The attribute of this synthetic protocol is the isolation of final
product from the reaction mixture. After completion of the
reaction polymer-supported catalyst was removed by using an
external magnet. The separated PSMRs could be further
reused by washing with organic solvent like dichloromethane
and treatment with hydrochloric acid. After removing the
PSMRs from the reaction mixture, excess of solvent is
removed by distillation. Products were further purified by
vacuum distillation.
Ando, H. J. Health Sci. 2001, 47, 75; (g) Miyata, Y.; Hui, D.
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0. Purohit, A. K.; Pardasani, D.; Tak, V.; Kumar, A.; Jain, R.;
1
Synthesis of O,O’-dialkyl alkylphospohonate starting from
dibasic alkylphosphonic acids using PSMRs was also
attempted. Dibasic alkylphosphonic acids afforded DAPs no
higher than 25% when reacted with alcohols in the presence
of PSMRs under the reaction conditions optimized for mono
basic acids. Varying the time, temperature and solvent also
did not improve the yield. Less reactivity of dibasic acids
could be attributed to their relatively lesser nucleophilicity
originating from stabilization of oxyanion over three oxygen
atoms. This study is in progress and will be reported in due
course.
In conclusion, we have developed an efficient process, for the
synthesis of O,O’-dialkyl alkylphospohonate & carboxylic
esters using PSMRs as recyclable catalyst. The PSMRs were
able to efficiently promote the esterification of a variety of O-
alkyl alkylphosphonic acid as well as carboxylic acid with
different alcohols in high yields under mild reaction
conditions. After completion of the reaction the PSMRs were
removed by an external magnet, which could be reused.
Dubey, D. K. Tetrahedron Lett. 2012, 53, 3795.
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3. Fernandes, S. A.; Natalino, R.; Gazolla, P. A. R.; Silva, M. J.;
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Supplementary data
Experimental details and spectroscopic data of synthesized
compounds are presented in supporting information.
15. Cohen, R. J.; Fox, D. L.; Eubank, J. F.; Salvatore, R. N.
Tetrahedron Lett. 2003, 44, 8617.
1
6. (a) Berhini, R.; Minciole, E.; Crisante, F.; Barontini, M.;
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Acknowledgment
We thank Prof. (Dr.) M.P. Kaushik, Director DRDE, Gwalior,
for his keen interest and encouragement.
6
557; (e) Lei, X.; Porco, J. A. Org. Lett. 2004, 6, 795; (f)
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21. General experimental procedure: A mixture of 50 mg
polymer-supported sulfonated magnetic resins (0.1 mmol)
and alkyl alkylphosphonic acid / carboxylic acid (1mmol)
and dry toluene (0.5ml) was stirred at room temperature for
15 minute. After that excess of alcohol (4 mmol) was added
4
.
O
to the reaction mixture and stirred at 70 C for further 30 min.
3
1
Progress of the reaction was monitored by TLC and
P
5
.
Gupta, H. K.; Pardasani, D.; Gupta, A. K.; Jain, R.; Dubey,
D. K. Aust. J. Chem. 2008, 61, 324.
NMR. After completion, the reaction mixture was cooled to
room temperature and placed near by a strong external
magnet and superanatent layer was separated from the
reaction mixture. Finally, excess of solvent was removed by
6
7
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1
31
distillation to get the colourless liquid. H and P NMR
spectra at 400 MHz were recorded in CDCl . Electron
ionization (EI+) mass spectra were recorded on Agilent GC-
MS system.
3
1995, 345, 980; (e) Miyata, Y.; Nonaka, H.; Yoshida, T.;
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