High-speed ball milling
Table 4. The coupling of 1-chloro-4-nitrobenzen and styrene by different methodsa
Entry
Method
Heatingb
Solid-state heatingc
Grindingd
HSBMe
Time
Yieldf (%)
1
2
3
4
5
8 h
8 h
1 h
1 h
1 h
45
trace
0
91
HSBM
13
a1-Chloro-4-nitrobenzen (5 mmol), styrene (7 mmol), Pd(OAc)2 (0.5 mol%), TBAB (5 mmol), K2CO3 (12.5 mmol), silica gel (4 g).
bHeating in DMF at 120 ꢀC, not using Silica gel.
cHeating at 120 ꢀC after mixing sufficiently.
dUsing a mortar and pestle.
eCooling the drum using constant cool water in ball milling.
fIsolated yield based on 1-chloro-4-nitrobenzene.
conditions owing to the relative stability of the C-Cl bond
towards oxidative addition (Table 3, entry 20). The activation of
deactivated aryl chlorides using other catalyst systems by HSBM
is now under investigation.
of International S&T Cooperation (No. 2008DFR40280) for finan-
cial help.
Further, in order to determine the factors which promoted the
reaction by HSBM, the coupling of 1-chloro-4-nitrobenzen and
styrene was performed by different methods. As shown in Table 4,
a good yield was obtained by HSBM (Table 4, entry 5). Compared
to HSBM, the yield was apparently low by heating in DMF, solid-
state heating or grinding (Table 4, entries 1–3). It was apparent
that simple heating or grinding could not promote the reaction
remarkably. The combination of compressive stress, internal
temperature and efficient mixing was the main factor which
promoted the reaction by HSBM.
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In summary, we have developed an efficient and simple strategy
for the synthesis of (E)- stilbenes by HSBM. A few notable advan-
tages of this procedure are: (i) the relatively low catalyst loading
without utilizing expensive ligands; (ii) reasonably good yields
and high selectivities; (iii) short reaction times; and (iv) neither
toxic solvents nor an inert atmosphere are required. We believe
that this method will be a more practical alternative to the
existing methods for other organic reactions.
SUPPORTING INFORMATION
Supporting information may be found in the online version of
this article.
Acknowledgments
We are grateful to the Natural Science Foundation of China
(Nos. 21006097 and 21176222), the Graduate Innovative Research
Project, Zhejiang Province (No. G0909116004521) and Program
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