Complexes of silicon and phosphorus chlorides with nitrogen-containing bases as the condensing agents in the synthesis of amides

Article abstract of DOI:10.1134/S1070363212080099

High effectiveness of new condensing agents on the basis of complexes of silicon and phosphorus chlorides with nitrogen-containing bases in the synthesis of amides from carboxylic acids and amines and also in heterocyclization is shown. Factors affecting the readiness of formation of the amide bond and the yields of the final products are established.

Full text of DOI:10.1134/S1070363212080099

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 8, pp. 1382–1390. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © L.V. Besgubenko, S.E. Pipko, A.D. Sinitsa, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 8, pp. 1302–1310.
Complexes of Silicon and Phosphorus Chlorides
with Nitrogen-Containing Bases as the Condensing Agents
in the Synthesis of Amides
L. V. Besgubenko, S. E. Pipko, and A. D. Sinitsa
Institute of Organic Chemistry of National Academy of Sciences of Ukraine, ul. Murmanskaya 5, Kiev, 02660 Ukraine
e-mail: besgubenko@mail.ru
Received May 5, 2011
Abstract—High effectiveness of new condensing agents on the basis of complexes of silicon and phosphorus
chlorides with nitrogen-containing bases in the synthesis of amides from carboxylic acids and amines and also
in heterocyclization is shown. Factors affecting the readiness of formation of the amide bond and the yields of
the final products are established.
DOI: 10.1134/S1070363212080099
The formation of amides in the reaction of amines
with carboxylic acids is of significant interest
especially for the synthesis of peptides and lactams.
The direct condensation of amines with carboxylic
acids takes place at high temperatures (160–180°C)
preventing the use of reagents with the labile
functional groups. Therefore for performing the attack
by amino group the activation of electrophilic
component by means of different methods is
necessary. The most part of these methods is based on
converting carboxylic acids into more reactive
compounds like acyl halides, anhydrides, acyl azides,
and activated esters or on using condensing agents like
cinimidyl carbonate, etc. [1–4]. Since recently instead
of carbodiimides and activated esters onium
derivatives [3, 4] are often used. Most effective among
them occurred to be ammonium and phosphonium
salts.
In the series of the latter triamidophosphonium salts
with dialkylamino- or pyrrolidine groups are the most
widespread. It could be expected that analogous
properties would be exhibited by the complexes of
phosphorus and silicon with 4-dimethylaminopyridine
and N-methylimidazole we formerly obtained.
We carried out an investigation of factors affecting
the amidation of carboxylic acids with aromatic
carbodiimides,
carbonyldiimidazole,
N,N'-disuc-
+
2+
N
N
2+
N
N
N
N
N
N
N
Cl
Cl
Cl
Cl
Cl
N
Cl_
Cl
2Cl_
2Cl_
P
Si
N
Si
N
N
Cl
N
N
Cl
N
N
N
N
N
I
III
II
1382

COMPLEXES OF SILICON AND PHOSPHORUS CHLORIDES
1383
amines while using phosphorus I [5] and silicon
complexes II, III as the condensing agents.
of substituents in the aromatic or heterocyclic ring of
the amine. Aromatic amines containing bulky and
especially electron-acceptor groups in the ortho-posi-
tion to the amino group significantly more difficultly
enter the reaction. For example, o-nitroaniline forms
amide VIb in 50% yield, and 2,4,6-trichloroaniline
under the analogous conditions practically gives no
amide VIe (see Table 1).
The reaction was carried out by heating in
acetonitrile a mixture of acid IV, amine V, one of
condensing agents I–III, and a base. Target amides VI
can be easily obtained in a pure state by treating the
reaction mixture with 10% aqueous alkali, and the
products of hydrolysis of condensing agent are easily
removed due to their solubility in water or alkali.
Acylation conditions are sufficiently mild which
permits to obtain amides VIm, VIp of the acids that
often form tar under the another acylation conditions.
Nature of the carboxylic acid weakly affects the
reaction time and the yields of the reaction products
VIl–VIq (Table 1). In the majority of cases the yields
of amides are high. Low yield of amide VIp is due to
the partial decomposition of the indolylacetic acid
under the reaction conditions.
O
I, II or III
R
+
R
H2N
R'
C
OH
While using diisopropylethylamine as a base
(methods a–c) the target amides often primarily form
oils which complicates their isolation. Due to that the
use of N-methylimidazole is preparatively more
convenient (method d).
By the reaction of the derivatives of benzoic and
phenoxyacetic acids with phenetidine in presence of
complex I (method a) the corresponding amides VIa,
VIn were prepared in high yields (Table 1). This
method is more convenient for practical use than
standard procedures with carbodiimides and carbo-
nyldiimidazole. In the last case the reaction is carried
out in two steps. In the first one the activated
derivative of the acid is obtained, and in the second
step the amine is added. The condensation effected by
complex I permits heating together equimolar amounts
of all three components.
The application of phosphorus I and silicon II, III
complexes is not limited only to the synthesis of
acyclic amides. Complex III was used also in amida-
tion leading to different types of heterocycles (method e,
Table 2).
For example, the reaction of thiosemicarbazides
VII with carboxylic acids gave the derivatives of
thiadiazole VIIIa–VIIIc in satisfactory yields. Yet
with hydrazines no cyclization takes place. Instead the
corresponding acylation products Xa, Xb are formed.
Yet at the use of phosphorus complexes a com-
peting phosphorylation of starting amines sometimes
takes place which decreases the yields of amides
though this decrease in insignificant. At the same time
the silicon complexes do not form by-products and
their use is preferred.
o-Aminothiophenol
(compounds XIIa,
and
XIIb)
o-phenylenediamine
were used in
heterocyclization. In the last case the yield of the
cyclic product decreases due to competing acylation of
both amino groups of o-phenylenediamine.
The investigation of the condensing ability of
complexes of silicon tetrachloride with 4-dimethyl-
aminopyridine II (method b) and N-methylimidazole
III (method c) showed the preparative preferability of
complex III due to its higher hydrolytic stability.
The reactions we have investigated show that the
obtained condensing agents may be widely used in the
synthesis of amides and in the heterocyclization. In
many cases this method can successively supplement
the other methods of synthesis of compounds
containing the amido group.
In the amidation reaction under study a broad range
of aromatic and heterocyclic amines and acids of
various nature was used. The process is also applicable
to the poorly nucleophilic nitoanilines and heteryl-
amines which are difficultly acylated by means of
usual condensing reagents. Yields of the amidation
products (25–90%) depend significantly on the nature
EXPERIMENTAL
1H NMR spectra were registered on a Varian VXR-
300 spectrometer (299.95 MHz) in CDCl3 and DMSO-d6.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012

1384
BESGUBENKO et al.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012

COMPLEXES OF SILICON AND PHOSPHORUS CHLORIDES
1385
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012

1386
BESGUBENKO et al.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012

COMPLEXES OF SILICON AND PHOSPHORUS CHLORIDES
1387
S
Ar1NH
NHNH2
S
Ar1NH
Ar
Ar
VII
III, (i-Pr)2NEt
N
N
VIII
O
Ar1
NHNH2
O
O
IX
Ar1
IV
NHNH
III, (i-Pr)2NEt
X
XH
X = NH, S
NH2
X
XI
Ar
III, (i-Pr)2NEt
N
XII
Chemical shifts were measured against internal TMS.
Synthesis of compounds II and III was carried out
under the anhydrous conditions in the flow of dry
argon. Anhydrous solvents were prepared by
distillation over phosphorus anhydride. The duration of
reactions, methods of synthesis, and the yields of
obtained amides are listed in Tables 1, 2. Greater part
of the amides synthesized was analytically pure and
required no additional purification.
oil), ν, cm–1: 1100 (C–N), 1300–1500 (C–C), 2900–
2980 (C–Harom). H NMR spectrum (DMSO-d6), δ,
1
ppm (J, Hz): 3.78 s (12H, NCH3), 7.1 s (4Harom), 7.42 s
(4Harom), 8.59 (4Harom). 13C NMR spectrum (DMSO-
d6), δC, ppm: 35.00 (NCH3), 122.03 (arom.), 126.64
(arom), 142.05 (arom.). Found, %: C 38.25; H 4.82; Cl
28.48; N 22.45; Si 5.61. C16H24Cl4N8Si. Calculated, %:
C 38.56; H 4.85, Cl 28.46; N 22.49; Si 5.64.
Synthesis of carboxamides (general procedure).
To a mixture of 2.35 mmol of amine and 2.82 mmol of
acid in 2 ml of acetonitrile 11.75 mmol of diiso-
propylethylamine was added with stirring. To the
obtained homogenous solution 2.35 mmol of complex
I was added, and the reaction mixture was refluxed for
1 h. After that it was treated with a solution of 1 g of
potassium carbonate in 20 ml of water, and the mixture
obtained was stirred for 0.5 h. The precipitate formed
was filtered off, washed with 1:1 water–acetonitrile
mixture, and dried in air.
Tetrakis(4-dimethylaminopyridine)dichloro-
silicium dichloride (II). To a solution of 5 g of 4-di-
methylaminopyridine in 30 ml of chloroform a solu-
tion of 1.07 g of tetrachlorosilane in 5 ml of chloro-
form was added dropwise with stirring. The obtained
oil crystallized at the addition of 20 ml of diethyl ether.
The obtained precipitate was filtered off, washed with
diethyl ether, and dried in a vacuum. Yield 2.5 g
(60%), decomposition point 250–260°C. IR spectrum
(mull in mineral oil), ν, cm–1: 1200 (C–N), 1350–1550
(C–C), 2900–2980 (C–Harom). 1H NMR spectrum
(DMSO-d6), δ, ppm (J, Hz): 3.21 s (24H, NCH3), 6.83
d (8Harom, JHH 8.1), 7.89 d (8Harom, JHH 8.1). 13C NMR
spectrum (DMSO-d6), δC, ppm: 41.02 (NCH3), 107.43
(arom), 138.37 (arom). Found, %: C 50.47; H 6.19; Cl
21.37; N 16.94; Si 4.16. C28H40Cl4N8Si. Calculated, %:
C 51.07; H 6.12; Cl 21.53; N 17.01; Si 4.26.
To a mixture of 4 mmol of amine and 4.4 mmol of
the acid in 8 ml of acetonitrile 3 ml of diisipro-
pylethylamine was added with stirring. The obtained
homogenous solution was treated with 4 mmol of
complex II, and the reaction mixture was refluxed
from 3 to 15 h depending on the nucleophilicity of the
1
amine. The reaction progress was monitored by H
Tetrakis(N-methylimidazol)dichlorosilicon(2+)
chloride (III). This compound was obtained ana-
logously to II from 5.074 g of N-methylimidazole and
1.5 g of tetrachlorosilane. Yield 4.1 g (93%), decom-
position point 225oC. IR spectrum (mull in mineral
NMR spectroscopy of the reaction mixture. After the
completion of the process the mixture obtained was
added gradually with stirring to 50 ml of 10% NaOH.
The product obtained precipitated from the
homogenous solution formed. In the case of formation
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012

1388
BESGUBENKO et al.
of oil the reaction mixture was left until the complete
evaporation of diisopropylethylamine, and gradual
crystallization of the product took place. The crystals
formed were filtered off, washed with water, and dried
in air.
spectrum (CDCl3)), δ, ppm (J, Hz): 2.27 s 6H, Ar'-
CH3), 2.44 s (3H, Ar-CH3), 7.12 m (3Harom), 7.30 d
(3Harom, JHH 8), 7.38 s (1H, NH), 7.80 d (2Harom, JHH 8).
4-Methyl-N-pyridin-2-ylbenzamide (VIg) was
prepared from 0.6 g of toluic acid and 0.376 g of 2-
aminopyridine, mp 105°C (105–106°C [12]). Spectral
data are consistent with the reported parameters [13].
The reaction was carried out analogously to the
procedure b. Complex III, 4 mmol, was used instead
of complex II.
4-Methyl-N-thiazol-2-ylbenzamide (VIh) was
prepared from 0.6 g of toluic acid and 0.4 g of 2-
amino-1,3-thiazole. The product was extracted from
alkaline solution with chloroform (3×10 ml), the
solvent was removed in a vacuum, and the residue was
crystallized from chloroform, mp 210°C (211–214°C
[14]). Spectral characteristics of the product are
consistent with the reported parameters [14].
The reaction was carried out as described in the
procedure b. Complex III, 4 mmol was used instead of
complex II, and N-methylimidazole, 4 mmol, was used
instead of diisopropylethylamine.
(4'-Ethoxy)-4-mehylbenzanilide (VIa) was prepared
from 0.6 g of toluic acid and 0.548 g of p-phenetidine,
mp 200–201°C (190–102°C [6]). Spectral data of the
product agree with the reported in [5].
4-Methyl-N-(4'methyl)thiazol-2-ylbenzamide (VIi)
was prepared from 0.6 g of toluic acid and 0.456 g of
2-amino-4-methyl-1,3-thiazole. The product was
extracted from alkaline solution with chloroform
(3×10 ml), the solvent was removed in a vacuum, and
the residue was crystallized from chloroform, mp
above 250°C. 1H NMR spectrum (DMSO-d6), δ, ppm
(J, Hz): 2.16 s (3H, Het-CH3), 2.31 s (3H, Ar-CH3),
(2'-Nitro)-4-methylbenzanilide (VIb) was prepared
from 0.6 g of toluic acid and 0.55 g o-nitroaniline, mp
1
101–102°C (110°C [7]). H NMR spectrum (DMSO-
d6), δ, ppm (J, Hz): 2.41 s (3H, Ar-CH3), 7.35 d
(2Harom, JHH 8), 7.36 d.d (1Harom, JHH 7, JHH 1), 7.73 d.d
(1Harom, JHH 8.6, JHH 1.5), 7.86 d (2Harom, JHH 8), 7.92
d.d (1Harom, JHH 8, JHH 1.25), 8.02 d.d (1Harom, JHH 8,
JHH 1.25), 10.68 s (1H, NH).
6.19 s (1Harom), 7.13 d (2Harom, JHH 8), 8.0 d (2Harom
,
JHH 8), 9.8 s (1H, NH). Found, %: C 62.06; H 5.15; N
11.98; S 13.75. C12H12N2OS. Calculated, %: C 62.04;
H 5.21; N 12.06; O 6.89; S 13.80.
(4'-Nitro)-4-methylbenzanilide (Vic) was prepared
from 0.6 g of toluic acid and 0.55 g of p-nitroaniline,
mp 200°C (207°C[8]). 1H NMR spectrum (DMSO-d6),
δ, ppm (J, Hz): 2.45 s (3H, ArCH3), 7.32 d (2Harom, JHH
8), 7.80 d (2Harom JHH 8 Hz), 7.84 d (2Harom, JHH 9),
8.14 s (1H, NH), 8.25 d (2Harom, JHH 9).
4-Methyl-N-triazol-3-yl1,2,4-benzamide (VIj) was
prepared from 0.6 g of toluic acid and 0.336 g of 3-
amino-1,2,4-triazole. The product was extracted with
butanol (3×10 ml), the solvent was removed in a
vacuum, and the residue was crystallized from ethanol,
N-2'-Chlorobenzyl-4-methylbenzamide (VId) was
prepared from 0.6 g of toluic acid and 0.56 g of 2-
chlorobenxylamine, mp 130–132°C (128–129°C [9]).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.39 s
(3H, Ar-CH3), 4.72 d (2H, NH-CH2, JHH 6), 6.60 s
(1H, NH), 7.24 m (4Harom), 7.39 d.d (1Harom, JHH 5, JHH
7), 7.47 d.d (1Harom, JHH 5, JHH 7), 7.69 d (2Harom, JHH
8).
1
mp 230–235°C. H NMR spectrum (DMSO-d6), δ,
ppm (J, Hz): 2.37 s (3H, Ar-CH3), 7.33 d (2Harom, JHH
8), 7.80 s (1Harom), 7.95 d (2Harom, JHH 7), 11.83 s (1H,
NH), 13.56 s (1H, NH). Found, %: C 59.30; H 4.95; N
27.75. C10H10N4O. Calculated, %: C 59.40; H 4.98; N
27.71; O 7.91.
N-Methyl-(4-methyl)benzanilide
(VIk)
was
(2',4',6'-Trichloro)-4-methylbenzanilide (VIe) was
prepared from 0.6 g of toluic acid and 0.428 g of N-
methylaniline, mp 70–72°C (69.5–71°C [15]). 1H
NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 2.21 s
(3H, Ar-CH3), 3.33 s (3H, NCH3), 6.99 d (2Harom, JHH
8), 7.13 m (5Harom), 7.25 d (2Harom, JHH 8), 7.27 s (1H,
NH).
prepared from 0.6 g of toluic acid and 0.785 g of 2,4,6-
1
trichloroaniline, mp 220°C (233°C [10]). H NMR
spectrum (DMSO-d6), δ, ppm (J, Hz): 2.38 s (3H, Ar-
CH3), 7.24 d (2Harom, JHH 8), 7.60 d (2Harom, JHH 8),
7.78 s (2Harom), 10.23 s (1H, NH).
(2',6'-Dimethyl)4-methylbenzanilide (VIf) was
(4'-Ethoxy)-4-nitrobenzanilide (VIl) was prepared
from 0.54 g of p-nitrobenzoic acid and 0.55 g of p-
phenetidine, mp 185–187°C (186–186°C [16]). 1H
prepared from 0.6 g of toluic acid and 0.484 g of 2,6-
1
dimethylaniline, mp 230°C (235°C [11]). H NMR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012

COMPLEXES OF SILICON AND PHOSPHORUS CHLORIDES
1389
NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.43 t (3H,
OCH2CH3, JHH 7), 4.03 q (2H, OCH2CH3, JHH 7), 6.92
d (2Harom, JHH 9), 7.52 d (2Harom, JHH 9), 7.82 s (1H,
NH), 8.04 d (2Harom, JHH 7), 8.33 d (2Harom, JHH 8).
8), 7.11 d (2Harom, JHH 5), 7.23 d (2Harom, JHH 7.5), 7.42
t (3Harom, JHH 7), 7.93 s (1H, NH).
5-(4-Bromophenyl)-N-phenyl-2-amino-1,3,4-
thiadiazole (VIIIb) was prepared from 0.884 g of p-
bromobenzoic acid and 0.67 g of phenylthiosemi-
carbazide, mp 250°C (320–323°C [22]). Spectral
characteristics of the product agree with the reported
data [22].
(4'-Ethoxy)-N-benzoylaminoacetanilide (VIm) was
prepared from 0.78 g of hyppuric acid 0.548 g of p-
phenetidine, mp 205°C (203°C [17]). 1H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 1.40 t (3H,
OCH2CH3, JHH 7), 4.03 q (2H, OCH2CH3, JHH 7), 4.34
d (2H, NHCH2, JHH 5.4), 6.85 d (2Harom, JHH 9), 7.32
5-(4-Bromophenyl)-N-(4-methylphenyl)-2-amino-
1,3,4-thiadiazole (VIIIc) was prepared from 0.88 g of
p-bromobenzoic acid and 0.725 g of p-tolylthio-
semicarbazide. The product was purified by column
chromatography, elution with 8:1 hexane–ethyl
acetate, mp above 250°C. 1H NMR spectrum (DMSO-
d6), δ, ppm (J, Hz):2.25 s (3H, Ar-CH3), 7.11 d
br.s (1H, CHarom), 7.46 d (2Harom, JHH 9), 7.47 t (2Harom
JHH 7.5), 7.54 t (1H, NHCH2, JHH 5.4), 7.87 d (2Harom
JHH 8), 8.6 s (1H,NH).
,
,
(4'-Ethoxy)-2-methylphenoxyacetanilide (VIn) was
prepared from 0.73 g of 2-methylphenoxyacetic acid
and 0.584 g of p-phenetidine, mp 112°C (112–113°C
[18]). Spectral data agree with the reported one [5].
(2Harom, JHH 8), 7.21 d (2Harom, JHH 8), 7.35 d (2Harom
,
JHH 8), 7.52 d (2Harom, JHH 8), 7.93 s (1H, NH). Found,
%: C 52.06, H 3.45, Br 23.07, N 12.10, S 9.32.
C15H12BrN3S. Calculated, %: C 52.03, H 3.49, Br
23.08, N 12.14, S 9.26.
(4'-Ethoxy)pyridin-2-yl-carboxyanilide (VIo) was
prepared from 0.73 g of pyridine-2-carboxylic acid and
0.548 g of p-phenetidine, mp 118°C (120–122°C [19]).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.43 t
(3H, OCH2CH3, JHH 7), 4.03 q (2H, OCH2CH3, JHH 7),
6.66 d (2Harom, JHH 9), 6.74 m (2H-pyridine), 6.85 d
(2Harom, JHH 9), 7.75 s (!H, NH).
N'-(4-Methylbenzoyl)-3-chlorobenzylhydrazide
(Xa) was prepared from 0.6 g of toluic acid and 0.682 g
1
of m-chlorophenylhydrazine, mp above 250°C. H
NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 2.36 s
(3H, Ar-CH3), 7.23 d (2Harom, JHH 8), 7.33 d (2Harom
,
(4'-Ethoxy)-1H-indol-3-ylacetanilide (VIp) was
prepared from 0.77 g of 1H-indol-3-ylacetic acid and
0.548 g of p-phenetidine, mp 153°C (154–155°C [20]).
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.37 t
(3H, OCH2CH3, JHH 7). 3.88 s (2H, CH2CO), 3.96 q
(2H, OCH2CH3, JHH 7), 6.76 d (2Harom, JHH 9), 7.24 m
(6Harom, indol), 7.43 d (1H indol, JHH 8.4), 7.63 d (1H
indol, JHH 8.4), 8.34 s (1H, NH), 10.58 s (1H, NH
indol).
JHH 5), 7.72 d (2Harom, JHH 8), 7.85 m (1Harom), 7.90 m
(1Harom). Found, %: C 66.50, H 4.15, Cl 13.12, N
10.32. C15H11ClN2O. Calculated, %: C 66.55, H 4.10,
Cl 13.10, N 10.35, O 5.91.
N'-(4-Bromobenzoyl)-4-methylbenzylhydrazide
(Xb) was prepared from 0.88 g of p-bromobenzoic
acid and 0.6 g of p-tolylhydrazine, mp above 250°C.
1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 2.37 s
(3H, Ar-CH3), 7.25 d (2Harom, JHH 8), 7.54 d (2Harom,
JHH 8.4), 7.76 d (2Harom, JHH 8), 7.85 d (2Harom, JHH
8.4), 10.55 s (2H, NH).
(4'-Ethoxy)-adamantylcarboxanilide (VIq) was
prepared from 0.79 g of adamant-1-ylcarboxylic acid
1
and 0.548 g of p-phenetidine, mp 208–210°C. H
NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.40 t (3H,
OCH2CH3, JHH 7), 1.76 s (6H adamantine), 1.96 s (6H
adamantame), 2.10 s (3H adamantane), 4.02 q (2H,
OCH2CH3, JHH 7), 6.86 d (2Harom, JHH 9), 7.19 s (1H,
NH), 7.40 d (2Harom, JHH 9). Found, %: C 76.10, H
8.45. N 4.65. C19H25NO2. Calculated, %: C 76.22, H
8.42, N 4.68, O 10.69.
2-(4-Methylphenyl)benzothiazole (XIIa) was
prepared from 0.6 g of toluic acid and 0.5 g of 2-
aminothiophenol. The product was purified by column
chromatography, elution with 9:1 hexane–ethyl
acetate, mp 85°C (82–84°C [23]). Spectral charac-
teristics of the product are consistent with the reported
parameters [23].
5-(4-Methylphenyl)-N-phenyl-2-amino-1,3,4-
thiadiazole (VIIIa) was prepared from 0.6 g of toluic
acid and 0.67 g of phenylthiosemicarbazide, mp 205°C
(208–209°C [21]). 1H NMR spectrum (DMSO-d6), δ,
ppm (J, Hz): 2.23 s (3H, Ar-CH3), 7.07 d (2Harom, JHH
2-(4-Methylphenyl)benzimidazole (XIIb) was
prepared from 0.6 g of toluic acid and 9.432 g of 1,2-
1
phenylenediamine. According to H NMR data the
product contained about 20% of acyclic product of
acylation of phenylenediamine at both amino groups.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012

1390
BESGUBENKO et al.
11. Grammaticakis, P., Compt. Rend., Ser. C, 1966,
Spectral characteristics of the product agree with the
reported data [24].
vol. 262, no. 4, p. 369.
12. Lyon, P.A. and Reese, C.B., J. Chem. Soc., Perkin
Trans. 1, 1974, p. 2645.
REFERENCES
1. Houben-Weyl, Methoden der Organoschen Chemie,
Houben-Weyl, Stuttgart: Georg Thieme Verlag, 1985,
p. 941.
13. Ko, S., Han, H., and Chang, S., Org. Lett., 2003, vol. 5,
no. 15, p. 2687.
14. Andreani, A., Leoni, A., Locatelli, A., Mofigi, R., and
Rambaldi, M., Coll. Czech. Chem. Commun., 1999,
vol. 64, no. 2, p. 299.
2. Barton, D. and Ollis, U.D., Obshchaya organicheskaya
khimiya
(Comprehensive
Organic
Chemistry),
Moscow: Khimiya, 1983, vol. 4, p. 48.
3. Montalbetti, C.A.G.N. and Falque, V., Tetrahedron,
15. Ring, R.N., Sharefkin, J.G., and Davidson, D., J. Org.
Chem., 1962, vol. 27, no. 7, p. 2428.
2004, vol. 61, no. 46, p. 10827.
16. Pyman, F.L., J. Chem. Soc., 1917, vol. 111, p. 167.
4. Han S-Y. and Kim, Y.-A., Tetrahedron, 2004, vol. 60,
17. Waldschmidt-Leits, E., Kuehn, E., and Hoppe-Seyler’s,
Z. Phisiol. Chem., 1950. vol. 285, p. 23.
no. 11, p. 2447.
5. Pipko, S.E., Bezgubenko, I.V., Sinitsa, A.D., Rusa-
nov, E.V., Kapustin, E.G., Povolotskii, M.I., and
Shvadchak, V.V., Heteroatom Chem., 2008, vol. 19,
no. 2, p. 171.
6. Maslivets, A.N., Smirnova, L.I., and Andreichi-
kov, Yu.Kh., Zh. Org. Khim., 1984, vol. 24, no. 6,
p. 1347.
18. Lederer, L., German Patent no. 82105, 1895; Fortschr.
Teer-farbenfarb. Verw. Industriezweige B, 1895, no. 4,
p. 1161.
19. Klosa, J., J. Pract. Chem., 1963, vol. 19, nos. 1–2, p. 45.
20. Eryshev, B.Ya., Ershova, T.D., and Berlyand, E.A.,
Pharm. Chem., J., 1975, vol. 9, no. 8, p. 569.
21. Dymek, W., Ann. Univ. Lublin, 1954, vol. AA9, p. 61;
Chem. Abstr., 1957, 5095 b.
22. Rostanizadeh, Sh., Aryan, R., Ghaieni, H., R., and
Amani, A.M., J. Heteroatom. Chem., 2010, vol. 47,
no. 3, p. 616.
7. Bruckner, A., Annalen der Chemie, 1880, vol. 205,
no. 1, p. 113.
8. Broxton, T.J., Carolane, C.J., and Deady, L.W., Austral.
J. Chem., 1975, vol. 28, no. 2, p. 451.
9. Blum, J., Fisher, A., and Greener, E., Tetrahedron,
23. Shi, D. and Dou, G., Rong Sh., Synt, Commun., 2010,
1973, vol. 29, no. 8, p. 1073.
vol. 40, no. 15, p. 2302.
10. Grammaticakis, P., Bull. Soc. Chim. France, 1963,
24. Lewis, J.C., Wu, J.Y., Nergman, R.G., and Ellman, J.A.,
p. 862.
Angew. Chem. Int. Ed., 2006, vol. 45, no. 10, p. 1589.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012