One-pot three-component synthesis of β-acylaminoketones containing a thiophene ring by the use of tetrachlorosilane-zinc chloride as a binary reagent under ambient conditions

Article abstract of DOI:10.1080/10426500802095921

A new route for the synthesis of β-acylaminoketones containing a thiophene ring through multicomponent condensation reaction of different ketones, different aldehydes, and different nitriles with tetrachlorosilane (TCS) and zinc chloride as the binary rea

Full text of DOI:10.1080/10426500802095921

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One-Pot Three-
Component Synthesis of β -
Acylaminoketones Containing a
Thiophene Ring by the Use of
Tetrachlorosilane-Zinc Chloride
as a Binary Reagent Under
Ambient Conditions
Doria S. Badawy a , Ebrahim Abdel-Galil a , E. M.
Kandeel a , Wahid M. Basyouni b , Khairy A. M. El-
Bayouki b & Tamer K. Khatab b
a Chemistry Department, Faculty of Science ,
Mansoura University , Mansoura , Egypt
b Organometallic and Organometalloid Chemistry
Department, National Research Centre , Dokki ,
Cairo , Egypt
Published online: 19 Dec 2008.
To cite this article: Doria S. Badawy , Ebrahim Abdel-Galil , E. M. Kandeel , Wahid
M. Basyouni , Khairy A. M. El-Bayouki & Tamer K. Khatab (2008) One-Pot Three-
Component Synthesis of β -Acylaminoketones Containing a Thiophene Ring by the Use
of Tetrachlorosilane-Zinc Chloride as a Binary Reagent Under Ambient Conditions,
Phosphorus, Sulfur, and Silicon and the Related Elements, 184:1, 220-233, DOI:
10.1080/10426500802095921
To link to this article: http://dx.doi.org/10.1080/10426500802095921
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Phosphorus, Sulfur, and Silicon, 184:220–233, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802095921
One-Pot Three-Component Synthesis of
β-Acylaminoketones Containing a Thiophene Ring by the
Use of Tetrachlorosilane-Zinc Chloride as a Binary
Reagent Under Ambient Conditions
Doria S. Badawy,1 Ebrahim Abdel-Galil,1 E. M. Kandeel,1
Wahid M. Basyouni,2 Khairy A. M. El-Bayouki,2
and Tamer K. Khatab2
1Chemistry Department, Faculty of Science, Mansoura University,
Mansoura, Egypt
2Organometallic and Organometalloid Chemistry Department, National
Research Centre, Dokki, Cairo, Egypt
A new route for the synthesis of β-acylaminoketones containing a thiophene ring
through multicomponent condensation reaction of different ketones, different alde-
hydes, and different nitriles with tetrachlorosilane (TCS) and zinc chloride as the
binary reagent is described.
Keywords β-Acylaminoketones; binary reagent; tetrachlorosilane; thiophene
INTRODUCTION
β-Acetamidoketones are versatile and potential intermediates and
exist in a number of biologically or pharmacologically important
derivatives,1–5 such as nikkomycin or neopolyoxin3 antibiotics. The
best known route for the synthesis of these compounds is the Dakin–
West reaction,6 which includes the condensation of an amino acid
with acetic anhydride in the presence of a base via an interme-
diate azalactone to give the acetamidoketones.7 According to the
previous method, other methods were developed to synthesize β-
acetamidoketones through condensation of an aryl aldehyde, acetophe-
8a
none, and acetyl chloride in acetonitrile in the presence of CoCl2 or
morillonite K-10 clay8b or SiO2-H2SO4 under thermal conditions, or
8c
Received 18 November 2007; accepted 28 March 2008.
Address correspondence to Ebrahim Abdel-Galil, Mansoura University,
Chemistry Department, Faculty of Science, B.O. 35516, Mansoura, Egypt. E-mail:
msebrahim2002@yahoo.com
220

β-Acylaminoketones Containing a Thiophene Ring
221
by using ZrOCl2.8H2O8d or BiCl3 generated in situ from BiOCl and
acetyl chloride at room temperature.8e−j Although these protocols are
valuable, they lack the generality to produce arrays of β-amido ketones,
and by way of a survey we found only one example of a β-benzamido
ketone that had been prepared by this method involving benzonitrile
via a long time (36 h).8d Concerning the multicomponent reactions
methods to produce β-amidoketones, an efficient one is still required.
Toward this aim, and in continuation of investigations on the devel-
opment and applications of new in situ reagents derived from tetra-
chlorosilane (TCS)9–11 in organic synthesis, we have developed an ef-
ficient, general, and convenient protocol for the one-pot synthesis of
β-amidoketones. The reaction proceeds via a three-component reac-
tion of various aldehydes, ketones, and nitriles including alkyl, aryl,
and α, β-unsaturated nitriles utilizing the inexpensive and readily
available tetrachlorosilane–zinc chloride reagent in dichloromethane
at room temperature.
RESULTS AND DISCUSSION
The development of new silane reagents derived from tetrachlorosilane
and their use in organic synthesis was applied in the present work.
Thus, the scope and limitation of the SiCl4-ZnCl2 combination sys-
tem with respect to the one-pot three-component reaction of aldehydes,
ketones, and nitriles was studied.
The following optimal conditions were found: a mixture of ben-
zaldehyde (10 mmol), 2-acetylthiophene (10 mmol), and acetonitrile
(10 mmol) in the presence of SiCl4 (30 mmol) and ZnCl2(30 mmol) in
dichloromethane as solvent was stirred at ambient temperature. The
reaction mixture proceeded with high selectivity to a single product as
detected by thin layer chromatography (TLC), as shown in Scheme 1.
The isolated product was identified as N-[3-oxo-1-phenyl-3-(thien-2-
yl)propyl]acetamide 1a.
After optimization, a variety of other aromatic aldehydes and
aromatic ketones having electron-donating as well as electron-
withdrawing substituents were shown to undergo the reaction
O
H
N
R2
SiCl4 / ZnCl2
CH2Cl2
H
R2-CN
S
CH3
+
+
S
O
O
R1
R1 = H, 4-CH3, 4-Cl, 3-Br
O
R1
R2 = CH3, C6H5, CH2=CH -
(1a-3d)
SCHEME 1

222
D. S. Badawy et al.
O
CH3
SiCl4 / ZnCl2
CH2Cl2
H
R
R2-CN
+
H
+
N
R2
S
R
O
O
O
R2 = CH3, C6H5, CH2=CH-
(4a - 6d)
R = H, 4-CH3, 4-Cl, 3-Br
S
SCHEME 2
smoothly, giving the desired products in good yields (Schemes 1 and 2).
For the one-pot condensation of the aldehyde containing an electron-
donating group (CH3) with 2-acetylthiophene, the reaction time was
reduced with increase of the product yield relative to the unsubti-
tuted benzaldehyde; for aldehydes containing electron-withdrawing
substituents (Cl, Br), the time of reaction increased and the yield
was reduced. In the reaction of thiophene-2-carbaldehyde with ace-
tophenones, it was noticed also that the presence of electron-donating
substituents increases the yield with reducing reaction time, but the
presence of electron-withdrawing substituents reduces the yield with
increasing reaction time (Tables I and II).
The structures of the obtained β-acylaminoketones were elucidated
by spectroscopic methods. Thus, their IR spectra showed peaks at
ν = 3350–3241, 1685–1655, and 1652–1634 cm−1 corresponding to the
NH, carbonyl of (COCH2), and amidic carbonyl (CONH) groups, respec-
tively. 1H NMR spectra of the synthesized products were characterized
TABLE I One-Pot Condensation of Acetylthiophene,
Substituted Benzaldehydes, and Different Nitriles Giving the
Corresponding β-Acetamidoketones
Entry
R1
R2
Product
Time (h)
Yield%
1
2
3
4
5
6
7
8
H
4-CH3
4-Cl
3-Br
H
4-CH3
4-Cl
3-Br
H
CH3
CH3
CH3
CH3
C6H5
C6H5
C6H5
C6H5
1a
1b
1c
1d
2a
2b
2c
2d
3a
3b
3c
3d
10
8
80
85
75
72
78
80
75
72
70
75
65
60
11
12
15
12
16
20
16
15
17
18
9
CH2 CH
CH2 CH
CH2 CH
CH2 CH
10
11
12
4-CH3
4-Cl
3-Br

β-Acylaminoketones Containing a Thiophene Ring
223
TABLE II One-Pot Condensation of Thiophene-2-carbaldehyde,
Substituted Acetophenones, and Different Nitriles Giving the
Corresponding β-Acetamidoketones
Entry
R
R2
Product
Time (h)
Yield%
1
2
3
4
5
6
7
8
H
4-CH3
4-Cl
4-Br
H
4-CH3
4-Cl
4-Br
H
CH3
CH3
CH3
CH3
C6H5
C6H5
C6H5
C6H5
4a
4b
4c
4d
5a
5b
5c
5d
6a
6b
6c
6d
8
6
90
92
85
80
85
88
77
75
72
75
70
65
10
12
12
10
14
16
14
12
13
15
9
CH2 CH
CH2 CH
CH2 CH
CH2 CH
10
11
12
4-CH3
4-Cl
4-Br
by the presence of two doublet signals at δ = 4.00–3.65 and 3.79–3.34
ppm (J= 5.60, 16.20 Hz) for (COCH2) and quartet signals at δ = 5.88–
5.26 ppm for CH-protons. The 13C NMR spectrum of compound 1b
showed the characteristic two signals at δ = 192.00 for ketonic (C O)
and at 170.32 for the amidic (CONH) carbonyl groups, at 145.50–127.55
for the CarH, at 47.81 for CHNH, at 45.43 for CH2CO, and at 26.1 and
21.9 for the two CH3 groups. Representative results are summarized
in Table I.
Following these good results that were obtained, we explored
the reaction of thiophene-2-carbaldehyde with different ketones and
nitriles. The reaction proceeded with high selectivity, affording β-
acylaminoketone derivatives (4a–6d) with good yields, as shown in
Scheme 2. Representative results are summarized in Table II.
Moreover, to optimize the reaction conditions, the reaction was car-
ried out in various solvents. Dichloromethane (CH2Cl2) was found to
be the most effective solvent,12 while donor solvents such as diethyl
ether completely inhibited the reaction. Stannous chloride (SnCl2) as
a Lewis acid was examined and similar results were obtained, but it
was found to be less effective than zinc chloride. It was noticed that
no reaction took place in the absence of either SiCl4or ZnCl2 under the
same reaction conditions.
The mechanism of the reformation of the Cl4Si-ZnCl2 system could
be explained as follows. The Zn2+-ion atom can accept a halide anion
to form a Cl3Si+-ZnCl3 species15,9b. In the presence of this ion-pair,
−
the three-component reaction involving ketone, aldehyde, and nitrile

224
D. S. Badawy et al.
SiCl4
+
ZnCl2
SiCl3
+
SiCl3
ZnCl3
R2
C
N
+
ZnCl3
+
R2
C
N
SiCl3
(I)
ZnCl3
O
Ar
H
CH3
O
H2O
O
+
2 SiCl
H
+
3
Ar
Ar
Ar
Ar
O
SiCl3
Ar
O
Ar = thien-2-yl, Ar = Phenyl
(II)
SiCl3
R2
C
N
SiCl3
(I)
ZnCl3
Ar
H
O
H
O
Ar = thien-2-yl, substituted phenyl,
R2 = CH3, C6H5, CH2=CH-
H3O+
N
Ar
N
R2
H
Ar
Ar
O
R2
(1a-6d)
(III)
SCHEME 3
occurs. The cyano group−of the nitrile is effectively activated16 by re-
acting with Cl3Si+-ZnCl3 under formation of the intermediate I. All
of these reactions proceed through the common aldol silyl enolether
II13–14 as intermediate, since the Cl3Si+-cation attacks the oxygen
atom of the aldol to activate the carbonyl group by way of forming
Cl3Si-O-CR2+. Support for the formation of the intermediate II came
from the reaction of 2-acetylthiophene with benzaldehyde in the pres-
ence of Cl3Si+-ZnCl3 but in the absence of any nitrile, which resulted
−
in the formation of 3-phenyl-1-(thien-2-yl)prop-2-en-1-one as the iso-
lated product.17 Indeed, all intermediates II react in essentially iden-
tical fashion with the intermediate I at room temperature.18 4H-1,3-
Oxazine derivatives III are formed, which undergo ring opening during
the work-up procedure with aqueous acidic (pH = 3) to give finally the
corresponding β-acylaminoketones (1a-6d) as shown in Scheme 3.
This approach would eliminate the necessity to prepare the β-
chloroketones,19 which requires the β-acylaminoketone20 as precursors
and also provides an additional diversity. Reasonable results can be
obtained for the addition of one position of diversity. Commercial avail-
ability of a wide range of nitriles, aldehydes, and methylene ketones
makes this a valuable approach for the preparation of highly diversified
combinatorial libraries of β-acylaminoketones.

β-Acylaminoketones Containing a Thiophene Ring
225
EXPERIMENTAL
Melting points are uncorrected. Microanalyses were carried out by the
Microanalytical Laboratory, National Research Center, Cairo, Egypt.
Infrared spectra (KBr) were recorded using a Jasco FT/IR-300E spec-
trophotometer. 1H NMR and 13C NMR spectra were measured in CDCl3
using Varian Mercury 300 MHz and Varian Gemini 200 MHz spectrom-
eters with chemical shifts using TMS as standard. Mass spectra were
recorded on a GC/MS Finnigan SSQ 7000 spectrophotometer. All reac-
tions were carried out under atmospheric conditions at room temper-
ature. Tetrachlorosilane (TCS) was obtained from commercial sources.
Anhydrous zinc chloride was used as obtained from Aldrich. The sol-
vents were distilled and dried before use. Reactions were monitored by
TLC on 0.25 mm Merck Silica gel sheets (60 GF 354) (4 × 2 cm), and
the spots were detected with UV light.
General Procedure
A mixture of ketone (10 mmol), aldehyde (10 mmol), nitrile (10 mmol),
anhydrous ZnCl2 (4.08 g, 30 mmol), and CH2Cl2 (20 mL) as solvent was
stirred with exclusion of moisture at 25◦C for 10 min. Tetrachlorosilane
(3.6 mL, 30 mmol) was then added, and the reaction mixture was stirred
again for the specified time. The reaction mixture was poured onto ice-
cold water (100 mL), neutralized with Na2CO3 solution, and extracted
with CHCl3 (2 × 50 mL). The extract was dried over anhydrous Na2SO4,
and the solvent was removed by distillation. Finally the residue was
purified by chromatographic methods to obtain the pure products.
N-[3-Oxo-1-phenyl-3-(thien-2-yl)propyl]acetamide (1a)
M.p.: 80–82◦C. Rf = 0.25 (PE/AcOEt 2:1). IR: ν = 3306 (NH), 3060–
3015 (CH, Ar), 2920–2850 (CH3, CH2, CH), 1682 (C O), 1645 (CONH),
–1
1590, 1560, 1515 (C C, Ar) cm
.
1H NMR: δ 6.82–7.75 (m, 9H,
ArH+NH), 5.29 (q, 1H, CH), 3.65 (dd, 3J= 4.5 Hz, 2J= 16.2 Hz,
1H, CH2), 3.34 (dd, 3J= 5.5 Hz, 2J= 16.2 Hz, 1H, CH2), 2.00 (s,
3H, CH3). MS: m/z (%) 273 (M+, 5.53); 230 (M+ COCH3, 15.5),
217(M+−NCOCH3, 15.5), 162 (M+−thenoyl, 18), 111 (thenoyl, 100).
Anal. Calcd. for C15H15NO2S (273.35): C, 65.91; H, 5.53; N, 5.12; S,
11.73. Found: C, 65.85; H, 5.60; N, 5.10; S, 11.65%.
N-[3-Oxo-3-(thien-2-yl)-1-p-tolylpropyl]acetamide (1b)
M.p.: 118◦C. Rf = 0.26 (PE/AcOEt 2:1). IR: ν 3295 (NH), 3080–3060
(CH, Ar), 2923–2880 (CH3, CH2, CH), 1662 (C O), 1638 (CONH), 1580,
1542, 1515 (C C, Ar) cm–1. 1H NMR: δ 7.84 (d, 3J= 6.4 Hz, 2H, ArH),

226
D. S. Badawy et al.
7.71 (d, 3J= 6.4 Hz, 2H, Ar), 7.80–7.30 (m, 4H, ArH+NH), 5.71 (q, 1H,
CH), 3.76 (dd, 3J= 4.6 Hz, 2J= 16.2 Hz, 1H, CH2), 3.34 (dd, 3J= 5.6 Hz,
2J= 16.2 Hz, 1H, CH2), 2.29 (s, 3H, CH3), 2.10 (s, 3H, CH3). 13C NMR: δ
192.00 (C O), 170.32 (CONH), 145.50–127.55 (10 Car), 47.81 (CHNH),
45.43 (CH2CO), 26.10, 21.90 (2 CH3). MS: m/z (%) 287 (M+, 4.6), 244
(M+−COCH3, 16), 230 (M+−NCOCH3, 30), 111 (thenoyl, 100). Anal.
Calcd. for C16H17NO2S (287.38): C, 66.87; H, 5.96; N, 4.87; S, 11.16.
Found: C, 66.83; H, 5.92; N, 4.82; S, 11.10%.
N-[1-(4-Chlorophenyl)-3-oxo-3-(thien-2-
yl)propyl]acetamide (1c)
M.p.: 110◦C. Rf = 0.20 (PE/AcOEt 2:1). IR: ν 3241 (NH), 3093–3046
(CH, Ar), 2991–2925 (CH3, CH2, CH), 1670 (C O), 1649 (CONH), 1583,
1565, 1523 (C C, Ar) cm–1. 1H NMR: δ 8.10 (d, 3J= 6.6 Hz, 2H, ArH),
7.88 (d, 3J= 6.6 Hz, 2H, Ar), 7.60–7.90 (m, 4H, ArH+NH), 5.80 (q, 1H,
CH), 4.00 (dd, 3J= 4.8 Hz, 2J= 16.3 Hz, 1H, CH2), 3.64 (dd, 3J= 5.8 Hz,
2J= 16.3 Hz, 1H, CH2), 2.10 (s, 3H, CH3). MS: m/z (%) 309 (M++2, 3.6),
307 (M+, 10), 264 (M+−COCH3, 20.2), 250 (M+−NCOCH3, 35), 182
(M+−thenoyl, 25), 111 (thenoyl, 100). Anal. Calcd. for C15H14ClNO2S
(307.80): C, 58.53; H, 4.58; N, 4.55; S, 10.42. Found: C, 58.50; H,4.51; N
4.52; S, 10.40%.
N-[1-(3-Bromophenyl)-3-oxo-3-(thien-2-
yl)propyl]acetamide (1d)
M.p.: 130–132◦C. Rf = 0.22 (PE/AcOEt 2:1). IR: ν 3294 (NH), 3068–
3035 (CH, Ar), 2922–2870 (CH3, CH2, CH), 1659 (C O), 1646 (CONH),
–1
1595, 1543, 1516 (C C, Ar) cm
.
1H NMR: δ 7.00–8.00 (m, 8H,
3
2
ArH+NH), 5.80 (q, 1H, CH), 4.00 (dd, J= 4.7 Hz, J= 16.3 Hz, 1H,
3
2
CH2), 3.64 (dd, J= 5.7 Hz, J= 16.3 Hz, 1H, CH2), 2.10 (s, 3H, CH3).
MS: m/z (%) 353 (M++2, 19.6), 351 (M+, 20), 307 (M+−COCH3, 24), 240
(33.3), 111 (thenoyl, 100). Anal. Calcd. for C15H14BrNO2S (352.25): C,
51.15; H, 4.01; N, 3.98; S, 9.10. Found: C, 51.13; H, 4.00; N, 3.93; S,
9.00%.
N-[3-Oxo-1-phenyl-3-(thien-2-yl)propyl]benzamide (2a)
M.p.: 115◦C. Rf = 0.45 (PE/AcOEt 2:1). IR: ν 3280 (NH), 3080–3030
(CH, Ar), 2922–2860 (CH2, CH), 1658 (C O), 1642 (CONH), 1600, 1545,
1515 (C C, Ar) cm–1. 1H-NMR: δ 6.82–7.78 (m, 14H, ArH+NH), 5.29 (q,
1H, CH), 3.64 (dd, 3J= 5 Hz, 2J= 16.1 Hz, 1H, CH2), 3.34 (dd, 3J= 5.6
Hz, 2J= 16.1 Hz, 1H, CH2). MS: m/z (%) 335 (M+, 16), 230 (M+−COPh,
25.5), 111 (thenoyl, 80), 105 (COPh, 100). Anal. Calcd. for C20H17NO2S

β-Acylaminoketones Containing a Thiophene Ring
227
(335.42): C, 71.62; H, 5.11; N, 4.18; S, 9.56. Found: C, 71.60; H, 5.80; N,
3.95; S, 9.52%.
N-[3-Oxo-3-(thien-2-yl)-1-ρ-tolylpropyl]benzamide (2b)
Mp.: 163◦C. Rf = 0.45 (PE/AcOEt 2:1). IR: ν 3291 (NH), 3080-3060
(CH, Ar), 2923–2880 (CH3, CH2, CH), 1658 (C O), 1641 (CONH), 1575,
1542, 1515 (C C, Ar) cm–1.1H NMR: δ 7.78 (d, J= 6.6 Hz, 2H, ArH),
3
7.67 (d, 3J= 6.6 Hz, 2H, Ar), 7.64–7.90 (m, 9H, ArH+NH), 5.54 (q, 1H,
3
2
3
CH), 3.76 (dd, J= 4.8 Hz, J= 16.3 Hz, 1H, CH2), 3.34 (dd, J= 5.6
Hz, 2J= 16.3 Hz, 1H, CH2), 2.30 (s, 3H, CH3). MS: m/z (%) 349 (M+, 5),
244 (M+−COPh, 30), 111 (thenoyl, 75), 105 (COPh, 100). Anal. Calcd.
for C21H19NO2S (349.45): C, 72.18; H, 5.48; N, 4.01; S, 9.18. Found: C,
72.13; H, 5.42; N, 4.00; S, 9.15%.
N-[1-(4-Chlorophenyl)-3-oxo-3-(thien-2-
yl]propyl)benzamide (2c)
M.p. 108◦C. Rf = 0.40 (PE/AcOEt 2:1). IR: ν 3349 (NH), 3070–3060
(CH, Ar), 2924–2853 (CH2, CH), 1670 (C O), 1637 (CONH), 1600, 1558,
1515 (C C, Ar) cm–1. H NMR: δ 7.95 (d, J= 6.8 Hz, 2H, ArH), 7.78
(d, 3J= 6.8 Hz, 2H, Ar), 7.70–790 (m, 9H, ArH+NH), 5.85 (q, 1H, CH),
3.87 (dd, 3J= 4.5 Hz, 2J= 16.3 Hz, 1H, CH2), 3.66 (dd, 3J= 5.7 Hz,
2J= 16.3 Hz, 1H, CH2). MS: m/z (%) 371 (M++2, 3.3), 369 (M+, 10), 264
(M+−COPh, 20), 250 (M+−NCOPh, 55), 111 (thenoyl, 80), 105 (COPh,
100). Anal. Calcd. for C20H16ClNO2S (369.86): C, 64.95; H, 4.36; N, 3.79;
S, 8.67. Found: C, 64.93; H, 4.30; N, 3.78; S, 8.62%.
1
3
N-[1-(3-Bromophenyl)-3-oxo-3-(thien-2-
yl)propyl]benzamide (2d)
M.p.: 168◦C. Rf = 0.43 (PE/AcOEt 2:1). IR: ν 3282 (NH), 3067–3030
(CH, Ar), 2922 (CH2, CH), 1655 (C O), 1644 (CONH), 1589, 1541, 1516
(C C, Ar) cm−1. 1H NMR: δ 7.00–8.00 (m, 13H, ArH+NH), 5.80 (q, 1H,
3
2
3
CH), 4.00 (dd, J= 4.8, J= 16.3 Hz, 1H, CH2), 3.64 (dd, J= 5.7 Hz,
2J= 16.3 Hz, 1H, CH2). MS: m/z (%) 414 (M++2, 14.5), 413 (M+, 15); 307
(M+−COPh, 20), 293 (M+−NCOPh, 50), 111 (thenoyl, 80), 105 (COPh,
100). Anal. Calcd. for C20H16BrNO2S (414.32): C, 57.98; H, 3.89; N,
3.38; S, 7.74. Found: C, 57.96; H, 3.85; N, 3.34; S, 7.70%.
N-[3-Oxo-1-phenyl-3-(thien-2-yl)propyl]acrylamide (3a)
M.p.: 78◦C. Rf = 0.30 (PE/AcOEt 2:1). IR: ν 3282 (NH), 3070–3060
(CH, Ar, alkene), 2923–2854 (CH2, CH), 1670 (C O), 1643 (CONH),
–1
1600, 1544, 1515 (C C, Ar) cm
.
1H NMR: δ 7.00–7.72 (m, 9H,
ArH+NH), 6.32 (d, 3J= 6.0 Hz, 1H, CH), 6.21 (dd, 3J= 5.4 Hz, 2J= 16.5

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D. S. Badawy et al.
3
Hz, 1H, CH2), 5.71 (m, 1H, CH2), 5.56 (q, 1H, CH), 3.66 (dd, J= 4.8
2
3
2
Hz, J= 16.2 Hz, 1H, CH2), 3.37 (dd, J= 5.7 Hz, J= 16.2 Hz, 1H,
CH2). MS: m/z (%) 285 (M+, 10), 229 (M+−COCH CH2, 90), 214
(M+−NCOCH CH2, 28), 119 (M+-acetylthiophene, 10), 111 (thenoyl,
100), 71 (NCOCH CH2, 15). Anal. Calcd. for C16H15NO2S (285.36): C,
67.34; H, 5.30; N, 4.91; S, 11.24. Found: C, 67.30; H, 5.27; N, 4.88; S,
11.22%.
N-[3-Oxo-3-(thien-2-yl)-1-ρ-tolylpropyl]acrylamide (3b)
M.p.: 88◦C. Rf = 0.32 (PE/AcOEt 2:1). IR: ν 3290 (NH), 3090-3030
(CH3, CH, Ar, alkene), 2923–2860 (CH2, CH), 1660 (C O), 1648
(CONH), 1590, 1545, 1515 (C C, Ar) cm–1. 1H NMR: δ 7.96 (d, 3J= 7.1
Hz, 2H, ArH), 7.68 (d, 3J= 7.1 Hz, 2H, ArH), 7.66–7.90 (m, 4H,
ArH+NH), 6.33 (d, 3J= 6.0 Hz, 1H, CH), 6.30 (dd, 3J= 5.5 Hz, 2J= 16.7
Hz, 1H, CH2), 5.87 (m, 1H, CH2), 5.85 (q, 1H, CH), 3.87 (dd, 3J= 5 Hz,
3
2
2J= 16.3 Hz, 1H, CH2), 3.66 (dd, J= 5.7 Hz, J= 16.3 Hz, 1H, CH2),
2.29 (s, 3H, CH3). MS: m/z (%) 299 (M+, 7), 244 (M+−COCH CH2,
90), 230 (M+−NCOCH CH2, 28), 133 (M+−acetylthiophene, 10), 111
(thenoyl, 100), 71 (NCOCH CH2, 12). Anal. Calcd. for C17H17NO2S
(299.39): C, 68.20; H, 5.72; N, 4.68; S, 10.71. Found: C, 68.17; H, 5.70;
N, 4.62; S, 10.66%.
N-[1-(4-Chlorophenyl)-3-oxo-3-(thien-2-
yl)propyl]acrylamide (3c)
M.p.: 165◦C. Rf = 0.22 (PE/AcOEt 2:1). IR: ν 3250 (NH), 3090–
3040 (CH, Ar, alkene), 2990–2925 (CH3, CH2, CH), 1675 (C O), 1652
(CONH), 1590, 1565, 1520 (C C, Ar) cm–1. 1H NMR: δ 8.00 (d, 3J= 7.0
3
Hz, 2H, ArH), 7.86 (d, J= 7.0, 2H, Ar), 7.00–7.85 (m, 4H, ArH+NH),
3
3
2
6.27 (d, d, J= 6.0 Hz, 1H, CH), 6.24 (dd, J= 5.3 Hz, J= 16.5 Hz,
3
1H, CH2), 5.88 (m, 1 H, CH2), 5.85 (q, 1H, CH), 3.88 (dd, J= 4.8 Hz,
2J= 16.2 Hz, 1H, CH2), 3.69 (dd, J= 5.8 Hz, J= 16.2 Hz, 1H, CH2).
MS: m/z (%) 321 (M++2, 1.3), 319 (M+, 4.3), 264 (M+−COCH CH2,
29), 248 (M+−NCOCH CH2, 75), 133 (M+−acetylthiophene, 10), 111
(thenoyl, 100), 71 (NCOCH CH2, 10). Anal. Calcd. for C16H14ClNO2S
(319.81): C, 60.09; H, 4.41; N, 4.38; S, 10.03. Found: C, 60.04; H, 4.4; N,
4.35; S, 10.00%.
3
2
N-[1-(3-Bromophenyl)-3-oxo-3-(thien-2-
yl)propyl]acrylamide (3d)
M.p.: 150◦C. Rf = 0.25 (PE/AcOEt 2:1). IR: ν 3300 (NH), 3080–3031
(CH, Ar, alkene), 2960–2925 (CH2, CH), 1660 (C O), 1634 (CONH),
–1
1600, 1544, 1519 (C C, Ar) cm
.
1H NMR: δ 7.00–8.00 (m, 8H,

β-Acylaminoketones Containing a Thiophene Ring
229
ArH+NH), 6.42 (d, 3J= 6 Hz, 1H, CH), 6.32 (dd, 3J= 5.4 Hz, 2J= 16.5
Hz, 1H, CH2), 5.83 (m, 1H, CH2), 5.81 (q, 1H, CH), 4.00 (dd, J= 5 Hz,
16.3 Hz, 1H, CH2), 3.74 (dd, J= 5.9 Hz, 16.3 Hz, 1H, CH2). MS: m/z
(%) 365 (M++2, 9.4), 363 (M+, 10), 307 (M+ COCH CH2, 30), 293
(M+ NCOCH CH2, 78), 189 (M+−acetylthiophene, 10), 111 (thenoyl,
100), 71 (NCOCH CH2, 10). Anal. Calcd. for C16H14BrNO2S (364.26):
C, 52.76; H, 3.87; N, 3.85; S, 8.80. Found: C, 52.74; H, 3.83; N, 3.81; S,
8.76%.
N-[3-Oxo-3-phenyl-1-(thien-2-yl)propyl]acetamide (4a)
M.p.: 90◦C. Rf = 0.25 (PE/AcOEt 2:1). IR: ν 3310 (NH), 3060-3020
(CH, Ar), 2920–2850 (CH3, CH2, CH), 1670 (C O), 1640 (CONH), 1595,
1535, 1515 (C C, Ar) cm–1. H NMR: δ 6.82–7.78 (m, 9H, ArH+NH),
1
3
2
5.29 (q, 1H, CH), 3.75 (dd, J= 4.5 Hz, J= 16.1 Hz, 1H, CH2), 3.44
(dd, 3J= 5.5 Hz, 2J= 16.1 Hz, 1H, CH2), 2.00 (s, 3H, CH3). MS:
m/z (%) 273 (M+, 7); 230 (M+−COCH3, 80), 216 (M+−NCOCH3, 28),
168 (M+−COPh, 28), 105 (COPh, 100). Anal. Calcd. for C15H15NO2S
(273.35): C, 65.91; H, 5.53; N, 5.12; S, 11.73. Found: C, 65.83; H, 5.61;
N, 5.8; S, 11.64%.
N-[3-Oxo-1-(thien-2-yl)-3-ρ-tolylpropyl]acetamide (4b)
M.p.: 125◦C. Rf = 0.26 (PE/AcOEt 2:1). IR: ν 3286 (NH), 3080–3060
(CH, Ar), 2920–2860 (CH3, CH2, CH), 1662 (C O), 1638 (CONH), 1580,
1542, 1515 (C C, Ar) cm–1. 1H NMR: δ 7.82 (d, 3J= 6.5 Hz, 2H, ArH),
7.78 (d, 3J= 6.5 Hz, 2H, Ar), 7.00–7.76 (m, 4H, ArH+NH), 5.71 (q, 1H,
CH), 3.76 (dd, 3J= 4.5 Hz, 2J= 16.2 Hz, 1H, CH2), 3.34 (dd, 3J= 5.6 Hz,
2J= 16.2 Hz, 1H, CH2), 2.29 (s, 3H, CH3), 2.10 (s, 3H, CH3). MS: m/z
(%) 287 (M+, 15), 244 (M+−COCH3, 60), 230 (M+−NCOCH3, 20), 168
(M+−CO-tolyl, 28), 119 (CO-tolyl, 100). Anal. Calcd. for C16H17NO2S
(287.38): C, 66.87; H, 5.96; N, 4.87; S, 11.16. Found: C, 66.82; H, 5.91;
N, 4.8; S, 11.11%.
N-[3-(4-Chlorophenyl)-3-oxo-1-(thien-2-
yl)propyl]acetamide (4c)
M.p.: 115◦C. Rf = 0.20 (PE/AcOEt 2:1). IR: ν 3246 (NH), 3090–3046
(CH, Ar), 2990–2930 (CH2, CH), 1667 (C O), 1644 (CONH), 1583, 1565,
1523 (C C, Ar) cm–1. 1H NMR: δ 8.10 (d, 3J= 6.6 Hz, 2H, ArH), 7.88 (d,
3J= 6.6 Hz, 2H, Ar); 7.00-7.80 (m, 4H, ArH+NH), 5.80 (q, 1H, CH), 3.82
(dd, 3J= 4.5 Hz, 2J= 16.3 Hz, 1H, CH2), 3.54 (dd, 3J= 5.8 Hz, 2J= 16.3
Hz, 1H, CH2), 2.12 (s, 3H, CH3). 13C-NMR: δ 197.00 (C O), 169.32
(CONH), 144.27-124.57 (10 Car), 45.80 (CHNH), 43.43 (CH2CO), 23.36
(COCH3). MS: m/z (%) 309 (M++2, 3.6), 307 (M+, 10), 264 (M+−COCH3,

230
D. S. Badawy et al.
20), 249 (M+−NCOCH3, 65), 139 (4-ClC6H4-CO, 100). Anal. Calcd. for
C15H14ClNO2S (307.80): C, 58.53; H, 4.58; N, 4.55; S, 10.42. Found: C,
58.52; H, 4.50; N, 4.5; S, 10.42%.
N-(3-(4-Bromophenyl)-3-oxo-1-(thien-2-
yl)propyl)acetamide (4d)
M.p.: 136◦C. Rf = 0.22 (PE/AcOEt 2:1). IR: ν 3268 (NH), 3090–3060
(CH, Ar), 2940–2880 (CH3, CH2, CH), 1669 (C O), 1643 (CONH), 1580,
1542, 1519 (C C, Ar) cm–1. 1H NMR: δ 8.20 (d, 3J= 6.6 Hz, 2H, ArH),
7.95 (d, 3J= 6.6 Hz, 2H, Ar), 7.00–7.60 (m, 4H, ArH+NH), 5,88 (q, 1H,
CH), 3.88 (dd, 3J= 5 Hz, 2J= 16.3 Hz, 1H, CH2), 3.64 (dd, 3J= 5.8 Hz,
2J= 16.3 Hz, 1H, CH2), 2.1 (s, 3H, CH3). MS: m/z (%) 353 (M++2, 19.6),
351 (M+, 20), 307 (M+−COCH3, 30), 294 (M+−NCOCH3, 80), 182 (4-
Br-C6H4-CO, 100). Anal. Calcd. for C15H14BrNO2S (352.25): C, 51.15;
H, 4.01; N, 3.98; S, 9.10. Found: C, 51.11; H, 4.0; N, 3.92; S, 88%.
N-[3-Oxo-3-phenyl-1-(thien-2-yl)propyl]benzamide (5a)
M.p.: 110◦C. Rf = 0.45 (PE/AcOEt 2:1). IR: ν 3282 (NH), 3080–3020
(CH, Ar), 2925 (CH2, CH), 1659 (C O), 1646 (CONH), 1600, 1545, 1515
(C C, Ar) cm–1. 1H NMR: δ 6.88–7.78 (m, 14H, ArH+NH), 5.29 (q, 1H,
CH); 3.62 (dd, 3J= 4.5 Hz, 2J= 16.1 Hz, 1H, CH2), 3.46 (dd, 3J= 5.6 Hz,
2J= 16.1 Hz, 1H, CH2). MS: m/z (%) 335 (M+, 4.22); 230 (M+−COPh,
33.3), 116 (NCOPh, 75), 105 (COPh, 100). Anal. Calcd. for C20H17NO2S
(335.42): C, 71.62; H, 5.11; N, 4.18; S, 9.56. Found: C, 71.61; H, 5.81; N,
3.96; S, 9.53%.
N-[3-Oxo-1-(thien-2-yl)-3-ρ-tolylpropyl]benzamide (5b)
M.p.: 150◦C. Rf = 0.46 (PE/AcOEt 2:1). IR: ν 3291 (NH), 3080–3060
(CH, Ar), 2923–2880 (CH3, CH2, CH), 1660 (C O), 1642 (CONH), 1575,
1542, 1515 (C C, Ar) cm–1. 1H NMR: δ 7.75 (d, 3J= 6.6 Hz, 2H, ArH),
7.67 (d, 3J= 6.6 Hz, 2H, Ar), 7.00–7.80 (m, 9H, ArH+NH), 5.58 (q, 1H,
CH), 3.79 (dd, 3J= 4.8 Hz, 2J= 16.3 Hz, 1H, CH2), 3.38 (dd, 3J= 5.6 Hz,
2J= 16.3 Hz, 1H, CH2), 2.30 (s, 3H, CH3). MS: m/z (%) 349 (M+, 8.2),
244 (M+−COPh, 33.3), 230 (M+−COtolyl, 43.3), 119 (COtolyl, 100), 105
(COPh, 90). Anal. Calcd. for C21H19NO2S (349.45): C, 72.18; H, 5.48; N,
4.01; S, 9.18. Found: C, 72.14; H, 5.40; N, 4.0; S, 9.14%.
N-[3-(4-Chlorophenyl)-3-oxo-1-(thien-2-
yl)propyl]benzamide (5c)
M.p.: 120◦C. Rf = 0.40 (PE/AcOEt 2:1). IR: ν 3350 (NH), 3070–3060
(CH, Ar), 2924–2853 (CH3, CH2, CH), 1675 (C O), 1635 (CONH), 1600,
1558, 1515 (C C, Ar) cm–1. 1H-NMR: δ 8.00 (d, 3J= 6.8 Hz, 2H, ArH),

β-Acylaminoketones Containing a Thiophene Ring
231
7.90 (d, 3J= 6.8 Hz, 2H, Ar), 7.00–7.85 (m, 9H, ArH+NH), 5.88 (q, 1H,
3
2
3
CH), 3.98 (dd, J= 4.6 Hz, J= 16.3 Hz, 1H, CH2), 3.76 (dd, J= 5.7
Hz, J= 16.3 Hz, 1H, CH2). MS: m/z (%) 371 (M+, 2.6), 369 (M+, 8),
2
264 (M+−COPh, 65), 230 (M+−4-Cl-C6H4-CO), 139 (4-Cl-C6H4, 50),
105 (COPh, 100). Anal. Calcd. for C20H16ClNO2S (369.86): C, 64.95; H,
4.36; N, 3.79; S, 8.67. Found: C, 64.92; H, 4.32; N, 3.77; S, 8.6%.
N-[3-(4-Bromophenyl)-3-oxo-1-(thien-2-
yl)propyl]benzamide (5d)
M.p.: 168◦C. Rf = 0.43 (PE/AcOEt 2:1). IR: ν 3290 (NH), 3070–3030
(CH, Ar), 2922 (CH2, CH), 1655 (C O), 1644 (CONH), 1580, 1541, 1516
(C C, Ar) cm–1. H NMR: δ 8.10 (d, J= 6.8 Hz, 2H, ArH), 7.95 (d,
3J= 6.8 Hz, 2H, Ar), 7.00-7.85 (m, 9H, ArH+NH), 5.88 (q, 1H, CH),
3.98 (dd, 3J= 4.5 Hz, 2J=16.3 Hz, 1H, CH2), 3.76 (dd, 3J= 5.7 Hz,
2J= 16.3 Hz, 1H, CH2). MS: m/z (%) 415 (M++2, 9.9), 413 (M+, 10),
307 (M+−COPh, 75), 230 (M+−4-Br-C6H4, 8), 182 (4-Br-C6H4-CO, 60),
105 (COPh, 100). Anal. Calcd. for C20H16BrNO2S (414.32): C, 57.98; H,
3.89; N, 3.38; S, 7.74. Found: C, 57.94; H, 3.84; N, 3.33; S, 7.71%.
1
3
N-[3-Oxo-3-phenyl-1-(thien-2-yl)propyl]acrylamide (6a)
M.p. 64◦C. Rf = 0.30 (PE/AcOEt 2:1). IR: ν 3282 (NH), 3070–3060
(CH, Ar, alkene), 2923–2854 (CH2, CH), 1670 (C O), 1643 (CONH),
–1
1600, 1544, 1515 (C C, Ar) cm
.
1H NMR: δ 6.89–7.74 (m, 9H,
ArH+NH), 6.24 (d, 3J= 6.0 Hz, 1H, CH), 6.21 (dd, 3J= 5.3 Hz, 2J= 16.5
Hz, 1H, CH2), 5.59 (m, 1H, CH2), 5.56 (q, 1H, CH), 3.66 (dd, 3J= 4.8 Hz,
16.2 Hz, 1H), 3.37 (dd, 3J= 5.7 Hz, 2J= 16.2 Hz, 1H, CH2). MS: m/z (%)
285 (M+, 10), 229 (M+ COCH CH2, 85), 216 (M+ NCOCH CH2, 38),
105 (COPh, 100), 71 (N COCH CH2, 12). Anal. Calcd. for C16H15NO2S
(285.36): C, 67.34; H, 5.30; N, 4.91; S, 11.24. Found: C, 67.32; H, 5.29;
N, 4.9; S, 11.21%.
N-[3-Oxo-1-(thien-2-yl)-3-ρ-tolylpropyl]acrylamide (6b)
M.p.: 105◦C. Rf = 0.31 (PE/AcOEt 2:1). IR: ν 3293 (NH), 3090–3030
(CH, Ar, alkene), 2925–2860 (CH2, CH), 1660 (C O), 1648 (CONH),
1595, 1545, 1515 (C C, Ar) cm–1. H NMR: δ 7.99 (d, J= 7.1 Hz, 2H,
1
3
3
ArH), 7.87 (d, J= 7.1 Hz, 2H, Ar), 7.00–7.80 (m, 4H, ArH+NH), 6.31
(d, 3J= 6.0 Hz, 1H, CH), 6.20 (dd, 3J= 5.4 Hz, 2J= 16.5 Hz, 1H, CH2),
5.88 (m, 1H, CH2), 5.85 (q, 1H, CH), 3.87 (dd, 3J= 4.6 Hz, 2J= 16.3 Hz,
3
2
1H, CH2), 3.66 (dd, J= 5.7 Hz, J= 16.3 Hz, 1H, CH2), 2.29 (s, 3H,
CH3). MS: m/z (%) 299 (M+, 4.4), 244 (M+ COCH CH2, 75), 230 (M+
NCOCH CH2, 48), 119 (COtolyl, 100), 71 (N COCH CH2, 12). Anal.

232
D. S. Badawy et al.
Calcd. for C17H17NO2S (299.39): C, 68.20; H, 5.72; N, 4.68; S, 10.71.
Found: C, 68.18; H, 5.72; N, 4.63; S, 10.68%.
N-[3-(4-Chlorophenyl)-3-oxo-1-(thien-2-
yl)propyl]acrylamide (6c)
M.p.: 130◦C. Rf = 0.22 (PE/AcOEt 2:1). IR: ν 3303 (NH), 3060,
3031(CH, Ar, alkene), 2900 (CH2, CH), 1685 (C O), 1636 (CONH),
1600, 1544, 1519 (C C, Ar) cm–1. H NMR: δ 8.20 (d, J= 7.0 Hz, 2H,
1
3
3
ArH), 7.96 (d, J= 7.0 Hz, 2H, Ar), 7.90–7.30 (m, 4H, ArH+NH), 6.34
(d, 3J= 6.0 Hz, 1H, CH), 6.32 (dd, 3J= 5.5 Hz, 2J= 16.7 Hz, 1H, CH2),
3
2
5.87 (m, 1H, CH2), 5.85 (q, 1H, CH), 3.95 (dd, J= 4.6 Hz, J= 16.2
3
2
Hz, 1H CH2), 3.79 (dd, J= 5.8 Hz, J= 16.2 Hz, 1H, CH2). MS: m/z
(%) 321 (M++2, 3.6), 319 (M+, 10), 264 (M+−COCH CH2, 74.3), 250
(M+−NCOCH CH2, 45), 180 (M+−4-Cl-C6H4, 5.4), 139 (4-Cl-C6H4-
CO+, 100). Anal. Calcd. for C16H14ClNO2S (319.81): C, 60.09; H, 4.41;
N, 4.38; S, 10.03. Found: C, 60.06; H, 4.38; N, 4.36; S, 10.01%.
N-[3-(4-Bromophenyl)-3-oxo-1-(thien-2-
yl)propyl]acrylamide (6d)
M.p.: 162◦C. Rf = 0.26 (PE/AcOEt 2:1). IR: ν 3297 (NH), 3080–3031
(CH, Ar, alkene), 2956–2925 (CH2, CH), 1660 (C O), 1634 (CONH),
1600, 1544, 1519 (C C, Ar) cm–1. H NMR: δ 8.20 (d, J= 6.9 Hz, 2H,
1
3
3
ArH), 7.95 (d, J= 6.9 Hz, 2H, Ar), 7.00-7.81 (m, 4H, ArH+NH), 6.40
(d, 3J= 6.0 Hz, 1H, CH), 6.31 (dd, 3J= 5.4 Hz, 2J= 16.5 Hz, 1H, CH2),
3
2
5.40 (m, 1H, CH2), 5.88 (q, 1H, CH), 3.88 (dd, J= 4.8 Hz, J= 16.1
3
2
Hz, 1H, CH2), 3.66 (dd, J= 5.8 Hz, J= 16.1 Hz, 1H, CH2). MS: m/z
(%) 365 (M++2, 17.6), 363 (M+, 18), 307 (M+−COCH CH2, 84.3), 294
(M+−NCOCH CH2, 38), 183 (4-Br-C6H4-CO, 100). Anal. Calcd. for
C16H14BrNO2S (364.26): C, 52.76; H, 3.87; N, 3.85; S, 8.80. Found: C,
52.73; H, 3.85; N, 3.82; S, 8.79%.
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