ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 2, p. 331.
Pleiades Publishing, Ltd., 2008.
Original Russian Text
No. 2, pp. 347 348.
D.P. Khrustalev, G.T. Khamzina, S.D. Fazylov, A.M. Gazaliev, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78,
LETTERS
TO THE EDITOR
Preparation of Diaminomethanes
under Microwave Irradiation
D. P. Khrustalev, G. T. Khamzina, S. D. Fazylov, and A. M. Gazaliev
Institute of Organic Synthesis and Coal Chemistry of the Kazakhstan Republic,
ul. Alikhanova 1, Karaganda, 100000 Kazakhstan
e-mail: khrustalev@mail.kz
Received July 6, 2007
DOI: 10.1134/S1070363208020308
Effect of microwave irradiation on organic reac-
tions is being extensively studied in view of the en-
hancing demand for resource-saving technologies,
Their structure and purity were established by means
of IR and NMR spectroscopy and TLC. Physico-
chemical constants of compounds I III agree with
published data [4]. Compound IV is a white crystal-
line substance, mp 94 C. H NMR spectrum (DMSO-
d6), ppm: 1.2 1.7 m (12H, piperidine), 2.4 s (2H,
[
1 3]. The advantages of microwave irradiation over
1
traditional activation sources include the absence of
heat carrier, uniform heating of the reaction mixture,
absence of heat-transfer inertia, possibility of solvent-
free conditions, and shorter reaction time.
CH ), 2.85 d (2H, NCH, piperidine), 3.59 d (4H,
2
NCH , piperidine), 7.38 8.46 m (8H, pyridine CH).
2
+
Mass spectrum, m/z (I , %): 336 [M] , 175 (100),
rel
We have explored the synthesis of diaminomethanes
under microwave irradiation, according to the follow-
ing scheme:
1
9
62 (6), 146 (4), 132 (36), 118 (10), 105 (13), 98 (3),
2 (23), 84 (18), 78 (7), 65 (11), 51 (8), 44 (85).
The IR spectra were registered in thin layer be-
MW
1
CHO + 2H N
N CH N
,
2
tween KBr plates in the range 400 4000 cm on a
H O
2
1
UR-20 spectrometer. The H NMR spectra were taken
I IV
on a Bruker DRX-500 (500.13 MHz) instrument. TLC
was carried out on Silufol UV-254 plates, eluent
propan-2-ol benzene ammonia (10:5:2), develop-
ment in iodine vapor. The mass spectrum was ob-
tained on an MX-1321 mass spectrometer, direct
sample admission, ionizing electron energy 70 eV.
N
Et
N
=
N
O ,
N
,
N
,
.
Et
N
I
II
III
IV
REFERENCES
Yields, %: 65 (I), 69.4 (II), 62.4 (III), 70 (IV).
1
2
. Tselinskii, I.V., Astrat’ev, A.A., and Brykov, A.S., Zh.
Obshch. Khim., 1996, vol. 66, no. 10, p. 1699.
It was found that under these conditions diamino-
methanes I IV are formed within 3 4 min without
solvent. The overall synthetic procedure involves
microwave activation (350 W) of a mixture of 0.01
mol of Paraform and 0.02 mol of a secondary amine.
The reaction products were isolated by vacuum
distillation.
. Grigor’ev, A.D., Dmitrieva, N.M., El’tsov, A.V., Iva-
nov, A.S., Panarina, A.E., and Sokolova, N.B., Zh.
Obshch. Khim., 1997, vol. 67, no. 6, p. 1042.
3. Hashemi, M.M., Rahimi, A., Karimi-Jaberi, Z., and
Ahmadbeni, Y., Acta Chim. Slov., 2005, vol. 52, p. 86.
Diaminomethanes I III are colorless strongly basic
liquids soluble in water and organic solvents.
4. Vlasova, L.M., Cand. Sci. (Chem.) Dissertation, Ka-
raganda, 1997.
331
Khrustalev
