670
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 3, March, 2015
Bren et al.
a Varian Excalibur 3100 FTꢀIR spectrometer by the frustrated
total internal reflection using a ZnSe crystal. H NMR spectra
OH); 11.46 (s, 1 H, OH). IR, /cm–1: 3509, 3033 (OH), 1610
(N—C(O)), 1563 (C=N), 1297 (C—O).
1
were recorded on a Varian Unity 300 spectrometer (300 MHz)
in CDCl3 or DMSOꢀd6, using residual signals of the solvent as
a reference ( 7.25 and 2.50). Electron absorption spectra were
recorded on a Varian Cary 100 spectrophotometer. Mass spectra
were recorded on a Shimadzu GCMSꢀQP2010 SE massꢀspectroꢀ
meter, using method of electron ionization with direct injection of
the sample into the source of ions (70 eV). Elemental analysis
was performed on a EuroVector EAꢀ3000 elemental analyzer.
Melting points were determined in glass capillaries on a PTP(M)
apparatus. Reaction progress and purity of compounds obtained
were monitored by TLC (Silufol Uꢀ254 plates, eluent chloroform—
methanol, 5 : 1; visualization by iodine vapors in a moist chamber).
5ꢀPhenylpyrazolidinꢀ3ꢀone (2) was synthesized according to
the procedure described earlier.19 M.p. 101—102 C (ethyl acetate);
cf. Ref. 19: m.p. 95—97 C (toluene); cf. Ref. 21: m.p. 101—102 C
(propanꢀ2ꢀol). Found (%): C, 66.58; H, 6.15; N, 17.35. C9H10N2O.
Calculated (%): C, 66.65; H, 6.21; N, 17.27.
Synthesis of azomethinimines (general procedure). Trifluoroꢀ
acetic acid (0.1 mL) was added to a mixture of 5ꢀphenylpyrazolꢀ
idinꢀ3ꢀone (2) (10 mmol) and the corresponding substituted
benzaldehyde (10 mmol) in propanꢀ2ꢀol (25 mL). The reaction
mixture was refluxed for 3 h. The reaction completion was deꢀ
termined by TLC. Then, the reaction mixture was cooled to
~20 C, a precipitate formed was filtered off, crystallized from
nꢀbutanol, and dried in air.
1ꢀ(2ꢀHydroxyꢀ5ꢀnitrobenzylidene)ꢀ3ꢀoxoꢀ5ꢀphenylpyrazoliꢀ
diniumꢀ1,2ꢀylide (3d) was obtained from pyrazolidone 2 and
2ꢀhydroxyꢀ5ꢀnitrobenzaldehyde. The yield was 38%. A yellow powꢀ
der, m.p. > 250 C (decomp.). MS (EI, 70 eV), m/z (Irel (%)):
311 [M]+ (16). Found (%): C, 61.81; H, 4.15; N, 13.43.
1
C16H13N3O4. Calculated (%): C, 61.73; H, 4.21; N, 13.50. H
NMR (DMSOꢀd6), : 2.59 (dd, 1 H, CH, 3J = 4.5 Hz, 2J = 16.8 Hz);
3
3.22 (dd, 1 H, CH, J = 9.8 Hz, 2J = 16.8 Hz); 6.02 (dd, 1 H,
CH, 3J = 4.5 Hz, 2J = 9.9 Hz); 7.05 (d, 1 H, CArH, 3J = 9.0 Hz);
7.37—7.48 (m, 4 H, CArH, CH=N); 8.22 (dd, 1 H, CArH,
3J = 3.0 Hz, 2J = 9.0 Hz); 9.82 (d, 1 H, CArH, 3J = 3.0 Hz);
12.40 (s, 1 H, OH). IR, /cm–1: 3111 (OH); 1637 (C=O); 1613
(N—C(O)); 1546 (C=N); 1491 (N=O); 1293, 1279 (C—O); 1250
(N=O); 1085 (C—N).
1ꢀ[(2ꢀHydroxynaphthalenꢀ1ꢀyl)methylidene]ꢀ3ꢀoxoꢀ5ꢀphenylꢀ
pyrazolidiniumꢀ1,2ꢀylide (3e) was obtained from pyrazolidone 2
and 2ꢀhydroxynaphthaleneꢀ1ꢀcarbaldehyde. The yield was 72%.
A light yellow powder, m.p. 223—224 C. Found (%): C, 76.01;
H, 5.03; N, 8.92. C20H16N2O2. Calculated (%): C, 75.93;
H, 5.10; N, 8.85. MS (EI, 70 eV), m/z (Irel (%)): 316 [M]+ (42).
1H NMR (CDCl3), : 3.01 (dd, 1 H, CH, 3J = 6.3 Hz, 2J =16.8 Hz);
3.41 (dd, 1 H, CH, 3J = 9.9 Hz, 2J =17.1 Hz); 5.70 (dd, 1 H,
CH, 3J = 6.3 Hz, 2J = 9.6 Hz); 7.10—7.52 (m, 9 H, CArH); 7.68
(s, 1 H, CH=N); 7.70—7.87 (m, 2 H, CArH); 12.01 (s, 1 H, OH).
IR, /cm–1: 3058 (OH); 1661 (C=O); 1594 (C=N); 1247, 1238
(C—O); 1101 (C—N).
1ꢀ(2ꢀHydroxybenzylidene)ꢀ3ꢀoxoꢀ5ꢀphenylpyrazolidiniumꢀ
1,2ꢀylide (3a) was obtained from pyrazolidone 2 and 2ꢀhydroxyꢀ
benzaldehyde. The yield was 45%. A light yellow powder, m.p.
234—235 C (decomp.). Found (%): C, 72.24; H, 5.25; N, 10.60.
C16H14N2O2. Calculated (%): C, 72.17; H, 5.30; N, 10.52. MS
This work was financially supported by the Ministry of
Education and Science of the Russian Federation (Project
No. 4.88.2014/K within the Project Part of the State
Assignment in the Academic Area) and by the Council on
Grants at the President of the Russian Federation (Grant
NShꢀ274.2014.3).
1
(EI, 70 eV), m/z (Irel (%)): 266 [M]+ (46). H NMR (CDCl3),
: 2.91 (dd, 1 H, CH, 3J = 6.0 Hz, 2J = 16.8 Hz); 3.33 (dd, 1 H,
CH, 3J = 10.0 Hz, 2J = 17.1 Hz); 5.52 (dd, 1 H, CH, 3J = 6.3 Hz,
2J = 9.9 Hz); 6.72—6.96 (m, 4 H, CArH); 7.22—7.45 (m, 6 H,
CArH, CH=N); 12.82 (s, 1 H, OH). IR, /cm–1: 3078 (OH);
1629 (C=O); 1600 (N—C(O)); 1558 (C=N); 1459 (N—N); 1260,
1246 (C—O); 1069 (C—N).
References
1ꢀ(4ꢀHydroxybenzylidene)ꢀ3ꢀoxoꢀ5ꢀphenylpyrazolidiniumꢀ
1,2ꢀylide (3b) was obtained from pyrazolidone 2 and 4ꢀhydroxyꢀ
benzaldehyde. The yield was 49%. A colorless powder, m.p.
> 250 C (decomp.). Found (%): C, 72.26; H, 5.22; N, 10.58.
C16H14N2O2. Calculated (%): C, 72.17; H, 5.30; N, 10.52.
MS (EI, 70 eV), m/z (Irel (%)): 266 [M]+ (42). 1H NMR
(DMSOꢀd6), : 2.35—2.53 (m, 1 H, CH); 3.07—3.21 (m, 1 H,
CH); 5.71—5.82 (m, 1 H, CH); 6.87 (d, 2 H, CArH, 3J = 7.5 Hz);
7.26 (s, 1 H, CH=N); 7.28—7.45 (m, 5 H, CArH); 8.17 (d, 2 H,
CArH, 3J = 7.5 Hz); 11.14 (s, 1 H, OH). IR, /cm–1: 3033 (OH),
1639 (C=O), 1610 (N—C(O)), 1577 (C=N), 1444 (N—N), 1296
(C—O), 1076 (C—N).
1ꢀ(2,4ꢀDihydroxybenzylidene)ꢀ3ꢀoxoꢀ5ꢀphenylpyrazolidinꢀ
iumꢀ1,2ꢀylide (3c) was obtained from pyrazolidone 2 and 2,4ꢀdiꢀ
hydroxybenzaldehyde. The yield was 42%. A light yellow powder,
m.p. > 250 C (decomp.). Found (%): C, 68.16; H, 4.92; N, 10.01.
C16H14N2O3. Calculated (%): C, 68.08; H, 5.00; N, 9.92. MS
(EI, 70 eV), m/z (Irel (%)): 282 [M]+ (29). 1H NMR (DMSOꢀd6),
: 2.47 (dd, 1 H, CH, 3J = 4.8 Hz, 2J = 14.1 Hz); 3.15 (dd, 1 H,
CH, 3J = 9.9 Hz, 2J = 16.5 Hz); 5.82 (dd, 1 H, CH, 3J = 4.5 Hz,
2J = 9.9 Hz); 6.27—6.38 (m, 2 H, CArH); 7.31—7.47 (m, 6 H,
CArH, CH=N); 8.36 (d, 1 H, CArH, 3J = 9.0 Hz); 10.36 (s, 1 H,
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