1 - V Liceum Ogólnokształcące im. Księcia Józefa Poniatowskiego

1 - V Liceum Ogólnokształcące im. Księcia Józefa Poniatowskiego

Synthesis of halomethyl phenyl sulfones and their
transformations into biological active compounds
1
Szymański ,
Jacek
1V
dr Zbigniew
2
Ochal
Liceum Ogólnokształcące im. Ks. Józefa Poniatowskiego w Warszawie,
2Faculty of Chemistry, Warsaw University of Technology
INTRODUCTION
BIOLOGICAL ACTIVITY
Halomethyl phenyl sulfones are of great practical importance,
either as biologically active compounds – mainly biocides and as
intermediates in various organic syntheses. Of particular interest
were found to be trihalomethyl phenyl sulfones and therefore the
new method of their synthesis was developed
Obtained trihalomethyl phenyl sulfones 3a, 3b were tested
for their fungicidal activity against six fungal pathogens.
Br
O
S
SYNTHESIS
O
SO2Na
+
Cl
bb
1
The β-ketosulfone 1 in the reaction with potassium halide
in the presence of hydrogen peroxide in room temperature
gives as main product α-halo-β-ketosulfone 2.
O
O
S
KX H2O 2
S
O
AcOH, rt
O
O
2
Applying the sodium hypohalite ,as a halogenating agent,
in the reaction of β-ketosulfone 1 carried out in higher
temperature, yielded trihalomethyl phenyl sulfones 3 in
good yields.
S
NaOXaq
O
70oC
1
S
X
O
X
X
3
R
S
KX1 H2O2
S
O
AcOH, rt
O
1
R
S
O
X
2
1
X1
S
NaOX2
O
70oC
R
1H
NMR spectrum of trihalomethyl phenyl sulfone 3b
A. alternata B. cinerea F. culmorum P. cactorum R. solani B. graminis
200 mg/ml
Concentration of the
1000 mg/ml
20 mg/ml
compound
Percentage
40
60
80
80
80
inhibition of colony
40
growth of the fungi
10
10
15
20
20
3a
30
50
80
80
90
3b
50
10
15
10
15
20
• Low-cost of substrates
• Mild reaction conditions
• High yield of reaction
• Simple laboratory devices
REFERENCES
O
O
NMR spectrum of trihalomethyl phenyl sulfone 3b
O
2
R
O
R
O
O
13C
ADVANTAGES OF NEW METHOD
Combining both above methods of halogenating βketosulfones, it is possible to receive in simple way
trihaloderivatives 4, containing two different halogens in
halomethylsulfonyl moiety.
O
a
The results of biological evaluation are expressed as the values of percentage inhibition of colony growth of the
fungi, derived from the following formula: I = 100 (C − T)/C, where I = percentage inhibition of colony growth
of the fungi, C = zone of growth of the fungus colony in mm in the control, T = zone of growth of the fungus
colony in mm in the examined sample.
O
O
bb
Fungal pathogens
X
R
1
R
dd
dd c
e
O
3b
3a
O
rt
R
R
O
Cl
S
PEG-400
O
Br
Cl
O
O
Br
R
O
S
Br
Cl
The First step of synthesis was the preparation of β-ketosulfones
in reaction of sodium aryl sulfinate with 2-bromo-1phenylethanone in organic solvent, i.e. polyethylene glycol (PEG400).
O
Cl
4
X1
X2
X2
1. K.M. Borys, M.D. Korzyński, Z. Ochal*, A simple and efficient
synthesis of trihalomethyl and dihalonitromethyl aryl sulfones,
Tetrahedron Lett., 2012, 53, 6606-6610.
2. N. Suryakiran, T. Srikanth Reddy, K. Ashalatha, M. Lakshman and
Y. Venkateswarlu Tetrahedron Letters 47 (2006) 3853–3856
3. N. Suryakiran, P. Prabhakar, T. Srikanth Reddy, K. Chinni Mahesh,
K. Rajesh and Y. Venkateswarlu Tetrahedron Letters 48 (2007)
877–881
Acknowledgements: Jacek Szymański wishes to thank the University of Young Investor program of the Ministry of Science and Higher Education