Poly(N-vinylimidazole) as efficient recyclable catalyst for the Michael addition of CH-acids to electron deficient alkenes in water

Article abstract of DOI:10.1007/s11172-011-0401-7

Efficiency of poly(N-vinylimidazole) as the basic recyclable catalyst for the Michael addition of CH-acids to acrylonitrile, methyl acrylate, methyl vinyl ketone and methyl vinyl sulfone in water at ambient temperature was studied. In these reactions, formation of both 1 : 1 and 1 : 2 adducts is possible.

Full text of DOI:10.1007/s11172-011-0401-7

Russian Chemical Bulletin, International Edition, Vol. 60, No. 12, pp. 2613—2616, December, 2011
2613
Poly(Nꢀvinylimidazole) as efficient recyclable catalyst for the Michael addition
of CHꢀacids to electron deficient alkenes in water*
E. A. Tarasenko,a V. S. Tyurin,b F. Lamaty,c and I. P. Beletskayaa
aDepartment of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 932 8846. Eꢀmail: eaꢀt@mail.ru, beletska@org.chem.msu.ru
bA. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
Build. 4, 31 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 952 5308
cInstitut des Biomolécules Max Mousseron (IBMM), Université Montpellier 2,
Place Eugène Bataillon cc1703, 34095 Montpellier, Cedex 05, France
Efficiency of poly(Nꢀvinylimidazole) as the basic recyclable catalyst for the Michael addiꢀ
tion of CHꢀacids to acrylonitrile, methyl acrylate, methyl vinyl ketone and methyl vinyl sulfone
in water at ambient temperature was studied. In these reactions, formation of both 1 : 1 and 1 : 2
adducts is possible.
Key words: poly(Nꢀvinylimidazole), CHꢀacids, electron deficient alkenes, basic catalysis,
recyclable catalyst, the Michael addition.
The Michael addition is one of the most important and
widely used methods for the carbon—carbon bond formaꢀ
tion.1,2 Catalysis by strong bases commonly used in this
reaction often led to formation of side products.3 Thereꢀ
fore, more selective catalysts were currently suggested, e.g.,
soft bases,4—7 Lewis acids, including salts and complexes
of transition metals and lanthanides,8,9 ionic liquids,10—12
enzymes,13 Amberlyst 15,14 SiO2.15 Among them, chiral
organic catalysts giving rise to nonꢀracemic products16—19
are of particular value.
From the economical and ecological viewpoints, the
catalysts which could be used repeatedly have major adꢀ
vantages.20 Often enough, such catalytic systems contain
synthetic polymers acting as supports for catalyst.21 Among
them, the catalysts suitable for the Michael addition are
also known.22—24 Soꢀcalled smart polymers capable of
changing physicochemical properties, especially solubiliꢀ
ty, depending on the conditions20,21 are of great imporꢀ
tance. This property makes it possible, on the one hand, to
perform the reaction in the homogeneous conditions, and,
on the other hand, to use the catalytic system repeatedly.
In some cases, the polymers themselves can exhibit cataꢀ
lytic properties similar to biopolymers. We have previousꢀ
ly shown that polymers bearing basic imidazole moieties
catalyzed the Michael addition of thiols25 and nitrogen
heterocycles26 to electron deficient alkenes.
In the present work, we studied the possibility to apply
poly(Nꢀvinylimidazole) with molecular weight 75300
as the basic catalyst for the Michael addition of the
CHꢀacids to electron deficient alkenes.
Results and Discussion
In the presence of poly(Nꢀvinylimidazole), CHꢀacids
such as malononitrile, ethyl nitroacetate, acetylacetone,
and 2ꢀnitropropane react with electron deficient alkenes,
e.g., methyl acrylate, acrylonitrile, methyl vinyl sulfone,
and methyl vinyl ketone (Scheme 1). Depending on the
nature of the CHꢀacid, these reactions give predominantly
the 1 : 1 (3a—h) or the 1 : 2 adducts (4a—e) (Table 1). The
reactions proceed in water at ambient temperature.
It was found that in the case of excess of alkene, maloꢀ
nonitrile yielded exclusively 1 : 2 adducts (see Table 1,
entries 1—3). Acetylacetone gave rise to the 1 : 1 adducts
(entries 4—6), whereas ethyl nitroacetate gave products,
whose composition depended on the nature of alkene and
the reactant ratio (entries 7—11). Ethyl (3ꢀacetylꢀ4ꢀhydrꢀ
oxyꢀ4ꢀmethylꢀ1ꢀnitrocyclohexane)carboxylate (5) was
synthesized with the excess of methyl vinyl ketone in 73%
yield. Apparently, compound 5 formed via addition of the
second molecule of methyl vinyl ketone to 1 : 1 adduct 3f
followed by intramolecular aldolꢀcrotonic condensation
(Scheme 2).
It is of note that in contrast to other studied Michael
acceptors, acrylonitrile readily reacts with malononitrile
* Dedicated to Academician of the Russian Academy of Sciences
R. Z. Sagdeev on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2561—2564, December, 2011.
1066ꢀ5285/11/6012ꢀ2613 © 2011 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 60, No. 12, December, 2011
Tarasenko et al.
Scheme 1
Scheme 2
1
a
b
c
d
R1
H
H
H
Me
R2
CN
C(O)Me
NO2
R3
CN
C(O)Me
CO2Et
NO2
Me
2: Z = CO2Me (a), CN (b), SO2Me (c), C(O)Me (d)
cyclable organic catalyst for the addition of CHꢀacids to
the Michael acceptors. Poly(Nꢀvinylimidazole) provides
performing these reactions under simple and costꢀeffecꢀ
tive conditions, e.g., with water as a solvent at ambient
temperature.
3
a
b
c
d
e
f
R1
H
H
H
H
H
H
Me
Me
R2
C(O)Me
C(O)Me
C(O)Me
NO2
NO2
NO2
Me
Me
R3
Z
C(O)Me
C(O)Me
C(O)Me
CO2Et
CO2Et
CO2Et
NO2
CO2Me
CN
SO2Me
CO2Me
CN
C(O)Me
SO2Me
C(O)Me
g
h
Experimental
NO2
4
a
b
c
d
e
R2
CN
CN
CN
NO2
NO2
R3
CN
CN
CN
CO2Et
CO2Et
Z
The course of the reactions was monitored by TLC on silica
gel precoated plates 60 F254 (Merck), visualization in iodine
vapor or in the KMnO4 solution. Silica gel Merck 60
(0.040—0.063 mm) was used for column chromatography. 1H
and 13C NMR spectra were run on a Bruker AMXꢀ400 instruꢀ
ment in CDCl3 and DMSOꢀd6 at working frequencies of 400.13
and 100.61 MHz, respectively; the chemical shifts are given in
the  scale relative to the residual signals of the solvents (CHCl3,
CO2Me
CN
SO2Me
SO2Me
C(O)Me
i. 10 mol.%
, H2O, 20—25 C.

7.27,  77.00; DMSO,  2.50,  39.51) as internal stanꢀ
H
C H C
dards. The starting methyl vinyl ketone (Aldrich) was purified by
vacuum distillation (b.p. 34—35 C (120 Torr)), other starting
compounds (Aldrich, AlfaAesar) were used as purchased. Polyꢀ
(Nꢀvinylimidazole) with M 75300 was synthesized by the known
procedure.27
to give exclusively 1 : 2 adduct (see Table 1, entry 2); in
the cases of acetylacetone and ethyl nitroacetate, the yields
were low (entries 5 and 8).
Addition of CHꢀacids (1a—d) to alkenes (2a—d) in the presꢀ
ence of poly(Nꢀvinylimidazole) (general procedure). To a stirred
solution of poly(Nꢀvinylimidazole) (14.1 mg, 0.15 mmol per
monomer unit) in distilled water (4 ml), CHꢀacid 1a—d
(1.5 mmol) was added followed by addition of alkene 2a—d
(4.5 mmol) after 5 min of stirring. The reaction mixture was
stirred at ambient temperature until complete consumption of
the reactants (see Table 1). In the case of formation of insoluble
products (3g, 4c, and 4d), the precipitates were separated by
filtration or centrifugation, washed with water and diethyl ether
and dried in vacuo. Compound 4d was additionally recrystallized
from AcOEt. All other products were extracted with AcOEt, the
organic layer was dried with Na2SO4, the solvent was removed
in vacuo, the residues were purified by column chromatography
(elution with petroleum ether—AcOEt (2 : 1) for 3a, 3f, 3h, 4a,
In the present work, we studied the possibility of the
catalyst recyclization on an example of the reaction beꢀ
tween malononitrile and methyl acrylate (see Table 1, enꢀ
try 1). It was found that at least the second cycle proceedꢀ
ed without loss of the catalyst activity. After completion of
the reaction (TLC monitoring), the product was extracted
with ethyl acetate, the organic layer was separated, and
the reactants and water in the amounts required for the
next step were added to the water phase. In the second
catalytic cycle, dimethyl 4,4ꢀdicyanoheptanedioate (4a)
was obtained in the yield of 90%.
In summary, poly(Nꢀvinylimidazole) can be used as
cheap, efficient, and most importantly easyꢀseparable reꢀ

Poly(Nꢀvinylimidazole) for the Michael addition
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 12, December, 2011
2615
4e, and 5, petroleum ether—AcOEt (1 : 1) for 4b, petroleum
ether—AcOEt (1 : 2) for 3c, petroleum ether—CH2Cl2 (1 : 1) for
3d). Compounds 3a, 3c, 3d, 3f, 3h, 4a, 4e, and 5 are colorless
oils, compound 4b is colorless crystals. Compounds 3b and 3e
were not isolated, their yields were determined by 1H NMR
spectroscopy of the mixtures obtained by extraction and removal
of the volatiles. Structures of known compounds were confirmed
by the comparison of the 1H and 13C spectra with published data
(references are given in Table 1). The 1H and 13C spectra and
elemental analysis data for hitherto unknown compounds are
given below.
3ꢀ(2ꢀMethylsulfonylethyl)pentaneꢀ2,4ꢀdione (3c). Colorless
oil. 1H NMR (CDCl3), : 2.19 (s, 1.8 H, CH3, enol); 2.25 (s, 6 H,
CH3, ketoꢀform); 2.29—2.36 (m, 2 H, CH2, ketoꢀform);
2.81—2.84 (m, 0.6 H, CH2, enol); 2.93 (s, 3 H, CH3S, ketoꢀ
form); 2.96 (s, 0.9 H, CH3S, enol); 3.01 (t, 2 H, CH2, ketoꢀ
form, J = 7.4 Hz); 3.05—3.06 (m, 0.6 H, CH2, enol); 4.02 (t, 1 H,
CH, ketoꢀform, J = 6.9 Hz). 13C NMR (CDCl3), : 19.97 (CH3,
enol); 20.33 (CH3, ketoꢀform); 22.96 (enol); 29.74 (ketoꢀform);
40.86 (ketoꢀform); 41.03 (enol); 51.69 (ketoꢀform); 54.33 (enol);
65.12 (CH, ketoꢀform); 106.38 (C=C, enol); 191.41 (C=C, enol);
202.82 (C=O, ketoꢀform). Found (%): C, 46.78; H, 6.73.
C8H14O4S. Calculated (%): C, 46.58; H, 6.84.
2,2ꢀBis(2ꢀmethylsulfonylethyl)malononitrile (4c). M.p.
209—211 C (purified by washing with water and diethyl ether).
1H NMR (DMSOꢀd6), : 2.65—2.70 (m, 4 H, CH2); 3.12 (s, 6 H,
CH3S); 3.43—3.47 (m, 4 H, CH2). 13C NMR (DMSOꢀd6), :
28.32 (CH3); 35.37 (C(2)); 40.44 (CH2); 49.38 (CH2); 114.33
(CN). Found (%): C, 39.10; H, 4.95; N, 10.15. C9H14N2O4S2.
Calculated (%): C, 38.83; H, 5.07; N, 10.06.
Ethyl 4ꢀmethylsulfonylꢀ2ꢀ(2ꢀmethylsulfonylethyl)ꢀ2ꢀnitrobutꢀ
anoate (4d). M.p. 110—114 C (from AcOEt). 1H NMR
(DMSOꢀd6), : 1.24 (t, 3 H, CH3, J = 7.1 Hz); 2.59—2.68
(m, 4 H, CH2); 3.06 (s, 6 H, CH3S); 3.16—3.31 (m, 4 H, CH2);
4.30 (q, 2 H, OCH2, J = 7.1 Hz). 13C NMR (DMSOꢀd6), :
13.59 (CH2CH3); 26.72 (CH3S); 40.11 (CH2); 48.19 (CH2);
63.75 (OCH2); 93.20 (C(2)); 164.83 (C=O). Found (%): C, 34.92;
H, 5.41; N, 3.88. C10H19NO8S2. Calculated (%): C, 34.77;
H, 5.54; N, 4.06.
This work was financially supported by the Ministry of
Education and Science of the Russian Federation (State
Contract 02.740.11.0630), the Russian Academy of Sciꢀ
ences (Program for Basic Research No. 3 "Design and
Study of Macromolecules and Macromolecular Structures
of Novel Generation" of the Division of Chemistry and
Materials Science of RAS).
3ꢀMethylꢀ1ꢀmethylsulfonylꢀ3ꢀnitrobutane (3g). M.p.
108—110 C (purified by washing with water and diethyl ether).
1H NMR (DMSOꢀd6), : 1.58 (s, 6 H, CH3); 2.29—2.34 (m, 2 H,
CH2); 3.01 (s, 3 H, CH3S); 3.12—3.16 (m, 2 H, CH2). 13C NMR
(DMSOꢀd6), : 25.06 (CH3); 31.68 (CH3); 40.14 (CH2); 48.93
(CH2); 87.17 (C). Found (%): C, 37.13; H, 6.65; N, 7.01.
C6H13NO4S. Calculated (%): C, 36.91; H, 6.71; N, 7.17.
References
1. M. E. Jung, in Comprehensive Organic Synthesis, Eds B. M.
Trost, I. Fleming, Pergamon Press, 1991, 4, 1.
2. P. Perlmutter, Conjugate Addition Reactions in Organic Synꢀ
thesis, Oxford, Pergamon Press, 1992, 394 p.
3. E. D. Bergman, D. Ginsburg, R. Pappo, Org. React., 1959,
10, 179.
4. Z. Zhang, Y.ꢀW. Dong, K. Komatsu, Synlett, 2004, 61.
5. W. Wang, M. Yu, Tetrahedron Lett., 2004, 45, 7141.
6. C. Xu, J. K. Bartley, D. I. Enache, D. W. Knight, G. J.
Hutchings, Synthesis, 2005, 3468.
Table 1. Addition of CH acids 1a—d to electron deficient alkꢀ
enes 2a—d in the presence of poly(Nꢀvinylimidazole) in water at
20—25 C
Entry CHꢀ Alkene Reagents t/hb Product Yieldc
acid
ratioa
(%)
7. K. Ko, K. Nakano, S. Watanabe, Y. Ichikawa, H. Kotsuki,
Tetrahedron Lett., 2009, 50, 4025.
8. J. Christoffers, Eur. J. Org. Chem., 1998, 1259.
9. J. Comelles, M. MorenoꢀMacas, A. Vallribera, Arkivoc, 2005,
9, 207.
10. B. C. Ranu, S. Banerjee, Org. Lett., 2005, 14, 3049.
11. B. C. Ranu, S. Banerjee, R. Jana, Tetrahedron, 2007, 63, 776.
12. E. A. Mistryukov, Mendeleev Commun., 2007, 17, 230.
13. G. A. Strohmeier, T. Sovic, G. Steinkellner, F. S. Hartner,
A. Andryushkova, T. Purkarthofer, A. Glieder, K. Gruber,
H. Griengl, Tetrahedron, 2009, 65, 5663.
1
1a
2a
1 : 3 : 0.1
8
4a28 90 (92d)
90d(cycle 2)
2
3
4
5
6
7
8
9
1a
1a
1b
1b
1b
1c
1c
1c
1c
1c
2b
2c
2a
2b
2c
2a
2b
2c
2d
2d
1 : 3 : 0.1
1 : 3 : 0.1
1 : 3 : 0.1
1 : 3 : 0.1
1 : 3 : 0.1
1 : 3 : 0.1
1 : 3 : 0.1 120
1 : 3 : 0.1 144
1 : 1.1 : 0.1
1 : 3 : 0.1
24
1
48
24
48
48
4be
4c
61 (90d)
98
3a29
3b30
3c
69
20d
30 (35d)
80
3d31
3e32
4d
34d
87
10
11
2
2
3f33
4e34
534
3g
84
25
73
14. B. Das, M. Krishnaiah, K. Laxminarayana, K. Damodar,
D. N. Kumar, Chem. Lett., 2009, 38, 42.
15. S. Banerjee, S. Santra, Tetrahedron Lett., 2009, 50, 2037.
16. Asymmetric Organocatalysts — from Biomimetic Concepts to
Applications in Asymmetric Synthesis, Eds A. Berkessel,
H. Gröger, WileyꢀVCH, Weinheim, 2005, 440 p.
17. Enantioselective Organocatalysis: Reactions and Experimental
Procedures, Ed. P. I. Dalko, WileyꢀVCH, 2007, 536 p.
18. Organocatalysis, Eds M. T. Reetz, B. List, S. Jaroch, H. Weinꢀ
mann, SpringerꢀVerlag, Berlin—Heidelberg, 2008, 341 p.
19. Top. Curr. Chem., Ed. B. List, SpringerꢀVerlag, Berlin—Heiꢀ
delberg, 2010, 291, 460 p.
12
13
1d
1d
2c
2d
1 : 1.1 : 0.1 120
1 : 1.1 : 0.1 12
47 (55d)
3h35 65 (87d)
a Molar ratio CHꢀacid : alkene : poly(Nꢀvinylimidazole) (per
monomer unit).
b Reaction time.
c Yield of the isolated product.
d Yield by the 1H NMR data using dimethyl fumarate as an interꢀ
nal standard.
e M.p. 90—92 C (cf. Ref. 11: 90—92 C).

2616
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 12, December, 2011
Tarasenko et al.
20. Recoverable and recyclable catalysts, Ed. M. Benaglia,
John Wiley and Sons Ltd., 2009, 471 p.
28. S. Paganelli, A. Schionato, C. Botteghi, Tetrahedron Lett.,
1991, 32, 2807.
21. Top. Curr. Chem., Ed. A. Kirschning, SpringerꢀVerlag, Berꢀ
lin—Heidelberg, 2004, 242, 337 p.
22. D. Benza, T. Constantieux, J. Rodriguez, Synthesis,
2004, 923.
23. C. Reddy, V. Reddy, J. G. Verkade, J. Org. Chem., 2007,
72, 3093.
24. R. Ballini, L. Barboni, L. Castrica, F. Fringuelli, D. Lanari,
F. Pizzo, L. Vaccaro, Adv. Synth. Catal., 2008, 350, 1218.
25. I. P. Beletskaya, E. A. Tarasenko, A. R. Khokhlov, V. S.
Tyurin, Zh. Org. Khim., 2007, 43, 1732 [Russ. J. Org. Chem.
(Engl. Transl.), 2007, 43, 1733].
26. I. P. Beletskaya, E. A. Tarasenko, A. R. Khokhlov, V. S.
Tyurin, Zh. Org. Khim., 2010, 46, 473 [Russ. J. Org. Chem.
(Engl. Transl.), 2010, 46, 461].
29. R. Chong, P. S. Clezy, Aust. J. Chem., 1967, 20, 123.
30. G. R. Zellars, R. Levine, J. Org. Chem., 1948, 13, 1911.
31. A. A. Smirnova, V. V. Perekalin, V. A. Shcherbakov, Zh. Org.
Khim., 1968, 4, 2245 [J. Org. Chem. USSR (Engl. Transl.),
1968, 4, 2166].
32. A. Dornow, A. Frese, J. Liebigs Ann. Chem., 1953, 581, 211.
33. R. E. Moskalyk, A. L. C. Mak, L. G. Chatten, R. A. Locock,
J. Pharm. Sciences, 1981, 70, 496.
34. M. Picquet, C. Brineau, P. H. Dixneuf, Tetrahedron, 1999,
55, 3937.
35. P. B. Kisanga, P. Ilankumaran, B. M. Fetterly, J. G. Verꢀ
kade, J. Org. Chem., 2002, 67, 3555.
27. I. P. Beletskaya, A. R. Khokhlov, E. A. Tarasenko, V. S.
Tyurin, J. Organomet. Chem., 2007, 692, 4402.
Received October 18, 2011;
in revised form December 2, 2011