The synthesis and ring opening of 3-aroyl(heteroaroyl)-1,2-dicyanocyclopropane-1,2-dicarboxylates

Article abstract of DOI:10.1016/j.tetlet.2015.02.092

3-Aroyl-1,1,2,2-tetracyanocyclopropanes undergo ring opening under the action of acetates, carbonates and hydroxides of alkali metals, resulting in the formation of stable 2-aroyl-1,1,3,3-tetracyanopropenide salts, which are of interest as potential co-ligands in the coordination polymers and as ionic liquid components. A method for producing new electron-deficient cyclopropanes, dimethyl 3-aroyl(heteroaroyl)-1,2-dicyanocyclopropane-1,2-dicarboxylates and their reactions with potassium acetate leading to the formation of the corresponding propenides is described.

Full text of DOI:10.1016/j.tetlet.2015.02.092

Accepted Manuscript
The synthesis and ring opening of 3-aroyl(heteroaroyl)-1,2-dicyanocyclopro-
pane-1,2-dicarboxylates
Sergey V. Karpov, Yakov S. Kayukov, Arthur A. Grigor’ev, Victor A. Tafeenko
PII:
S0040-4039(15)00373-1
DOI:
http://dx.doi.org/10.1016/j.tetlet.2015.02.092
TETL 45962
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
5 December 2014
30 January 2015
18 February 2015
Please cite this article as: Karpov, S.V., Kayukov, Y.S., Grigor’ev, A.A., Tafeenko, V.A., The synthesis and ring
opening of 3-aroyl(heteroaroyl)-1,2-dicyanocyclopropane-1,2-dicarboxylates, Tetrahedron Letters (2015), doi:
http://dx.doi.org/10.1016/j.tetlet.2015.02.092
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Graphical Abstract
The synthesis and ring opening of 3-aroyl(heteroaroyl)-
1,2-dicyanocyclopropane-1,2-dicarboxylates
Sergey V. Karpov, Yakov S. Kayukov, Arthur A. Grigor'ev, Victor A. Tafeenko

1
Tetrahedron Letters
journal homepage: www.els evier.com
The synthesis and ring opening of 3-aroyl(heteroaroyl)-1,2-
dicyanocyclopropane-1,2-dicarboxylates
Sergey V. Karpova* , Yakov S. Kayukova, Arthur A. Grigor'eva, Victor A. Tafeenkob
aI.N. Ul’yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015, Russia
b Lomonosov Moscow State University, Leninskiye Gory 1-3, Moscow, 119991, Russia
* Corresponding author. Tel.: +79170640970; fax: +78352450279; e-mail: serg31.chem@mail.ru.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
3-Aroyl-1,1,2,2-tetracyanocyclopropanes undergo ring opening under the action of
acetates, carbonates and hydroxides of alkali metals, resulting in the formation of
stable 2-aroyl-1,1,3,3-tetracyanopropenide salts, which are of interest as potential co-
ligands in the coordination polymers and as ionic liquid components. A method for
producing new electron-deficient cyclopropanes, dimethyl 3-aroyl(heteroaroyl)-1,2-
dicyanocyclopropane-1,2-dicarboxylates, and their reactions with potassium acetate
leading to the formation of the corresponding propenides is described.
Available online
Keywords:
Cyclopropanes
Propenides
2014 Elsevier Ltd. All rights reserved.
Cyano group
Organic nitriles
Ring opening reactions
3-Aroyl-1,1,2,2-tetracyanocyclopropylketones undergo ring-
opening in the presence of bases, such as alkoxides, carbonates
and hydroxides of alkali metals.1,2 For example, 2-aroyl-1,1,3,3-
tetracyanopropenides, are easily obtained by using acetates as
bases.3,4 Currently, there is considerable interest in the salts of
The general method for the preparation of 3-alkyl- or 3-aryl-
substituted 1,2-dicyanocyclopropane-1,2-dicarboxylates is via the
reaction
between
carbonyl
compounds
and
α-
bromocyanoacetates under Wideqvist-type reaction conditions.20
We have found that inclusion of α-ketoaldehydes in this reaction
does not lead to the formation of the corresponding
cyclopropanes, but results in resinification of the reaction mass.
Therefore, we used another synthetic strategy for the synthesis of
3-aroyl(heteroaroyl)-1,2-dicyanocyclopropane-1,2-
polycyano-containing
organic
anions,
including
the
tetracyanoallyl (TCA) structural fragment. TCA anions are
bridging ligands with variable denticity that allow the
construction of various 1D, 2D and 3D supramolecular
structures. Among these are known coordination polymers with
dicarboxylates, based on the successive reaction of glyoxal
hydrates 1 with two equivalents of methyl cyanoacetate in the
presence of sodium hydroxide, followed by bromination (Scheme
1).
interesting
structural,5-8
magnetic,9-11
thermochromic,12
semiconducting,13 and photomagnetic14,15 properties. Some
representatives of 1,1,3,3-tetracyanopropenides have low melting
points and act as ionic liquids.16 They also show potential for
creating spin-crossover (SCO) materials.17 In some publications,
compounds of this type are prospective new components of
propellants.18 Most publications describe anions containing only
coordinately active cyano groups, but the presence of other
functional groups may result in significant changes in the
coordinating ability of such ligands and is of interest.19
O
O
E
E
NC
E
OH
EtOH, NaOH
R
R
CN
+
CN
OH
1a-h
A
O
O
CN
E
CN
E
1) HCl
2) Br2
R
O
E
E
In this article, we have extended the method for the synthesis
of 1,1,3,3-tetracyanopropenides to similar new salts containing
two ester groups in addition to two cyano groups. The choice of
the ester groups was based on the fact that they have sufficient
electron-withdrawing ability and are stable. The ester group
shows the ability to form complexes via the donor oxygen atom.
It can also influence intermolecular interactions and reduces the
melting points of the compounds, which is a very important
property for ionic liquids.
R
or +
R
CN
CN
CN
E
CN
H
H
E
B
2a-h
E = C(O)OCH3
3a-h
Scheme 1. Synthesis of 3-aroyl(heteroaroyl)-1,2-
dicyanocyclopropane-1,2-dicarboxylates 2 and 3.

2
Tetrahedron
The mechanism proposed involves an initial condensation to
the nitrile groups with ester groups did not affect significantly the
reactivity of the cyclopropane ring-opening reactions. We
form the Knoevenagel derivative A. Next, addition of excess
cyanoacetate leads to the formation of the adduct B via a Michael
reaction, the bromination of which completes the synthesis with
synthesized
dimethyl
3-aroyl(heteroaroyl)-1,2-
dicyanocyclopropane-1,2-dicarboxylates and reacted them with
potassium acetate to produce the corresponding potassium 2-
aroyl(heteroaroyl)-1,3-dicyano-1,3-
1
formation of the corresponding cyclopropane. According to H
NMR spectroscopy, the reaction gave diastereomeric
cyclopropanes 2 and 3 with a predominance generally for the cis-
isomer 2 (Table 1).
bismethoxycarbonylpropenides 4 (Scheme 2).
We found that the ratio of isomers 2 and 3 was dependent on the
temperature of the reaction mass. Compound 2a was obtained
with virtually no isomer 3a during bromination at 50 °C.
Running this reaction at room temperature led to the formation of
O
O
R
CH3COO-
R
E
E
-CH3COOH
CN
CN
E
E
1
CN
CN
a mixture of 2a and 3a in the ratio 1:1, according to H NMR
spectroscopy.
2,3
R
O
R
O
Table 1. The ratios and yields of cyclopropanes 2 and 3
Reactant
R
Temp
Ratio
Yield
(%)
73
K+
E
E
E
E
(°C)
2:3
CN CN
CN CN
1a
1a
Ph
51-52
20-22
21-22
51-52
20-22
49-51
20-22
100:0
50:50
K+
4
Ph
68
1b
1c
1d
1e
1f
C6H5C6H4
thienyl
4-CH3C6H4
furyl
50:50
100:0
57:43
100:0
60:40
87:13
84:16
75
66
71
79
61
71
76
Scheme 2. Reaction of 3-aroyl(heteroaroyl)-1,2-
dicyanocyclopropane-1,2-dicarboxylates with potassium acetate
The proposed mechanism for this reaction involves
deprotonation of the substrate by acetate anions and subsequent
ring-opening of the resulting cyclopropyl carbanion. The most
probable mechanism for opening of the three-membered ring
compounds 2 and 3 is via an electrocyclic reaction. According to
theory, in this case, ring-opening should occur in a conrotatory
fashion. Propenide 4a, formed by the reaction of the cis-isomer
of cyclopropane 2a with potassium acetate has a cis-arrangement
4-CH3OC6H4
1g
1h
3,4-(CH3O)2C6H4 35-36
5-bromothienyl
35-36
The
structure
of
dimethyl
3-benzoyl-1,2-
1
of the benzoyl group and the two ester groups according to H
NMR spectroscopy and X-ray diffraction, which formally
dicyanocyclopropane-1,2-dicarboxylate (2a) was established by
single-crystal X-ray diffraction analysis (Figure 1)
corresponds to a disrotatory process.
The structure of potassium 2-benzoyl-1,3-dicyano-1,3-
bismethoxycarbonylpropenide (4a) was established by single-
crystal X-ray diffraction analysis (Figure 2)
Figure 1. ORTEP diagram of dimethyl 3-benzoyl-1,2-
dicyanocyclopropane-1,2-dicarboxylate (2a).
Figure 1 shows the atom numbering in 2a. Displacement
ellipsoids are drawn at the 50% probability level. In the unit cell,
molecules of 2a form centrosymmetric dimers via –CN…NC-
dipole-dipole and π…π interactions. Cell parameters (2a): a=
20.70730(7) Å, b= 9.5889(2) Å, c = 15.3387(5) Å, α= 90°, β=
96.546(3)°, γ = 90°; V= 3025.80(9) Å3, Z=8, dcalc=1.371. The
crystals are monoclinic and the space group is C2/c.
Figure 2. ORTEP diagram of 2-benzoyl-1,3-dicyano-1,3-
bismethoxycarbonylpropenide (4a)
Figure 2 shows the atom numbering in 4a. Displacement
ellipsoids are drawn at the 50% probability level. Symmetry
codes: i=0.5-x, -0.5+y, 1.5-z; ii = 0.5+x, 0.5-y, -0.5+z; iii= 0.5-x,
0.5+y, 1.5-z. In the crystal, the K+ cation coordinates via four
nitrogen and three oxygen atoms. The distances K…L are within
the range of 2.69-3.33 Å (L = N,O of the molecule coordinated to
K). Cell parameters (4a): a = 9.5491(5) Å, b = 9.7519(5) Å, c =
Tetracyanocyclopropylketones are able to undergo ring-
opening under the action of bases. The reactions of these
compounds with sodium or potassium acetate gave the known
and stable 2-acyl-1,1,3,3-tetracyanopropenides3,4 salts. Replacing

3
17.4837(10) Å, α= 90°, β= 104.124(3) °, γ = 90°; V=1578.90(15)
Å3, Z= 4, dcalc=1.704. The crystal is monoclinic and the space
group is P21/n.
(CN), 1751 (CO2Ме), 1681 (COAr). MS (EI, 70 eV): m/z (%)
312 [M]+ (27), 281 [M–CH3O]+ (11), 253 [M–CH3CO2]+ (24),
105 [PhCO]+ (100), 77 [Ph]+ (31), 59 [CH3CO2]+ (44). Anal.
Calcd for C16H12N2O5: C, 61.54; H, 3.87; N, 8.97. Found: C,
61.49; H, 3.91; N, 8.91.
The reaction of a mixture of isomeric compounds 2a and 3a
with potassium acetate produced propenide 4a, without any of
the corresponding trans-isomer. Propenides 4b-h, derived from
cyclopropanes 2,3b-h, also have the cis-arrangement of the
benzoyl and ester groups.
1
Mixture of 2а+3a: mp 122-124 ºС (dec.); H NMR (500.13
MHz, DMSO-d6): δ, selected H NMR signals of diastereomer
1
3a: 3.63 (3Н, s, СН3), 3.94 (3Н, s, СН3), 4.89 (1Н, s, СН), 7.62
(2H, t, J=7.9 Hz, С6Н5), 7.74 (1H, t, 3J=7.5 Hz, С6Н5), 7.92 (2H,
3
These results can be explained by the instability of the trans-
isomers of salts 4, which transform into the more stable cis-
isomers during the reaction (Scheme 3).
d, J=7.4 Hz, С6Н5). IR (mineral oil, cm–1): 3111, 3055 (CH),
3
2260, 2252 (CN), 1751, 1749 (CO2Ме), 1681, 1679 (COAr). MS
(EI, 70 eV): m/z (%) 312 [M]+ (21), 281 [M-CH3O]+ (9), 253 [M-
CH3CO2]+ (27), 105 [PhCO]+ (100), 77 [Ph]+ (27), 59 [CH3CO2]+
(52). Anal. Calcd for C16H12N2O5: C, 61.54; H, 3.87; N, 8.97.
Found: C, 61.95; H, 4.08; N, 8.64.
O
R
O
R
O
R
conrotatory
CN
E
E
E
CN
NC
E
E
CN CN
CN
E
4
2
Typical procedure for the preparation of potassium 2-
aroyl(heteroaroyl)-1,3-dicyano-1,3-
Scheme 3. A possible mechanism for the formation of the cis-
isomers of propenides 4.
di(methoxycarbonyl)propenides 4.
Dimethyl 3-aroyl (heteroaroyl)-1,2-dicyanocyclopropane-1,2-
dicarboxylate (5 g) was added to a 20% aqueous solution of
KOAc in H2O (75 ml), and the mixture was stirred at 70-75 °C
until the solids had dissolved. The resulting yellow solution was
filtered and the filtrate allowed to cool. To the filtrate was added
saturated KCl solution (75 ml). The resulting yellow precipitate
was filtered and recrystallized from H2O.
Alternative mechanisms for the ring-opening reaction of
compounds 2 and 3, in which the formation of predominantly one
isomer of the propenide, regardless of the spatial structure of the
initial cyclopropane, are also possible.
In conclusion, the potassium 2-aroyl(heteroaroyl)-1,3-
dicyano-1,3-bismethoxycarbonylpropenides 4 obtained are stable
salts, containing an allylic-type anion. They are soluble in water
and polar organic solvents. These salts might be of interest as
new ligands in coordination chemistry and as precursors in
organic synthesis.
Potassium 2-benzoyl-1,3-dicyano-1,3-
di(methoxycarbonyl)propenide (4a)
Compound 4a: mp 250-260 ºС (dec.); 1H NMR (500.13 MHz,
DMSO-d6): δ 3.35 (6Н, s, СН3), 7.39-7.50 (3H, m, Ar), 7.64-
7.70 (2H, m, Ar). IR (mineral oil, cm–1): 2191 (CN), 1700
(CO2Ме), 1680 (COAr). Anal. Calcd for C16H11KN2O5: C, 54.85;
H, 3.16; N, 8.00. Found: C, 54.38; H, 3.23; N, 7.93.
CCDC 1037222 and 1037223 for 2a and 4a respectively,
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from the Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif
Typical procedure for the preparation of dimethyl 3-
aroyl(heteroaroyl)-1,2-dicyanocyclopropane-1,2-dicarboxylates
2 and 3
Acknowledgments
This work was supported by RFBR, research project № 14-03-
31821 "мол_a". The X-ray study was supported in part by M. V.
Lomonosov Moscow State University Program of Development.
Glyoxal hydrate 1 (0.05 mol) and methyl cyanoacetate (9.9 g,
0.1 mol) were dissolved in EtOH (100 ml). To the mixture under
stirring was added a solution NaOH (1.8 g) in EtOH (30 ml). The
mixture was stirred for 3 min and then neutralized by addition of
concentrated HCl. The mixture was heated to the appropriate
temperature (see Table 1), after which Br2 (8.0 g, 0.05 mol) was
added dropwise with vigorous stirring. The reaction was cooled
to room temperature and poured into 500 ml of distilled H2O.
The brown oil which formed was separated from the solution and
dissolved in 50 ml of boiling EtOH. After cooling, the formed
white solid precipitate was filtered and recrystallized from
AcOH.
References and notes
1. Bardasov I. N., Kayukova O. V., Kayukov Ya. S., Ershov O. V., Nasakin
O. E., Belikov M. Yu. Russ. J. Org. Chem. 2007, 43, 1565-1566.
2. Kayukov Ya. S., Bardasov I. N., Karpov S. V., Ershov O. V., Nasakin O.
E., Kayukova O. V., Tafeenko V. A. Russ. J. Org. Chem. 2012, 48, 1447-
1455.
3. Bardasov I. N., Kayukova O. V., Kayukov Ya. S., Ershov O. V., Nasakin
O. E., Tafeenko V. A. Russ. J. Org. Chem. 2009, 45, 1325-1335.
4. Karpov S. V., Kayukov Ya. S., Bardasov I. N., Kayukova O. V., Ershov
O. V., Nasakin O. E. Russ. J. Org. Chem. 2011, 47, 405-407.
5. Schlueter J. A., Geiser U. Acta Cryst. 2003, C59, m146-m148.
6. Samia B., Fatima S., Carlos J. G.-G., Smail T., Coronado E., Saluan J.-Y.
J. Mol. Struct. 2008, 890, 255–262.
7. Thétiot, F., Triki, S., Sala Pala, J., Galán-Mascarós, J.-R., Martínez-
Agudo, J. M., Dunbar, K. R. Eur. J. Inorg. Chem. 2004, 3783–3791.
8. Bruce M. I., Buntine M. A., Costuas K., Ellis B. G., Halet J.-F., Low P.
J., Skelton B. W., White A. H. J. Organomet. Chem. 2004, 689, 3308-
3326.
Dimethyl
3-benzoyl-1,2-dicyanocyclopropane-1,2-
dicarboxylate (2a and 3a)
Compound 2а (cis-isomer): mp 131-133 ºС; 1H NMR (500.13
MHz, DMSO-d6): δ 3.87 (6Н, s, СН3), 4.66 (1Н, s, СН), 7.66
3
(2H, t, J=7.9 Hz, С6Н5), 7.80 (1H, t, 3J=7.5 Hz, С6Н5), 8.09 (2H,
9. Smaïl T., Franck T., Fanny V., Jean S.-P., Carlos J. G.-G. Inorg. Chem.
2005, 44, 4086–4093.
3
d, J=7.4 Hz, С6Н5). IR (mineral oil, cm–1): 3055 (CH), 2252

4
Tetrahedron
10. Yuste C., Bentama A., Marino N., Armentano D., Setifi F., Triki S.,
Lloret F., Julve M. Polyhedron 2009, 28, 1287-1294.
11. Conan F., Cosquer N., Kerbaol J.-M., Sala Pala J., Kubicki M. M. Inorg.
Chem Acta. 2005, 358, 2513-2522.
12. Setifi F., Benmansour S., Marchivie M., Dupouy G., Triki S., Sala-Pala
J., Salaün J.-Y. Inorg. Chem. 2009, 48, 1269-1271.
13. Sekizaki S., Tada C., Yamochi H., Saito G. J. Mater. Chem. 2001, 11,
2293-2302.
14. Dupouy G., Marchivie M., Triki S., Sala-Pala J., Gómez-García C. J.,
Pillet S., Lecomte C., Létard J.-F. Chem. Commun. 2009, 3404-3406.
15. Dupouy G., Triki S., Marchivie M., Cosquer N., Gómez-García C. J.,
Pillet S., Bendeif E.-E., Lecomte C., Asthana S., Létard J.-F. Inorg.
Chem. 2010, 49, 9358–9368.
16. Yoshida Y., Kondo M., Saito G. J. Phys. Chem. B. 2009, 113, 8960–
8966.
17. Benmansour S., Atmani C., Setifi F., Triki S., Marchivie M.,Gómez-
García C.-J. Coord. Chem. Rev. 2010, 254, 1468-1478.
18. Gao H., Zeng Z., Twamley B., Jean'nel M. Chem. Eur. J. 2008, 14,
1282–1290.
19. Turner D.R., Chesman A. S. R., Murray K. S., Deacon G. B., Batten S.
R. Chem. Commun. 2011, 47, 10189–10210.
20. Elinson M. N, Lizunova T. L., Ugrak B. I., Dekaprilevich M. О.,
Nikishin G. I., Struchkov Y. T. Tetrahedron Lett. 1993, 34, 5795-5798.