxy On the other hand, imidazole reacts well with terminal epoxy
31
groups with imidazole is well described in the literature, only groups.[7–9] The reaction of 9,10 epoxy methyl oleate with
32
one source describes the ring opening reaction of 9,10 epoxy imidazole results in 9-hydroxy-10-(1H-imidazol-1-yl) methyl
33
methyl stearate with imidazole to the best of our octadecanoate (1 a) and the corresponding isomer 1 b
34
knowledge.[7–10] Furthermore, heterocyclic fatty acid com- (Scheme 1: reaction a). The isomers 1 a and 1 b are the starting
35
pounds with tetrazole structures were described as pharmaco- material for further functionalization (Scheme 1). This function-
36
logically interesting materials.[11] alization includes the reaction of the OH group with meth-
37
In this work, we describe the ring opening reaction of 9,10 acrylic anhydride resulting in 9-(methacryloyloxy)-10-(1H-Imida-
38
epoxy methyl stearate with imidazole followed by quaterniza- zol-1-yl) methyl octadecanoate (2 a) and the corresponding
39
tion of the imidazole ring using 4-iodomethyl styrene on the isomer 2 b (Scheme 1: reaction b) and quaternization of the
40
one hand, and esterification of the hydroxy group with imidazole substituent of 2 a and 2 b with benzyl bromide that
41
methacrylic anhydride followed by quaternization of the gives 1-(10-(methacryloyloxy)-18-methoxy-18-oxo-octadecan-9-
42
imidazole substituent with benzyl bromide on the other hand. yl)-3-benzyl-1H-imidazolium bromide (3 a) and isomer 3 b
43
Exchange of bromide and iodide, respectively of the resulting (Scheme 1: reaction c).
44
new imidazolium compounds using lithium bis(trifluoromethyl- Furthermore, the isomers 1 a and 1 b were quaternized with
45
sulfonyl)imide resulted in formation of two new glass forming 4-iodomethyl styrene, which was made from 4-vinylbenzyl
46
ionic liquids with low glass transition temperatures. chloride and potassium iodide.[13] This resulted in 1-(10-
47
hydroxy-18-methoxy-18-oxo-octadecan-9-yl)-3-(4-vinylbenzyl)-
48
1H-imidazolium iodide (4 a) and isomer 4 b as described in
49
Scheme 1, reaction d. The isomers 3 a and 3 b as well as 4 a and
50 [a] Dr. S. Walther, Prof. Dr. V. Strehmel
Faculty of Chemistry, Institute for Coatings and Surface Chemistry, 4 b contain the imidazolium structures directly bond at the
51
Niederrhein University of Applied Sciences, Adlerstrasse 32, D-47798 fatty acid methyl ester. Although the yield on the isomers 1 a
52 Krefeld, Germany and 1 b is only 30% after purification by crystallization, it is
53 E-mail: veronika.strehmel@hsnr.de
significantly higher for the consecutive functionalization steps
54 Homepage: https://web.hs-niederrhein.de/chemie/personen/prof-dr-ver-
onika-strehmel resulting in formation of 2–4 (Table 1). These compounds
55
Supporting information for this article is available on the WWW under consist of isomers assigned as a and b. The new ionic liquids 5
56
https://doi.org/10.1002/slct.201900240 and 6 were obtained in sufficient yield by counter ion
57

ChemistrySelect 2019, 4, 4679 – 4681 4679 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Full Papers
isomers 5 a/5 b and 6 a/6 b, respectively as depicted in
1
Scheme 2.
2
All functionalized compounds (1 - 6) consisting of isomers
3
were made using methyl oleate as starting material. All
4
compounds were analyzed by IR, 1H and 13C NMR spectroscopy.
5
The spectra are depicted in the Supporting Information.
6
Though the adjacent structures are similar for both substituents
7
attached to the center of the aliphatic chain in case of
8
compound 1, no information was obtained from the NMR
9
spectra about the ratio of the isomers 1 a and 1 b neither for
10
the crude product nor after purification of 1 by crystallization.
11
Furthermore, the NMR spectra of the compounds 2–6 give also
12
no information about the ratio of the two isomers because the
13
neighborhood does not change by additional functionalization
14
steps depicted in the Schemes 1 and 2. Although compound 1
15 Scheme 1. a) reaction of 9,10 epoxy methyl oleate with imidazole to methyl is semicrystalline, the functionalized compounds 2–6 exhibit
16 9-hydroxy-10-(1H-imidazol-1-yl) octadecanoate (1 a) and isomer 1 b; b)
glass transition temperatures below the melting point of water
17 reaction of 1 with methacrylic anhydride to methyl 9-(methacryloyloxy)-10-
(1H-imidazol-1-yl) octadecanoate (2 a) and isomer 2 b; c) quaternization of (Table 1).
18
the isomers 2 a and 2 b with benzyl bromide to 1-(10-(methacryloyloxy)-18- Moreover, compound 1 and the methacrylates 3 and 5
19 methoxy-18-oxo-octadecan-9-yl)-3-benzyl-1H-imidazolium bromide (3 a) and were selected for investigation of antimicrobial activity using
20 isomer (3 b); d) quaternization of the isomers 1 a and 1 b with 4-iodomethyl
the minimal inhibitory concentration (MIC) test. The Gram-
21 styrene resulting in 1-(10-hydroxy-18-methoxy-18-oxo-octadecan-9-yl)-3-(4-
vinylbenzyl)-1H-imidazolium iodide (4 a) and isomer 4 b. negative bacterium Escherichia coli was applied for the MIC test
22
(see Supporting Information). The results obtained give a first
23
hint that MIC values of these monomers (Table S1 in the
24
Table 1. Yield on functionalized methyl oleates 1–6 and their glass Supporting Information) are comparable with other imidazo-
25
transition temperatures obtained by DSC using heating and cooling rates lium salts described in the literature showing antimicrobial
26 of 20 K/min. acitivity.[14]
27
Isomers Yield [%] Tg [°C] Tm [°C]
28
29 1a and 1b 30 -55 63 Conclusions
2a and 2b 85 -63 -
30
3a and 3b 92 -29 - New imidazolium derivatives comprising fatty acid methyl ester
31 4a and 4b 71 -61 - structures were successfully synthesized. The new compounds
32 5a and 5b 71 -43 -
6a and 6b 71 -51 -
are additionally substituted with a methacrylate or a vinyl
33
benzyl substituent. These functional groups can polymerize in
34
the presence of a thermal initiator or a photoinitiator. There-
35
fore, these new compounds may be useful as monomers for
36
exchange of 3 and 4 using lithium bis(trifluoromethylsulfonyl) applications e. g. in coatings, adhesives, and composites. Their
37
imide (Scheme 2). These new ionic liquids consist of the low glass transition temperatures may be advantageous for
38
processing of mixtures and for polymerization reactions in the
39
absence of any solvent. Furthermore, the new compounds with
40
various counter ions (halide or bis(trifluoromethylsulfonyl)
41
imide) may be also interesting as surfactants because of their
42
long alkyl substituents derived from the fatty acid methyl ester
43
structure on the one hand and their ionic structure on the
44
other hand. Furthermore, counter ion exchange of halides with
45
other anions may open the possibility for manufacturing of a
46
high number of electrolytes, which may be interesting for
47
manufacturing of polyelectrolytes. Moreover, the new imidazo-
48
lium compounds may open a new way for synthesis of new N-
49
heterocyclic carbenes being interesting as ligands for com-
50
Scheme 2. Anion metathesis of 3 and 4 using lithium bis(trifluoromethylsul- plexes. The latter may be applicable in catalysis of various
51
fonyl) imide results in a) 3-benzyl-1-(10-(methacryloyloxy)-18-methoxy-18- reactions.
52 oxo-octadecan-9-yl)-1H-imidazol-3-ium bis(trifluoromethylsulfonyl) imide
53 (5 a) and isomer 5 b; b) 1-(10-hydroxy-18-methoxy-18-oxo-octadecan-9-yl)-3-
54 (4-vinylbenzyl)-1H-imidazol-3-ium bis(trifluoromethylsulfonyl)imide (6 a) and
isomer 6 b.
55
56
57

ChemistrySelect 2019, 4, 4679 – 4681 4680 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Full Papers
[1] S. P. Bunker, R. P. Wool, J. Polym. Sci. A, Polym. Chem. Ed. 2002, 40, 451–
1 Supporting Information Summary 458.
2 [2] O. D. Dailey Jr., N. T. Prevos, G. D. Strahan, J. Am. Oil. Chem. Soc. 2009,
Experimental details including FT IR and NMR spectra as well as 86, 1101–1114.
3
first results obtained during antimicrobial activity investigation [3] U. Biermann, W. Friedt, S. Lang, W. Lühs, G. Machmüller, J. O. Metzger,
4
against Escherichia coli are given in the Supporting Information. M. Rüsch, gen. Klaas, H. J. Schäfer, M. P. Schneider, Angew. Chem. Int. Ed.
5 2000, 39, 2206–2224.
6 [4] G. Fayter, in Perspektiven nachwachsender Rohstoffe in der Chemie (Ed. :
7 Acknowledgments H. Eierdanz), Wiley-VCH, Weinheim, 1996, pp. 107–118.
[5] H. Baumann, M. Bühler, H. Fochem, F. Hirsinger, H. Zoebelein, J. Falbe,
8
The authors gratefully acknowledge the BMBF for financial Angew. Chem. 1988, 100, 42–62 ; Angew. Chem. Int. Ed. Engl. 1988, 27,
9 41–62.
support within the FHProfUnt project MoMaDruDig (grant
10 [6] S. Walther, N. Strehmel, M Schlörholz, B. Strehmel, V. Strehmel, J.
03FH022PX4). Furthermore, the authors gratefully acknowledge A. Photopolym. Sci. Technol. 2016, 29, 123–132.
11
Nickisch-Hartfiel and A. Gülz (Niederrhein University of Applied [7] A. Farkas, P. F. Strohm, J. Appl. Polym. Sci. 1968, 12, 159–168.
12
Sciences) for their kind support in the determination of minimal [8] M. Fedtke, V. Strehmel, Polymer Bulletin 1989, 21, 549–554.
13 [9] M. Fedtke, V. Strehmel, Acta Polymerica 1989, 40, 497–504.
inhibitory concentration (MIC).
14 [10] G. Feldmann, H. J. Schaefer, Oléagineux, Corps Gras, Lipides 2001, 8(1),
15 60–62.
[11] S. Fürmeier, J. O. Metzger, Eur. J. Org. Chem. 2003, 5, 885–893.
16 Conflict of Interest [12] B. R. Moser, S. Z. Erhan, J. Am. Oil Chem. Soc. 2006, 83, 959–963.
17 [13] C. T. Womble, G. W. Coates, K. Matyjaszewski, K. J. T. Noonan, ACS Macro
The authors declare no conflict of interest.
18 Lett., 2016, 5, 253–257.
19 [14] M. Messali, M. R. Aouad, W. S. El-Sayed, A. Al.-S. Ali, T. B. Hadda, B.
Keywords: Anions · Fatty acids · Imidazolium · Ionic liquids · Hammouti, Molecules 2014, 19, 11741–11759.
20
21 Nitrogen heterocycles
22 Submitted: January 20, 2019
23 Accepted: April 9, 2019
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57

ChemistrySelect 2019, 4, 4679 – 4681 4681 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim