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RSC Advances
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Journal Name
DOI: 10.1039/C5RA11710K
ARTICLE
1H NMR (DMSO-d6) (ppm): 0,88 (t, 6H); 1,26 (m, 48H); 1,54 (m,
2H); 1,74 (m, 2H); 2,11 (m, 2H); 3,18 (s, 6H); 3,23 (m, 2H); 4,73
(m, 2H); 7,43 (m, 3H); 7,56 (m, 2H).
13C NMR (DMSO-d6) δ (ppm): 14,0; 21,7; 22,6;26,2; 27,0; 29,2;
31,8; 38,9; 50,0; 63,7; 67,5; 126,8; 127,6; 129,0; 130,4; 132,9;
173,3.
Hexadecyltrimethylammonium cocoate (12)
1H NMR (CDCl3) (ppm): 0,88 (t, 6H); 1,26 (m, 42H); 1,56 (m, 2H); 1,71 (m,
2H); 2,11 (m, 2H); 3,34 (s, 9H); 3,45 (t, 2H).
13C NMR (CDCl3) δ (ppm): 13,9; 22,5; 25,2; 26,1; 27,0; 29,5; 31,7; 39,0;
52,9; 66,6; 179,8.
Benzalkonium oleate (6)
1H NMR (DMSO-d6) (ppm): 1,01 (t, 6H); 1,38 (m, 30H); 1,72 (m,
2H); 1,89 (m, 2H); 2,12 (m, 4H); 2,29 (m, 2H); 3,34 (s, 6H); 3,46
(m, 2H); 4,94 (m, 2H); 5,46 (m, 2H); 7,58 (m, 3H); 7,69 (m, 2H).
13C NMR (DMSO-d6) δ (ppm):14,0; 21,7; 22,6; 26,2; 27,1; 29,5;
31,8; 34,6; 39,1; 49,7; 63,8; 67,6; 127,5; 129,1; 130,5; 133,0;
173,3.
Conclusions
This study presents a new method of obtaining ILs from
natural sources. It is focused on the use of natural vegetable
oils as anionic moieties for synthesis of biologically active ILs.
The salts were synthesized with high yield and purity. It was
established that both the physicochemical properties
(solubility, phase transition temperatures and thermal
stability) and activity of the studied ILs depend on their
chemical structures. The feeding deterrent activity was very
good to good in the case of Sitophilus granarius (beetle),
Tribolium confusum (larvae), Trogoderma granarium (beetle)
and medium to good in case of Tribolium confusum (beetle).
Comparison of anti-microbial properties of the obtained ILs
and precursor compounds revealed that the studied ILs were
characterized by similar activity. A species-specific diversity in
the efficiency of the ILs could be observed during both the
feeding deterrent activity and anti-microbial activity assays,
which is most likely associated with their structural
differences. Furthermore, the biodegradation tests confirmed
that most of the ILs exhibited high biodegradation efficiency (
> 80%) and may be classified as readily biodegradable. The
tests revealed a notable influence of the cations (ILs with
alkyltrimethylammonium cation were more biodegradable
compared to ILs with dialkyldimethylammonium cation),
followed by the effect of anions (ILs with unsaturated oleate
and canola oil anions were more biodegradable compared to
ILs with saturates stearate and coconut oil anions). These
findings confirm that the described method may be
successfully used for synthesis of ILs from natural products and
elucidates valuable guidelines for the design of efficient
products with attractive properties for a wide range of
applications.
Benzalkonium canolate (7)
1H NMR (CDCl3) (ppm): 0,88 (t, 6H); 1,26 (m, 38H); 1,61 (m,
2H); 1,76 (m, 2H); 2,01 (m, 4H); 2,18 (m, 2H); 3,23 (s, 6H); 3,34
(m, 2H); 4,86 (m, 2H); 5,33 (m, 2H); 7,45 (m, 3H); 7,58 (m, 2H).
13C NMR (CDCl3) δ (ppm): 14,0; 22,6; 25,3; 26,2; 27,2; 29,5;
31,8; 34,6; 39,2; 49,6; 63,1; 67,4; 127,6; 129,0; 129,8; 130,4;
133,0; 179,9.
Benzalkonium cocoate (8)
1H NMR (CDCl3) (ppm): 0,88 (t, 6H); 1,26 (m, 36H); 1,60(m, 2H);
1,76 (m, 2H); 2,18 (m, 2H); 3,23 (s, 6H); 3,36 (m, 2H0; 4,86 (m,
2H); 7,45 (m, 3H); 7,60 (m, 2H).
13C NMR (CDCl3) δ (ppm): 14,0; 22,5; 25,2; 26,2; 27,1; 29,4;
29,4; 31,7; 34,6; 39,2; 49,5; 63,1; 67,5; 127,5; 129,0; 133,0;
179,9.
Hexadecyltrimethylammonium stearate (9)
1H NMR (DMSO-d6) (ppm): 0,88 (t, 6H); 1,25 (m, 52H); 1,54 (m,
2H); 1,72 (m, 2H); 2,11 (m, 2H); 3,34 (s, 9H); 3,43 (m, 2H).
13C NMR (DMSO-d6) δ (ppm):14,0; 22,6; 24,9; 26,1; 29,6; 31,8;
38,9; 53,2; 66,8; 173,8.
Elemental analysis calc. (%) for C37H77NO2 (568,01 g/mol):
C 78.24, H 13.66, N 2.47. Found C 78.03, H 13.29, N=2.79.
Hexadecyltrimethylammonium oleate (10)
1H NMR (DMSO-d6) (ppm): 0,88 (t, 6H); 1,26 (m, 46H); 1,54 (m,
2H); 1,72 (m, 2H); 2,00 (m, 4H); 2,11 (m, 2H); 3,33 (s, 9H); 3,43
(m, 2H); 5,35 (m, 2H).
13C NMR (DMSO-d6) δ (ppm): 14,0; 22,6; 23,1; 24,8; 26,9; 29,6;
31,8; 38,7; 53,1; 72,7; 129,7; 180,4.
Acknowledgements
This work was supported by National Science Center, Poland,
(grant No. DEC-2012/07/B/ST5/00806)
Elemental analysis calc. (%) for C37H75NO2 (566,00 g/mol):
C 78.52, H 13.36, N 2.47. Found C 78.71, H 13.71, N 2.72.
Notes and references
1
P. Wasserscheid and T. Welton, Ionic Liquids in Synthesis,
Wiley-VCH VerlagGmbh& Co. KGaA, Weinheim, 2nd edn,
2008.
H. Olivier-Bourbigou, L. Magna and P. Morvan, Appl. Catal. A-
Gen., 2010, 373, 1.
J. P. Hallet and T. Welton, Chem. Rev., 2011, 111, 3508.
M. Smiglak, J. M. Pringle, X. Lu, L. Han, S. Zhang, H. Gao, D. R.
MacFarlane and R. D. Rogers, ChemComm, 2014, 50, 9228.
Hexadecyltrimethylammonium canolate (11)
1H NMR (CDCl3) (ppm): 0,88 (t, 6H); 1,26 (m, 44H); 1,56 (m,
2H); 1,71 (m, 2H); 2,01 (m, 4H); 2,12 (m, 2H); 3,34 (s, 9H); 3,43
(t, 2H); 5,33(m, 2H).
2
3
4
13C NMR (CDCl3) δ (ppm): 13,9; 22,5; 25,2; 26,1; 27,0; 29,5;
31,8; 39,0; 53,0; 66,6; 129,7; 179,9,
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