Tetrachlorosilane-zinc chloride as a new potent binary reagent for one-pot, three-component synthesis of mannich-type products

Article abstract of DOI:10.1080/10426500802589907

A combination of tetrachlorosilane and zinc chloride in dichloromethane as an efficient and ambient binary reagent to promote a one-pot amidoalkylation reaction of enolizable ketones, aromatic aldehydes with acetonitriles, or benzonitrile have been develo

Full text of DOI:10.1080/10426500802589907

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Phosphorus, Sulfur, and Silicon
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Tetrachlorosilane-Zinc Chloride
as a New Potent Binary Reagent
for One-Pot, Three-Component
Synthesis of Mannich-Type
Products
Doria S. Badawy a , Ebrahim Abdel-Galil a , Ezzat M.
Kandeel a , Wahid M. Basyouni 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: 03 Nov 2009.
To cite this article: Doria S. Badawy , Ebrahim Abdel-Galil , Ezzat M. Kandeel ,
Wahid M. Basyouni & Tamer K. Khatab (2009) Tetrachlorosilane-Zinc Chloride as a
New Potent Binary Reagent for One-Pot, Three-Component Synthesis of Mannich-
Type Products, Phosphorus, Sulfur, and Silicon and the Related Elements, 184:11,
2799-2812, DOI: 10.1080/10426500802589907
To link to this article: http://dx.doi.org/10.1080/10426500802589907
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Phosphorus, Sulfur, and Silicon, 184:2799–2812, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802589907
Tetrachlorosilane–Zinc Chloride as a New Potent Binary
Reagent for One-Pot, Three-Component Synthesis of
Mannich-Type Products
Doria S. Badawy,1 Ebrahim Abdel-Galil,1 Ezzat M.
Kandeel,1 Wahid M. Basyouni,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 combination of tetrachlorosilane and zinc chloride in dichloromethane as an effi-
cient and ambient binary reagent to promote a one-pot amidoalkylation reaction of
enolizable ketones, aromatic aldehydes with acetonitriles, or benzonitrile have been
developed. The newly synthesized β-acetamidoketones 3 and β-benzamidoketones 5
were obtained in good yields.
Keywords β-Acylaminoeketones; amidoalkylation; binary reagent; multicomponent;
naphthyl; tetrachlorosilane
INTRODUCTION
Multicomponent condensation reactions (MCRs) represent efficient
methods of rapidly increasing molecular complexity in a modular fash-
ion,1 from early examples, such as the Strecker,2 Hantsch,3 and Man-
nich4 reactions to more recent reports.1,5–11 MCRs are important for
the achievement of high levels of diversity, as they allow more than two
building blocks to be combined in practical, time-saving, one-pot oper-
ations, giving rise to complex structures by simultaneous formation of
two or more bonds, according to the domino principle.1
Also, MCRs contribute to the requirements of an environmentally
friendly process by reducing the number of synthetic steps, energy
consumption, and waste production. Researchers have transformed this
powerful technology into one of the most efficient and economic tools for
Received 30 July 2008; accepted 29 October 2008.
Address correspondence to Dr. Ebrahim Abdel-Galil, Chemistry Department,
Faculty of Science, Mansoura University, Mansoura, B.O. 35516, Egypt. E-mail:
msebrahim2002@yahoo.com
2799

2800
D. S. Badawy et al.
combinatorial and parallel synthesis.1,5 Due to their inherently simple
experimental procedures and their one-pot character, they are perfectly
suited for automated synthesis. Thus, MCRs play an important role in
combinatorial chemistry because of their ability to synthesize a small
drug-like molecule in a few steps and usually in a one-pot operation.12
Another typical benefit from these reactions is simplified purification,
because all of the reagents are incorporated into the final product.
Acetamido- or amino-ketone derivatives are important for their bio-
logical and pharmaceutical properties,13 and in the preparation of an-
tibiotic drugs such as nikkomycine or neopolyoxines.14 The best known
route for the synthesis of this class of compounds is the Dakin–West re-
action,15a which involves the condensation of an amino acid with acetic
anhydride in the presence of a base.15b Recently, other synthetic meth-
ods have been used for the formation of β-acetamidoketones through
the multicomponent condensation of aryl aldehydes, enolizable ketones,
and acetyl chlorides in acetonitrile in the presence of Lewis or Br nsted
acid catalysts such as CoCl2,16,17 Montmorillonite K-10 clay,18 silica sul-
furic acid,19 BiCl3 generated from BiOCl,20 ZrOCl2.8H2O,21 heteropoly
acid,22 sulfuric acid absorbed on silica gel,23 Sc(OTf)3,24 silica supported
H3PW12O4,25 Fe(HSO4)3,26 Nafion-H,27 NaHSO4·H2O,28 and iron(III)
chloride.29
RESULTS AND DISCUSSION
In recent years, tetrachlorosilane30 (TCS) and its reagents in
combination with ethanol,31 sodium iodide,32 sodium azide,33 N-
36
bromosuccinimide,34 potassium cyanide,35 and zinc chloride
have
gained much interest in organic synthesis. Since zinc chloride is a
commercially available, low-cost, and eco-environmentally reagent, we
report in this article a mild and efficient method for the preparation of β-
acylamino ketones by one-pot three-component reactions of enolizable
ketones 1a–e, aromatic aldehydes 2a–g, and acetonitrile or benzonitrile
in the presence of TCS/ZnCl2 as a binary reagent at room temperature
(Scheme 1).
Our initial study was performed on the reaction between 2-
acetylnaphthalene (1a), benzaldehyde (2a), and acetonitrile in the
presence of TCS/ZnCl2 in dichloromethane at room temperature.
The progress of the reaction was monitored by TLC. To our
delight, the desired reaction products, N-(3-naphth-2-yl)-3-oxo-1-
phenylpropyl)acetamide (3aa) and 1-naphth-2-yl-3-phenylprop-2-en-1-
one (4aa), were obtained in (80%) and (10%), respectively. Then, the

Tetrachlorosilane–Zinc Chloride
2801
SCHEME 1
reaction was carried out under various conditions as shown in Ta-
ble I. When the ratio of TCS/ZnCl2 was increased to 15 mmol, N-
(3-(naphth-2-yl)-3-oxo-1-phenylpropyl)acetamide (3aa) was obtained in
80% yield within 20 h; when 5 mmol of TCS/ZnCl2 was used, 3aa was
obtained in 51% yield after a prolonged reaction time. In addition, the
reaction was found to be solvent-dependent. It proceeded smoothly in
chloroform or acetonitrile with a relatively longer reaction time than
in dichloromethane, but it failed in diethyl ether or tetrahydrofuran.
Therefore, dichloromethane was proven to be the best solvent and was
selected for the following investigation.
The scope of the reaction of 2-acetylnaphthalene (1a) with vari-
ous aromatic aldehydes 2b–2e containing both electron-donating 2b
and electron-withdrawing 2c substituents was investigated under the
same experimental conditions. We have found that the correspond-
ing β-acetamidoketones are produced in good yields (Table II, entries
2 and 3). Similarly, polynuclear and heterocyclic aldehydes such as
1-naphthaldehyde (2d) and thiophene-2-carbaldehyde (2e) also react
under the same experimental conditions and provided the desired
TABLE I Experimental Results of TCS/ZnCl2-Mediated Ami-
doalkylation Reaction of 2-Acetylnaphthalene (1a), Benzalde-
hyde (2a), and Acetonitrile Under Normal Conditions
Yield
Entry
1a (mmol) 2a (mmol) TCS/ZnCl2
Solvent
Time (h) (%) 3aa
1
2
3
4
5
6
7
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
CH2Cl2
CH2Cl2
CH2Cl2
CHCl3
CH3CN
(C2H5)2O
THF
20
20
20
25
45
50
50
51
59
80
49
50
—
—
10
15
15
15
15
15

2802
D. S. Badawy et al.
TABLE II TCS/ZnCl2-Catalyzed Multicomponent Reaction
of Enolizable Ketones, Aromatic Aldehydes, and Acetoni-
trile or Benzonitrile in CH2Cl2 at Room Temperature
Entry
Ketones
Aldehydes
Time (h)
Products (yield)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
1a
1a
1a
1a
1a
1b
1c
1d
1e
1a
1a
1a
1a
1b
1c
1d
1e
1b
2a
2b
2c
2d
2e
2d
2d
2d
2d
2a
2c
2e
2f
20
15
18
30
16
20
16
22
19
22
17
22
20
22
20
24
18
40
3aa (80)
4aa (10)
4ab (15)
4ac (20)
4ad (50)
4ae (20)
4bd (18)
4cd (12)
4dd (15)
4ed (16)
4aa (20)
4ac (25)
4ae (30)
4af (14)
4bd (18)
4cd (15)
4dd (20)
4ed (15)
4bg (80)
3ab (75)
3ac (75)
3ad (45)
3ae (70)
3bd (75)
3cd (78)
3dd (76)
3ed (77)
5aa (70)
5ac (70)
5ae (60)
5af (78)
5bd (72)
5cd (75)
5dd (70)
5ed (75)
5bg (0)
2d
2d
2d
2d
2g
products (Table II, entries 4 and 5) easily. To demonstrate the versatil-
ity of this binary reagent (TCS/ZnCl2)-catalyzed, multicomponent re-
actions, a variety of acetophenone derivatives 1b–1e were reacted with
1-naphthaldehyde (2d) and acetonitrile in the presence of TCS/ZnCl2
under the same experimental conditions to provide the correspond-
ing β-acetamidoketones (Table II, entries 6–9) in good yields. Next,
the preparative utility and generality of this one-pot, multicompo-
nent reaction were extended by replacing acetonitrile with benzoni-
trile. Thus, under the optimized reaction conditions, when a variety of
aromatic aldehydes 2a–f were treated with 2-acetylnaphthalene (1a)
or acetophenone derivatives 1b–e and benzonitrile in the presence of
TCS/ZnCl2, the corresponding β-benzamidoketones 5aa–5ed were ob-
tained in good yields (Table II, entries 10–17).
Interestingly, as shown in Scheme 2, during the course of our study,
we have noticed that when anthracene-9-carbaldehyde (2g) is treated
with acetophenone (1b) and acetonitrile or benzonitrile under the same
experimental conditions, it gives only the aldol condensations product
4bg instead of the expected β-acylaminoketones 3bg, 5bg (Table II,
entry 18). Although the exact explanation of this anomaly is yet to be
determined, the formation of the aldol condensation as the sole product

Tetrachlorosilane–Zinc Chloride
2803
SCHEME 2
seems to be due to the steric hindrance of the bulky anthracenyl group.
It is noteworthy to mention that no reaction was observed in the absence
of either tetrachlorosilane (TCS) or zinc chloride. All these products
were fully characterized through spectral and elemental analysis.
Next we turned our attention to a study of the mechanistic aspect of
this one-pot three component reaction. A plausible mechanism for the
present reaction proceeds as depicted in Scheme 3 through addition of
stiochiometric Cl3Si+-−ZnCl337-like species generated in situ from the
reaction of TCS and ZnCl2 in 1:1 molar ratio to the carbonyl group of the
aldehydes and enolizable ketones, as well as to the cyano group of the
nitrile led to the formation of intermediate I and II,38–40 respectively.
In conclusion, we have developed a new synthetic methodology us-
ing a cheap, readily available, and efficient TCS/ZnCl2 binary reagent
for the one-pot synthesis of β-acetamidoketone derivatives 3 and β-
benzamidoketone derivatives 5. In addition, a thorough but not ex-
tensive investigation on the mechanistic aspect of this one-pot, three-
component reaction in this article was performed.
SCHEME 3

2804
D. S. Badawy et al.
EXPERIMENTAL
Melting points are uncorrected. Microanalyses were carried out by the
Microanalytical Laboratory, National Research Center, Cairo, Egypt.
Infrared spectra (KBr-disc) were recorded using a Jasco FT/IR-300E
spectrometer. 1H NMR and 13C NMR spectra were measured in CDCl3
using Varian Mercury 300 MHz and Varian Gemini 200 MHz with
chemical shifts using TMS as standard solvent. Mass spectra were
recorded on a GC/MS Finnigan SSQ 7000 spectrometer. All reactions
were carried out under atmospheric conditions at room temperature.
Tetrachlorosilane (TCS) was obtained from commercial sources. Anhy-
drous zinc chloride was used as obtained from Aldrich. The solvents
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
In a dry, two-necked, round-bottomed flask equipped with a rubber
septa, a magnetic stirring bar, and a dry condenser, a mixture of ketone
(5 mmol), aldehyde (5 mmol), nitrile (5 mmol), and anhydrous ZnCl2 (15
mmol) in CH2Cl2 (20 mL) was allowed to stir with exclusion of moisture
at room temperature for 5 min, then tetrachlorosilane (15 mmol) was
added, and the reaction mixture was stirred for the specified time,
poured onto ice cold water (100 mL), neutralized by Na2CO3, extracted
with CHCl3 (3 × 30 mL), and dried over anhydrous Na2SO4. The solvent
was removed under reduced pressure, and the residue was purified by
chromatographic methods to obtain the products.
N-(3-(Naphth-2-yl)-3-oxo-1-phenylpropyl)acetamide (3aa)
Mp 166◦C Rf 0.42 (pet.ether:ethylacetate 1:1): IR (KBr) ν (cm−1):
3340 (NH), 3065 (CH, Ar), 2926–2850 (CH3, CH2, CH), 1666 (CO),
1645 (CONH), 1600 (C C, Ar). H NMR (CDCl3): δ (ppm) 2.08 (s, 3H,
CH3), 3.45–3.62 (dd, 1H, J = 16, 6.5, HZ, CH2CH), 3.72–3.80 (dd, 1H, J
= 16, 5.5 HZ, CH2CH), 6.31–6.40 (m, 1H, CH2CH), 7.30–8.20 (m, 13H,
ArH + NH) MS: (m/z,%) 317 (M+, 6), 274 (M+—COCH3, 100), 258 (M+-
NHCOCH3, 25), 155 (C10H7CO, 40), 127 (naphthyl C10H7, 55). Anal.
Calcd. for C21H19NO2 (317.38): C, 79.47, H, 6.03, N, 4.41. Found: C,
79.33, H, 6.00, N, 4.62%.
1-(Naphth-2-yl)-3-phenylprop-2-en-1-one (4aa)
Mp 83◦C (lit45, mp 85–86◦C).

Tetrachlorosilane–Zinc Chloride
2805
N-(1-(4-Methoxyphenyl)-3-(naphth-2-yl)-3-
oxopropyl)acetamide (3ab)
Mp 110◦C Rf 0.35 (pet.ether:ethylacetate 1:1): IR (KBr) ν (cm−1):
3306 (NH), 3080 (CH, Ar), 2921–2830 (CH3, CH2, CH), 1680 (CO), 1652
(CONH), 1600, 1541 (C C, Ar). H NMR (CDCl3): δ (ppm) 2.08 (s, 3H,
CH3), 3.57–3.66 (dd, 1H, J = 16.5, 6 HZ, CH2CH), 3.85 (s, 3H, -OCH3),
4.78–4.86 (dd, 1H, J = 16.5, 5 HZ, CH2CH), 6.38 (m, 1H, CH2CH),
8.15–7.16(m, 12H, ArH + NH), MS: (m/z,%) 347 (M+, 15), 304 (M+-
COCH3, 5), 288 (M+- NH2COPh, 15), 181 (M+-CH2COnaphthyl, 100),
155 (M+—COnaphthyl, 30). Anal. Calcd for C22H21NO3 (347.41): C,
76.06, H, 6.09, N, 4.03. Found: C, 76.00, H, 5.95, N, 3.97%.
1-(Naphth-2-yl)-3-p-methoxyphenylprop-2-en-1-one (4ab)
Mp 96◦C (lit42, mp 95–97◦C).
N-(1-(4-Fluorophenyl)-3-(naphth-2-yl)-3-oxopropyl)acetamide
(3ac)
Mp 160◦C Rf 0.40 (pet.ether:ethylacetate 1:1): IR (KBr) ν (cm−1):
3286 (NH), 3064 (CH, Ar), 2920–2900 (CH3, CH2, CH), 1681 (CO), 1644
(CONH), 1548 (C C, Ar). H NMR (CDCl3): δ (ppm) 1.99 (s, 3H, CH3),
3.49–3.50 (dd, 1H, J = 16, 6 HZ, CH2CH), 3.82–3.83 (dd, 1H, J = 16,
5 HZ, CH2CH), 5.52–5.54 (m, 1H, CH2CH), 7.82–8.37 (m, 12H, ArH +
NH). 13C NMR: δ (ppm) 198.52 (C O), 169.55 (CONH), 130.15–123.42
(16 Aromatic carbon atoms), 49.37 (CHNH), 43.00 (CO), 23.50 (CH3).
MS: (m/z,%) 335 (M+, 15), 292 (M+ -COCH3, 40), 180 (M+- COnaph-
thyl, 10), 155 (COnaphthyl, 100), 127 (naphthyl, 40). Anal. Calcd. for
C21H18FNO2 (335.37): C, 75.21, H, 5.41, F, 5.66, N, 4.18. Found: C,
75.12, H, 5.35, N, 4.05%.
3-(4-Fluorophenyl)-1-(naphth-2-yl)prop-2-en-1-one (4ac)
Mp 150◦C (lit41, mp 150–152◦C).
N-(1-(Naphth-1-yl)-3-(naphth-2-yl)-3-oxopropyl)acetamide
(3ad)
Mp 198–195◦C Rf 0.35 (pet.ether:ethylacetate 1:1). IR (KBr) ν (cm−1):
3303 (NH), 3032–3061 (CH, Ar), 2900 (CH3, CH2, CH), 1685 (CO), 1636
(CONH), 1600, 1586 (C C, Ar). H NMR (CDCl3): δ (ppm) 1.99 (s, 3H,
CH3), 3.82–3.94 (dd, 1H, J = 16, 6 HZ, CH2CH), 4.13–4.20 (dd, 1H, J
= 16, 5 HZ, CH2CH), 6.58–6.72 (m, 1H, CH2CH)), 7.28–8.38 (m, 15H,
ArH + NH). MS: (m/z,%) 367 (M+, 5), 324 (M+-COCH3, 15), 308 (M+-
NH2COCH3, 30), 212 (M+-COnaphthyl, 45), 155 (COnaphthyl, 100).

2806
D. S. Badawy et al.
Anal. Calcd. for C25H21NO2 (367.44): C, 81.72, H, 5.76, N, 3.81. Found:
C, 81.70, H, 5.74, N, 3.79%.
3-(Naphth-1-yl)-1-(naphth-2-yl)prop-2-en-1-one (4ad)
Mp 158◦C (lit43, m- 156–158◦C).
N-(3-(Naphth-2-yl)-3-oxo-1-(2-thienyl)propyl)acetamide (3ae)
Mp 148◦C Rf 0.4 (pet.ether:ethylacetate 1:1): IR (KBr) ν (cm−1): 3288
(NH), 3065 (CH, Ar), 2950–2850 (CH3, CH2, CH), 1685 (aliphatic- CO),
1642 (CONH), 1600, 1550 (C C, Ar). H NMR (CDCl3): δ (ppm) 2.08 (s,
3H, CH3), 3.43–3.48 (dd, 1H, J = 16.5, 6.5, HZ, CH2CH), 3.52–3.58 (dd,
1H J = 16.5, 4.8 HZ, CH2CH), 5.23–5.28 (m, 1H, CH2CH), 6.96–8.12 (m,
11H, ArH + NH). MS: (m/z,%) 323 (M+, 10), 280 (M+-COCH3, 45), 264
(M+- NH2COCH3, 60), 168 (M+- CO naphthyl ion, 15), 155 (COnaphthyl
ion, 100). Anal. Calcd. for C19H17NO2S (323.41): C, 70.56, H, 5.30, N,
4.33, S, 9.91. Found: C, 70.42, H, 5.25, N, 4.30, S, 9.77%.
1-(Naphth-2-yl)-3-(2-thienyl)prop-2-en-1-one (4ae)
Mp 83◦C (lit45, mp 85–86◦C).
N-(1-(Naphth-1-yl)-3-oxo-3-phenylpropyl)acetamide (3bd)
Mp 180◦C Rf 0.42 (pet.ether : ethyl acetate 1:1). IR (KBr) ν (cm−1):
3341 (NH), 3064 (CH, Ar), 2922–2850 (CH3, CH2, CH), 1669 (CO), 1649
(CONH), 1605 (C C, Ar). H NMR (CDCl3): δ (ppm) 2.00 (s, 3H, CH3),
3.45–3.62 (dd, 1H, J = 17, 6.5 HZ, CH2CH), 3.72–3.80 (dd, 1H, J =
16.9, 5.5 HZ, CH2CH), 6.31–6.40 (m, 1H, CH2CH), 7.32–8.21 (m, 13H,
ArH + NH). MS: (m/z,%) 317 (M+, 45), 274 (M+—COCH3, 85), 258 (M+-
NHCOCH3, 35), 212 (M+—COPh, 15), 156 (naphthylamine ion, 100),
105 (COPh, 95). Anal. Calcd. for C21H19NO2 (317.38): C, 79.47, H, 6.03,
N, 4.41. Found: C, 79.35, H, 6.00, N, 4.66%.
3-(Naphth-1-yl)-1-phenylprop-2-en-1-one (4bd)
Mp 87◦C (lit47, mp 88–89◦C).
N-(1-(Naphth-1-yl)-3-oxo-3-p-tolylpropyl)acetamide (3cd)
Mp 134–136◦C Rf 0.42 (pet.ether:ethylacetate 1:1).IR (KBr) ν (cm−1):
3304 (NH), 3090, 3059 (CH, Ar), 2920–2850 (CH3, CH2, CH), 1684 (CO),
1650 (CONH), 1607, 1557 (C C, Ar). H NMR (CDCl3): δ (ppm) 2.05 (s,
3H, CH3), 2.35 (s, 3H, CH3), 3.57–3.66 (dd, 1H, J = 17, 6.5 HZ, CH2CH),
3.78–3.86 (dd, 1H, J = 17, 5 HZ, CH2CH), 6.30–6.42 (m, 1H, CH2CH),
7.16–8.15 (m, 12H, ArH + NH), 13C NMR: δ (ppm) 198.10 (C O), 169.30
(CONH), 144.32–123.03 (16 Aromatic carbon atoms), 46.28 (CHNH),

Tetrachlorosilane–Zinc Chloride
2807
42.37 (CO), 23.26, 21.67 two (CH3). MS: (m/z,%) 331 (M+, 5), 288 (M+-
COCH3, 35), 272 (M+- NH2COCH3, 30), 212 (M+—COtolyl, 8), 119 (CO-
tolyl, 100). Anal. Calcd. for C22H21NO2 (331.41): C, 79.73, H, 6.39, N,
4.23. Found: C, 79.70, H, 6.20, N, 4.10%.
3-(Naphth-1-yl)-1-p-tolylprop-2-en-1-one (4cd)
Mp 85◦C (lit44, mp 84–86◦C).
N-(3-(4-Bromophenyl)-1-(naphth-1-yl)-3-oxopropyl)acetamide
(3dd)
Mp 125–126◦C Rf 0.36 (pet.ether:ethylacetate 1:1). IR (KBr) ν (cm−1):
3311 (NH), 3061 (CH, Ar), 2920–2850 (CH3, CH2, CH), 1688 (CO), 1649
(CONH), 1584 (C C, Ar). H NMR (CDCl3): δ (ppm) 2.08 (s, 3H, CH3),
3.59–3.70 (dd, 1H, J = 16.8, 6 HZ, CH2CH), 3.85–3.90 (dd, 1H, J = 16.8,
5 HZ, CH2CH), 6.31–6.42 (m, 1H, CH2CH), 7.28–8.18 (m, 12H, ArH +
NH). MS: (m/z,%) 397 (M++2, 8), 395 (M+, 10), 352 (M+-COCH3, 30),
336 (M+—NCOCH3, 20), 198 (M+-p-(Br)COPh, 95),156 (naphthylamine
ion, 100). Anal. Calcd. for C21H18BrNO2 (396.28): C, 63.65, H, 4.58, Br,
20.16, N, 3.53. Found: C, 63.60, H, 4.45, Br, 20.10, N, 3.43%.
1-(4-Bromophenyl)-3-(naphth-1-yl)prop-2-en-1-one (4dd)
Mp 107◦C (lit46, mp 108–110◦C).
N-(3-(4-Chlorophenyl)-1-(naphth-1-yl)-3-oxopropyl)acetamide
(3ed)
Mp 128–130◦C Rf 0.38 (pet.ether:ethylacetate 1:1). IR (KBr) ν (cm−1):
3300 (NH), 3060 (CH, Ar), 2900–2850 (CH3, CH2, CH), 1665 (aliphatic-
CO), 1630 (CONH), 1590 (C C, Ar). H NMR (CDCl3): δ (ppm) 2.1 (s,
3H, CH3), 3.62–3.75 (dd, 1H, J = 16.5, 6 HZ, CH2CH), 3.85–3.92 (dd,
1H, J = 16.5, 5 HZ, CH2CH), 6.30–6.40 (m, 1H, CH2CH), 7.33–8.18 (m,
12H, ArH + NH). M.S: (m/z,%) 353 (M++2, 25), 351 (M+, 90), 308 (M+-
COCH3, 100), 292 (M+-NH2COCH3, 40), 212 (M+—p-(Cl)COPh, 10),
198 (M+- p-(Cl)PhCOCH2, 20), 169(M+- (p-(Cl)COPh+COCH3), 35), 138
(p-(Cl)COPh, 38). Anal. Calcd. for C21H18ClNO2 (351.83): C, 71.69, H,
5.16, Cl, 10.08, N, 3.98. Found: C, 71.66, H, 5.15, Cl, 10.02, N, 3.95%.
1-(4-Chlorophenyl)-3-(naphth-1-yl)prop-2-en-1-one (4ed)
Mp 100◦C (lit46, mp 99–100◦C).
N-(3-(Naphth-2-yl)-3-oxo-1-phenylpropyl)benzamide (5aa)
Mp 143◦C Rf 0.45 (pet.ether:ethylacetate 1:1). IR (KBr) ν (cm−1): 3310
(NH), 3060 (CH, Ar), 2910–2850 (CH2, CH), 1690 (CO), 1632 (CONH),

2808
D. S. Badawy et al.
1599 (C C, Ar). H NMR (CDCl3): δ (ppm) 3.71–3.79 (dd, 1H, J = 16.5,
6.6 HZ, CH2CH), 3.95–4.02 (dd, 1H, J = 16.5, 4.8 HZ, CH2CH), 6.58–6.59
(m, 1H, CH2CH), 7.24–8.24 (m, 18H, ArH + NH), MS: (m/z,%) 379 (M+,
12), 274 (M+- COPh, 100), 257(M+- NH2COPh, 70), 155 (COnaphthyl,
35), 105 (COPh, 45). Anal. Calcd. for C26H21NO2 (379.45): C, 82.30, H,
5.58, N, 3.69. Found: C, 82.23, H, 5.52, N, 3.60%.
1-(Naphth-2-yl)-3-phenylprop-2-en-1-one (4aa)
Mp 142◦C (lit41, mp 142–143◦C).
N-(1-(4-Fluorophenyl)-3-(naphth-2-yl)-3-oxopropyl)benzamide
(5ac)
Mp 180◦C Rf 0.43 (pet.ether:ethylacetate 1:1). IR (KBr) ν (cm−1):
3275 (NH), 3080–3060 (CH, Ar), 2920–2880 (CH2, CH), 1683 (-
CH2CO), 1643 (CONH), 1600, 1550 (C C, Ar). H NMR (CDCl3): δ
(ppm) 3.43–3.48 (dd, 1H, J = 16.8, 6.5 HZ, CH2CH), 4.12–4.18 (dd,
1H, J = 16.8, 5 HZ, CH2CH), 6.17–6.21 (m, 1H, CH2CH), 6.98–8.11
(m, 17H, ArH + NH). MS: (m/z,%) 397 (M+, 5), 354 (M+ -CONH,
30), 198 (C10H7COCH2CH2N, 24), 183 (C10H7COCH2CH2, 34), 170
(C10H7COCH2CH3, 63).156 (C10H7CHO, 100), 127 (C10H7, 23). Anal.
Calcd. for C26H20FNO2 (397.44): C, 78.57, H, 5.07, F, 4.78, N, 3.52.
Found: C, 78.45, H, 4.98, N, 3.45%.
3-(4-Fluorophenyl)-1-(naphth-2-yl)prop-2-en-1-one (4ac)
Mp 150◦C (lit41, mp 150–152◦C.
N-(3-(Naphth-2-yl)-3-oxo-1-(2-thienyl)propyl)benzamide (5ae)
Mp 145◦C Rf 0.45 (pet.ether:ethylacetate 1:1). IR (KBr) ν (cm−1):
3280 (NH), 3099, 3055 (CH, Ar), 2959 (CH2, CH), 1685 (CO), 1642
(CONH), 1591 (C C, Ar). H NMR (CDCl3): δ (ppm) 3.71–3.79 (dd, 1H,
J = 17.2, 6.6 HZ, CH2CH), 3.96–4.03 (dd, 1H, J = 17.2, 4.8 HZ, CH2CH),
6.57–6.59 (m, 1H, CH2CH), 7.26–8.24 (m, 16H, ArH + NH). MS: (m/z,%)
385 (M+, 3), 264 (M+-NH2COPh, 100), 230 (M+- COnaphthyl, 12), 155
(COnaphthyl, 15), 127 (naphthyl, 35). Anal. Calcd. for C24H19NO2S
(385.48): C, 74.78, H, 4.97, N, 3.63, S, 8.32. Found: C, 74.76, H, 4.94, N,
3.59, S, 8.29%.
1-(Naphth-2-yl)-3-(2-thienyl)prop-2-en-1-one (4ae)
Mp 83◦C (lit45, mp 85–86◦C).

Tetrachlorosilane–Zinc Chloride
2809
N-(3-(Naphth-2-yl)-3-oxo-1-p-tolylpropyl)benzamide (5af)
Mp 160◦C Rf 0.46 (pet.ether:ethylacetate 1:1). IR (KBr) ν (cm−1): 3287
(NH), 3055 (CH, Ar), 2967–2840 (CH2, CH), 1679 (CO), 1643 (CONH),
1550 (C C, Ar). H NMR (CDCl3): δ (ppm) 2.28 (s, 3H, CH3), 3.60–3.75
(dd, 1H, J = 16.5, 6.6 HZ, CH2CH), 3.90–4.00 (dd, 1H, J = 16.5, 4.8 HZ,
CH2CH), 6.40–6.48 (m, 1H, CH2CH), 7.28–8.35 (m, 17H, 16ArH+NH).
MS: (m/z,%) 393 (M+, 5), 288 (M+- COPh, 18), 273 (M+- NH2COPh, 100),
155(COnaphthyl ion, 60), 105 (COPh, 80). Anal. Calcd for C27H23NO2
(393.48): C, 82.42, H, 5.89, N, 3.56. Found: C, 82.41, H, 5.87, N, 3.53%.
1-(Naphth-2-yl)-3-p-tolylprop-2-en-1-one (4af)
Mp 105◦C (lit42, mp 105–107◦C).
N-(1-(Naphth-1-yl)-3-oxo-3-phenylpropyl)benzamide (5bd)
Mp 220◦C Rf 0.46 (pet.ether: ethylacetate 1:1). IR (KBr) ν (cm−1):
3318 (NH), 3060 (CH, Ar), 2912–2850 (CH2, CH), 1691 (CO), 1632
(CONH), 1598 (C C, Ar). H NMR (CDCl3): δ (ppm) 3.71–3.79 (dd,
1H, J = 16.8, 6.6 HZ, CH2CH), 3.96–4.03 (dd, 1H, J = 17, 4.8 HZ,
CH2CH), 6.57–6.59 (m, 1H, CH2CH), 7.26–8.24 (m, 18H, ArH + NH).
MS: (m/z,%) 379 (M+, 18), 301 (M+-Ph, 18), 273 (M+- COPh, 25), 156
(naphthylamine ion, 10), 105 (COPh, 100), 77(Ph, 67). Anal. Calcd. for
C26H21NO2 (379.45): C, 82.30, H, 5.58, N, 3.69. Found: C, 82.26, H, 5.50,
N, 3.61%.
3-(Naphth-1-yl)-1-phenylprop-2-en-1-one (4bd)
Mp 87◦C (lit47, mp 88–89◦C).
N-(1-(Naphth-1-yl)-3-oxo-3-p-tolylpropyl)benzamide (5cd)
Mp 156◦C Rf 0.44 (pet.ether:ethylacetate 1:1). IR (KBr) ν (cm−1): 3329
(NH), 3062 (CH, Ar), 2956–2856 (CH2, CH), 1676 (CO), 1629 (CONH),
1577 (C C, Ar). H NMR (CDCl3): δ (ppm) 2.30 (s, 3H, CH3), 3.65–3.79
(dd, 1H, J = 16.8, 6 HZ, CH2CH), 4.11–4.22 (dd, 1H, J = 16.8, 5 HZ,
CH2CH), 6.55–6.65 (m, 1H, CH2CH), 7.22–8.00 (m, 17H, ArH + NH),.
Anal. Calcd. for C27H23NO2 (393.48): C, 82.42, H, 5.89, N, 3.56. Found:
C, 82.40, H, 5.85, N, 3.50%.
3-(Naphth-1-yl)-1-p-tolylprop-2-en-1-one (4cd)
Mp 85◦C (lit44, mp 84–86◦C).

2810
D. S. Badawy et al.
N-(3-(4-Bromophenyl)-1-(naphth-1-yl)-3-oxopropyl)benzamide
(5dd)
Mp 172–170◦C Rf 0.40 (pet.ether:ethylacetate 1:1). IR (KBr) ν (cm−1):
3297 (NH), 3085–3052 (CH, Ar), 2920–2880 (CH2, CH), 1687 (CO), 1636
(CONH), 1582 (C C, Ar). H NMR (CDCl3): δ (ppm) 3.78–3.89 (dd, 1H,
J = 17, 6.5 HZ, CH2CH), 4.00–4.18 (dd, 1H, J = 17, 5.5 HZ, CH2CH),
6.40–6.52 (m, 1H, CH2CH), 7.30–8.35 (m, 17H, ArH + NH). MS: (m/z,%)
459 (M++2, 9), 457 (M+, 10), 352 (M+- COPh, 15), 334 (M+- NH2COPh,
100), 182 (M+-p-(Br)COPh, 35). Anal. Calcd. for C26H20BrNO2 (458.35):
C, 68.13, H, 4.40, Br, 17.43, N, 3.06. Found: C, 68.02, H, 4.32, Br, 17.35,
N, 3.00%.
1-(4-Bromophenyl)-3-(naphth-1-yl)prop-2-en-1-one (4dd)
Mp 107◦C (lit46, mp 108–110◦C).
N-(3-(4-Chlorophenyl)-1-(naphth-1-yl)-3-oxopropyl)benzamide
(5ed)
Mp 205◦C Rf 0.42 (pet.ether:ethylacetate 1:1). IR (KBr) ν (cm−1): 3294
(NH), 3061 (CH, Ar), 2924–2855 (CH2, CH), 1684 (CO), 1637 (CONH),
1586 (C C, Ar). H NMR (CDCl3): δ (ppm) 3.66–3.78 (dd, 1H, J = 16.5,
6 HZ, CH2CH), 3.95–4.10 (dd, 1H, J = 16.5, 5 HZ, CH2CH), 6.51–6.66
(m, 1H, CH2CH), 7.28–8.40 (m, 17H, ArH + NH). MS: (m/z,%) 413 (M+,
0.27), 308 (M+—PhCO, 100), 292 (M+-NH2COPh, 35), 155 (p-(Cl)C6H4-
COCH3, 50), 139(p-(Cl)C6H4-CO, 40), 127 (naphthyl, 15). Anal. Calcd.
for C26H20ClNO2 (413.9): C, 75.45, H, 4.87, Cl, 8.57, N, 3.38. Found: C,
75.42, H, 4.85, Cl, 8.52, N, 3.36%.
1-(4-Chlorophenyl)-3-(naphth-1-yl)prop-2-en-1-one (4ed)
Mp 100◦C (lit46, mp 99–100◦C).
3-(Anthracen-9-yl)-1-phenylprop-2-en-1-one (4bg)
The general procedure yielded only chalcone, mp 125◦C (lit43, mp
124–125◦C).
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