ISSN 1070-4272. Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 3, pp. 421 424. Pleiades Publishing, Inc., 2006.
Original Russian Text A.I. Rakhimov, N.A. Storozhakova, Khaled Khedar Nasser Akhmed, R.G. Fedunov, 2006, published in Zhurnal Prikladnoi
Khimii, 2006, Vol. 79, No. 3, pp. 429 431.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Catalytic Synthesis of N-Benzoyl (N-Nitrobenzoyl) Derivatives
of -Aminocaproic Acid Oligomers
A. I. Rakhimov, N. A. Storozhakova, Khaled Khedar Nasser Akhmed,
and R. G. Fedunov
Volgograd State Technical University, Volgograd, Russia
Institute of Chemical Problems of the Environment, Russian Academy of Sciences, Volgograd, Russia
Received August 23, 2005
Abstract The synthesis of N-benzoyl [N-(m-nitrobenzoyl)] derivatives of -aminocaproic acid oligomers
by the reaction of -caprolactam with benzoic (nitrobenzoic) acid in the presence of p-toluenesulfonic acid
as catalyst was studied.
DOI: 10.1134/S1070427206030177
It is known that -aminocaproic acid oligomers in-
hibit reproduction of respiratoric viruses. Acid-cata-
lyzed oligomerization of -caprolactam with car-
boxylic acids yields N-acyl derivatives of -amino-
caproic acid oligomers [1 5].
N-Benzoyl derivatives of -aminocaproic acid
oligomers, R = H (BACA) (II). Ampules filled with
the reaction mixture (CL 1.9 g, BA 2 g, and TsOH
0.30 g; reactant molar ratio 1 : 1 : 0.1) were kept in
a thermostat at 150 C. At 15-min intervals these am-
pules were successively removed, and chloroform was
added. Unchanged CL and BA dissolved in chloro-
form and were separated from the insoluble residue of
BACA oligomer mixture containing oligomers with 9
and 10 monomeric units. To separate these oligomers,
the solid residue was mixed with ethanol and heated
to boil. The resulting solution was filtered and then
In this study, N-benzoyl (BACA) and N-nitroben-
zoyl (m-NBACA) derivatives of -aminocaproic acid
oligomers were prepared by the reaction of -capro-
lactam (CL) with benzoic (BA) and nitrobenzoic
(m-NBA) acids in the temperature range 150 210 C.
p-Toluenesulfonic acid (TsOH) was used as catalyst.
cooled. Under these conditions BACA
precipitates
n=10
=O
NH
C
and BACA
separated from BACA
was isolated from the filtered solution by ethanol
remains in ethanol. BACA
was
n=9
n=10
COOH
+
by filtration. BACA
n=9
n=9
R
I
evaporation and then recrystallized. BACA
: yield
CL
n=9
0.66 g (35%), mp 165 167 C. Found, %: N 10.92.
Calculated, %: N 11.05. BACA : yield 0.85 g
TsOH
C(O)[NH(CH2 )5C(O)nOH,
n=10
(45%), mp 188 190 C. Found, %: N 11.20. Cal-
culated %: N 11.27.
R
where R = H (BA), m-NO (m-NBA) (I); R = H
2
The molecular structures of BACA
and
n=9
(BACA), m-NO (m-NBACA) (II); n =1, 9, 10.
1
2
BACA
were characterized by IR and H NMR
n=10
spectroscopy. The IR spectrum of BACA
contains
n=9
EXPERIMENTAL
the amide I and amide II absorption bands (1638 and
1
1584 cm , respectively) and the absorption bands
The IR spectra (KBr pellets or a mulls in Vaseline
oil) were recorded on a Specord M-82 IR spectrom-
eter. The H NMR spectra were recorded on a Varian
of the stretching vibrations of the NH groups at about
1
3292 cm . The IR spectrum of BACA
contains
n=10
1
the amide I and amide II absorption bands (1636 and
1
Mercury Plus spectrometer (300 MHz) in DMSO-d
1536 cm , respectively) and the absorption band of
6
with TMS as internal reference. The reagent consump-
tion rate was determined by an ampule technique.
the stretching vibrations of the NH group at about
3200 cm .
1
421