Synthesis of azole-containing allylamines

Full text of DOI:10.1134/S1070363212030280

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 3, pp. 515–516. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © Yu.L. Piterskaya, I.V. Suvorova, M.V. Karpov, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 3, pp. 523–524.
LETTERS
TO THE EDITOR
Synthesis of Azole-Containing Allylamines
Yu. L. Piterskaya, I. V. Suvorova, and M. V. Karpov
St. Petersburg State Technological Institute (Technical University),
Moskovskii pr. 26, St. Petersburg, 190013 Russia
e-mail: siv@itcwin.com
Received November 28, 2011
DOI: 10.1134/S1070363212030280
Allylamine derivatives like terbinafine and naftifine
are known to be effective modern fungicidal drugs [1,
2]. There are no data on the use of α,β-acetylene
aldimines [3, 4] in the synthesis of allylamines.
3-Heteroaryl-substituted allylamines were found to be
obtained via the sequential double nucleophilic addi-
tion [3] of 1-methyl-2-mercaptoimidazole and sodium
borohydride to α,β-acetylene aldimine.
Ph
Ph
N
N
MeOH
+
HS
S
N
N
N
N
I
III
II
H1
Cl_
Ph
Ph
S
N
N
NaBH4
HCl
2
S
NH
CH2
N
N
H2N+
IV
V
The reaction proceeds in methanol. Initially, thiol II
reacts with α,β-acetylene aldimine I to form azadiene
III, which is then reduced with sodium borohydride to
allylamine IV. The allylamine was isolated as a
crystalline hydrochloride V, which is stable in air and
The one-pot method of synthesis allows the
preparation of previously unknown and inavailable
azole-containing allylamines and isolating them as
crystalline hydrochlorides.
1
tert-Butyl-[3-(1-methyl-1H-benzimidazol-2-ylsulfan-
yl)-3-phenylallyl]amine (V). To a solution of 0.01 mol
of acetylene aldimine in 50 ml of methanol was added
with stirring a solution of 0.01 mol of 1-methyl-2-
mercapto-1H-benzimidazole. After 30 min to the
reaction mixture was added in small portions a 3-fold
molar excess of sodium borohydride. The mixture was
has a distinct melting point. The H NMR spectrum of
compound V contains the proton signals characteristic
of the protonated allylamine groups: a triplet of
methylidene proton (Н1) at δ 6.87 ppm (3JНН 7.1 Hz)
and a multiplet of two methylene protons at δ 4.09 ppm.
A signal of two protons of the ammonium group
(NH2+) appears as a broadened singlet at δ 10.02 ppm.
515

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PITERSKAYA et al.
3
refluxed for 15 min, then cooled and diluted with 10-
fold excess of water. The resulting emulsion was twice
extracted with diethyl ether. The combined extracts
were dried over anhydrous sodium sulfate. The solvent
was evaporated in a vacuum on a rotary evaporator,
and the residue was dissolved in acetone. Since allyl-
amines obtained are thick viscous oils, which are
difficult to crystallize, they were isolated as hydro-
chlorides by adding dropwise concentrated hydro-
chloric acid to pH 5. The precipitated crystals were
filtered off and dried in air. The resulting compound is
colorless crystals, readily soluble in ethanol and
(1Н, JНН 7.1 Hz), 10.02 s (2Н). 13C NMR spectrum,
δС, ppm (101 MHz, DMSO-d6): 147.22, 138.07,
134.22, 133.61, 129.78, 129.14, 127.86, 125.82,
125.58, 115.22, 112.62, 56.80, 41.53, 32.45, 25.61.
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2. Marks, S., Cantrell, W., Varma, R., and Elewski, B.,
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3. Shimizu, M., Hachiya, I., and Mizota, I., Chem.
Commun., 2009, vol. 1, no. 3, p. 874.
1
methanol. Yield 75%, mp 242°С. Н NMR spectrum,
δ, ppm (400.13 MHz, DMSO-d6): 1.44 s (9Н), 3.97 s
(3Н), 4.09 m (2Н), 6.87 t (1Н, 3JНН 7.1 Hz), 7.15–7.34
m (3Н), 7.35–7.48 m (2Н), 7.63–7.64 m (2Н), 7.74 d
4. Stadnichuk, M.D., Khramchikhin, A.V., Piterskaya, Yu.L.,
and Suvorova, I.V., Zh. Obshch. Khim., 1999, vol. 69,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 3 2012