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Thus, treatment of 1,3-dimethylolurea with propane-1,3-diamine gave a tricyclic docosane derivative
rather than the expected 5-substituted 1,3,5-triazinan-2-one. This product can be formally considered as a
macrocyclic Mannich base formed as a result of a multistage process in which urea acts as substrate,
formaldehyde as the methylene component, and propane-1,3-diamine as the amine component. A special
feature of the structure of the obtained products is the fact that the nitrogen atoms of each of the two
propanediamine fragments is "joined" in pairs by methylene bridges, the source of which is evidently
formaldehyde eliminated in the course of the reaction from the 1,3-dimethylolurea.
IR spectra were recorded on a Shimadzu FTIR-8400S spectrophotometer using KBr pellets. 1H and 13C
NMR spectra were recorded on a Bruker Avance III-400 spectrometer (400 and 100 MHz, respectively) using
CDCl3 with the residual solvent signal as internal references (7.26 ppm for the 1H nucleus and 77.0 ppm for 13C
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nucleus). H–13C{1H} HMQC and H–1H COSY experiments were performed under the same condition on the
same instrument. Mass spectra were recorded on a Bruker micrOTOF 10223 mass spectrometer (ESI-TOF).
Elemental analysis was performed on a Leco CHNS(O) 942 analyzer. Melting points were determined on a
PTP-M apparatus and are not corrected. For the recrystallization of compound 3, commercial solvents were
used, which were purified by distillation and rejection of the first 5% and the last 10% of the distillate.
1,3-Bis(hydroxymethyl)urea (1) was prepared by an improved method [13] from 35% formalin
(189.0 g, 2.2 mol) and urea (65.8 g, 1.1 mol) in the presence of Et3N (1.5-2.0 ml) (in the study [13] in the
presence of Ba(OH)2) with the reaction mixture being held at room temperature for 30 h. Yield 57%. White
powder. Mp 122-125ºC (mp 126ºC [11], mp 121-126ºC [13, 16]).
1,3,5,7,11,13,15,17-Octaazatricyclo[15.3.1.17,11]docosane-4,14-dione (3). 1,3-Bis(hydroxymethyl)urea (1)
(9.61 g, 80.0 mmol) and propane-1,3-diamine (2.97 g, 3.36 ml, 40.1 mmol) were mixed in 96% EtOH (15 ml) at 5ºC.
Cooling was removed, and the reaction mixture was heated to reflux with continuation of the stirring. Reflux was
continued in the flask fitted with a reflux condenser for 1 h, heating was removed, stirring was continued for a further
1 h, and the reaction mixture was held for 1 day at room temperature. The precipitate formed was filtered off, washed
with 96% EtOH (cooled to 5ºC), and dried in air. Yield 3.53 g (52%). After 4 days a further precipitate had formed to
give more product (0.61 g, 9%). Overall yield 4.14 g (61%). Coarse, transparent, colorless crystals which whitened in
air without a change in the spectroscopic properties. Mp 205-207C (MeCN). IR spectrum, ν, cm-1: 1561 (C–N),
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1591 (def. NH), 1677 (С=О), 2723, 2747, 2794, 2867, 2927 (CH2), 3050, 3215, 3259 (NH), 3467 (ОН). Н NMR
spectrum, δ, ppm (J, Hz: 1.69 (2Н, dm, 2J = 13.3, 9,19-СНВ); 1.79 (2Н, pseudo qt, 2J = 12.5, 3J = 12.5, 3 J = 4.3,
9,19-СНА); 2.13 (4Н, pseudo td, 2J = 11.7, 3J = 11.7, 3J = 3.0, 8,10,18,20-СНВ); 2.45 (2Н, d, 2J = 9.5, 21,22-СНВ);
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2.84 (4Н, dm, J = 11.0, 8,10,18,20-СНА); 3.40 (4Н, dd J = 12.2, J = 3.1, 2,6,12,16-СНВ); 3.97 (2Н, d, J = 9.5,
21,22-СНA); 4.29 (4Н, dd, 2J = 12.1, 3J = 10.1, 2,6,12,16-СНA); 8.48 (4Н, dd, 3J = 9.9, 3J = 2.9, 4NH). 13С{1H} NMR
spectrum, δ, ppm: 157.9 (C-4,14); 70.2 (C-21,22); 59.6 (C-2,6,12,16); 50.4 (C-8,10,18,20); 24.6 (C-9,19). Found,
m/z: 341.2411 [M+H]+. С14Н29N8О2. Calculated m/z: 341.2408. Found, %: С 45.62; Н 8.78; N 30.02.
С14Н28N8О2·2Н2О·0.5С2Н3N. Calculated, %: С 45.38; Н 8.51; N 29.99.
X-ray structural analysis of compound 3 was carried out on an Agilent Technologies SuperNova
Atlas single crystal diffractometer using the program packages CrysAlisPro [17] and SIR2011 [18]. Structure of
32H2O·0.5CH3CN (a 18.1167(5), b 12.3467(3), c 18.9588(5) Å; 91.525(2)º; V 4239.25(19) Å3; Z 8)
crystallizing in a monoclinic crystal system, space group P21/n, R 0.041, Rw 0.053, GOOF 0.99. Measured
parameters: 100 K, microfocussed monochromator CuK-radiation (min 3.33º, max 76.84º), 8900 reflections,
8314 independent reflections, F > 3F; single crystal size 0.16×0.19×0.22 mm. The crystallographic data has
been placed at the Cambridge Crystallographic Data Center (deposit CCDC 996106).
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Files accompanying this information, containing the H–13C{1H} HMQC and H–1H COSY spectra of
This work was undertaken in the framework of the baseline of the State Assignment of the Ministry of
Education and Science of the Russian Federation for scientific activity 2014/191, project code 644. X-ray
structural studies were performed with partial financial support from the Russian Foundation for Basic Research
(grant 13-03-00888).
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