Silica-supported barium chloride (SiO2-BaCl2) - Efficient and heterogeneous catalyst for the environmentally friendly preparation of N, N ′-alkylidene bisamides under solvent-free conditions

Article abstract of DOI:10.1139/v11-007

A series of N,N′-alkylidene bisamides were prepared via a green and environmentally friendly synthetic protocol from the reaction of phenyl acetylene or hex-1-yne, aromatic aldehyde, and benzamide or acetamide. Silica-supported barium chloride (SiO₂-BaCl₂) catalyzes the process of the reaction. The prepared catalysts were characterized by X-ray diffraction, and the products were obtained with high conversions and yields.

Full text of DOI:10.1139/v11-007

555
Silica-supported barium chloride (SiO2–BaCl2) —
Efficient and heterogeneous catalyst for the
environmentally friendly preparation of N,N’-
alkylidene bisamides under solvent-free
conditions
Mohammad Reza Mohammad Shafiee
Abstract: A series of N,N’-alkylidene bisamides were prepared via a green and environmentally friendly synthetic protocol
from the reaction of phenyl acetylene or hex-1-yne, aromatic aldehyde, and benzamide or acetamide. Silica-supported ba-
rium chloride (SiO2–BaCl2) catalyzes the process of the reaction. The prepared catalysts were characterized by X-ray diffrac-
tion, and the products were obtained with high conversions and yields.
Key words: SiO2–BaCl2, heterogeneous catalyst, environmentally friendly synthesis, N,N’-alkylidene bisamides.
Résumé : On a préparé une série de N,N’-alkylidène bisamides par un protocole de synthèse écologique impliquant la réac-
tion du phénylacétylène ou de l’hex-1-yne, d’un aldéhyde aromatique et du benzamide ou de l’acétamide. Du chlorure de
baryum déposé sur de la silice (SiO2–BaCl2) catalyse la réaction. Les catalyseurs préparés ont été caractérisés par diffraction
des rayons-X et les produits ont été obtenus avec des taux de conversion et des rendements élevés.
Mots‐clés : SiO2–BaCl2, catalyse hétérogène, synthèse écologique, N,N’-alkylidène bisamides.
[Traduit par la Rédaction]
persion of active reagent sites, associated selectivity, and
easier work-up.3
Introduction
The development of simple, efficient, and environmentally
benign chemical processes or methodologies for widely used
pharmacophores from readily available reagents and catalysts
are the major challenges for chemists throughout the world.1
To plan and manage chemical reactions with “green” experi-
mental protocol is an enormous challenge that chemists have
to confront to improve the quality of the environment for
present and future generations.2 Over the past, chemists have
been aware of the environmental implications of their chem-
istry. Nowadays, they are trying to develop new synthetic
methods, reaction conditions, and uses of chemicals that re-
duce risks to humans and the environment. Organic solvents
are high on the list of damaging chemicals because they are
employed in huge amounts and are usually volatile liquids
that are difficult to store.3
Compounds bearing amide and bisamide groups are impor-
tant intermediates in organic synthesis, since these groups
can be easily transformed into other functionalities (such as
gem-diaminoalkyl and aminoalkyl groups) and are of consid-
erable interest in the synthesis of pharmacological materials
such as peptidomimetic compounds.4 Therefore, preparation
of amides has attracted considerable attention in the past and
in recent years.
The common approach for the synthesis of bisamides is
the direct reaction of aldehydes with the corresponding
amides or nitriles.5–10
In this paper various acidic catalysts such as sulfuric acid
(85%; also as solvent),5 sulfonic acid,6 triflic acid,8 sulfamic
acid,10a or chlorosulfonic acid10b were examined.
Considering that most of the organic reagents involved in
fine chemical synthesis are sensitive to harsh conditions, it is
desirable to choose catalysts that can catalyze organic trans-
formations under mild conditions.
The aim of the present protocol was to summarize the data
for the one-pot preparation of N,N’-alkylidene bisamide de-
rivatives in high yield using a three-component condensation
of an alkyne, aromatic aldehydes, and amides in the presence
One important aspect of clean technology is the use of en-
vironmentally friendly catalysts — typically a solid catalyst
that can be recovered easily when the reaction is complete.
Heterogeneous organic reactions have proven useful to chem-
ists in the laboratory as well as in an industrial context.
These reactions are affected by the reagents immobilized on
the porous solid supports and have advantages over the con-
ventional solution-phase reactions because of the good dis-
Received 3 October 2010. Accepted 12 January 2011. Published at www.nrcresearchpress.com/cjc on 16 May 2011.
M.R.M. Mohammad Shafiee. Faculty of Sciences, Islamic Azad University – Najafabad Branch, Najafabad, Esfahan, Iran.
Corresponding author: M.R. Mohammad Shafiee (e-mail: mohammadreza.mohammadshafiee@gmail.com).
Can. J. Chem. 89: 555–561 (2011)
doi:10.1139/V11-007
Published by NRC Research Press
PROOF/ÉPREUVE

Pagination not final/Pagination non finale
556
Can. J. Chem. Vol. 89, 2011
Scheme 1.
Scheme 2.
Scheme 3.
of silica-supported barium chloride (SiO2–BaCl2) as the cata-
lyst under thermal, solvent-free conditions (Scheme 1).
As expected, this reaction proceeded smoothly, and the de-
sired products were obtained in good to excellent yields. A
series of aromatic aldehydes with either electron-donating or
electron-withdrawing groups attaching to aromatic rings were
investigated (Table 1, entries 1–9). However, when aromatic
aldehydes with electron-withdrawing groups (such as nitro-)
were reactants, the reaction time was shorter than that with
electron-donating groups (such as methoxy-). Although
meta- and para-substituted aromatic aldehydes gave good
results, ortho-substituted aromatic aldehydes (such as 2-
nitrobenzadehyde) gave lower yields and longer reaction
times because of the steric effects. These good results were
also obtained in the case of the hex-1-yne (Table 1, entries
14 and 15).
Results and discussion
Hung et al.11 reported that the condensation of phenyl acety-
lene, aromatic aldehyde, and urea with acetic acid / trifluoroacetic
acid as the catalyst and acetonitrile as the solvent lead to the
formation of 4H-[1,3]oxazines. In continuation of this theme,
we are trying to develop new synthetic methods, reaction
conditions, and uses of heterogeneous catalysts that reduce
risks to humans and the environment. Thus, the reaction of
phenyl acetylene, benzaldehydes, and benzamide in the pres-
ence of a catalytic amount of SiO2–BaCl2 as the catalyst
under thermal, solvent-free conditions was investigated
(Scheme 1). As can be seen from Scheme 1 we did not ob-
serve 2-phenyl(methyl)-4H-1,3-oxazine derivatives, and a ser-
ies of N,N’-alkylidene bisamides formed.
Within our plan to investigate the structures of bisamide
and needing an alkyne or a catalyst for the formation of bis-
amides, the reaction including benzaldehyde, benzamide, and
a catalytic amount of SiO2–BaCl2 under heating at 100 °C
failed to give the correlative product in the absence of phenyl
acetylene, which indicated that phenyl acetylene plays an im-
portant role in the reaction (Scheme 2). Chromatographic
studies (TLC) confirmed that the alkyne was completely dis-
appearing when the product was formed.
As a result the reaction of butyraldehyde with phenyl ace-
tylene and benzamide failed to give any product (Table 1, en-
try 10).
Encouraged by the results obtained with benzamide, we
turned our attention to acetamide (Table 1). As shown in Ta-
ble 1, the reactions of phenyl acetylene and aryl aldehyde
with acetamide under the mentioned reaction conditions pro-
gressed smoothly but with longer reaction times, and the de-
sired products were obtained in good yields. (Table 1, entries
11 and 12). However, ortho-substituted aromatic aldehydes
(such as 2-nitrobenzadehyde) failed to give any product (Ta-
ble 1, entry 13).
As a result the mentioned reaction failed to give any prod-
ucts in the absence of the catalyst.
To improve the yield and optimize the reaction conditions,
the reaction was carried out using phenyl acetylene, benzal-
dehyde, and benzamide in the presence of SiO2–BaCl2 as the
catalyst (Scheme 3). Initially, the effect of temperature on the
rate of the reaction was investigated (Table 1). At 80 °C, the
reaction proceeded smoothly and almost complete conversion
of the product was observed. A further increase in tempera-
ture to 100 °C increased the rate of the reaction. Therefore,
the reaction temperature was kept at 100 °C (giving a short
reaction time and high yield).
To explain the formation of bisamides via the one-pot multi-
component reaction, we have proposed a plausible reaction
mechanism, which is illustrated in Scheme 4. Firstly, the in-
teraction of aldehyde with an empty p orbital of the Lewis
acid occurs to form a cation intermediate. Therefore, the for-
mation of A resulting from the cyclocondensation of an acti-
vated aldehyde with phenyl acetylene is established. The
second step is the addition of amide to A to yield b-amido
ketones (B) that protonate and convert to the bisamide as the
product by an attack of the amide (Scheme 4).
We then tried to optimize the amount of catalyst for this
reaction. It should be noted that 0.025 g of SiO2–BaCl2 was
efficient enough to catalyze the reaction, and increasing the
amount of catalyst did not significantly improve the yield
(Table 1). Finally, an optimimal set of conditions was
achieved using 0.025 g of SiO2–BaCl2 as the catalyst and
100 °C. The results are summarized in Table 1.
Using these optimized reaction conditions, the scope and
efficiency of these procedures were explored for the synthesis
of a wide variety of substituted bisamides (Scheme 1). The
results are summarized in Table 2.
Conclusion
In conclusion, a rapid and environmentally benign protocol
for the preparation of N,N’-alkylidene bisamides in a one-pot
procedure wasn developed. The work-up procedure is very
clear-cut; that is, the products were isolated and purified by
simple filtration and crystallization from aqueous ethanol (or
diethyl ether). Our protocol avoids the use of dry media dur-
ing the reaction process, making it superior to the reactions
that use solvent.
Published by NRC Research Press
PROOF/ÉPREUVE

Mohammad Shafiee
Table 1. Preparation of N,N’-alkylidene bisamide derivatives.
557
Time
(min)
mp (°C)
Entry
Aldehyde
Amide
Alkyne
Yield (%)a
[lit. mp)ref
Published by NRC Research Press
PROOF/ÉPREUVE

Pagination not final/Pagination non finale
558
Can. J. Chem. Vol. 89, 2011
Table 1. (concluded).
Time
(min)
mp (°C)
Entry
Aldehyde
Amide
Alkyne
Yield (%)a
[lit. mp)ref
aIsolated yields.
Table 2. Optimization amount of SiO2–BaCl2 and reaction tem-
peratures.
Scheme 4. Proposed mechanism for the formation of N,N’-alkyli-
dene bisamides.
Time
Entry
Catalyst (g)
0.025
0.025
0.1
0.05
0.025
0.01
T (°C)
rt
80
100
100
100
100
(min)
300
450
180
170
120
160
Yield (%)a
1
2
3
4
5
6
—
55
62
73
74
60
Note: rt, room temperature.
aIsolated yield (based on phenyl acetylene (1 mmol), benzaldehyde
(1.1 mmol), and benzamide (2.5 mmol)).
Experimental
All reagents were purchased from Merck and Sigma-
Aldrich and used without further purification. All yields refer
to isolated products after purification based on the amount of
aldehyde. Products were characterized by comparison of
spectroscopic data (IR and 1H NMR spectra) and melting
points with authentic samples. The NMR spectra were re-
corded on a Bruker Avance DPX 300 MHz instrument. The
Published by NRC Research Press
PROOF/ÉPREUVE

Mohammad Shafiee
559
Fig. 1. X-ray diffraction (XRD) pattern of SiO2–BaCl2.
spectra were measured in DMSO-d6 relative to TMS
(0.00 ppm). IR spectra were recorded on a PerkinElmer 781
spectrophotometer. Melting points were determined in open
capillaries with a BUCHI 510 melting point apparatus. TLC
was performed on silica gel polygram SIL G/UV 254 plates.
Preparation of SiO2–BaCl2
In
a
250 mL flask, barium chloride dihydrate
(BaCl2·2H2O, 1 g) was dissolved in water (50 mL) and silica
gel (10 g) (Silica gel 60 for column chromatography,
230 mesh) was added to this mixture, which was vigorously
stirred under rotary evaporation until the water was com-
pletely evaporated. This powder was kept in an oven at
100 °C for 1 h to give the active catalyst.
X-ray diffraction (XRD)
1581, 1534, 1505, 1340, 1271, 1211, 1140, 1054, 873, 736,
716. H NMR (300 MHz, DMSO-d6, ppm) d: 7.11 (t, J =
Powder X-ray diffraction measurements were performed
using a D8 Advance diffractometer made by Bruker AXS,
Germany. Scans were taken with a 2q step size of 0.02 and a
counting time of 1.0 s using a Cu Ka radiation source gener-
ated at 40 kV and 30 mA. Specimens for XRD were prepared
by compaction into a glass-backed aluminum sample holder.
Data were collected over a 2 u range from 48° to 70°, and
phases were identified by matching experimental patterns to
entries in the Diffractplus version 6.0 indexing software. The
fresh catalyst was characterized by XRD and its pattern is
presented in Fig. 1. As shown in Fig. 1, the actual phases
were silicon oxide (silica) – SiO2 (cubic) and BaCl2.
1
7.3 Hz, 1H), 7.47–7.60 (m, 6H), 7.71 (t, J = 7.9 Hz, 1H),
7.94–7.96 (m, 5H), 8.21 (d, J = 8.1 Hz, 2H), 8.36 (s1, H),
9.27 (d, J = 7.3 Hz, 2H). 13C NMR (75 MHz, DMSO-
d6, ppm) d: 59.5, 122.3, 123.6, 128.5, 129.2, 130.8, 132.6,
134.4, 134.6, 143.3, 148.7, 166.8. Anal. calcd for
C21H17N3O4 (%): C 67.19, H 4.56, N 11.19; found: C 67.32,
H 4.65, N 11.29.
N-Benzoylamino(2-nitrophenyl)methyl benzamide
(Table 1, entry 3)
IR (KBr, cm–1): 3275, 3073, 3030, 1648, 1610, 1531,
1481, 1347, 1274, 1189, 1146, 1086, 1059, 854, 796, 703.
General procedure for the synthesis of N,N’-alkylidene
bisamides
1H NMR (300 MHz, DMSO-d6, ppm) d: 7.41–7.61 (m, 8H),
7.76–7.81 (m, 2H), 7.91 (d, J = 7.0 Hz, 4H), 7.98 (d, J =
8.1 Hz, 1H), 9.19 (d, J = 6.9 Hz, 2H). 13C NMR (75 MHz,
DMSO-d6, ppm) d: 56.7, 125.3, 128.6, 129.1, 129.7, 130.1,
132.5, 133.9, 134.4, 134.6, 149.4, 166.9. Anal calcd for
C21H17N3O4 (%): C 67.19, H 4.56, N 11.19; found: C 67.26,
H 4.63, N 11.24.
To a mixture of aryl aldehyde (1.1 mmol), benzamide or
acetamide (2.5 mmol), and phenyl acetylene or hex-1-yne
(1 mmol) was added SiO2–BaCl2 (0.025 g) and the mixture
was heated at 100 °C in an oil bath for the appropriate time
(Table 1). The progress of the reaction was monitored by
TLC. After completion of the reaction, the mass was cooled
to 25 °C, and the mixture was dissolved in boiling ethanol.
The catalyst was removed by simple filtration. The solvent
was concentrated and the solid product was purified by a re-
crystallization procedure in the appropriate solvent (ethanol
40% or diethyl ether).
N-Benzoylamino(4-fluorophenyl)methyl benzamide
(Table 1, entry 4)
IR (KBr, cm–1): 3277, 3065, 3026, 1643, 1521, 1480,
1350, 1275, 1141, 1072, 1037, 800, 753, 699. 1H NMR
(300 MHz, DMSO-d6, ppm) d: 7.19 (t, J = 6.9 Hz, 1H),
7.36–7.69 (m, 10H), 7.94 (d, J = 7.2 Hz, 4H), 9.11 (d, J =
7.0 Hz, 2H). 13C NMR (75 MHz, DMSO-d6, ppm) d: 58.1,
127.9, 128.2, 128.5, 129.0, 129.3, 129.6, 130.3, 130.4,
132.4, 133.4, 134.7, 138.2, 166.6. Anal. calcd for
C21H17FN2O2 (%): C 72.40, H 4.92, N 8.04; found: C 72.49,
H 4.98, N 8.11.
All products were characterized by IR, H NMR, and 13C
NMR spectra.
1
N-Benzoylamino(4-nitrophenyl)methyl benzamide
(Table 1, entry 1)
IR (KBr, cm–1): 3264, 3085, 3028, 2963, 1650, 1633,
1608, 1579, 1548, 1486, 1345, 1295, 1277, 1201, 1143,
1
1083, 1055, 875, 852, 794, 718, 695. H NMR (300 MHz,
N-Benzoylamino(2,4-dichlorophenyl)methyl benzamide
(Table 1, entry 5)
DMSO-d6, ppm) d: 7.08 (t, J = 7.3 Hz, 1H), 7.47–7.60 (m,
6H), 7.75 (d, J = 8.6 Hz, 2H), 7.93 (d, J = 7.1 Hz, 4H),
8.26 (d, J = 8.7 Hz, 2H), 9.22 (d, J = 7.4 Hz, 2H). 13C
NMR (75 MHz, DMSO-d6, ppm) d: 59.4, 124.4, 128.5,
128.9, 129.2, 132.6, 134.4, 147.9, 148.4, 166.8. Anal. calcd
for C21H17N3O4 (%): C 67.19, H 4.56, N 11.19; found: C
67.36, H 4.60, N 11.26.
IR (KBr, cm–1): 3290, 3214, 3066, 3028, 1639, 1602,
1579, 1543, 1514, 1364, 1330, 1261, 1145, 1078, 1043,
1
860, 827, 744, 698. H NMR (300 MHz, DMSO-d6, ppm) d:
7.14 (t, J = 6.8 Hz, 1H), 7.45–7.68 (m, 9H), 7.93 (d, J =
7.1 Hz, 4H), 9.13 (d, J = 6.8 Hz, 2H). 13C NMR (75 MHz,
DMSO-d6, ppm) d: 57.9, 128.0, 128.5, 129.1, 129.7, 130.7,
132.4, 134.1, 134.4, 134.6, 137.4, 166.7. Anal. calcd for
C21H16Cl2N2O2 (%): C 63.17, H 4.04, N 7.02; found: C
63.19, H 4.08, N 7.05.
N-Benzoylamino(3-nitrophenyl)methyl benzamide
(Table 1, entry 2)
IR (KBr, cm–1): 3313, 3259, 3086, 2969, 1649, 1602,
Published by NRC Research Press
PROOF/ÉPREUVE

Pagination not final/Pagination non finale
560
Can. J. Chem. Vol. 89, 2011
N-Benzoylamino(2-chlorophenyl)methyl benzamide
(Table 1, entry 6)
7.7 Hz, 1H), 7.19 (t, J = 8.8 Hz, 2H), 7.32–7.37 (dd, J =
5.6, 8.4 Hz, 2H), 8.53 (d, J = 7.7 Hz, 2H). 13C NMR
(75 MHz, DMSO-d6, ppm) d: 23.3, 57.6, 115.7, 116.0,
129.2, 129.3, 137.5, 137.6, 160.8, 164.0, 169.4. Anal. calcd
for C11H13FN2O2 (%): C 58.92, H 5.84, N 12.49: found: C
59.01, H 5.95, N 12.56.
IR (KBr, cm–1): 3280, 3092, 1649, 1547, 1506, 1343,
1274, 1228, 1146, 1062, 830, 790, 703. 1H NMR
(300 MHz, DMSO-d6, ppm) d: 7.01 (t, J = 7.5 Hz, 1H),
7.18–7.24 (m, 2H), 7.46–7.59 (m, 8H), 7.91 (d, J = 7.1 Hz,
4H), 9.05 (d, J = 7.6 Hz, 2H). 13C NMR (75 MHz, DMSO-
d6, ppm) d: 58.1, 117.3, 117.7, 128.3, 129.2, 129.5, 129.8,
132.5, 134.6, 137.5, 164.1, 166.5. Anal. calcd for
C21H17ClN2O2 (%): C 69.14, H 4.70, N 7.68: found: C
69.19, H 4.81, N 7.72.
N-Acetylamino(4-nitrophenyl)methyl acetamide (Table 1,
entry 14)
IR (KBr, cm–1): 3270, 3116, 2999, 2949, 1670, 1605,
1563, 1518, 1353, 1273, 1089, 1017, 852, 825, 772. 1H
NMR (300 MHz, DMSO-d6, ppm) d: 1.88 (s, 6H), 6.56 (t,
J = 7.7 Hz, 1H), 7.58 (d, J = 8.4 Hz, 2H), 8.23 (d, J =
8.5 Hz, 2H), 8.71 (d, J = 7.6 Hz, 2H). 13C NMR (75 MHz,
DMSO-d6, ppm) d: 23.3, 57.8, 124.3, 128.6, 147.8, 148.7,
169.7. Anal. calcd for C11H13N3O4 (%): C 52.59, H 5.22, N
16.73; found: C 52.63, H 5.30, N 16.83.
N-Benzoylamino(phenyl)methyl benzamide (Table 1, entry 7)
IR (KBr, cm–1): 3285, 3088, 1651, 1543, 1497, 1342,
1269, 1137, 1047, 875, 802, 702. 1H NMR (300 MHz,
DMSO-d6, ppm) d: 7.05 (t, J = 7.7 Hz, 1H), 7.29–7.58 (m,
11H), 7.92 (d, J = 7.1 Hz, 4H), 9.03 (d, J = 7.7 Hz, 2H).
13C NMR (75 MHz, DMSO-d6, ppm) d: 59.6, 127.4, 128.4,
128.5, 129.2, 132.5, 134.7, 141.1, 166.5. Anal. calcd for
C21H18N2O2 (%): C 76.34, H 5.49, N 8.48; found: C 76.39,
H 5.55, N 8.51.
N-Benzoylamino butyl benzamide (Table 1, entry 15)
IR (KBr, cm–1): 3237, 3106, 2966, 2927, 1648, 1557,
1518, 1483, 1365, 1333, 1288, 1134, 1079, 1053, 995, 844,
1
809, 764. H NMR (300 MHz, DMSO-d6, ppm) d: 0.93 (t,
J = 7.3 Hz, 3H), 1.37 (six, J = 7.4 Hz, 2H), 1.82 (q, J =
7.6 Hz, 2H), 5.88 (quin, J = 7.4 Hz, 1H), 7.43–7.55 (m,
6H), 7.86 (d, J = 7.0 Hz, 4H), 8.57 (d, J = 7.6 Hz, 2H). 13C
NMR (75 MHz, DMSO-d6, ppm) d: 14.5, 19.3, 37.2, 57.7,
128.2, 129.1, 132.2, 135.1, 166.4. Anal. calcd for
C18H20N2O2 (%): C 72.95, H 6.80, N 9.45; found: C 73.00,
H 6.89, N 9.55.
N-Benzoylamino(4-(1,1-dimethylethyl)phenyl)methyl
benzamide (Table 1, entry 8)
IR (KBr, cm–1): 3271, 3060, 2965, 1646, 1601, 1579,
1555, 1511, 1352, 1271, 1136, 1075, 871, 833, 710. 1H
NMR (300 MHz, DMSO-d6, ppm) d: 1.29 (s, 9H), 7.03 (t,
J = 7.6 Hz, 1H), 7.36–7.58 (m, 10H), 7.93 (d, J = 7.8 Hz,
4H), 9.02 (d, J = 7.7 Hz, 2H). 13C NMR (75 MHz, DMSO-
d6, ppm) d: 32.0, 35.1, 59.4, 125.9, 127.1, 128.1, 128.4,
129.2, 132.4, 134.7, 138.3, 166.4. Anal. calcd for
C25H26N2O2 (%): C 77.69, H 6.78, N 7.25; found: C 77.80,
H 6.89, N 7.29.
Acknowledgments
We are thankful to the Islamic Azad University – Najafabad
Branch Research Council for partial support of this research.
References
N-Benzoylamino(4-methoxyphenyl)methyl benzamide
(Table 1, entry 9)
(1) (a) Bannwarth, W.; Hinzen, B. Combinatorial Chemistry:
From Theory to Application; Wiley/VCH: Weinheim, 2006;
(b) Laszlo, P. Preparative Chemistry Using Supported
Reagents; Academic Press, Inc.: San Diego, 1987; (c) Smith,
K. Solid Supports and Catalyst in Organic Synthesis; Ellis
Horwood: Chichester, UK, 1992.
(2) (a) Corma, A. Curr. Opin. Solid State Mater. Sci. 1997 2 (1),
63. doi:10.1016/S1359-0286(97)80107-6;; (b) Tanaka, K.;
Kaupp, G. Solvent-free Organic Synthesis; Wiley-VCH:
Weinheim, 2009.
IR (KBr, cm–1): 3273, 3068, 2958, 1648, 1546, 1511,
1280, 1249, 1177, 1065, 815, 765, 703. 1H NMR
(300 MHz, DMSO-d6, ppm) d: 3.74 (s, 3H), 6.93–6.99 (m,
3H), 7.39–7.55 (m, 8H), 7.91 (d, J = 7.3 Hz, 4H), 8.97 (d,
J = 7.3 Hz, 2H). 13C NMR (75 MHz, DMSO-d6, ppm) d:
56.0, 59.3, 114.5, 128.3, 128.6, 129.2, 132.4, 133.3, 134.8,
159.7, 166.3. Anal. calcd for C22H20N2O3 (%): C 73.32, H
5.59, N 7.77; found: C 73.37, H 5.65, N 7.89.
(3) (a) Varma, R. S. Green Chem. 1999 1 (1), 43. doi:10.1039/
a808223e;; (b) Anastasas, P. T.; Warner, J. C. Green
Chemistry: Theory and Practice; Oxford University Press:
New York, 1988; (c) Shaterian, H. R.; Ghashang, M.; Feyzi,
M. Appl. Catal. A Gen. 2008 345 (2), 128. doi:10.1016/j.
apcata.2008.04.032;; (d) Shaterian, H. R.; Ghashang, M.;
Hassankhani, A. Dyes Pigments 2008 76 (2), 564. doi:10.
1016/j.dyepig.2006.11.004.
(4) (a) Dingermann, T. Steinhilber, D.; Folkers, G. In Molecular
Biology in Medicinal Chemistry; Wiley-VCH: Weinheim,
2004; (b) Shen, A. Y.; Tsai, C. T.; Chen, C. L. Eur. J. Med.
Chem. 1999 34 (10), 877. doi:10.1016/S0223-5234(99)00204-
4;; (c) Shaterian, H. R.; Hosseinian, A.; Ghashang, M. Can. J.
Chem. 2008 86 (5), 376. doi:10.1139/V08-013.
N-Acetylamino(phenyl)methyl acetamide (Table 1, entry 11)
IR (KBr, cm–1): 3278, 3119, 3060, 3029, 2932, 1663,
1563, 1517, 1371, 1273, 1094, 848, 749, 696. 1H NMR
(300 MHz, DMSO-d6, ppm) d: 1.86 (s, 6H), 6.52 (t, J =
7.8 Hz, 1H), 7.26–7.38 (m, 5H), 8.57 (d, J = 7.8 Hz, 2H).
13C NMR (75 MHz, DMSO-d6, ppm) d: 23.3, 58.1, 127.2,
128.4, 129.1, 141.4, 169.4. Anal. calcd for C11H14N2O2 (%):
C 64.06, H 6.84, N 13.58; found: C 64.16, H 6.91, N 13.66.
N-Acetylamino(4-fluorophenyl)methyl acetamide (Table 1,
entry 12)
IR (KBr, cm–1): 3276, 3124, 3016, 2957, 1665, 1555,
1515, 1369, 1237, 1093, 1028, 861, 823. 1H NMR
(300 MHz, DMSO-d6, ppm) d: 1.86 (s, 6H), 6.48 (t, J =
(5) Magat, E. E.; Faris, B. F.; Reith, J. E.; Salisbury, L. F. J. Am.
Chem. Soc. 1951 73 (3), 1028. doi:10.1021/ja01147a042.
Published by NRC Research Press
PROOF/ÉPREUVE

Mohammad Shafiee
561
(6) Zhu, S.; Xu, G.; Chu, Q.; Xu, Y.; Qui, C. J. Fluor. Chem. 1999
93 (1), 69. doi:10.1016/S0022-1139(98)00286-3.
(7) Pernak, J.; Błazej, M.; Józef, W. Synthesis 1994 1994 (12),
(10) (a) Anary-Abbasinejad, M.; Mosslemin, M.; Hassanabadi, A.;
Safa, S. T. Synth. Commun. 2010 40 (15), 2209. doi:10.1080/
00397910903219617;; (b) Anary-Abbasinejad, M.; Mosslemin,
M. H.; Hassanabadi, A. J Chem. Res. 2009 2009 (4), 218.
doi:10.3184/030823409X435937.
1415. doi:10.1055/s-1994-25705.
(8) Herrera Fernández, A.; Martínez Alvarez, R.; Morales Abajo,
T. Synthesis 1996 1996 (11), 1299. doi:10.1055/s-1996-4385.
(9) Selvam, N. P.; Saranya, S.; Perumal, P. T. Can. J. Chem. 2008
86 (1), 32. doi:10.1139/V07-134.
(11) Huang, S.; Pan, Y.; Zhu, Y.; Wu, A. Org. Lett. 2005 7 (17),
3797. doi:10.1021/ol051458e.
Published by NRC Research Press
PROOF/ÉPREUVE