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IGNATOVICH et al.
stirred at 70–80°C for 4 h (TLC control), and upon
completion of the reaction the catalyst was separated
by filtration, and the precipitate was washed with
ethanol. The filtrate was evaporated to reduce by 2/3
its original volume and acidified with 0.4 mL of
concentrated HCl to pH 1, and the resulting 1,3-phe-
nylenediamine dihydrochloride precipitate was washed
with dilute HCl (1 : 1), dried, and recrystallized from a
methanol–hexane mixture.
N-(4-Methyl-3-aminophenyl)-4-(pyrid-3-yl)pyri-
midin-2-amine (12). Yield 74–80%, yellow crystals,
mp 160–162°C (mp 164–165°C [14]). IR spectrum, ν,
cm–1: 3440–3360, 1630, 1580, 1450. Mass spectrum,
m/z (Irel, %): 277 (100) [M]+, 262 (78) [M – CH3]+, 121
(9), 77 (5.5).
N-(2-Methyl-5-aminophenyl)-4-(pyrid-3-yl)pyri-
midin-2-amine (13). Yield 69–77%, yellow crystals,
mp 138–140°C (mp 134–136°C [15]). IR spectrum, ν,
cm–1: 3340, 3235, 3044, 1580, 1551, 1450. Mass
spectrum, m/z (Irel, %): 277 (100) [M]+, 262 (90) [M –
CH3]+, 121 (20), 77 (4.5).
1,3-Phenylenediamine dihydrochloride (11). Yield
88–90%, white crystals, mp >205°C (decomp.). IR
spectrum, ν, cm–1: 3410, 2965 b (NH), 1608, 1584,
1600, 1490, 1200, 1185. Mass spectrum, m/z (Irel, %):
108.05 (90) [M – H]+. Found, %: C 39.79; H 5.59; N
15.46; Cl 39.17. C6H10Cl2N2. Calculated, %: C 39.80;
H 5.57; N 15.47; Cl 39.16.
N-(3-Aminophenyl)-4-(pyrid-3-yl)pyrimidin-2-
amine (14). Yield 75–77%, yellow crystals, mp 89–
91°C (mp 89–92°C [14]). IR spectrum, ν, cm–1: 3414,
3315, 1630, 1579, 1560, 1410. Mass spectrum, m/z
(Irel, %): 262 (100) [M]+, 263 (80) [M + 1]+, 247 (11)
[M – NH2]+, 156 (6.3).
Reduction of nitroarylaminopyrimidines 6–8 and
nitroanilines 1, 9, 10. a. To 0.177 g (0.5 mmol) of 1
or 6–10, the nanocatalyst (0.05 mmol, 0.1 equiv.)
dispersed in 2 mL of methanol was added at room
temperature, after which 0.3 mL of hydrazine hydrate
(3.5 mmol, 5 or 8 equiv.) was poured dropwise into the
resulting mass. The reaction mixture was refluxed for
1–4 h; after ~15 min of heating it started to foam.
Warm reaction mixture was filtered through Celite,
washed with methanol, and the combined filtrate was
evaporated. The residue was dissolved in 10 mL of
ethyl acetate, washed with water, dried, and evaporated
to reduce by 2/3 its original volume, and the product
was precipitated by the addition of petroleum ether.
4-Methyl-1,3-phenylenediamine dihydrochloride
(15). Yield 82%, white crystals, mp > 200°C
(decomp.). IR spectrum, ν, cm–1: 3300, 2980 (NH),
1612, 1580, 1475, 1200, 1190. Mass spectrum, m/z
(Irel, %): 122.05 (100) [M]+, 108.02 (52) [M – CH3]+,
78.01 (26), 51 (15), Found, %: C 43.00; H 6.22; N
14.35; Cl 36.37. C7H12Cl2N2. Calculated, %: C 43.10;
H 6.20; N 14.36; Cl 36.35.
1,4-Phenylenediamine dihydrochloride (16). Yield
82%, white crystals, mp > 220°C (decomp.). IR
spectrum, ν, cm–1: 3995, 2923 (NH), 1620, 1512, 1435,
1250, 1130. Mass spectrum, m/z (Irel, %): 108.05 (100)
[M]+, 80.01 (44), 51 (17). Found, %: C 39.79; H 5.58;
N 15.47; Cl 39.17. C6H10Cl2N2. Calculated, %: C
39.80; H 5.57; N 15.47; Cl 39.16.
b. To a suspension of 0.5 mM of nitro derivative in
1 mL of ethanol, the Ni/Co or PVP(Ni/Co) sol
(0.05 mmol in 1 mL of ethanol) was added under
stirring and heating to 50°C. After 5–7 min, 0.18 mL
of hydrazine hydrate (3.5 mmol, 5 equiv.) was added.
The reaction mixture was refluxed for 0.3–0.75 h (TLC
control). Upon completion of the reaction, warm
reaction mixture was filtered through Celite, washed
with ethanol, and the combined filtrate was eva-
porated. The residue was dissolved in 10 mL of ethyl
acetate, washed with water, evaporated to reduce by
2/3 its original volume, and the product was pre-
cipitated by the addition of petroleum ether. To isolate
the products of reduction of compounds 1, 9, and 10,
the filtrate was acidified with 0.4 mL of concentrated
HCl to pH 1. The dihydrochloride precipitated was
washed with dilute HCl (1 : 1), dried, and
recrystallized from a methanol–hexane mixture.
REFERENCES
1. Saha, A. and Ranu, B., J. Org. Chem., 2008, vol. 73,
no. 17, p. 6867. doi 10.1021/jo800863m
2. Cantillo, D., Moghaddam, M.M., and Kappe, C.O.,
J. Org. Chem., 2013, vol. 78, no. 9, p.4530. doi
10.1021/jo400556g
3. Blaser, H.U., Steiner, H., and Studer, M., Chem. Cat.
Chem., 2009, vol. 1, p. 210. doi 10.1002/cctc.200900129
4. Ignatovich, Zh.V., Kadutskii, A.P., Koroleva, E.V.,
Baranovskii, A.V., and Gusak, K.N., Russ. J. Org.
Chem., 2009, vol. 45, no. 7, p. 1083. doi 10.1134/
S1070428009070148
5. Mitsudome, T. and Kaneda, K., Chem. Cat. Chem.,
2013, vol. 5, no. 7, p. 1681. doi 10.1002/cctc.201200724
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 3 2018