Animal Bone Meal (ABM)
Letters in Organic Chemistry, 2010, Vol. 7, No. 3
271
[6]
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Preparation of ABM: Animal bones were collected from nearby
butcher shops. All of the attached meat and fat were removed and
cleaned from the bones which were then washed several times with
tap water and left in open air for several days to get rid of odours.
Later, they were transferred to the oven at 80°C for drying. The
dried bones were crushed and milled into different particle sizes in
the range 45-200 μm, calcined at 800°C for 2h. The residue was
washed with water and was used after drying 24 h at 80°C. The
residue was washed with water and was dried overnight at 100°C in
a conventional draying oven then calcined at a heating rate of
2°C/min to 400°C and in a last step kept at this temperature for 4h.
General procedure for the synthesis of III. A mixture containing an
equimolar mixture (1.0 mmol) of chalcone I and thiol II in MeOH
(1.5 mL) and ABM (0.1 g) was stirred at room temperature until
completion of the reaction. The reaction mixture was filtered and
the catalyst washed with CH2Cl2 (2x3 mL). After reduction of the
filtrate under reduced pressure, the residue was subjected to
recrystallization (EtOAc/CH2Cl2) or distillation under vacuum
leading to the Michael adduct.
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reaction (monitored by TLC), the 2-sulfido ketones III were
obtained by filtration, evaporation and recrystallization or
distillation.
By-products from 1,2-addition, polymerisation and bis-
addition were never observed. With PhSH, the reaction
proved to be very efficient using a chalcone bearing an EWG
or an unsubstituted one (entries 1-2). We were pleased to
establish that reactions were achieved in a few minutes and
the yields were up to 94%. Addition of an electrodonor
group on III decreased the reactivity of the double bond. The
yield and the reaction time were both affected (entries 3-4).
This chalcone substituent effect was solved by the use of the
2-aminobenzene thiol (entries 5-9). In only 5 minutes, the
attempted products were isolated in near quantitative yields.
By using the aliphatic mercaptoacetic acid ethyl ester, a
decrease of the reactivity was observed (entries 10-13). The
completion occurred after 30-60 minutes whereas the
chalcone substitution effects were enhanced. All reactions
appeared as quite quantitative on TLC but the distillation
steps reduced the yields in isolated compounds 11 and 14.
[7]
CONCLUSION
In summary, we described the first efficient and selective
Michael addition of aliphatic and aromatic thiols on
chalcones using the Animal Bone Meal ABM as
heterogeneous liquid phase catalyst. The ABM is a new and
attractive solid support which can contribute to the
development of catalytic processes and reduced
environmental problems.
[8]
ACKNOWLEDGEMENTS
[9]
S. Routier, G. Guillaumet and S. Lazar thank the
Volubilis Hubert Curien program for financial support.
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