Vinamidinium salts
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 5, May, 2006
863
washed with cold water, and recrystallized from 50% aqueous
MeOH. Salt 2 was obtained in a yield of 13 g (0.035 mol, 35%),
m.p. 245—246 °C. Found (%): C, 48.56; H, 4.82; Cl, 9.39;
N, 11.28. C15H18ClN3O6. Calculated (%): C, 48.52; H, 4.85;
Cl, 9.43; N, 11.32. 1H NMR (D2O), δ: 2.9 (s, 6 H, 2 NMe); 3.3
(s, 6 H, 2 NMe); 7.8 (s, 2 H, CH azometh.); 8.0 (dm, 4 H,
arom.). IR (Nujol mulls), ν/cm–1: 1780 (C=O), 1600 (C=N),
1100 br (ClO4–), 1710 (C=O).
1H NMR (CDCl3), δ: 2.9 (s, 12 H, Me); 6.8 and 7.8 (both s,
2 H each, azometh.); 7.8 (dm, 8 H, arom.). IR (Nujol
mulls), ν/cm–1: 1780 (C=O), 1710 (C=O), 1640 (C=N),
1600 (C=C).
4ꢀSalicylideneaminopyrazole (7). A mixture of perchlorate 2
(1.113 g, 3 mmol) and hydrazine hydrate (0.68 mL, 12 mmol)
was refluxed in methanol (100 mL) for 10 h. Then methanol was
evaporated. The residue was dissolved in benzene (50 mL) and
refluxed with salicylaldehyde (0.31 mL, 3 mmol) for 12 h. The
reaction mixture was chromatographed on silica gel (benzene),
and the fraction with Rf 0.2 (TLC control) was collected.
Pyrazole 7 was obtained in a yield of 0.01 g (0.054 mmol, 18%),
m.p. 188—190 °C. Found (%): C, 64.25; H, 4.76; N, 22.39.
C10H9N3O. Calculated (%): C, 64.17; H, 4.81; N, 22.46.
1H NMR (CDCl3), δ: 6.8 (t, 2 H, CH arom., J = 7.6 Hz); 7.3 (t,
1 H, arom., J = 7.8 Hz); 7.4 (d, 1 H, arom., J = 8.1 Hz); 7.8 (s,
2 H, CH, pyrazole); 8.8 (s, 1 H, CH, azometh.); 12.80 (br.s,
1 H, NH); 12.94 (s, 1 H, OH). IR (Nujol mulls), ν/cm–1: 3150
(NH), 3100 (OH), 1610 (C=N), 1570 (C=C).
Nꢀ[2ꢀPhthalimidoꢀ3ꢀ(pꢀtolyl)propꢀ1ꢀenyl]ꢀpꢀtoluidine (3).
A mixture of perchlorate 2 (556 mg, 1.5 mmol), pꢀtoluidine
(321 mg, 3 mmol), and triethylamine (0.21 mL, 1.5 mmol) was
refluxed in MeOH (100 mL) for 3 h. The yellow precipitate that
formed was filtered off and washed with hot MeOH (2×25 mL).
The mother liquor was refluxed for 3 h, concentrated, and cooled.
The yellow precipitate that formed was filtered off and washed
with hot methanol (2×25 mL). The combined precipitates were
dried in a drying oven at 40—50 °C. Toluidine 3 was obtained in
a yield of 0.495 g (1.25 mmol, 85%), m.p. 275 °C. Found (%):
C, 76.02; H, 5.26; N, 10.57. C25H21N3O2. Calculated (%):
1
C, 75.95; H, 5.31; N, 10.63. H NMR (CDCl3), δ: 2.3 (s, 6 H,
2 Me); 7.2 and 7.4 (both d, 4 H each, arom. toluid., J = 8.3 Hz);
7.7 (d, 2 H, arom. phthal., J = 7.5 Hz); 7.9 (d, 2 H, arom.
phthal., J = 7.5 Hz); 8.6 (s, 2 H, CH azometh.). IR (Nujol
mulls), ν/cm–1: 3170 br. (NH), 1710 (C=O), 1680 (C=O), 1610
(C=N), 1580 (C=C).
This study was financially supported by the US Civilꢀ
ian Research and Development Foundation (CRDF) and
the Ministry of Education and Science of the Russian
Federation (Program "Fundamental Studies and Higher
Education," Grant Y1ꢀCꢀ04ꢀ01).
1ꢀPhenylꢀ4ꢀphthalimidopyrazole (4). A mixture of perchlorꢀ
ate 2 (742 mg, 2 mmol), phenylhydrazine sulfate (842 mg,
4 mmol), and triethylamine (0.84 mL, 6 mmol) was refluxed in
methanol (50 mL) for 10 h. The precipitate that formed upon
cooling was filtered off and dried in air. Recrystallization from
benzene (100 mL) afforded pyrazole 4 in a yield of 0.135 g
(0.47 mmol, 23.5%), m.p. 157—159 °C. Found (%): C, 70.66;
H, 3.75; N, 14.47. C17H11N3O2. Calculated (%): C, 70.59;
H, 3.81; N, 14.5. 1H NMR (CDCl3), δ: 7.3, 7.5, and 7.9 (all m,
2 H each, CH, toluid.); 7.8 (m, 4 H, CH, arom. phthal.);
8.4 and 8.6 (both s, 1 H each, CH, pyrazole). IR (Nujol
mulls), ν/cm–1: 1870 (C=O), 1740 (C=O), 1690 (C=N),
1580 (C=C).
References
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Zinc Nꢀ[2ꢀphthalimidoꢀ3ꢀ(pꢀtolyl)propꢀ1ꢀenyl]ꢀpꢀtoluidinate
(5). A solution of anhydrous ZnCl2 (136 mg, 0.1 mol) in methaꢀ
nol (10 mL) was added to a suspension of compound 3 (395 mg,
0.1 mol) in methanol (50 mL). The reaction mixture was reꢀ
fluxed for 30 min. Then a solution of NaOH (40 mg, 0.1 mol) in
methanol (10 mL) was added. The precipitate of the complex
that formed was filtered off, washed with hot methanol, and
dried in air. The product was obtained in a yield of 196 mg
(46%), m.p. 280—282 °C. Found (%): C, 70.39; H, 4.63;
N, 9.78; Zn, 7.68. C50H40N6O4Zn. Calculated (%): C, 70,34;
H, 4.69; N, 9.85; Zn, 7.62. 1H NMR (CDCl3), δ: 2.2 (s, 6 H,
2 Me); 6.9 and 7.1 (both d, 4 H each, arom. toluid., J = 8.3 Hz);
7.7 (s, 2 H, azometh.); 7.8 and 8.0 (m, 2 H, arom., phthal.).
IR (Nujol mulls), ν/cm–1
:
1780 (C=O), 1700 (C=O),
1600 (C=N).
1,8ꢀBis(dimethylamino)ꢀ2,7ꢀbisphthalimidoꢀ4,5ꢀdiazaoctaꢀ
1,3,5,7ꢀtetraene (6). A mixture of perchlorate 2 (742 mg,
2 mmol) and hydrazine hydrate (0.12 mL, 2 mmol) in MeOH
(25 mL) was refluxed for 1 h. The red precipitate that formed
was filtered off, washed with hot methanol, and dried in air.
Compound 6 was obtained in a yield of 0.157 g (0.326 mmol,
32.6%), m.p. 242 °C. Found (%): C, 64.51; H, 4.9; N, 17.32.
11. J. F. W. McOmie, Protective Groups in Organic Chemistry,
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12. A. K. Bose, F. Greer, and C. C. Price, J. Org. Chem., 1958,
23, 1335.
13. G. M. Coppola, G. E. Hardtmannn, and B. S. Huesi,
J. Heterocycl. Chem, 1974, 11, 51.
C
26H24N6O4. Calculated (%): C, 64.46; H, 4.96; N, 17.32.