Protic ionic liquids based on 1,1-dimethylhydrazine and arylheteroacetic acids

Full text of DOI:10.1134/S1070363212080221

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 8, pp. 1455–1456. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © S.N. Adamovich, R.G. Mirskov, A.N. Mirskova, M.G. Voronkov, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 8,
pp. 1394–1395.
LETTERS
TO THE EDITOR
Protic Ionic Liquids Based on 1,1-Dimethylhydrazine
and Arylheteroacetic Acids
S. N. Adamovich, R. G. Mirskov, A. N. Mirskova, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: mir@irioch.irk.ru
Received December 19, 2011
DOI: 10.1134/S1070363212080221
Previously we have performed the reaction of
biogenic (2-hydroxyethyl)amines with the biologically
active arylheteroacetic acids to give the solid salts,
which have a structure of the protic ionic liquids Ar
(Het)XCH2COO–·HN+Rn(CH2CH2OH)3–n; X = O, S,
SO2; n = 0–2. They are the pharmacologically active
substances of low toxicity (LD50 1300–6000 mg kg–1)
possessing anti-aggregatory, membrane stabilizing,
anti-sclerotic, immunomodulatory, antitumor, adapto-
genic, and other activities [1–7].
1,1-Dimethylhydrazinium 2-methylphenoxyacetate
(I). To an alcohol solution of 1.662 g (0.01 mol) of 2-
СН3C6H4OCH2COOH was added dropwise 0.601 g
(0.01 mol) of dimethylhydrazine while stirring and
heating at 45°C for 15 min. The solvent was distilled
off. The oily residue was washed several times with
diethyl ether and dried in a high vacuum. Yield 2.20 g
(97%). IR spectrum, ν, cm–1: 1591 (С=О), 2521–2796
(N+H), 3158, 3308 (NН2). 1Н NMR spectrum, δН, ppm:
7.11–6.77 m (4Н, Ph), 4.54 s (2Н, PhОСН2), 3.32 s
(2Н, NН2), 2.87 s (6Н, NМе2). 13С NMR spectrum, δС,
ppm: 174.05 (С=О), 130.337–111.10 (Ph), 66.32
(PhОСН2), 46.06 (NМе2), 15.17 (PhСН3). 15N NMR
spectrum, δС, ppm: –257.5 (NМе2), –286.0 (NH2).
In order to obtain the new biologically active ionic
liquids we carried out the reaction of arylheteroacetic
acids with 1,1-dimethylhydrazine.
Ме2N–NH2 + HО(О)ССН2XR
→ [Me2N+Н–NH2]·O–(O)CCH2XR,
1,1-Dimethylhydrazinium 4-chlorophenylsulfanyl-
acetate (II) was obtained similarly from 4-СlC6H4·
SCH2COOH and dimethylhydrazine. Yield 91%. IR
spectrum, ν, cm–1: 1574 (С=О), 2518–2741 (N+H),
Х = О, R = 2-СН3C6H4 (I); Х = S, R = 4-ClC6H4 (II); Х =
SO2, R = 4-ClC6H4 (III); Х = S, R = Ind (IV).
Compounds I–IV are viscous liquids, very well
soluble in water and poorly soluble in ether and al-
cohols. The structure of the obtained compounds was
1
3268, 3389 (NН2). Н NMR spectrum, δН, ppm: 7.72–
7.38 m (4Н, Ph), 3.40 s (2Н, SСН2), 3.22 t (2Н, NН2),
2.79 s (6Н, NMe2). 13С NMR spectrum, δС, ppm:
175.18 (С=О), 136.76–110.00 (Ph), 57.65 (SСН2),
40.44 (NMe2).
1
confirmed by the NMR Н, 13С, 15N and IR spec-
troscopy methods.
The selection of dimethylhydrazine (a tonnage
toxic component of rocket fuel) was underlain by the
fact that its quaternization involving Me2N group [8, 9]
results in non-hazardous compounds with high
antimicrobial, antifungal, and anti-cardiotropic acti-
vities, comparable with the effect of pharmaceuticals
[10, 11]. The combination of arylheteroacetic acids
and dimethylhydrazine properties in one molecule
offers great opportunities for further investigation of
the synthesized ionic liquids.
1,1-Dimethylhydrazinium 4-chlorophenylsulfonyl-
acetate (III) was obtained similarly from 4-ClC6H4·
SO2CH2COOH and dimethylhydrazine. Yield 92%. IR
spectrum, ν, cm–1: 1581 (С=О), 2588–2770 (N+H),
3169, 3330 (NН2). 1Н NMR spectrum, δН, ppm: 7.87–
7.57 m (4Н, Ph), 4.47 s (2Н, SО2СН2), 3.20 t (2Н,
NН2). 2.81 s (6Н, NСН3). 13С NMR spectrum, δС,
ppm: 177.08 (С=О), 137.96–111.11 (Ph), 67.65
(SО2СН2), 44.44 (NMe2).
1455

1456
ADAMOVICH et al.
no. 4, p. 561.
1,1-Dimethylhydrazinium indole-3-yl-sulfanyl-
acetate (IV) was obtained by analogy from the indole-
3-ylsulfanylacetic acid and dimethylhydrazine. Yield
93%. IR spectrum, ν, cm–1: 1574 (С=О), 2600–2790
(N+H), 3200, 3333 (NН2). 1Н NMR spectrum, δН, ppm:
7.71–7.11 m (5Н, Ind), 3.39 s (2Н, SСН2), 3.22 t (2Н,
NН2). 2.78 s (6Н, NMe2). 13С NMR spectrum, δС,
ppm: 175.18 (С=О), 136.76–103.86 (Ind), 57.18
(SСН2), 40.44 (NMe2).
5. Mirskova, A.N., Adamovich, S.N., Mirskov, R.G., and
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6. Kolesnikova, O.P., Mirskova, A.N., Adamovich, S.N.,
Kudaeva, O.T., Mirskov, R.G., and Voronkov, M.G.,
Bull. Sib. Otd. Ross. Akad. Med. Nauk, 2010, no. 6 (30),
p. 12.
7. Mirskova, A.N., Levkovskaya, G.G., Kolesnikova, O.P.,
Perminova, O.M., Rudyakova, E.V., and Adamovich, S.N.,
Izv. Akad. Nauk, Ser. Khim., 2010, no. 12, p. 2181.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012