Effective method of β-keto sulfones synthesis

Full text of DOI:10.1134/S1070428014020274

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 2, pp. 296−297. © Pleiades Publishing, Ltd., 2014.
Original English Text © R.D. Savka, N.T. Pohodylo, M.D. Obushak, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 2, pp. 303−304.
SHORT
COMMUNICATIONS
Effective Method of β-Keto Sulfones Synthesis
R. D. Savka, N. T. Pohodylo, and M. D. Obushak
Ivan Franko Lviv National University, Lviv, 79005 Ukraine
e-mail: obushak@in.lviv.ua
Received September 20, 2013
DOI: 10.1134/S1070428014020274
β-Keto sulfones are widely used in organic synthe-
sis as reagents in Michael and Knoevenagel reactions
[1–3], for preparation of vinyl sulfones [4], polyfunc-
tional 4Н-pyrans [3], chalcones, alkynes, allenes, and
compounds of other classes [1,5–9]. In this connection
various approaches are developed to the synthesis of
β-keto sulfones [10–18], but many among them require
severe conditions, preparation of initial compounds, and
the yields of products in these reactions are often low.
the formation of a mixture of β-keto sulfone Va and
methylsulfonylbenzene in a ratio 2 : 1 [21]. Keto sulfides
may be oxidized with potassium permanganate [22], but
at the oxidation β-keto sulfides III in this way sulfones
V formed in low yields. Considering these results we
protected the keto group in compounds IIIа–IIIh by
converting them in 1,3-dioxolanes IVа–IVh. At the oxi-
dation of compounds IVа–IVh with hydrogen peroxide
in acetic acid followed by treating the reaction mixture
with water the target β-keto sulfones Vа–Vh formed in
high yields (see the table).
Looking for an efficient and cheap method of β-keto
sulfones synthesis aiming at their application as methy-
lene-active reagents in the preparation of 1,2,3-triazoles
[19] we developed a procedure for the synthesis of
β-keto sulfones with the use of available thiols I and
β-haloketones II. The reaction of thiophenol (Ia) and
4-methylthiophenol (Ib) with β-haloketones IIа–IIh af-
forded β-keto sulfides IIIа–IIIh. The oxidation of these
compounds with hydrogen peroxide in acetic acid [20]
did not result in selective formation of sulfones V, but
gave a mixture of reaction products. This result may be
ascribed to the concurrent reaction of the keto group
oxidation analogously to Baeyer-Villiger reaction. For
instance, the oxidation of compound IIIa with hydro-
gen peroxide in acetic acid at room temperature led to
General procedure of preparation of β-keto
sulfones Vа–Vh [1-(arylsulfonyl)alkan-2-ones Vа, Vb
and 1-aryl-2-(arylsulfonyl)ethan-1-ones Vc–Vh]. To
a solution of 2.8 g (50 mmol) of KОН and 50 mmol of
thiophenol (Ia) or 4-methylthiophenol (Ib) in 25 mL of
ethanol was added 50 mmol of β-haloketone IIа–IIh. The
mixture was left standing for 1 h at room temperature and
then it was diluted with water. The obtained (arylsulfanyl)
alkan-2-one (β-keto sulfide) III was separated from wa-
ter phase and used in the next stage without additional
purification. The solution of 40 mmol of β-keto sulfide
IIIа–IIIh, 8.2 mL (144 mmol) of ethylene glycol, and
8.8 mg (0.08 mmol) of p-toluenesulfonic acid in 45 mL
O
O
O
O
R2
HO
OH
KOH
EtOH
S
S
X
+
R2
IIIa_IIIh
SH
R1
R1
R2
R1
PhH, TsOH
IVa_IVh
a_
IIa–IIh
II IIh
Ia, Ib
(1) 30% H O , AcOH
30% H O ,
AcOH
2
2
2
2
O
O
R1
O
(2) H O
2
S
R2
Va_Vh
296

SILICA-ALUMINA CATALYSIS OF 2,4-PENTANEDIONE REACTION
297
β-Keto sulfones Vа–Vh
Compound no.
X (IIа–IIh)
R1
R2
Yield, %а
Referencesb
Va
Vb
Vc
Vd
Ve
Cl
Cl
Br
Br
Br
Br
Br
Ph
Ph
Me
CH2CH(CH3)2
Ph
4-MeC6H4
4-MeOC6H4
4-FC6H4
69
67
70
68
67
70
71
[21]
[15]
[14]
[14]
[14]
[14]
[14]
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
Vf
Vg
4-ClC6H4
Vh
Br
4-MeC6H4
4-NO2C6H4
65
[14]
a Yields are reported with respect to initial compounds I, II.
b Constants and spectral characteristics of sulfones Vа–Vh are in agreement with published data.
2001, vol. 12, p. 513.
9. Sengupta, S., Sarma, D.S., and Mondal, S., Tetrahedron,
1998, vol. 54, p. 9791.
10. Julia, M. and Paris, J.-M., Tetrahedron Lett., 1973, vol. 14,
p. 4833.
11. Durst, T., In Comprehensive Organic Chemistry,
Barton, D.H.R. and Ollis, W.D., Eds., Oxford: Pergamon,
Press, 1979, vol. 4, p. 174.
12. Trost, B.M., Chem. Rev., 1978, vol. 78, p. 363.
13. Holmquist, C.R. and Roskamp, E.J., Tetrahedron Lett.,
1992, vol. 33, p. 1131.
14. Kamigata, N., Udodaira, K., and Shimizu, T., J. Chem. Soc.,
Perkin, Trans. I, 1997, p. 783.
15. Kartrizky, A.R., Abdel-Fattah, A.A.A., and Wang, M.,
J. Org. Chem., 2003, vol. 68, p. 1443.
16. Grossert, J.S., Dubey, P.K., Gill, G.H., Stancey, T.,
Cameron, T.S., and Gardner, P.A., Can. J. Chem., 1984,
62, p. 798.
of benzene was boiled collecting the distilled water in
the Dean–Stark trap. On the completion of the reaction
the mixture was cooled to room temperature and twice
washed with water. The organic layer was separated,
dried with MgSO4, and evaporated. The residue, 1,3-di-
oxolane IVа–IVh, was further used without additional
purification. To a solution of 25 mmol of 1,3-dioxolane
IVа–IVh in 15 mLof acetic acid was added in small por-
tions 7.4 mL of 30% Н2О2 solution, the reaction mixture
was heated to the temperature no higher than 75°С, then
for 3 h at 80–85°С. The mixture was cooled to room
temperature, diluted with water, and left overnight. The
precipitated white crystals of compounds Vа–Vh were
filtered off and washed with water.
REFERENCES
17. Mitin, A.V., Kashin, A.N., and Beletskaya, I.P., Russ. J.
Org. Chem., 2004, vol. 40, p. 841.
18. Suryakiran, N., Srikanth, Reddy, T., Asha, Latha, K.,
Lakshman, M., and Venkateswarlu, Y., Tetrahedron Lett.,
2006, vol. 47, p. 3853.
19. Pokhodylo, N.T., Matiychuk, V.S., and Obushak, M.D.,
Synthesis, 2009, p. 2321.
20. Serushkina, O.V., Dutov, M.D., Sapozhnikov, O.Yu.,
Ugrak, B.I., and Shevelev, S.A., Russ. J. Org. Chem., 2002,
vol. 38, p. 1819.
1. Simpkins, N.S., Sulfones in Organic Synthesis, Bald-
win, J.E., Ed., Oxford: Pergamon, Press, 1993.
2. Marco, J.-L., Fernandez, I., Khiar, N., Fernandez, P., and
Romero, A., J. Org. Chem., 1995, vol. 60, p. 6678.
3. Marco, J.L., J. Org. Chem., 1997, vol. 62, p. 6575.
4. Sengupta, S., Sarma, D.S., and Mondal, S., Tetrahedron
Asymm., 1998, vol. 9, p. 2311.
5. Ihara, M., Suzuki, S., Taniguchi, T., Tokunaga, Y., and
Fukumoto, K., Tetrahedron, 1995, vol. 51, p. 9873.
6. Baldwin, J.E., Adlington, R.M., Crouch, N.P., Hill, R.L.,
and Laffey, T.G., Tetrahedron Lett., 1995, vol. 36, 7925.
7. Looker, J.J., J. Org. Chem., 1966, vol. 31, p. 2714.
8. Gotor, V., Rebolledo, F., and Liz, R., Tetrahedron Asymm.,
21. Prakash, G.K.S., Zhao, X., Chacko, S., Wang, F.,
Vaghoo, H., and Olah, G.A., Beilst. J. Org. Chem., 2008,
vol. 4, no. 17, p. 1860.
22. Looker, J.J., J. Org. Chem., 1966, vol. 31, p. 2973.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 2 2014