Synthesis of dimethyl 2-(2-alkyl-1,3-diaryl-3-oxopropyl)malonates and their reactions with amines

Article abstract of DOI:10.1007/s11176-005-0279-x

Zinc enolates generated from 1-aryl-2-bromoalkanones and zinc react with dimethyl 2-(1-arylmethylene)malonate to form dimethyl 2-(2-alkyl-1,3-diaryl-3- oxopropyl)malonates. The latter react with benzylamine or cyclohexylamine to form the corresponding dis

Full text of DOI:10.1007/s11176-005-0279-x

Russian Journal of General Chemistry, Vol. 75, No. 4, 2005, pp. 597 604. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005,
pp. 636 641.
Original Russian Text Copyright
2005 by Shchepin, Korzun, Poroshina.
Synthesis of Dimethyl
2-(2-Alkyl-1,3-diaryl-3-oxopropyl)malonates
and Their Reactions with Amines
V. V. Shchepin, A. E. Korzun, and N. Yu. Poroshina
Perm State University, Perm, Russia
Received November 18, 2003
Abstract Zinc enolates generated from 1-aryl-2-bromoalkanones and zinc react with dimethyl 2-(1-aryl-
methylene)malonate to form dimethyl 2-(2-alkyl-1,3-diaryl-3-oxopropyl)malonates. The latter react with
benzylamine or cyclohexylamine to form the corresponding disubstituted amides, while the reactions with
piperidine, morpholine, and p-methoxyaniline provide monosubstituted amides of the corresponding target
derivatives.
A number of syntheses of dialkyl malonates con-
taining a 3-oxopropyl fragment in the position have
been reported [1 7]. The first group of procedures is
based on condensation of dialkyl -benzylidenemalo-
nates with carbonyl compounds in the presence of
bases [6]. The second group involves the Michael re-
action of anions derived from -dicarbonyl com-
pounds and their analogs with , -unsaturated car-
bonyl compounds [1 5, 7]. However, in the cited
works we found no syntheses of alkyl 2-(2-alkyl-1,3-
diaryl-3-oxopropyl)malonates. Therefore, we set
ourselves the task to develop methods for preparing
the latter compounds on the basis of the Reformatsky
reaction. We reacted -bromoketones Ia Ig, zinc, and
dimethyl 2-(1-arylmethylene)malonates IIIa IIId in
diethyl ether ethyl acetate (1:3 v/v) under conditions
of the Reformatsky reaction. It was shown that the
reaction occurs by the following scheme.
R
H
OZnBr
Ar1
Zn
RCHBrCOAr1
IIa IIg
Ia Ig
O
H
Ar1
O
Ar1
H
CO2Me
CO2Me
H2O
Zn(OH)Br
IIa IIg
R
R
H
Ar2
H
CO2Me
H
CO2Me
CO2Me
ZnBr
CO2Me
H
Ar2
Ar2
IIIa IIId
IVa IVn
Va Vn
I, II, R = Me, Ar1 = 4-MeC6H4 (a), 2,4-Me2C6H3 (b), 4-FC6H4 (c), 4-BrC6H4 (d); R = Et, Ar1 = Ph (e), 4-BrC6H4 (f),
4-ClC6H4 (g); III, Ar2 = Ph (a), 4-BrC6H4 (b), 4-ClC6H4 (c), 3,4-(MeO)2C6H3 (d); IV, V, R = Me, Ar1 = 4-MeC6H4,
4-ClC6H4 (a), 4-BrC6H4 (b); Ar1 = 4-FC6H4, Ar2 = 4-BrC6H4 (c); Ar1 = 4-BrC6H4, Ar2 = 4-ClC6H4 (d), 4-BrC6H4 (e),
Ar1 = 2,4-(Me)2C6H3, Ar2 = 4-ClC6H4 (f), 4-BrC6H4 (g), 3,4-(MeO)2C6H3 (h); R = Et, Ar1 = Ar2 = Ph (i), Ar1 =
4-ClC6H4, Ar2 = 4-ClC6H4 (j), 4-BrC6H4 (k), 3,4-(MeO)2C6H3 (l), Ar1 = 4-BrC6H4, Ar2 = 4-ClC6H4 (m), 4-BrC6H4 (n).
Zinc enolates IIIa IIId formed in the first stage
add as nucleophilic reagents to the double bond of
electrophilic substrates IIIa IIId to form inter-
mediates IVa IVn whose hydrolysis gives rise to
target products Va Vn (Table 1). The reaction suc-
cessfully proceeds with zinc enolates containing
various aryl groups, except for the zinc enolate
derived from 2-bromo-1-mesityl-1-butanone, which is
1070-3632/05/7504-0597 2005 Pleiades Publishing, Inc.

598
SHCHEPIN et al.
Table 1. Yields, melting points, IR spectra, 1H NMR spectra, and elemental analyses of dimethyl 2-(2-alkyl-1,3-
diaryl-3-oxopropyl)malonates Va Vn
IR spectrum,
Calculated,
%
Found, %
1
, cm
mp, C
1H NMR spectrum, , ppm
Formula
C
H
C
H
Va
Vb
42 93 96 1750 1675 0.82 d (3H, CHMe, J 7 Hz), 2.42 s 65.63 5.69
(3H, MeC6H4), 3.37 s, 3.55 s (6H,
C22H23ClO5 65.59 5.75
C22H23BrO5 59.07 5.18
C21H20BrFO5 55.89 4.47
C21H20BrClO5 53.93 4.31
C21H20Br2O5 49.25 3.94
C23H25ClO5 66.26 6.04
COOMe, COOMe), 3.85 m (1H, 4-
ClC6H4CH), 4.05 m (1H, CHMe),
4.08 d [1H, CH(COOMe)2, J 10 Hz],
7.18 d, 7.38 d (4H, 4-ClC6H4, J 8 Hz),
7.32 d, 7.90 d (4H, 4-MeC6H4, J 8 Hz)
45 111
112
1750 1675 0.82 d (3H, CHMe, J 7 Hz), 2.42 s 59.12 5.14
(3H, MeC6H4), 3.37 s, 3.55 s (6H,
COOMe, COOMe), 3.83 m (1H, 4-
BrC6H4CH), 4.05 m (1H, CHMe),
4.08 d [1H, CH(COOMe)2, J 10 Hz],
7.12 d, 7.45 d (4H, 4-BrC6H4, J 8 Hz),
7.37 d, 7.90 d (4H, 4-MeC6H4, J 8 Hz)
1750 1675 0.83 d (3H, CHMe, J 7 Hz), 3.37 s, 55.79 4.53
3.55 s (6H, COOMe, COOMe), 3.83 m
Vc 38
Vd 43
Ve 40
Vf 67
105
107
(1H, 4-BrC6H4CH), 4.08 d [1H,
CH(COOMe)2, J 10 Hz], 4.10 m (1H,
CHMe), 7.15 d, 7.45 d (4H, 4-BrC6H4,
J 8 Hz), 7.40 d.d, 8.10 d (4H, 4-
FC6H4, J 8 Hz)
121
123
1720 1675 0.82 d (3H, CHMe, J 7 Hz), 3.37 s, 53.92 4.29
1750
3.55 s (6H, COOMe, COOMe), 3.84 m
(1H, 4-ClC6H4CH), 4.07 m (1H,
CHMe), 4.09 d [1H, CH(COOMe)2, J
10 Hz], 7.20 d, 7.33 d (4H, 4-ClC6H4,
J 8 Hz), 7.80 d, 7.94 d (4H, 4-BrC6H4,
J 8 Hz)
126
128
1725 1675 0.82 d (3H, CHMe, J 7 Hz), 3.37 s, 49.23 3.97
3.55 s (6H, COOMe, COOMe), 3.82 m
(1H, 4-BrC6H4CH), 4.07 m (1H,
CHMe), 4.09 d [1H, CH(COOMe)2, J
10 Hz], 7.12 d, 7.45 d (4H, 4-BrC6H4,
J 8 Hz), 7.80 d, 7.93 d (4H, 4-BrC6H4,
J 8 Hz)
101
103
1755 1675 0.83 d (3H, CHMe, J 7 Hz), 2.25 s, 66.18 6.14
2.35 s (6H, Me2C6H3), 3.37 s, 3.61 s
(6H, COOMe, COOMe), 3.82 m (1H,
4-ClC6H4CH), 3.92 m (1H, CHMe),
4.11 d [1H, CH(COOMe)2, J 10 Hz],
7.13 d, 7.30 d (4H, 4-ClC6H4, J 8 Hz),
7.15 s, 7.20 d, 7.78 d [3H, 2,4-
(Me)2C6H3, J 8 Hz]
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

SYNTHESIS OF DIMETHYL 2-(2-ALKYL-1,3-DIARYL-3-OXOPROPYL)MALONATES
Table 1. (Contd.)
599
IR spectrum,
Calculated,
%
Found, %
1
, cm
mp, C
1H NMR spectrum, , ppm
Formula
C
H
C
H
Vg 62
101
102
1755 1675 0.83 d (3H, CHMe, J 7 Hz), 2.25 s, 59.80 5.49
2.35 s (6H, Me2C6H3), 3.37 s, 3.60 s
(6H, COOMe, COOMe), 3.80 m (1H,
4-BrC6H4CH), 3.90 m (1H, CHMe),
4.12 d [1H, CH(COOMe)2, J 10 Hz],
7.07 d, 7.45 d (4H, 4-BrC6H4, J 8 Hz),
7.15 s, 7.20 d, 7.77 d [3H, 2,4-
(Me)2C6H3, J 8 Hz]
C23H25BrO5 59.88 5.46
Vh 60
106
108
1755 1675 0.87 d (3H, CHMe, J 7 Hz), 2.23 s, 67.87 6.81
2.35 s (6H, Me2C6H3), 3.37 s, 3.60 s
(6H, COOMe, COOMe), 3.68 s, 3.72 s
[6H, 3,4-(MeO)2C6H3], 3.76 m (1H,
CHMe), 3.88 m [1H, 3,4-(MeO)2C6
C25H30O7
67.86 6.83
H3CH], 4.08 d [1H, CH(COOMe)2, J
10 Hz], 6.60 d, 6.65 s, 6.80 d [3H, 3,4-
(MeO)2C6H3, J 8 Hz], 7.15 s, 7.20 d,
7.77 d [3H, 2,4-(Me)2C6H3, J 8 Hz]
Vi 38
114
115
1750 1675 0.75 t (3H, CH2Me, J 7 Hz), 1.62 m 71.68 6.52
(2H, CH2Me), 3.35 s, 3.65 s (6H,
COOMe, COOMe), 3.80 m (1H,
C6H5CH), 3.98 d [1H, CH(COOMe)2,
J 10 Hz], 4.15 m (1H, CHEt), 7.05
7.20 m (5H, CHC6H5), 7.45 7.76 m
(5H, COC6H5)
C22H24O5
71.72 6.57
Vj 85
131
134
1750 1675 0.55 t (3H, CH2Me, J 7 Hz), 1.34 m, 60.49 5.12
1.42 m (2H, CH2Me), 3.37 s, 3.52 s
C22H22Cl2O5 60.42 5.07
(6H, COOMe, COOMe), 3.80 m (1H,
4-ClC6H4CH),
4.01
d
[1H,
CH(COOMe)2, J 10 Hz], 4.05 m (1H,
CHEt), 7.25 d, 7.34 d (4H, 4-ClC6H4
CH, J 10 Hz), 7.65 d, 8.05 d (4H, 4-
ClC6H4CO, J 8 Hz)
Vk 70
135
136
1740 1675 0.55 t (3H, CH2Me, J 7 Hz), 1.33 m, 54.76 4.68
1.40 m (2H, CH2Me), 3.37 s, 3.52 s
(6H, COOMe, COOMe), 3.78 m (1H,
4-BrC6H4CH), 4.01 d [1H, CH
(COOMe)2, J 10 Hz], 4.05 m (1H,
CHEt), 7.20 d, 7.45 d (4H, BrC6H4, J
8 Hz), 7.65 d, 8.05 d (4H, ClC6H4, J
8 Hz)
C22H22BrClO5 54.85 4.60
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600
SHCHEPIN et al.
Table 1. (Contd.)
IR spectrum,
Calculated,
%
Found, %
1
, cm
mp, C
1H NMR spectrum, , ppm
Formula
C
H
C
H
Vl 45
99
102
1750 1675 0.55 t (3H, CH2Me, J 7 Hz), 1.40 m 62.31 5.83
(2H, CH2Me), 3.37 s, 3.51 s (6H,
COOMe, COOMe), 3.73 s [6H,
(MeO)2C6H3], 3.75 m [1H, 3,4-
(MeO)2C6H3CH], 3.98 d [1H, CH
(COOMe)2, J 10 Hz], 4.00 m (1H,
CHEt), 6.70 d, 6.78 s, 6.83 d [3H, 3,4-
(MeO)2C6H3, J 8 Hz], 7.65 d, 8.05 d
(4H, 4-ClC6H4, J 8 Hz)
C24H27ClO7 62.27 5.88
Vm 66
120
122
1755 1685 0.55 t (3H, CH2Me, J 7 Hz), 1.34 m, 54.71 4.65
1.41 m (2H, CH2Me), 3.37 s, 3.52 s
(6H, COOMe, COOMe), 3.79 m (1H,
4-ClC6H4CH), 4.01 d [1H, CH
(COOMe)2, J 10 Hz], 4.04 m (1H,
CHEt), 7.25 d, 7.33 d (4H, 4-ClC6H4,
J 8 Hz), 7.75 d, 7.96 d (4H, 4-BrC6H4,
J 8 Hz)
C22H22BrClO5 54.85 4.60
Vn 58
127
1755 1685 0.55 t (3H, CH2Me, J 7 Hz), 1.33 m, 50.29 4.41
1.40 m (2H, CH2Me), 3.37 s, 3.52 s
(6H, COOMe, COOMe), 3.78 m (1H,
4-BrC6H4CH), 4.02 d [1H, CH
(COOMe)2, J 10 Hz], 4.04 m (1H,
CHEt), 7.20 d, 7.45 d (4H, 4-BrC6H4
CH, J 8 Hz), 7.80 d, 7.95 d (4H, 4-
BrC6H4CO, J 8 Hz)
C22H22Br2O5 50.21 4.21
explained by the steric effect of the mesityl group.
1,3-diaryl-3-oxopropyl)malonates with N-nucleo-
philes, specifically amines (see scheme below).
The composition and structure of compounds Va Vn
1
were proved by the elemental analyses and H NMR
Compounds Va Vn contain three electrophilic
carbonyl-containing groups: one ketone and two ester,
and, therefore, the reaction can occur by tree electro-
philic centers, i.e. the carbon atoms of these three
groups. Therefore, we used a threefold excess on
boiling in o-xylene one substrate molecule reacts with
two primary amine (benzylamine and cyclohexyl-
amine) molecules; therewith, reacting are the ester
groups. As a result, disubstituted amides, N1-R-N2-R-
2-(1-aryl-2-aroylbutyl)malonamides VIa and VIb are
formed. The ketone group is not touched in these
conditions, probably because it is less sterically ac-
cessible than the alkoxycarbonyl groups.
and IR spectra (Table 1).
The IR spectra of compounds Va Vn contain
ketone and ester carbonyl absorption bands at 1675
1
1685 and 1720 1755 cm , respectively. The 1H NMR
spectra, too, provide evidence to show that the reac-
tion occurs stereoselectively to form as the major
diastereomer an isomer whose CH(CO2Me)2 methine
proton gives a doublet signal with J 10 Hz. The frac-
tion of the minor diastereomer (J < 2 Hz) is some-
times 10%, but in most cases tends to zero. With the
spectral evidence in hand we are unable to make
rigorous diastereomeric assessment of the major and
minor components.
Evidence for the importance of steric effects in the
reaction in hand is provided by the reaction of the
Further we reacted the resulting dimethyl 2-(2-ethyl-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

SYNTHESIS OF DIMETHYL 2-(2-ALKYL-1,3-DIARYL-3-OXOPROPYL)MALONATES
601
O
Ar1
RNH2
Et
H
CONHR
H
H
Ar2
CONHR
VIa, VIb
O
H
O
Ar1
Ar1
Et
Et
H
X
NH
H
CO2Me
H
CO2Me
CO2Me
H
H
Ar2
Ar2
N
X
O
Vk, Vm
VIIa VIId
O
Cl
Et
H
CO2Me
H
NH2
MeO
H
N
H
OMe
O
Br
VIII
VI, R = cyclo-C6H11, Ar1 = 4-ClC6H4, Ar2 = 4-BrC6H4 (a); R = Bn, Ar1 = 4-BrC6H4, Ar2 = 4-ClC6H4 (b); VII, X = CH2,
Ar1 = 4-ClC6H4, Ar2 = 4-BrC6H4 (a), Ar1 = 4-BrC6H4, Ar2 = 4-ClC6H4 (b); X = O, Ar1 = 4-ClC6H4, Ar2 = 4-BrC6H4 (c),
Ar1 = 4-BrC6H4, Ar2 = 4-ClC6H4 (d).
same substrate with secondary amines (piperidine and
morpholine). Increased steric bulk of such amines
results in that only one alkoxycarbonyl groups can
VIId, there are bands of amide, ketone, and ester
carbonyl groups at 1640 1645, 1675 1685, and
1
1720 1730 cm , respectively. The IR spectrum of
exhibit activity, and these reactions yield monoamides, compound VIII displays amide, ketone, and ester
1
methyl 3-aryl-4-aroyl-2-(piperidinocarbonyl)- and
-(morpholinocarbonyl)hexanoates VIIa VIId.
carbonyl bands at 1655 1670, 1720, and 3320 cm ,
1
respectively. The H NMR spectra of compounds VIa
and VIb are given in Experimental, and of VIIa VIId
and VIII, in Table 2.
On the other hand, electronic effects in amines, too,
are of importance for the above reactions. Thus, no
target amides could be prepared with weakly basic
aromatic amines, such as p-toluidine. At the same
time, the electron-donor methoxy substituent in the
benzene ring of an aromatic amine renders the latter
more basic; as a result, a monoamide, methyl 3-(4-
bromophenyl)-4-(4-chlorobenzoyl)-2-(4-methoxy-
phenylcarbamoyl)hexanoate (VIII) could be prepared.
EXPERIMENTAL
The IR spectra were measured on a UR-20 instru-
1
ment in mineral oil. The H NMR spectra were re-
corded for DMSO-d6 solutions on a Bruker-DRX
instrument (500 MHz), internal reference TMS.
Dimethyl 2-(2-alkyl-1-,3-diaryl-3-oxopropyl)-
malonates Va Vn. To 2 g of fine zinc turnings in
7 ml of diethyl ether and 7 ml of ethyl acetate,
0.08 mol of dimethyl 2-(4-arylmethylene)malonate
IIIa IIId and 0.015 mol of 1-aryl-2-bromoalkanone
Ia Ig were added. The mixture was heated to initiate
reaction, after which spontaneous reaction was ob-
served. After the reaction was complete, the mixture
The composition and structure of compounds VIa,
VIb, VIIa VIId, and VIII are proved by the elemen-
tal analyses and H NMR and IR spectra.
1
The IR spectra of diamides VIa and VIb contain
absorption bands of amide and ketone carbonyl and
1
NH groups at 1650 1680, 1650 1680, and 3300 cm ,
respectively. In the IR spectra of monoamides VIIa
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

602
SHCHEPIN et al.
1
Table 2. Yields, melting points, IR spectra, H NMR spectra, and elemental analyses of methyl 3-aryl-4-aroyl-2-(piperidi-
nocarbonyl)-, -(morpholinocarbonyl)-, and -(4-methoxyphenylcarbamoyl)hexanoates VIIa VIId and VIII
IR spectrum,
Calculated,
%
Found, %
1
, cm
1H NMR spectrum,
, ppm
mp, C
Formula
C
H
C
H
VIIa 55
212
215
1640 1675 1720 0.63 t (3H, CH2Me, J 7 Hz), 58.40 5.49 C26H29BrClNO4 58.38 5.46
1.40 1.65 m, 3.50 m, 3.70 m
(10H, C4H10N), 1.46 m (2H,
CH2Me),
3.32
s
(3H,
COOMe),
3.65
m
(1H,
CHEt), 3.86 d.
BrC6H4CH,
d
(1H, 4-
J
6, 10 Hz),
4.62 d (1H, CHCOOMe, J
10 Hz), 7.00 d, 7.37 d (4H,
4-BrC6H4, J 8 Hz), 7.65 d,
8.08 d (4H, 4-ClC6H4, J 8 Hz)
VIIb 29
196
198
1640 1685 1725 0.64 t (3H, CH2Me, J 7 Hz), 58.36 5.51 C26H29BrClNO4 58.38 5.46
1.40 1.65 m, 3.50 m, 3.72 m
(10H, C4H10N), 1.46 m (2H,
CH2Me),
3.32
s
(3H,
COOMe),
3.65
m
(1H,
CHEt), 3.88 d.d (1H, 4-
ClC6H4CH, 6, 10 Hz),
J
4.62 d (1H, CHCOOMe, J
10 Hz), 7.06 d, 7.23 d (4H,
ClC6H4, J
8 Hz), 7.80 d,
8.00 d (4H, 4-BrC6H4, J 8 Hz)
1640 1675 1720 0.64 t (3H, CH2Me, J 7 Hz), 55.85 5.10 C25H27BrClNO5 55.93 5.07
1.46 m (2H, CH2Me), 3.35 s
VIIc 37
186
188
(3H, COOMe), 3.45 3.85 m
(8H, C4H8NO), 3.67 m (1H,
CHEt), 3.89 d.d (1H, 4-
BrC6H4CH, J 6, 10 Hz),
4.62
d (1H, CHCOOMe,
J 10 Hz), 7.03 d, 7.39 d (4H,
4-BrC6H4, J 8 Hz), 7.65 d,
8.08 d (4H, 4-ClC6H4, J 8 Hz)
VIId 36
171
173
1645 1685 1730 0.64 t (3H, CH2Me, J 7 Hz), 55.90 5.11 C25H27BrClNO5 55.93 5.07
1.46 m (2H, CH2Me), 3.35 s
(3H, COOMe), 3.45 3.85 m
(8H, C4H8NO), 3.66 m (1H,
CHEt), 3.89 d. d (1H, 4-
ClC6H4CH,
J 6, 10 Hz),
4.63 (1H, CHCOOMe,
d
J 10 Hz), 7.07 d, 7.25 d (4H,
4-ClC6H4, J 8 Hz), 7.80 d,
8.00
d
(4H, 4-BrC6H4,
J 8 Hz)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

SYNTHESIS OF DIMETHYL 2-(2-ALKYL-1,3-DIARYL-3-OXOPROPYL)MALONATES
Table 2. (Contd.)
603
IR spectrum,
Calculated,
%
Found, %
1
, cm
1H NMR spectrum,
, ppm
mp, C
Formula
C
H
C
H
VIIIa 35 178
180
1655 1670 1720 0.65 t (3H, CH2Me, J 7 Hz), 59.00 4.81 C28H27BrClNO5 58.70 4.75
1.45 m (2H, CH2Me), 3.63 s,
3.69
s
(6H, COOMe, 4-
MeOC6H4), 3.85
m
(2H,
CHEt, 4-BrC6H4CH), 4.19 d
(1H, CHCOOMe, J 10 Hz),
6.75 d, 7.05
BrC6H4, J 8 Hz), 7.12 d,
7.47 (4H, 4-MeOC6H4,
d (4H, 4-
d
J 8 Hz), 7.65 d, 8.05 d (4H,
4-ClC6H4, J 8 Hz), 9.85 s (1H,
NH)
a
1
The (NH) band of compound VIII appears at 3320 cm
.
was heated under reflux for 15 20 min and then
cooled, hydrolyzed with 10% HCl, treated with di-
ethyl ether, the organic layer was separated, wshed to
neutral with 10% sodium bicarbonate, dried with
sodium sulfate, and the solvents were removed by
distillation. The final products were purified by
double crystallization from methanol.
N,N -Dibenzyl-2-[1-(4-bromophenyl)-2-(4-chloro-
benzoyl)butyl]malonamide (VIb), yield 35%, mp
1
224 226 C. IR spectrum, , cm : 1660 1675 (amide
1
C=O), (ketone C=O), 3300 (N H). H NMR spectrum
(DMCO-d6), , ppm: 0.60 t (3H, CH2Me, J 7 Hz),
1.46 m, 1.56 m (2H, CH2Me) 3.56 m (1H, 4-ClC6H4
CH), 3.88 m (1H, CHEt), 3.99 d [1H, CH(CONH)2,
J 10 Hz], 4.00 d, 4.09 d, 4.35 d, 4.42 d (4H, 2NH
CH2C6H5, J 8 Hz), 6.67 d, 6.85 d, 7.10 m, 7.25 m,
7.32 m (10H, 2C6H5, J 8 Hz), 7.10 d, 7.24 d (4H,
4-ClC6H4, J 8 Hz), 7.75 d, 7.86 d (4H, 4-BrC6H4, J
8 Hz), 8.17 br.s, 8.57 br.s (2H, NH, NH). Found, %:
C 64.59; H 5.22. C34H32BrClN2O3. Calculated, %: C
64.62; H 5.10.
N,N-R2-2-(1-Aroyl-2-aroylbutyl)malonamides
VIa and VIb. To 2.1 mmol of dimethyl 2-(1-aryl-3-
aryl-3-oxo-2-ethylpropyl)malonate Vl and Vn, dis-
solved in 10 ml of o-xylene, 6.3 mmol of amine
(cyclohexylamine or benzylamine) was added. The
mixture was heated for 6 h. The solvent was removed
by distillation, and amide VIa or VIb that precipitated
was doubly crystallized from methanol.
Methyl 3-aryl-4-aroyl-2-(piperidinocarbonyl)-,
-(morpholinocarbonyl)-, -(4-methoxyphenylcarba-
moyl)hexanoates VIIa VIId and VIII were prepared
like VIa and VIb, but using piperidine, morpholine,
and p-anisidine (Table 2).
N,N -Dicyclohexyl-2-[1-(4-bromophenyl)-2-(4-
chlorobenzoyl)butyl]malonamide (VIa), yield 42%,
1
mp 220 221 C. IR spectrum, , cm : 1655 (amide
1
C=O), 1680 (ketone C=O), 3300 (N H). H NMR
spectrum (DMSO-d6), , ppm: 0.64 t (3H, CH2Me, J
7 Hz), 0.79 1.80 m (20H, 2 cyclo-C6H11), 1.43 m,
1.52 m (2H, CH2Me), 3.64 m [3H, CH(CONH)2,
CHEt, NHCH], 3.77 m (2H, 4-BrC6H4CH, NHCH),
6.80 d, 7.36 d (4H, 4-BrC6H4, J 8 Hz), 7.39 br.s,
7.77 br.s (2H, NH, NH), 7.69 d, 8.05 d (4H, 4-
ClC6H4, J 8 Hz). Found,%: C 62.45; H 6.50.
C32H40BrClN2O3. Calculated, %: C 62.39; H 6.54.
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project no. 04-03-
96036).
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604
SHCHEPIN et al.
ewicz, J., and Kasprizyc, H., Bull. Acad. Pol. Sci., Ser.
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