1104
VLASOVA et al.
10 mL). The organic layer was dried over anhydrous
Na2SO4, and the solvent was removed at atmospheric
pressure. Yield 11.4 g (91%).
1.33 m (20H, C17H2, C16H2, C15H2, C14H2, C13H2,
C12H2, C7H2, C6H2, C5H2, C4H2), 1.61 m (4H, C3H2,
NHCH2CH2CH2), 1.94 m (4H, C11H2, C8H2), 2.24 t
2
[2H, J 7.2 Hz, CH2N(CH3)2], 2.89 s [6H, N(CH3)2],
N-[3-(Dimethylamino)propyl]butanamide
hy-
2
3.14 t (2H, J 7.1 Hz, C2H2), 3.29 m (2H, NHCH2),
drochloride IVа. Gaseous HCl was passed for 1.5 h
through a solution of 20.7 g (0.120 mol) of N-[3-
(dimethylamino)propyl]butanamide IIIа in 90 mL
of CH2Cl2. The solvent was removed at atmospheric
pressure. Yield 22.5 g (90%). 1Н NMR spectrum
(CD3OD), δ, ppm: 0.78 t (3H, 2J 7.3 Hz, C4H3), 1.48 m
(2H, NHCH2CH2CH2), 1.78 m (2H, C3H2), 2.07 t (2H,
2J 7.3 Hz, C2H2), 2.72 s [6H, N(CH3)2], 2.97 t [2H,
2J 7.2 Hz, CH2N(CH3)2], 3.14 m (2H, NHCH2), 5.33 br.s
(1H, NH). 13C NMR spectrum (CD3OD), δ, ppm: 12.57
(C4), 19.00 (C3), 24.17 (NHCH2CH2CH2), 36.27 (C2),
36.85 (NHCH2), 42.10 [N(CH3)2], 55.05 [CH2N(CH3)2],
176.21 (C=О). Found, %: С 51.76, H 10.15, Сl 17.00,
N 13.45. C9H21ClN2O. Calculated, %: C 51.79, H 10.14,
Cl 16.99, N 13.42.
5.34 s (2H, C9H, C10H), 5.50 s (1H, NH). 13C NMR
spectrum (CD3OD), δ, ppm: 13.06 (C18), 22.31 (C17),
24.54 (C3), 25.53 (NHCH2CH2CH2), 26.70 (C8), 28.75
(C11), 28.81 (C4), 28.92 (C14, C6, C5), 29.01 (C15), 29.17
(C13), 29.33 (C7), 29.41 (C12), 31.62 (C16), 35.48 (C2),
35.61 (NHCH2), 42.07 [N(CH3)2], 55.14 [CH2N(CH3)2],
129.34 (C9), 129.45 (C10), 175.77 (C=O). Found,
%: С 68.49, H 11.74, Сl 8.77, N 6.97. C23H47ClN2O.
Calculated, %: C 68.53, H 11.75, Cl 8.80, N 6.95.
RESULTS AND DISCUSSION
Numerous quaternary ammonium salts have been
described in the literature. The majority of them have
one cationic site and one hydrophobic substituent [7–9].
Data on preparation of cationic surfactants containing,
along with a long-chain alkyl radical, an amide group
and a cationic site in the form of a positively charged
quaternary ammonium group are lacking.
N-[3-(Dimethylamino)propyl]octadecanamide
hydrochloride IVb. Gaseous HCl was passed for
1.5 h through a solution of 15.0 g (0.041 mol) of N-[3-
(dimethylamino)propyl]octadecanamide IIIb in 90 mL
of CH2Cl2.The solvent was removed at reduced pressure.
1
In this study, we developed a two-step procedure
for preparing N-[3-(dimethylamino)propyl]alkanamide
hydrochlorides from carboxylic acid (butyric, stearic,
oleic) esters and N,N-dimethyl-1,3-diaminopropane
and evaluated the hydrophobizing properties of these
compounds.
Yield 16.0 g (97%). Н NMR spectrum (CD3OD), δ,
ppm: 0.90 t (3H, 2J 7.0 Hz, C18H3), 1.28–1.32 m (24H,
C17H2, C16H2, C15H2, C14H2, C13H2, C12H2, C11H2,
C10H2, C9H2, C8H2, C7H2, C6H2), 1.60–1.63 m (4H,
C4H2, C5H2), 1.92–1.97 m (4H, C3H2, NHCH2CH2CH2),
2.25 t (2H, 2J 7.1 Hz, C2H2,), 2.89 s [6H, N(CH3)2], 3.14 t
2
[2H, J 7.2 Hz, CH2N(CH3)2], 3.28 m (2H, NHCH2),
There are numerous procedures for preparing fatty
acid amides [8, 9], which are intermediates in synthesis
of surfactants. These amides are prepared, as a rule,
by reaction of acids or their esters with amines on
heating. We have found that the catalytic reaction of
fatty acid methyl esters Ia–Ic with N,N-dimethyl-1,3-
diaminopropane II in 1 : 1.1 molar ratio for 12 h at
115–120°C in the presence of aluminosilicate catalysts
used previously for esterification of carboxylic acids
[10] leads to the formation of N-[3-(dimethylamino)
propyl]alkanamides IIIa and IIIb and of (9Z)-N-[3-
(dimethylamino)propyl]octadec-9-enamide IIIc in 90,
95, and 93% yield, respectively. It should be noted that,
when the reaction is performed under thermal conditions
(115–120°C) and in the presence of catalytic amounts of
sodium glycerate or methylate (10 wt %), the yield of
the target products does not exceed 65%:
5.31 s (1H, NH). 13C NMR spectrum (CD3OD), δ, ppm:
13.03 (C18), 22.31 (C17), 24.48 (NHCH2CH2CH2),
24.59 (C3), 25.54 (C4), 28.75(C6) 28.94 (C7), 29.01
(C8), 29.04 (C15), 29.15 (C5), 29.20 (C14), 29.26 (C12),
29.35 (C13, C11, C10, C9), 31.64 (C16), 35.38 (C2), 35.71
(NHCH2), 42.05 [N(CH3)2], 55.11 [CH2N(CH3)2],
175.95 (C=O). Found, %: С 68.31, H 12.16, Сl 8.77,
N 6.90. C23H49ClN2O. Calculated, %: C 68.19, H 12.19,
Cl 8.75, N 6.92.
(9Z)-N-[3-(Dimethylamino)propyl]octadec-9-
enamide hydrochloride IVc. Gaseous HCl was passed
for 3 h through a solution of 15.0 g (41 mmol) of (9Z)-
N-[3-(dimethylamino)propyl]octadec-9-enamide IIIc in
90 mL of benzene. The solvent was removed at reduced
1
pressure. Yield 16.35 g (99%). Н NMR spectrum
(CD3OD), δ, ppm: 0.90 t (3H, 2J 7.0 Hz, C18H3), 1.28–
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 90 No. 7 2017