4-Functionally substituted 3-heterylpyrazoles: XIV. N-benzyl-N-[3- aryl(heteryl)-4-pyrazolylmethylene]amines and their derivatives

Article abstract of DOI:10.1007/s11178-005-0128-8

Reduction with sodium tetrahydridoborate of Schiff bases derived from 3-aryl(heteryl)pyrazole-4-carbaldehydes and benzylamines gave N-benzyl-N-[3-aryl(heteryl)-4-pyrazolylmethylene]amines which were acylated with benzoyl chloride and succinic and maleic anhydrides to obtain the corresponding amides. Treatment of the title compounds with phenyl isothiocyanate afforded substituted thioureas. 2005 Pleiades Publishing, Inc.

Full text of DOI:10.1007/s11178-005-0128-8

Russian Journal of Organic Chemistry, Vol. 41, No. 1, 2005, pp. 98 -102. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1,
2005, pp. 98-103.
Original Russian Text Copyright Ó 2005 by Bratenko, Panimarchuk, Chornous, Vovk.
4-Functionally Substituted 3-Heterylpyrazoles:
XIV.* N-Benzyl-N-[3-aryl(heteryl)-4-pyrazolylmethylene]amines
and Their Derivatives
M. K. Bratenko1, O. I. Panimarchuk1, V. A. Chornous1, and M. V. Vovk2
1 Bukovina State Medical Academy, Teatral’naya pl. 2, Chernovtsy, 58000 Ukraine
2 Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine
Received April 15, 2003
Abstract—Reduction with sodium tetrahydridoborate of Schiff bases derived from 3-aryl(heteryl)pyrazole-4-
carbaldehydes and benzylamines gave N-benzyl-N-[3-aryl(heteryl)-4-pyrazolylmethylene]amines which were
acylated with benzoyl chloride and succinic and maleic anhydrides to obtain the corresponding amides. Treatment
of the title compounds with phenyl isothiocyanate afforded substituted thioureas.
Scheme 1.
We previously described [2–4] a series of new func-
tionalized 3-aryl(heteryl)pyrazole derivatives in which
functional substituent is linked to the C4 atom of the
pyrazole ring through a CH2 or CH unit. The present
communication reports on the synthesis and some general
transformations of N-benzyl-N-(4-pyrazolyl)methan-
amines. Except for 3,5-diaminomethyl-1-phenylpyrazole
[5], there are no published data on such compounds.
&+2
1
&+ 1&+ $U
$U&+ 1+
ꢀꢀꢀꢀꢀ,,Dꢀꢁ,,E
5
5
1
1
1
3K
3K
,D ,M
,,,D ,,,N
+
1
&O
$U
3K
5
1D%+ ꢁ+&O
1
1
,9D ,9N
X = Cl, OH, CH, SCN, NCS.
I, R = Ph (a), 4-BrC6H4 (b), 4-ClC6H4 (c), 4-FC6H4 (d),
4-MeC6H4 (e), 4-MeOC6H4 (f), 2-thienyl (g), 3-pyridyl (h),
4-pyridyl (i), 2-benzofuryl (j); II, Ar = Ph (a), 4-FC6H4
(b); III, IV, Ar = R = Ph (a); Ar = Ph, R = 4-BrC6H4 (b),
4-ClC6H4 (c), 4-FC6H4 (d), 4-MeC6H4 (e), 4-MeOC6H4
(f), 2-thienyl (g), 3-pyridyl (h), 4-pyridyl (i), 2-benzofuryl
As initial compounds we used pyrazole-4-carb-
aldehydes Ia–Ij; they were treated with benzylamines
IIa and IIb according to the procedure developed by us
previously [4]. Schiff bases IIIa–IIIk thus obtained were
reduced with sodium tetrahydridoborate under mild
conditions (Scheme 1). The reduction products, N-benzyl-
N-[3-aryl(heteryl)-4-pyrazolylmethyl]amines, were
undistillable viscous oily liquids. Their analytically pure
samples were isolated as hydrochlorides IVa–IVk.
Compounds IVh and IVi possessing a pyridine substituent
in position 3 of the pyrazole ring were the corresponding
dihydrochlorides.
(j); Ar = 4-FC H4, R = 4-MeOC6H4 (k).
6
the 1H NMR spectra which contained singlets at d 8.8–
9.1 ppm typical of the 5-H proton in the pyrazole ring.As
a rule, signals from the methylene protons overlap each
other and appear as a broadened singlet or multiplet at
d 4.2–4.3 ppm. Exceptions are compounds IVd, IVh,
1
and IVj; in their H NMR spectra the singlet from the
Hydrochlorides IVa–IVk are colorless high-melting
crystalline substances. Their structure was confirmed by
methylene group attached to the pyrazole ring is displaced
slightly downfield relative to the signal from the benzyl
methylene protons.
* For communication XIII, see [1].
1070-4280/05/4101-0098Ó2005 Pleiades Publishing, Inc.

4-FUNCTIONALLY SUBSTITUTED 3-HETERYLPYRAZOLES: XIV.
99
Scheme 2.
3K
1
3K
5
2
1
1
3K
9D 9G
3K
$U
2
2
2
2
2
2
3K&ꢀ2ꢁ&O
1
1
&22+
1
1
&22+
,9D ,9Kꢀꢁ,9Mꢀꢁ,9N
5
2
5
2
3K1&6
$U
1
1
3K
3K
9,D ,9G
9,,
1
1+3K
5
6
1
1
3K
9,,,D 9,,,F
Thioureas VIIIa–VIIIc are characterized by a higher
barrier to rotation about the C–N bond, as compared to
amides [7, 8]; therefore, they exist in DMSO-d6
exclusively as the corresponding E isomers, in keeping
with the presence in their H NMR spectra of singlet
signals from the above protons.
We examined the behavior of amine hydrochlorides
IVa–IVh, IVj, and IVk in reactions with typical
electrophiles such as benzoyl chloride, succinic and maleic
anhydrides, and phenyl isothiocyanate. These reactions
were complete in 3 h on heating in acetonitrile (in reactions
with phenyl isothiocyanate, it is better to use ethanol as
solvent) in the presence of an organic base. We thus
obtained a series of new N,N-disubstituted benzamides
Va–Vd, succinamic acids VIa–VId, maleamic acid VII,
and thioureas VIIIa–VIIIc (Scheme 2).
1
EXPERIMENTAL
The IR spectra were recorded on a UR-20
spectrometer from samples prepared as KBr pellets. The
1
In the H NMR spectra of amides V–VII in
Scheme 3.
DMSO-d6 we observed more complex signals from the
methylene protons, 5-H, and a-CH= (VII). Protons of
the methylene groups gave rise to a multiplet consisting
of three overlapping signals, the intensity of one of these
being approximately equal to the overall intensity of the
two other signals. The 5-H proton appeared as two nearby
singlets with approximately equal intensities, and the
b-CH= proton in VII gave two doublets. This pattern is
likely to result from the existence of compounds V–VII
in DMSO-d6 as mixtures of stereoisomers due to restrict-
ed rotation about the amide C–N bond [6] (Scheme 3);
accurate assignment of signals to particular isomers
requires an additional study.
3K
1
1
2
2
5ꢀ
5ꢀ
5
1
1
3K
1
5
1
=ꢁIRUP
(ꢁIRUP
9,,
R' = Ph, CH=CHCOOH, CH2CH2COOH.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005

100
BRATENKO et al.
1H NMR spectra were measured on a Varian Gemini
instrument (300 MHz) using DMSO-d6 as solvent and
TMS as internal reference.
Harom), 8.53 s (1H, 5-H), 8.96 s (1H, CH=). Found, %:
C 79.31; H 4.86; N 11.33. C25H19N3O. Calculated, %:
C 79.57; H 5.04; N 11.14.
Compound IIIk. Yield 83%, mp 112–113°C. 1H NMR
spectrum, d, ppm: 3.82 s (3H, CH3O), 4.75 s (2H, CH2),
7.03 d (2H, Harom, J = 7.8 Hz), 7.30–7.49 m (7H, Harom),
7.65 d (2H, Harom, J = 7.8 Hz), 7.93 d (2H, Harom, J =
7.7 Hz), 8.53 s (1H, 5-H), 8.83 s (1H, CH=). Found, %:
C 74.56; H 5.02; N 10.70. C24H20FN3O. Calculated, %:
C 74.80; H 5.19; N 10.91.
Compounds IIIa–IIIc and IIIg were synthesized by
the procedure reported in [4].
N-Benzyl-N-[3-aryl(heteryl)-1-phenyl-1H-pyr-
azol-4-ylmethylene]amines IIId–IIIf and IIIh–IIIk
(general procedure). Benzylamine IIa or IIb, 0.01 mol,
and glacial acetic acid, 0.2 ml, were added to a solution
of 0.01 mol of aldehyde Id–If or Ih–Ij in 20 ml of toluene,
and the mixture was heated for 1 h in a flask equipped
with a Dean–Stark trap. The mixture was cooled, the
solvent was distilled off, the residue was treated with
3 ml of diethyl ether and 5 ml of hexane, and the
precipitate was filtered off and recrystallized from
ethanol.
Compound IIId. Yield 79%, mp 65–66°C. 1H NMR
spectrum, d, ppm: 4.72 s (2H, CH2), 7.23–7.97 m (14H,
Harom), 8.49 s (1H, 5-H), 8.94 s (1H, CH=). Found, %:
C 77.53; H 4.98; N 11.69. C23H18FN3. Calculated, %:
C 77.74; H 5.07; N 11.83.
N-Benzyl-N-[3-aryl(heteryl)-1-phenyl-1H-pyr-
azol-4-ylmethyl]amines IVa–IVk (general proce-
dure). A solution of 0.003 mol of Schiff base IIIa–IIIk
in 40 ml of methanol was heated to 50–55°C, and a
suspension of 1 g of sodium tetrahydridoborate in 50 ml
of ethanol was added. The mixture was left to stand for
3 h at room temperature, diluted with 100 ml of water,
and extracted with benzene (3´40 ml). The extract was
dried over anhydrous sodium sulfate and saturated with
dry hydrogen chloride, and the precipitate was filtered
off and dried under reduced pressure.
Compound IVa. Yield 91%, mp 215–216°C. 1H NMR
spectrum, d, ppm: 4.21 br.s (4H, CH2), 7.39–7.83 m (15H,
Harom), 8.88 s (1H, 5-H), 9.78 br.s (2H, H2N+). Found,
%: C 73.15; H 5.63; N 11.01. C23H22ClN3. Calculated,
%: C 73.50; H 5.85; N 11.18.
Compound IIIe. Yield 75%, mp 107–108°C. 1H NMR
spectrum, d, ppm: 2.42 s (3H, CH3), 4.72 s (2H, CH2),
7.28–7.90 m (14H, Harom), 8.46 s (1H, 5-H), 8.78 s (1H,
CH=). Found, %: C 81.97; H 5.89; N 11.87. C24H21N3.
Calculated, %: C 82.05; H 5.98; N 11.96.
Compound IVb. Yield 93%, mp 228–229°C. 1H NMR
spectrum, d, ppm: 4.22–4.24 m (4H, CH2), 7.24–7.79 m
(14H, Harom), 8.88 s (1H, 5-H), 9.79 br.s (2H, H2N+).
Found, %: C 60.39; H 4.47; N 9.03. C23H21BrClN3.
Calculated, %: C 60.72; H 4.62; N 9.24.
Compound IVc. Yield 91%, mp 210–211°C. 1H NMR
spectrum, d, ppm: 4.23 br.s (4H, CH2), 7.28–7.83 m (14H,
Harom), 8.90 s (1H, 5-H), 9.80 br.s (2H, H2N+). Found,
%: C 67.69; H 5.21; N 10.03. C23H21Cl2N3. Calculated,
%: C 67.32; H 5.12; N 10.24.
Compound IVd. Yield 86%, mp 212–214°C. 1H NMR
spectrum, d, ppm: 4.21–4.24 m (4H, CH2), 7.20–7.80 m
(14H, Harom), 8.80 s (1H, 5-H), 9.79 br.s (2H, H2N+).
Found, %: C 69.90; H 5.15; N 10.48. C23H21ClFN3.
Calculated, %: C 70.14; H 5.33; N 10.67.
Compound IVe. Yield 78%, mp 219–221°C. 1H NMR
spectrum, d, ppm: 2.36 s (3H, CH3), 4.28–4.30 m (4H,
CH2), 7.26–7.52 m (10H, Harom), 7.60 d (2H, Harom, J =
7.8 Hz), 7.90 d (2H, Harom, J = 7.9 Hz), 8.98 s (1H, 5-H),
9.84 br.s (2H, H2N+). Found, %: C 74.28; H 5.98;
N 10.56. C24H24ClN3. Calculated, %: C 73.94; H 6.16;
N 10.78.
Compound IIIf. Yield 73%, mp 101–103°C. 1H NMR
spectrum, d, ppm: 3.85 s (3H, CH3O), 4.75 s (2H, CH2),
7.05 d (2H, Harom, J = 7.8 Hz), 7.26–7.50 m (8H, Harom),
7.69 d (2H, Harom, J = 7.8 Hz), 7.97 d (2H, Harom, J =
7.7 Hz), 8.50 s (1H, 5-H), 8.88 s (1H, CH=). Found, %:
C 78.69; H 5.60; N 11.28. C24H21N3O. Calculated, %:
C 78.47; H 5.72; N 11.44.
Compound IIIh. Yield 82%, mp 99–100°C. 1H NMR
spectrum, d, ppm: 4.77 s (2H, CH2), 7.31–7.95 m (10H,
Harom), 8.18 d (2H, Harom, J = 7.6 Hz), 8.62 m (1H, Harom),
8.90 s (1H, Harom), 8.53 s (1H, 5-H), 8.97 s (1H, CH=).
Found, %: C 77.81; H 5.19; N 16.39. C22H18N4.
Calculated, %: C 78.10; H 5.32; N 16.56.
Compound IIIi. Yield 76%, mp 92–93°C. 1H NMR
spectrum, d, ppm: 4.79 s (2H, CH2), 7.25–7.51 m (8H,
Harom), 7.83 d (1H, Harom, J = 6.0 Hz), 7.94 d (2H, Harom
,
J = 7.8 Hz), 8.64 d (1H, Harom, J = 6.0 Hz), 8.59 s (1H,
5-H), 8.91 s (1H, CH=). Found, %: C 77.93; H 5.47;
N 16.30. C22H18N4. Calculated, %: C 78.10; H 5.32;
N 16.56.
Compound IIIj. Yield 88%, mp 128–130°C. 1H NMR
spectrum, d, ppm: 4.76 s (2H, CH2), 7.03–7.94 m (15H,
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005

4-FUNCTIONALLY SUBSTITUTED 3-HETERYLPYRAZOLES: XIV.
101
Compound IVf. Yield 77%, mp 217–218°C. 1H NMR
spectrum, d, ppm: 3.72 s (3H, CH3O), 4.29 br.s (4H, CH2),
7.04 d (2H, Harom, J = 7.9 Hz), 7.22–7.53 m (8H, Harom),
7.66 d (2H, Harom, J = 7.9 Hz), 7.94 d (2H, Harom, J =
7.8 Hz), 8.96 s (1H, 5-H), 9.83 br.s (2H, H2N+). Found,
%: C 70.73; H 5.70; N 10.08. C24H24ClN3O. Calculated,
%: C 71.02; H 5.92; N 10.36.
Compound IVg. Yield 81%, mp 187–189°C. 1H NMR
spectrum, d, ppm: 4.27 br.s (4H, CH2), 7.13–7.80 m (13H,
Harom), 8.82 s (1H, 5-H), 9.76 br.s (2H, H2N+). Found,
%: C 66.31; H 5.16; N 10.83. C21H20ClN3S. Calculated,
%: C 66.05; H 5.24; N 11.07.
acetonitrile. The mixture was heated for 3 h under reflux,
and 2 ml of water and 1 ml of ethanol were added to the
hot mixture. The mixture was cooled, and the precipitate
was filtered off, washed with water, dried, and
recrystallized from ethanol (Va–Vd) or benzene (VIa–
VId, VII).
Compound Va. Yield 75%, mp 115–116°C. IR
–1 1
spectrum: nC=O 1715 cm . H NMR spectrum, d, ppm:
4.38–4.58 m (4H, CH2), 7.03–7.56 m (18H, Harom),
7.92 d (2H, Harom, J = 7.8 Hz), 8.31 s and 8.48 s (1H,
5-H). Found, %: C 80.97; H 5.51; N 9.33. C30H25N3O.
Calculated, %: C 81.26; H 5.64; N 9.48.
Compound IVh. Yield 73%, mp 208–209°C. 1H NMR
spectrum, d, ppm: 4.24 br.s (4H, CH2), 7.38–7.84 m (12H,
Harom), 8.23 d (1H, Harom, J = 8.1 Hz), 8.72 s (1H, Harom),
8.95 s (1H, 5-H), 9.84 br.s (2H, H2N+). Found, %:
C 63.40; H 5.17; N 13.41. C22H22Cl2N4. Calculated, %:
C 63.11; H 5.30; N 13.49.
Compound Vb. Yield 70%, mp 130–131°C. IR
spectrum: nC=O 1710 cm . H NMR spectrum, d, ppm:
4.36–4.60 m (4H, CH2), 7.11–7.79 m (17H, Harom),
7.88 d (2H, Harom, J = 7.9 Hz), 8.35 s and 8.49 s (1H,
5-H). Found, %: C 75.16; H 4.91; N 8.58. C30H24ClN3O.
Calculated, %: C 75.39; H 5.03; N 8.79.
–1 1
Compound IVi. Yield 77%, mp 222–223°C. 1H NMR
spectrum, d, ppm: 4.28 s (2H, CH2), 4.40 s (2H, CH2),
7.41–7.66 m (8H, Harom), 7.89 d (2H, Harom, J = 7.9 Hz),
8.35 d (2H, Harom, J = 7.8 Hz), 8.97 d (2H, Harom, J =
7.8 Hz), 9.10 s (1H, 5-H), 10.19 br.s (2H, H2N+). Found,
%: C 63.43; H 5.45; N 13.30. C22H22Cl2N4. Calculated,
%: C 63.11; H 5.30; N 13.49.
Compound IVj. Yield 85%, mp 228–230°C. 1H NMR
spectrum, d, ppm: 4.32 s (2H, CH2), 4.44 s (2H, CH2),
7.29–7.69 m (13H, Harom), 7.88 d (2H, Harom, J = 7.8 Hz),
8.93 s (1H, 5-H), 9.88 br.s (2H, H2N+). Found, %:
C 71.88; H 5.13; N 10.02. C25H22ClN3O. Calculated, %:
C 72.20; H 5.29; N 10.10.
Compound IVk. Yield 79%, mp 214–216°C. 1H NMR
spectrum, d, ppm: 3.78 s (3H, CH3O), 4.28 br.s (4H, CH2),
7.08 d (2H, Harom, J = 7.8 Hz), 7.29–7.51 m (7H, Harom),
7.64 d (2H, Harom, J = 7.8 Hz), 7.94 d (2H, Harom, J =
7.8 Hz), 8.95 s (1H, 5-H), 9.90 br.s (2H, H2N+). Found,
%: C 68.20; H 5.15; N 9.90. C24H23ClFN3O. Calculated,
%: C 68.00; H 5.47; N 9.91.
Compound Vc. Yield 76%, mp 122–123°C. IR
spectrum: nC=O 1710 cm . H NMR spectrum, d, ppm:
2.34 s (3H, CH3), 4.35–4.56 m (4H, CH2), 7.07–7.51 m
(17H, Harom), 7.88 d (2H, Harom, J = 7.8 Hz), 8.34 s and
8.51 s (1H, 5-H). Found, %: C 81.71; H 5.64; N 8.95.
C31H27N3O. Calculated, %: C 81.40; H 5.90; N 9.19.
–1 1
Compound Vd. Yield 83%, mp 146–148°C. IR
–1 1
spectrum: nC=O 1715 cm . H NMR spectrum, d, ppm:
4.53–4.71 m (4H, CH2), 6.99–7.62 m (18H, Harom),
7.97 d (2H, Harom, J = 7.9 Hz), 8.49 s and 8.61 s (1H,
5-H). Found, %: C 79.16; H 5.01; N 8.47. C32H25N3O2.
Calculated, %: C 79.50; H 5.17; N 8.69.
Compound VIa. Yield 92%, mp 147–149°C. IR
–1
spectrum, n, cm : 1685, 1700 (C=O). 1H NMR spectrum,
d, ppm: 2.41–2.71 m (4H, CH2CH2), 4.52–4.57 m (4H,
CH2), 7.10–7.83 m (15H, Harom), 8.18 s and 8.36 s (1H,
5-H), 11.98 br.s (1H, COOH). Found, %: C 74.07;
H 5.75; N 9.66. C27H25N3O3. Calculated, %: C 73.80;
H 5.69; N 9.57.
Compound VIb. Yield 92%, mp 175–176°C. IR
N-Benzyl-N-[3-aryl(heteryl)-1-phenyl-1H-
pyrazol-4-ylmethyl]benzamides Va–Vd, N-benzyl-N-
[3-aryl-1-phenyl-1H-pyrazol-4-ylmethyl]-succinamic
acids VIa–VId, and N-benzyl-N-[3-(4-methoxy-
phenyl)-1-phenyl-1H-pyrazol-4-yl-methyl]maleamic
acid (VII). Benzoyl chloride, maleic anhydride, or succinic
anhydride, 0.001mol, and triethylamine, 0.001 mol (with
succinic or maleic anhydride) or 0.002 mol (with benzoyl
chloride), were added to a suspension of 0.001 mol of
hydrochloride IVa–IVe, IVj, or IVk in 10 ml of
–1
spectrum, n, cm : 1690, 1705 (C=O). 1H NMR spectrum,
d, ppm: 2.45–2.74 m (4H, CH2CH2), 4.48–4.59 m (4H,
CH2), 7.07–7.83 m (14H, Harom), 8.26 s and 8.37 s (1H,
5-H), 11.89 br.s (1H, COOH). Found, %: C 62.28;
H 4.40; N 7.97. C27H24BrN3O3. Calculated, %: C 62.55;
H 4.63; N 8.11.
Compound VIc. Yield 84%, mp 169–170°C. IR
–1
spectrum, n, cm : 1690, 1705 (C=O). 1H NMR spectrum,
d, ppm: 2.38–2.74 m (4H, CH2CH2), 4.46–4.57 m (4H,
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005

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BRATENKO et al.
CH2), 7.20–7.83 m (14H, Harom), 8.27 s and 8.36 s (1H,
5-H), 12.01 br.s (1H, COOH). Found, %: C 70.66;
H 5.17; N 8.95. C27H24FN3O3. Calculated, %: C 70.90;
H 5.25; N 9.19.
7.54 d (2H, Harom, J = 7.7 Hz), 7.81 d (2H, Harom, J =
7.6 Hz), 8.22 s (1H, 5-H, 9.36 s (1H, NH). Found, %:
C 73.46; H 5.40; N 10.90. C31H28N4OS. Calculated, %:
C 73.81; H 5.55; N 11.11.
Compound VId. Yield 88%, mp 165–166°C. IR
Compound VIIIb. Yield 68%, mp 131–133°C. IR
–1
–1
spectrum, n, cm : 1680, 1700 (C=O). 1H NMR spectrum,
spectrum: nNH 3360 cm . 1H NMR spectrum, d, ppm:
d, ppm: 2.41–2.70 m (4H, CH2CH2), 3.81 s (3H, CH3O),
4.48–4.54 m (4H, CH2), 6.29–7.82 m (13H, Harom),
8.15 s and 8.32 s (1H, 5-H), 11.98 br.s (1H, COOH).
Found, %: C 69.35; H 5.19; N 8.40. C28H26FN3O4.
Calculated, %: C 68.99; H 5.34; N 8.62.
5.09 s (2H, CH2), 5.13 s (2H, CH2), 7.09–7.53 m (16H,
H
arom), 7.80 d (2H, Harom, J = 7.6 Hz), 8.24 s (1H, 5-H),
9.42 s (1H, NH). Found, %: C 70.15; H 4.89; N 11.48.
C28H24N4S2. Calculated, %: C 70.00; H 5.00; N 11.67.
Compound VIIIc. Yield 65%, mp 146–147°C. IR
–1
Compound VII. Yield 80%, mp 155–156°C. IR
spectrum: nNH 3350 cm . 1H NMR spectrum, d, ppm:
–1
spectrum, n, cm : 1695, 1705 (C=O). 1H NMR spectrum,
5.04 s (2H, CH2), 5.13 s (2H, CH2), 7.13–7.59 m (14H,
d, ppm: 4.42–4.50 m (4H, CH2), 5.98 d (J = 15.2 Hz),
6.06 d (1H, b-CH=, J = 15.2 Hz), 6.74 d (1H, a-CH=,
J = 15.2 Hz), 6.91–7.45 m (11H, Harom), 7.82 d (2H,
Harom, J = 8.0 Hz), 8.35 s and 8.38 s (1H, 5-H), 11.82 br.s
(1H, COOH). Found, %: C 69.02; H 4.79; N 8.48.
C28H24FN3O4. Calculated, %: C 69.28; H 4.95; N 8.66.
Harom), 7.84 d (2H, Harom, J = 7.8 Hz), 8.01 d (1H, Harom,
J = 7.7 Hz), 8.55 d (1H, Harom, J = 2.6 Hz), 8.84 s (1H,
Harom), 8.33 s (1H, 5-H), 9.38 s (1H, NH). Found, %:
C 73.04; H 5.42; N 14.60. C29H25N5S. Calculated, %:
C 73.24; H 5.30; N 14.72.
REFERENCES
N-Benzyl-N-[3-aryl(heteryl)-1-phenyl-1H-pyr-
azol-4-ylmethyl)-N'-phenylthioureas VIIIa–VIIIc
(general procedure). To a solution of 0.001 mol of
hydrochloride IVf–IVh in 10 ml of ethanol we added
0.001 mol (0.002 mol in the reaction with IVh) of
triethylamine and 0.175 g (0.0013 mol) of phenyl
isothiocyanate, and the mixture was heated for 1 h under
reflux. The mixture was cooled, and the precipitate was
filtered off, washed with water, dried, and recrystallized
from acetic acid.
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Org. Chem., 2005, vol. 41, p. 95.
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Org. Chem., 2001, vol. 37, p. 556.
5. Diehl, V., Cuny, E., and Lichtantalen, F.W., Heterocycles,
1998, vol. 48, p. 1193.
6. Fisher, H.P., Tetrahedron Lett., 1968, p. 4289.
7. Siddol, T.N., Stewart, W.E., and Knight, F.D., J. Phys. Chem.,
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Compound VIIIa. Yield 70%, mp 154–157°C. IR
–1
spectrum: nNH 3355 cm . 1H NMR spectrum, d, ppm:
3.81 s (3H, CH3O), 5.02 s (2H, CH2), 5.06 s (2H, CH2),
6.96 d (2H, Harom, J = 7.7 Hz), 7.18–7.49 m (13H, Harom),
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005