Allylation reactions of aromatic aldehydes with antimony in aqueous media under ultrasonic irradiation

Article abstract of DOI:10.1080/00397910802654856

The allylation reactions of aromatic aldehydes with allyl bromide were carried out in 89-98% yield with Sb-H₂O-KF-CH₃OH under ultrasound irradiation at rt for 2.5h. The reactions in the same system gave allylic alcohols in 30-69% yie

Full text of DOI:10.1080/00397910802654856

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Allylation Reactions of
Aromatic Aldehydes with
Antimony in Aqueous Media
Under Ultrasonic Irradiation
Yan-Jiang Bian a , Hong-Mei Zhao a & Xu-Guang Yu b
a Department of Chemistry , Langfang Normal
College , Hebei, Langfang, China
b Beijing General Research Institute of Mining and
Metallurgy , Beijing, China
Published online: 01 Jun 2009.
To cite this article: Yan-Jiang Bian , Hong-Mei Zhao & Xu-Guang Yu (2009)
Allylation Reactions of Aromatic Aldehydes with Antimony in Aqueous Media Under
Ultrasonic Irradiation, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 39:13, 2370-2377, DOI:
10.1080/00397910802654856
To link to this article: http://dx.doi.org/10.1080/00397910802654856
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Synthetic Communications1, 39: 2370–2377, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802654856
Allylation Reactions of Aromatic Aldehydes with
Antimony in Aqueous Media Under Ultrasonic
Irradiation
Yan-Jiang Bian,1 Hong-Mei Zhao,1 and Xu-Guang Yu2
1Department of Chemistry, Langfang Normal College, Hebei,
Langfang, China
2Beijing General Research Institute of Mining and Metallurgy, Beijing, China
Abstract: The allylation reactions of aromatic aldehydes with allyl bromide were
carried out in 89–98% yield with Sb-H2O-KF-CH3OH under ultrasound irra-
diation at rt for 2.5 h. The reactions in the same system gave allylic alcohols in
30–69% yield with stirring for 24 h. The main advantages of the present procedure
are shorter reaction time, better yield, and environmental friendliness.
Keywords: Allylation, antimony, ultrasound irradiation
Carbon–carbon bond formation is the essence of organic synthesis. One
of the most powerful methods for constructing carbon–carbon bonds is
the allylation reaction between an allyl halide and carbonyl com-
pounds.[1] Metals such as tin,[2–6] indium,[7] samarium,[8] gallium,[9] yetter-
bium,[10] manganese,[11] magnesium,[12] and zinc,[13–18] have been found to
be effective for such transformations. However, there were always some
troubles because of long reaction time or critical reduction.
Ultrasound has been increasingly used in organic synthesis. Many
metal-mediated organic reactions have been accelerated with ultra-
sound.[19–23] A search of the literature revealed that no report has
appeared on the results of allylation reactions using antimony under
Received September 24, 2008.
Address correspondence to Yan-Jiang Bian, Department of Chemistry,
Langfang Normal College, Hebei, Langfang 065000, China. E-mail:
bianyanjiang@126.com
2370

Allylic Alcohol Synthesis
2371
Table 1. Optimization of the allylation reaction of C6H5CHO mediated by Sb in
aqueous media under ultrasonic irradiation with various conditions
CH3OH Time Isolated
(h)
Entry
Reaction system
(mL)
yield (%)
1
2
3
4
5
6
7
8
Benzaldehyde=allyl bromide=Sb ¼ 1:2.5:5
Benzaldehyde=allyl bromide=Sb ¼ 1:2.5:5
Benzaldehyde=allyl bromide=Sb ¼ 1:2.5:5
Benzaldehyde=allyl bromide=Sb ¼ 1:2.5:5
Benzaldehyde=allyl bromide=Sb ¼ 1:2.5:5
Benzaldehyde=allyl bromide=Sb ¼ 1:2.5:5
Benzaldehyde=allyl bromide=Sb ¼ 1:2.5:5
Benzaldehyde=allyl bromide=Sb ¼ 1:2.5:5
2
2
2
2
2
1
2
3
1
1.5
2
2.5
3
2.5
2.5
2.5
43
62
86
93
93
81
93
93
Notes. Isolated yield based on the substrate. KF (aqueous): 4 mL. Ultrasound
irradiation: 40 KHz. Temperature: rt.
ultrasound irradiation to date. Herein, we report the results of the
allylation reactions of aromatic aldehydes by antimony (Sb) with stirring
or ultrasound irradiation.
To optimize the conditions, we screened the reaction of benzaldehyde
with allyl bromide in a variety of Sb-H2O-KF-CH3OH reaction systems
(Table 1). From the results in Table 1, the optimized reaction conditions
are benzaldehyde=allyl bromide=Sb 1:2.5:5 and time of 2.5 h. To demonstr-
ate the positive effect of ultrasound irradiation on the reaction, the same
reaction in entries a–f, Table 2 also has been researched using stirring.
Table 2. Allylation reactions of aromatic aldehydes using Sb-H2O-KF-CH3OH
system under ultrasound irradiation or stirring
Isolated yield (%)
Entry
Substrate
C6H5CHO
4-ClC6H4CHO
Furfural
Cinnamaldehyde
3,4-(OCH2O)C6H3CHO
4-CH3OC6H4CHO
C6H5COC6H5
Stirring (24 h)
Ultrasound (2.5 h)
Rfa
1a
1b
1c
1d
1e
1f
60
66
30
61
69
65
—
—
93
89
97
98
94
96
—
—
0.61
0.59
0.52
0.68
0.53
0.50
—
1g
1h
C6H5COCH3
—
Notes. Isolated yield based on the substrate. Ultrasound irradiation time: 2.5 h.
Stirring time: 24 h.
aEluent: petroleum ether=diethyl ether (v=v) ¼ 1:1.

2372
Y.-J. Bian, H.-M. Zhao, and X.-G. Yu
Scheme 1.
As shown in Table 2, the allylation reaction was carried out under
ultrasonic irradiation, giving great yield. For example, benzaldehyde
(1a), 4-ClC6H4CHO (1b), furfural (1c), cinnamaldehyde (1d), piperonal
(1e), and 4-CH3OC6H4CHO (1f) reacted with allyl bromide in a Sb-
H2O-KF-CH3OH system to give a nearly quantitative yield of the cor-
responding homoallylic alcohols (2a, 2b, 2c, 2d, 2e, 2f) under ultrasonic
irradiation for 2.5 h, whereas with stirring for 24 h, the yields of the cor-
responding homoallylic alcohols were only 60, 66, 30, 61, 69, and 65%
respectively. The data indicate that the reaction time is reduced and yields
improved under ultrasound irradiation. To expose the effects of the car-
bonyl group of ketone, we choose benzophenone (1g) and acetophenone
(1h) as substrates. It is found that no the corresponding products were
obtained under ultrasound irradiation or stirring, respectively. We can
infer that the steric hindrance around the carbonyl group may inhibit
the allylation reactions.
It was reported that the allylation reaction proceeded via a single
electron-transfer mechanism[24] (Scheme 2). In the present process, homo-
allylic alcohols were be obtained by forming an allyl radical anion, which
nucleophilically attacks a carbonyl group, leading to homoallylic radical
formation while proceeding via a single electron-transfer. This can be
protonated by Hþ to give homoallylic alcohols as the product. Accord-
ingly, sonication promotes generation of the radicals and initiates
the electron-transfer process. Ultrasound irradiation favors the reaction
Scheme 2.

Allylic Alcohol Synthesis
2373
via single electron-transfer mechanism. Aromatic aldehydes exhibited
greater reactivity than aromatic ketones; perhaps the steric hinderance
around the carbonyl group of aromatic ketones inhibits the addition
reaction.
Based on these results, we demonstrated that ultrasound irradiation
can speed up markedly the allylation reaction of aromatic aldehydes with
the Sb-H2O-KF-CH3OH system. The main advantages of the present
procedure are the greater yield and the shorter reaction time. This new
approach shows considerable practical value because of its efficiency
and simplicity.
EXPERIMENTAL
Liquid substrates were distilled before use. Infrared (IR) spectra were
recorded on a Bio-Rad FTS-40 spectrometer (KBr). Mass spectra (MS)
1
were determined on an AEI MS-50 SD90 spectrometer (EI, 70 eV). H
NMR spectra were measured on a VXR-300S spectrometer (300 MHz)
by using CDCl3 as solvent and tetramethylsilane (TMS) as internal stan-
dard. Sonication was performed in a Shanghai SK8200LH ultrasonic
cleaner (with a frequency of 40 kHz and a nominal power of 500 W;
Shanghai Kudos Ultrasonic Instrument Co., Ltd.). The reaction flask
was located at the maximum energy area in the cleaner, where the surface
of reactants is slightly less than the level of the water. (Observation of the
surface of the reaction solution during vertical adjustment of vessel depth
showed the optimum position by the point at which maximum surface
disturbance occurred.) The reaction temperature was controlled by
addition or removal of water from the ultrasonic bath. The calorimetric
transfer efficiency of ultrasonic bath is 1.26. (The calorimetric power
measurements were carried out as the literature.[26]
A 50-ml Pyrex flask was charged with the desired aldehyde (1 mmol),
allyl bromide (2.5 mmol), antimony (5 mmol), KF (aqueous) (4 mL), and
CH3OH (2 mL). The mixture was irradiated in the water bath of an ultra-
sonic cleaner under air conditions at 25–30ꢀC for 2.5 h (or stirring for
24 h). After the completion of the reaction, the resulting suspension
was filtered to remove the Sb. The filtrate was extracted with ethyl acetate
(3 ꢁ 10 mL). The combined organic layers were washed with saturated
aqueous NaHCO3 solution and brine, then dried over anhydrous magne-
sium sulfate for 12 h. Ethyl acetate was evaporated under reduced pres-
sure to give the crude product, which was separated by column
chromatography on silica (200–300 mesh) and eluted with a mixture of
petroleum ether and diethyl ether. All the products were confirmed their
1
IR, MS, H NMR, and spectral data.

2374
Y.-J. Bian, H.-M. Zhao, and X.-G. Yu
Data
Compound 2a[25]
1
Oil; H NMR: dH 2.40 (t, J ¼ 6.6 Hz, 2H), 2.90–2.98 (br, 1H), 4.58 (t,
J¼ 6.6 Hz, 1H), 5.02–5.05 (m, 1H), 5.04–5.06 (m, 1H), 5.64–5.70 (m, 1H),
7.25–7.68 (m, 5H). MS m=z (%): 148 (Mþ). IR (KBr) n: 3405, 1191,
990 cmꢂ1
.
Compound 2b[25]
Oil; 1H NMR: dH 2.41 (t, J ¼ 6.6 Hz, 2H), 3.03–3.10 (br, 1H), 4.57
(t, J ¼ 6.6 Hz, 1H), 5.05–5.08 (m, 1H), 5.10 (m, 1H), 5.68–5.72 (m, 1H),
7.18 (d, J ¼ 8.2 Hz, 2H), 7.24 (d, J ¼ 8.2 Hz, 2H). MS m=z (%): 182
(Mþ). IR (KBr) n: 3406, 1195, 985 cmꢂ1
Compound 2c[25]
.
Oil; 1H NMR: dH 1.90–2.15 (br, 1H), 2.63 (q, J ¼ 7.1 Hz, 2H), 4.72
(t, J ¼ 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 ¼ 3.3 Hz, 1H), 7.26–7.40 (m, J ¼ 3.3 Hz, 1H).
MS m=z (%): 138 (Mþ). IR (KBr) n: 3401, 1192, 992 cmꢂ1
.
Compound 2d[25]
1
Oil; H 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 (Mþ). IR (KBr) n: 3400, 1642, 988 cmꢂ1
.
Compound 2e[25]
1
Oil; H NMR: dH 2.40 (t, J ¼ 6.4 Hz, 2H), 2.49–2.60 (br, 1H), 4.56 (t,
J ¼ 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 (Mþ). IR (KBr)
n: 3420, 1192, 990 cmꢂ1
.
Compound 2f[25]
Oil; 1H NMR: dH 2.43 (q, J ¼ 6.6 Hz, 2H), 2.79–2.86 (br, 1H), 3.76 (s, 3H),
4.61 (t, J ¼ 6.6, 1H), 5.04–5.09 (m, 1H), 5.08–5.12 (m, 1H), 5.72–5.82

Allylic Alcohol Synthesis
2375
(m, 1H), 6.82 (d, J ¼ 8.8, 2H), 7.21 (d, J ¼ 8.8, 2H). MS m=z (%): 178
(Mþ). IR (KBr) n: 3410, 1191, 991.
ACKNOWLEDGMENTS
The project was supported by the Technology Foundation of Hebei
Province (04213041) and the Science Foundation of Hebei Lang Fang
Normal College (200804).
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