1
298
KAPITANOV et al.
line should ensure more efficient substrate concentra-
tion in micellar pseudophase and more significant
micellar effects of surfactants.
A solution of 1.0 g (7 mmol) of 1,3-dichloropropan-2-
one oxime in 10 ml of acetonitrile was added in small
portions over a period of 5 h at room temperature to
a solution of 3.3 g (14 mmol) of 1-dodecyl-1H-imid-
azole in 10 ml of acetonitrile. The precipitate was
filtered off and thoroughly washed with acetonitrile.
Yield 4.2 g (98%), mp 186–190°C (decomp.).
EXPERIMENTAL
1
The H NMR spectra were recorded on a Bruker
Avance II 400 spectrometer at 400 MHz using tetra-
methylsilane as internal reference. Esters I and III
were prepared as reported in [4, 8]. Commercial ester
II (Aldrich, ≥90%) and inorganic reagents of analytical
or ultrapure grade were used without additional purifi-
cation. Solutions were prepared using doubly distilled
water.
1
H NMR spectrum (CDCl ), δ, ppm: 0.88 t (6H, CH ,
3
3
J = 6.7 Hz), 1.20–1.44 m [36H, (CH ) ], 1.84–1.98 m
2
9
+
(
4H, CH ), 4.18–4.27 m (4H, CH N ), 5.43 s (2H,
2
2
+
+
CH N ), 5.62 s (2H, CH N ), 7.33 s (1H, Harom), 7.54 s
2
2
(
1H, Harom), 7.87 s (1H, Harom), 8.05 s (1H, Harom),
0.07 s (1H, Harom), 10.14 s (1H, Harom). Found, %:
C 64.45; H 10.02; Cl 11.51; N 11.38. C H Cl N O.
1
3
3
61
2
5
1
,3-Dichloropropan-2-one oxime was synthesized
Calculated, %: C 64.47; H 10.00; Cl 11.53; N 11.39.
3
0
according to the procedure described in [17]. n
.5041; published data [17]: nD = 1.5044. H NMR
=
D
The kinetics of decomposition of substrates I–III
were studied by spectrophotometry (Genesys 10S UV-
Vis, Thermo Electron Corp., 25°C), following accumu-
lation of 4-nitrophenoxide ion at λ 400–420 nm. The
acidity of the medium was monitored using a Metrohm
3
0
1
1
spectrum (CDCl ), δ, ppm: 4.29 s (2H, CH ), 4.41 s
3
2
(
2H, CH ), 7.91 br.s (1H, NOH). Found, %: C 25.40;
2
H 3.52; Cl 49.91; N 9.89. C H Cl NO. Calculated, %:
3
5
2
C 25.38; H 3.55; Cl 49.94; N 9.86.
,3′-[2-(Hydroxyimino)propan-1,3-diyl]bis-
1-methyl-1H-imidazol-3-ium) dichloride (VI).
A solution of 1.9 g (0.014 mol) of 1,3-dichloropropan-
-one oxime in 10 ml of anhydrous THF was added in
portions to a solution of 2.0 g (0.025 mol) of 1-methyl-
H-imidazole (Aldrich, ≥99%) in 10 ml of anhydrous
7
44 pH meter. The procedures for kinetic experiments
3
and calculation of the observed pdeudofirst-order rate
constants (k , s ) were described in [3–5, 8]. The
critical micelle concentrations were determined on the
basis of the kinetic data: the CMC values corresponded
to the bend on the k —c plot [4]. The error in the
–
1
(
obs
2
obs
0
m
1
determination of k2 from the kinetic data did not
THF. The mixture was kept for 15 h at 5–10°C, and
the precipitate was filtered off and washed with THF.
Yield 3.0 g (50%), mp 221–222°C (decomp.). H NMR
exceed 10%, and in the determination of K and CMC,
S
20%. The pK values were determined by spectro-
a
1
photometry from variation of the UV spectra versus
pH (Fig. 1) according to the equation
spectrum (DMSO-d ), δ, ppm: 3.88 s (6H, CH ), 5.15 s
6
3
(
(
9
2H, CH ), 5.24 s (2H, CH ), 7.72 s (2H, Harom), 7.73 s
2 2
a i i i
pK = pH + log[(Dmax – D )/(D – Dmin),
1H, Harom), 7.76 s (1H, Harom), 9.29 s (1H, Harom),
.35 s (1H, Harom), 12.23 s (1H, NOH). Found, %:
C 43.12; H 5.58; Cl 23.19; N 22.90. C H Cl N O.
where Dmax and Dmin are, respectively, the maximum
and minimum optical densities at a given wavelength,
and D is the optical density at the same wavelength
at pH . The analytical wavelength was selected so that
to ensure the maximum difference between Dmax and
Dmin [3, 18].
11
17
2
5
Calculated, %: C 43.15; H 5.60; Cl 23.16; N 22.87.
-Dodecyl-1H-imidazole. A mixture of 4.1 g
0.06 mol) of imidazole, 14.4 ml (0.06 mol) of
-bromododecane (Aldrich, ≥97%), and 3.9 (0.07 mol)
i
1
i
(
1
of thoroughly ground potassium hydroxide in 60 ml of
anhydrous acetone was heated for 8 h under reflux.
The mixture was evaporated on a rotary evaporator,
and the residue was distilled under reduced pressure.
Yield 13.0 g (92%), bp 165–170°C (0.5–0.8 mm).
REFERENCES
1
2
. Popov, A.F., Pure Appl. Chem., 2008, vol. 80, p. 1381.
. Morales-Rojas, H. and Moss, R.A., Chem. Rev., 2002,
vol. 102, p. 2497.
. Kivala, M., Cibulka, R., and Hampl, F., Collect. Czech.
Chem. Commun., 2006, vol. 71, p. 1642.
. Simanenko, Yu.S., Karpichev, E.A., Prokop’eva, T.M.,
Latt, A., Popov, A.F., Savelova, V.A., and Belouso-
va, I.A., Russ. J. Org. Chem., 2004, vol. 40, p. 206.
1
H NMR spectrum (CDCl ), δ, ppm: 0.88 t (3H, CH ,
3
3
3
4
J = 6.8 Hz), 1.19–1.40 m [18H, (CH ) ], 1.71–1.81 m
2
9
(
2H, CH ), 3.92 t (2H, CH N, J = 7.2 Hz), 6.90 s (1H,
2 2
Harom), 7.05 s (1H, Harom), 7.48 s (1H, Harom). Found,
%
: C 76.24; H 11.92; N 11.83. C H N . Calculated,
15 28 2
%
: C 76.21; H 11.94; N 11.85.
,3′-[2-(Hydroxyimino)propan-1,3-diyl]bis-
1-dodecyl-1H-imidazol-3-ium) dichloride (VII).
5
. Kapitanov, I.V., Belousova, I.A., Turovskaya, M.K.,
Karpichev, E.A., Prokop’eva, T.M., and Popov, A.F.,
Russ. J. Org. Chem., 2012, vol. 48, p. 651.
3
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013