The allylation reactions of aromatic aldehydes and ketones with tin dichloride in water

Article abstract of DOI:10.1016/j.ultsonch.2009.05.008

The allylation reactions of aromatic aldehydes and ketones were carried out in 31-86% yield using SnCl₂-H₂O system under ultrasound irradiation at r.t. for 5 h. The reactions in the same system gave homoallyl alcohols in 21-84% yield

Full text of DOI:10.1016/j.ultsonch.2009.05.008

Ultrasonics Sonochemistry 17 (2010) 58–60
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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch
The allylation reactions of aromatic aldehydes and ketones
with tin dichloride in water
a
b
Yan-Jiang Bian a, , Wei-Li Xue , Xu-Guang Yu
*
a Department of Chemistry, Langfang Normal College, Hebei, Langfang 065000, PR China
b Beijing General Research Institute of Mining and Metallurgy, Beijing 100044, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 23 July 2008
Received in revised form 26 February 2009
Accepted 8 May 2009
Available online 18 May 2009
The allylation reactions of aromatic aldehydes and ketones were carried out in 31–86% yield using SnCl2–
H2O system under ultrasound irradiation at r.t. for 5 h. The reactions in the same system gave homoallyl
alcohols in 21–84% yield with stirring at r.t. for 24 h. Compared with traditional stirring methods, ultra-
sonic irradiation is more convenient and efficient.
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Ultrasound irradiation
Allylation
Tin dichloride
Water
1. Introduction
tions of aromatic aldehydes and ketones using tin dichloride in
water under ultrasound irradiation.
Carbon–carbon bond formation is the essence of organic
synthesis. One of the most powerful methods for constructing car-
bon–carbon bond is the allylation reaction between an allyl halide
and carbonyl compounds [1]. Metals such as tin [2–6], indium [7],
samarium [8], gallium [9], ytterbium [10], manganese [11], magne-
sium [12], zinc [13–18], have been found to be effective for such
transformations. However, there were always some troubles due
to long reaction time or the critical reduction. Recently, the chem-
ists have been pursuing the simple and efficient synthetic method
and searching for safe and harmless reaction solvent. In this area,
organic reactions in aqueous media have been attracted consider-
able interests because water is considered to be a safe and environ-
mentally benign solvent.
Ultrasound has increasingly been used in organic synthesis.
Sonochemistry is also becoming more and more important for a
variety of synthetic organic reactions as an energy source to
generate radicals and initiate the electron-transfer process. Many
metal-mediated organic reactions have been accelerated under
ultrasound [19]. Ultrasound irradiation can activate the surface of
metal and reduce the particle size, and bring about an effective
surface modification. Recently, we reported that ultrasonic irradia-
tion can promote the allylation reactions of aromatic aldehydes by
using Zn [20], Sn [21], La [22], Nd [23] and Li [24] in aqueous med-
ia. This prompted us to study the possibility of the allylation reac-
A search of the literature revealed that no report has appeared
the results of the allylation reactions using tin dichloride under
ultrasound irradiation in water to date. Herein, we wish to report
the results of the allylation reactions of aromatic aldehydes and ke-
tones by tin dichloride in water with stirring or under ultrasound
irradiation, respectively (Scheme 1).
2. Method
2.1. Apparatus and analysis
Liquid substrates were distilled before use. IR spectra were
recorded on Bio-Rad FTS-40 spectrometer (KBr). MS spectra were
measured on an AEI MS-50 SD90 spectrometer (EI, 70 eV). 1H
NMR spectra were measured on VXR-300S spectrometer
(300 MHz) with CDCl3 as solvent and TMS as internal standard.
Sonication was performed in a Shanghai SK8200LH ultrasonic
cleaner (with a frequency of 40 kHz and a nominal power 500 W;
Shanghai Kudos ultrasonic instrument Co., Ltd.). The reaction flask
was located at the maximum energy area in the cleaner, the
surface of reactants is slightly lower than the level of the water.
The reaction temperature was controlled by bath water.
2.2. General procedure
A 50 ml Pyrex flask was charged with the desired aldehyde or
ketone (1 mmol), allyl bromide (3 mmol), tin dichloride (0.2 g,
* Corresponding author.
E-mail address: bianyanjiang@126.com (Y.-J. Bian).
1350-4177/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2009.05.008

Y.-J. Bian et al. / Ultrasonics Sonochemistry 17 (2010) 58–60
59
Table 1
OH
O
C
Optimization of the allylation reaction of C6H5CHO mediated by SnCl2 in water under
ultrasonic irradiation with various conditions.
SnCl2/H2O
CH2
CH
CH2
Br
CH
CH2
R1
R2
C
CH2
R2
Entry
Reaction system
Time/h
Isolated yield/%
R1
1
2
3
4
5
6
7
8
benzaldehyde:allyl bromide:SnCl2 = 1:1:1
benzaldehyde:allyl bromide:SnCl2 = 1:1:1
benzaldehyde:allyl bromide:SnCl2 = 1:1:1
benzaldehyde:allyl bromide:SnCl2 = 1:1:1
benzaldehyde:allyl bromide:SnCl2 = 1:1:1
benzaldehyde:allyl bromide:SnCl2 = 1:1:1
benzaldehyde:allyl bromide:SnCl2 = 1:1:1
benzaldehyde:allyl bromide:SnCl2 = 1:2:1
benzaldehyde:allyl bromide:SnCl2 = 1:3:1
benzaldehyde:allyl bromide:SnCl2 = 1:4:1
benzaldehyde:allyl bromide:SnCl2 = 1:3:1
benzaldehyde:allyl bromide:SnCl2 = 1:3:2
1
2
3
4
5
6
5
5
5
5
5
5
38
45
60
72
76
77
75
80
86
85
86
85
1 (a-h)
2 (a-h)
Scheme 1.
1 mmol) and H2O (4 mL). The mixture was irradiated in the water
bath of an ultrasonic cleaner under an air conditions at 25–30 °C
for 5 h or stirring 24 h (monitored by TLC). After the completion
of the reaction, the resulting suspension was filtered. The filtrate
was extracted with ethyl acetate (3Â10 mL). The combined organic
layers were washed with saturated aqueous NaHCO3 solution and
brine, dried over anhydrous magnesium sulfate for 12 h and fil-
tered. Ethyl acetate was evaporated under reduced pressure to give
the crude product, which was separated by column chromatogra-
phy on silica (200–300 mesh), eluted with petroleum ether or a
mixture of petroleum ether and diethyl ether. All the products
were confirmed by IR, MS, 1H NMR, spectral data.
9
10
11
12
Isolated yield based on the substrate; H2O: 4 ml; Ultrasound irradiation: 40 kHZ.
Table 2
The allylation reactions of aromatic aldehydes and ketones mediated in SnCl2–H2O
system under ultrasound irradiation or stirring.
Entry
Substrate
Isolated yield (%)
Stirring (24 h)
2a 1H NMR: dH2.40 (t, J = 6.6 Hz, 2H), 2.90–2.98 (br, 1H), 4.58 (t,
J = 6.6 Hz, 1H), 5.02–5.05 (m, 1H), 5.04–5.06 (m, 1H), 5.64–5.70 (m,
Ultrasound (5 h)
1H), 7.25–7.68 (m, 5H). MS m/z (%): 148 (M+). IR (KBr)
m: 3405,
1a
1b
1c
1d
1e
1f
C6H5CHO
4-ClC6H4CHO
furfural
cinnamaldehyde
3, 4-(OCH2O)C6H3CHO
4-CH3OC6H4CHO
C6H5COC6H5
84
77
58
71
77
84
–
86
76
59
73
79
84
–
1191, 990 cmÀ1
.
2b 1H NMR: dH2.41 (t, J = 6.6 Hz, 2H), 3.03–3.10 (br, 1H), 4.57 (t,
J = 6.6 Hz, 1H), 5.05–5.08 (m, 1H), 5.10 (m, 1H), 5.68–5.72 (m, 1H),
7.18 (d, J = 8.2 Hz, 2H), 7.24 (d, J = 8.2 Hz, 2H). MS m/z (%): 182
(M+). IR (KBr) : 3406, 1195, 985 cmÀ1
m .
1g
1h
C6H5COCH3
21
31
2c 1H NMR: dH 1.90–2.15 (br, 1H), 2.63 (q, J = 7.1 Hz, 2H), 4.72 (t,
J = 7.1 Hz, 1H), 5.15–5.18 (m, 1H), 5.15–5.20 (m, 1H), 5.76–5.82 (m,
1H), 6.28–6.36 (m, J = 3.3 Hz, 1H), 7.26–7.40 (m, J = 3.3 Hz, 1H). MS
Ultrasound irradiation time for 5 h and stirring for 24 h.
m/z (%): 138 (M+). IR (KBr) : 3401, 1192, 992 cmÀ1
m .
ing homoallylic alcohols(2a, 2b, 2d, 2e, 2f) was only 84%, 77%, 71%,
77% and 84%, respectively. The data indicates that the reaction time
gets reduced remarkably under ultrasound irradiation condition. In
order to expose the effects of carbonyl group of ketone, we choose
benzophenone (1g) and acetophenone (1h) as substrates. It is
found that there were no products with benzophenone as sub-
strate. While acetophenone as substrate the corresponding prod-
ucts were obtained only in 31% and 21% yield under ultrasound
irradiation or stirring respectively. We can infer that the steric hin-
drance around the carbonyl group may inhibit the allylation
reactions.
2d 1H NMR: dH 2.02 (1H, s), 2.40–2.50 (2H, m), 4.32–4.44 (1H, t),
5.14–5.26 (2H, m), 5.78–5.88 (1H, m), 6.60–6.72 (1H, m), 7.18–7.40
(5H, m). MS m/z (%): 174 (M+). IR (KBr) : 3400, 1642, 988 cmÀ1
m .
2e 1H NMR: dH 2.40 (t, J=6.4 Hz, 2H), 2.49–2.60 (br, 1H), 4.56 (t,
J = 6.4 Hz, 1H), 5.08 (m, 1H), 5.10 (m, 1H), 5.68–5.76 (m, 1H), 5.90
(s, 2H), 6.68–6.74 (m, 2H), 6.80 (s, 1H). MS m/z (%): 192 (M+). IR
(KBr) m .
: 3420, 1192, 990 cmÀ1
2f 1H NMR: dH 2.43 (q, J = 6.6 Hz, 2H), 2.79–2.86 (br, 1H), 3.76 (s,
3H), 4.61 (t, J = 6.6, 1H), 5.04–5.09 (m, 1H), 5.08–5.12 (m, 1H),
5.72–5.82 (m, 1H), 6.82 (d, J = 8.8, 2H), 7.21(d, J = 8.8, 2H). MS m/
z (%): 178 (M+). IR (KBr)
m: 3410, 1191, 991.
2h 1H NMR: dH 1.23–1.42 (s, 3H), 1.48–1.73 (s, 1H), 2.26–2.60
(d, 2H), 4.62–5.08 (d, 2H), 5.16–5.69 (m, 1H), 6.86–7.39 (m, 5H).
4. Conclusion
MS m/z (%): 162 (M+). IR (KBr)
m: 3430, 1192, 990.
Based on those results, we demonstrated that ultrasound irradi-
ation can speed up markedly the allylation reaction of aromatic
aldehydes and ketones with SnCl2–H2O system. Compared with tra-
ditional stirring methods, ultrasonic irradiation is more convenient
and efficient. More importantly, the allylation reaction was carried
out in water, so the environmental concerns were improved.
3. Result and discussion
With our optimized the conditions, we screened the reaction of
benzaldehyde with allyl bromide in a variety of SnCl2–H2O reaction
system (Table 1). From the result in Table 1, the optimized reaction
conditions are: benzaldehyde:allyl bromide:SnCl2 = 1:3:1, time:
5 h.
Acknowledgement
In order to demonstrate the positive effect of ultrasound irradi-
ation on the reaction, the same reaction in Entries(a–h) (Table 2)
also has been researched under stirring.
The project was supported by Science and Technology Founda-
tion of Hebei Province (04213041) and Science Foundation of He-
bei Lang Fang Normal College.
As shown in Scheme 1 and Table 2, the allylation reaction was
carried out under ultrasonic irradiation or stirring giving higher
yield. For example, benzaldehyde (1a), p-Cl-benzaldehyde (1b),
Cinnamaldehyde (1d), Piperonal (1e) and p-CH3O-benzaldehyde
(1f) reacted with allyl bromide in SnCl2–H2O system giving 86%,
76%, 73%, 79% and 84% yield of the corresponding homoallylic alco-
hols (2a, 2b, 2d, 2e, 2f) under ultrasonic irradiation for 5 h.
Whereas in case with stirring for 24 h, the yield of the correspond-
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