1570
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 7, July, 2004
Valeeva et al.
and the resulting mixture was refluxed for 5 h. Then the reaction
mixture was poured into water, and the crystals precipitated
were filtered off and washed with a solution of KOH and water.
Compound 1 was obtained in 96% yield (3.5 g), m.p. 115—117 °C
(acetone). 1Н NMR, δ: 1.30 (t, 6 Н, Me, J = 7.40 Hz); 2.90 (q,
4 H, СН2Me, J = 7.40 Hz); 3.51 (s, 4 H, ОСН2СН2О); 3.68 (t,
4 H, NСН2СН2O, J = 5.78 Hz); 4.38 (t, 4 H, NСН2СН2O, J =
5.78 Hz); 7.32 (dd, 2 H, Н(6) or Н(7), quinox., J = 8.23 Hz, J =
6.29 Hz); 7.29 (ddd, 2 H, Н(6) or Н(7), quinox., J = 8.09 Hz,
J = 6.71 Hz, J = 1.38 Hz); 7.49 (ddd, 2 H, Н(6) or Н(7),
quinox., J = 8.33 Hz, J = 6.94 Hz, J = 1.39 Hz); 7.54 (dd, 2 H,
Н(8), quinox., J = 8.09 Hz, J = 0.92 Hz); 7.74 (dd, 2 H, Н(5),
quinox., J = 7.86 Hz, J = 1.14 Hz). IR, ν/cm–1: 460, 717, 748,
873, 1029, 1075, 1092, 1115, 1177, 1224, 1262, 1313, 1354,
1424, 1496, 1569, 1604, 1650. Found (%): C, 67.76; H, 6.45;
N, 12.26. C26H30N4O4. Calculated (%): C, 67.51; H, 6.54;
N, 12.11.
calculated by the weighing leastꢀsquares method, and arithꢀ
metic mean values of three measurements differed by at most
5% were used in the calculation. The surface tension was deterꢀ
mined by the ring method using the Du Nouy tensiometer26
at 20 °C.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 03ꢀ03ꢀ
32865).
References
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1,14ꢀBis(3ꢀethylꢀ1,2ꢀdihydroꢀ2ꢀoxoquinoxalinꢀ1ꢀyl)ꢀ
3,6,9,12ꢀtetraoxatetradecane (2). A mixture of 3ꢀethylquinꢀ
oxalinꢀ2(1Н )ꢀone (1.00 g, 5.6 mmol), KOH (0.5 g, 8.9 mmol),
and dioxane (20 mL) was heated with boiling for 1—3 min, and
a solution of 1,14ꢀditosylateꢀ3,6,9,12ꢀtetraoxatetradecane (1.6 g,
2.9 mmol) in dioxane (5 mL) was added. The resulting mixture
was refluxed for 3 h, poured into water, and extracted with
toluene (3×20), and then the solvent was evaporated with a
water jet pump. Compound 2 was obtained as an oil, which was
dissolved in tertꢀbutyl methyl ether (20 mL) and filtered through
a column (300×15 mm) packed with silica gel (5 g). The filtrate
was washed with tertꢀbutyl methyl ether (100 mL), and the
solvent was evaporated. Analytically pure crystalline compound
2 was obtained in 75% yield (1.2 g), m.p. 33—34 °C (butyl
1
methyl ether). Н NMR, δ: 1.26 (t, 6 H, Me, J = 736 Hz); 2.87
(q, 4 H, СН2Me, J = 7.36 Hz); 3.42 (s, 4 H, N(CH2)2ꢀ
О(СН2)2ОCH2CH2O(CH2)2O(CH2)2N); 3.46—3.51 (m, 4 H,
N(CH2)2ОСН2CH2О(CH2)2OCH2CH2O(CH2)2N); 3.53—3.57
(m, 4 H, N(CH2)2ОСН2CH2О(CH2)2OCH2CH2O(CH2)2N);
3.80 (t, 4 H, NCH2CH2О(СН2)2О(CH2)2O(CH2)2OCH2ꢀ
CH2N, J = 5.96 Hz); 4.46 (t, 4 H, NCH2CH2О(СН2)2ꢀ
О(CH2)2O(CH2)2OCH2CH2N, J = 5.96 Hz); 7.31 (ddd, 2 H,
Н(6) or Н(7), quinox., J = 8.04 Hz, J = 7.01 Hz, J = 1.40 Hz);
7.53 (ddd, 2 H, Н(6) or Н(7), quinox., J = 8.40 Hz, J = 7.04 Hz,
J = 1.40 Hz); 7.63 (d, 2 H, Н(8), quinox., J = 8.04 Hz); 7.75
(dd, 2 H, Н(5), quinox., J = 8.08 Hz, J = 1.40 Hz). IR, ν/cm–1
:
464, 599, 637, 717, 751, 878, 952, 974, 1021, 1038, 1090, 1119,
1182, 1249, 1311, 1354, 1433, 1571, 1602, 1650. Found (%):
C, 65.36; H, 7.15; N, 10.26. C30H38N4O6. Calculated (%):
C, 65.44; H, 6.96; N, 10.17.
Compounds 3—5 were synthesized according to a known
procedure.25 Cetyltrimethylammonium bromide (Sigma)
was used as received. The hydrolysis kinetics was studied
spectrophotometrically on
a Specord Мꢀ400 instrument
in the pseudoꢀfirst order mode by a change in the abꢀ
sorbance of the pꢀnitrophenoxide anion (λ = 400 nm).
The observed rate constants were determined from the depenꢀ
dence
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17. Z.ꢀG. Cui, J. P. Canselier, Colloid Polym. Sci., 2001,
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ln(А∞ – А) = –kobst + const,
18. E. J. Fendler and J. H. Fendler, Adv. Phys. Org. Chem.,
1970, 8, 271.
where А and А∞ are the absorbancies of the solution at the
moment t and at the end of the reaction, respectively. They were
19. I. V. Berezin and K. Martinek, Osnovy fizicheskoi khimii
fermentativnogo kataliza [Foundations of Physical Chemistry