Sharp difference in the rate of formation and stability of the Diels–Alder reaction adducts with 2,3-dicyano-1,4-benzoquinone and N-phenylimide-1,4-benzoquinone-2,3-dicarboxylic acid

Article abstract of DOI:10.1002/kin.21534

This work reports new studies of the activity and Diels–Alder kinetics of a series of dienophiles: tetracyanoethylene (1), 2,3-dicyano-p-benzoquinone (10), and N-phenylimide-1,4-benzoquinone-2,3-dicarboxylic acid (11). Rate differences are interpreted in terms of the donor–acceptor properties of the reagents. The relative π-acceptor properties of the dienophiles are probed by measuring their interaction energies with a series π-donor solvents: benzene, toluene, o-xylene, and chlorobenzene. The normalized interaction energies of 1, 10, and 11 are found to be 100:64:28. Despite the increased energy of the donor–acceptor interaction, dienophile 10 is 255 times less active in the reaction with 9,10-dimethylanthracene than 11. It is suggested that this is due to the significantly lower energy of π-bond cleavage in bicyclic dienophile 11, compared with monocyclic 10.

Full text of DOI:10.1002/kin.21534

Received: 19 May 2021
DOI: 10.1002/kin.21534
Revised: 11 August 2021
Accepted: 11 August 2021
R E S E A RC H A RT I C L E
Sharp difference in the rate of formation and stability of the
Diels–Alder reaction adducts with
2,3-dicyano-1,4-benzoquinone and
N-phenylimide-1,4-benzoquinone-2,3-dicarboxylic acid
Vladimir D. Kiselev
Ildar F. Dinikaev
Anastasia O. Kolesnikova
Dmitry A. Kornilov
Alexey A. Shulyatiev
The A.M. Butlerov Chemical Institute,
Kazan Federal University, Kazan, Russian
Federation
Abstract
This work reports new studies of the activity and Diels–Alder kinetics of a series
of dienophiles: tetracyanoethylene (1), 2,3-dicyano-p-benzoquinone (10), and N-
phenylimide-1,4-benzoquinone-2,3-dicarboxylic acid (11). Rate differences are
interpreted in terms of the donor–acceptor properties of the reagents. The rel-
ative π-acceptor properties of the dienophiles are probed by measuring their
interaction energies with a series π-donor solvents: benzene, toluene, o-xylene,
and chlorobenzene. The normalized interaction energies of 1, 10, and 11 are
found to be 100:64:28. Despite the increased energy of the donor–acceptor
interaction, dienophile 10 is 255 times less active in the reaction with 9,10-
dimethylanthracene than 11. It is suggested that this is due to the significantly
lower energy of π-bond cleavage in bicyclic dienophile 11, compared with mono-
cyclic 10.
Correspondence
Vladimir D. Kiselev, The A.M. Butlerov
ChemicalInstitute, KazanFederal Univer-
sity, Kremlevskaya str., 18, Kazan420008,
RussianFederation.
Email:vkiselev.ksu@gmail.com
K E Y WO R D S
2, 3-dicarboxylic acid, 3-dicyano-p-benzoquinone, 4-benzoquinone-2, Diels–Alder reaction, N-
phenylimide-1, rate constant, reaction enthalpy
benzoquinone (9) with cyclopentadiene (4),2 the bisadduct
of which was used in the formation of tweezers and rib-
1
INTRODUCTION
bons for the first time.3–5 Quinone derivatives are stim-
ulating increased interest due to the peculiarity of their
chemical behavior and widespread use as drugs.6,7 Many
compounds with a p-benzoquinone fragment exhibit pro-
nounced antitumor,6,8–10 anti-inflammatory,11 and antimi-
crobial activity.12 However, it was noted that the rate of 1,4-
benzoquinone with dienes in the DAR is low, and the reac-
tion products are thermally unstable.13–15
Substituted quinones, such as 2,3-dicyano-p-
benzoquinone (10), N-phenylimide-1,4-benzoquinone-
2,3-dicarboxylic acid (11), have two different reaction
centers and large differences in the rate of formation
The search for active reagents in the Diels–Alder reac-
tion (DAR) is important for expanding its capabilities
in the synthesis of new cyclic products, as well as for
the rapid completion of reactions. Such active reagents
often make it possible to successfully involve even inac-
tive partners in DARs with deep conversion. The most
active dienophiles are tetracyanoethylene (1), dicyanoma-
leic anhydride (2), 4-phenyl-1,2,4-triazolinediones (3), and
among the dienes, the most active are cyclopentadiene (4),
2,5-diphenylisobenzofuran (5), 9,10-dimethylanthracene
(6a), quadricyclane (7), 1,4-disubstituted 2,3,5,6-tetrazine
(8).1 One of the earliest studied DAR is the reaction of 1,4-
Int J Chem Kinet. 2021;1–8.
wileyonlinelibrary.com/journal/kin
© 2021 Wiley Periodicals LLC
1

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KISELEV et al.
and stability of their adducts. In bicyclic dienophiles, the
activity of the C═C bond shared by the two rings is of
particular interest. The shared C═C bond is known to
increase the strain energy of the molecule, and therefore
significantly reduces the energy of cleavage of the π-bond.
For example, the direct route of obtaining cantharidin,
used in the treatment of oncological diseases, by DAR
of furan with dimethylmaleic anhydride turned out to
be impossible even in a wide range of temperatures and
pressures, while the bicyclic derivative 12 with a strained
C═C bond easily reacts with furan.16,17
Tetracyanoethylene (1) is the most active
dienophile1,18,19 due to the high energy of electron
affinity (Ea ∼ 2.9–3.2 eV.20,21 Replacement of two cyano
groups in tetracyanoethylene with an anhydride fragment
makes dicyanomaleic anhydride (2) more active than
tetracyanoethylene.18 For the bicyclic dienophile, dian-
hydride ethylenetetracarboxylic acid (13) one can expect
an even higher reactivity.18 However, due to the high
structural tension and, probably, a slight rupture of the
strained C═C π-bond of dianhydride 13 cannot be isolated
in a free form.18,22
NMR spectra (spectrometer Bruker Avance 400) of 2,3-
dicyano-p-benzoquinone (10), and m.p. (178–180◦C) coin-
cided with the literature data.26 The synthesis of N-
phenylimide-1,4-benzoquinone-2,3-dicarboxylic acid (11)
was carried out as described.27,28 The obtained N-
phenylimide-hydroquinone-2,3-dicarboxylic acid (2.661 g,
0.0104 mol) was mixed with 6 ml of water and 2 ml of 65%
nitric acid was added dropwise. Stirring for 1.5 h at room
temperature followed by washing with copious amounts
of cold water gave 2.4 g (90%) of crude product 11, which
was recrystallized from acetone. M.P. 225, lit.27 230◦C. 1H
NMR spectrum in CD3COCD3: 7.02 (s, 2 H), 7.36–7.52 (m,
5 H), similar to that described previously.28 Cyclopentadi-
ene (4) was obtained by cracking the dimer at 180–200◦C,
dried over CaCl2, and distilled before each series of mea-
surements. Anthracene (6b) and 9,10-dimethylanthracene
(6a) (Alfa Aesar, 99%) were used as purchased.
2.1
Kinetic measurements
The rate of fast reactions (t0.5 < 1 s) in 1,2-dichloroethane
at 25, 35, and 45◦C was monitored by the “stopped
flow” method on a Varian Cary 50 Bio spectropho-
tometer with an attachment “RX2000” (Applied photo-
physics). The reaction 4+10→14 was followed by the
change in the absorption of 2,3-dicyano-p-benzoquinone
Removal of the great structural tension of quadricyclane
(7) in the reaction of [2π + 2σ + 2σ] cycloaddition with
dienophiles is the reason of its high activity and the largest
known exothermicity of the reactions.23
4-Phenyl-1,2,4-triazolinedione (3) has moderate energy
of donor–acceptor interaction with π-donors, close to that
observed for the structural analog, N-phenylmaleimide.
Due to the large difference in the cleavage energies of
N═N (418) and C═C (611 kJ mol−1) bonds, dienophile 3
is much more active than other dienophiles, including
tetracyanoethylene24 (Scheme 1). It follows from the above
comparison that the difference in the energy of intermolec-
ular orbital stabilization of interacting reagents does not
always determine the difference in the reaction rate.
Therefore, in this work, we determined and com-
pared the energies of the intermolecular donor–acceptor
interaction of a bicyclic dienophile, N-phenylimide 1,4-
benzoquinone-2,3-dicarboxylic acid (11), and a monocyclic
dienophile, 2,3-dicyano-1,4-benzoquinone (10), kinetic
and thermochemical parameters of some DARs with the
participation of these dienophiles (Scheme 2).
(10), λ = 440 nm, where cyclopentadiene and monoadduct
are optically transparent. The rate of the fast reaction 4+11
could not be determined due to the need to work with low
concentrations of reagents and, therefore, with their low
absorption. The reactions 6a+11 and 6b+11 were moni-
tored by the change in the absorption of dienes, λ 360–
390 nm, log(ε) 3.5–4.0, where the dienophile and adducts
were transparent. The initial concentrations of 11 and
6a were 1.5 × 10−3 and 1.5 × 10−4 mol L−1, respectively.
The error in maintaining the temperature during kinetic
measurements was 0.1◦C. Reactions at a moderate rate
were monitored by the change in absorption of dienes or
dienophiles where the adducts were transparent (Hitachi
U-2900 spectrophotometer).
2.2
Calorimetry
2
EXPERIMENTAL
To compare the enthalpies of reactions, the heat effects
were determined with the participation of the same
diene, cyclopentadiene in both reactions: 4+10→14 and
4+11→16. A known amount of solution of cyclopen-
tadiene in 1,2-dichloroethane, after equalizing the
temperature in the calorimeter cell, was introduced into
a solution of excess dienophile 11. The heat of reac-
tion 4+10→14 was determined earlier.29 The heat of
All solvents were purified by known methods.25 2,3-
Dicyano-1,4-benzoquinone (10) was synthesized by oxi-
dation of 2,3-dicyanohydroquinone (Sigma–Aldrich; 98%)
with nitric acid (60% yield) as suggested in Ref. 26.
The resulting 2,3-dicyanobenzoquinone (10) was puri-
fied by sublimation (120–130◦C, 100 Pa). 1H and 13C

KISELEV et al.
3
S C H E M E 1 Some active dienes and dienophiles in the Diels–Alder reaction
reaction 4+11→16 was determined twice. The obtained
erties of the reagents.1 Therefore, it is useful to com-
pare the π-acceptor properties of N-phenylimide-1,4-
benzoquinone-2,3-dicarboxylic acid (11) and 2,3-dicyano-
1,4-benzoquinone (10). According to the data on the
energy of the maximum of the charge transfer band
(Ec.t.) in the π, π-complex with hexamethylbenzene in
1,2-dichloroethane, dienophile 10 can be considered a
stronger π-acceptor (λmax 575 nm, Ec.t. 2.16 eV)29 than 11
(λmax = 530 nm, Ec.t. 2.34 eV) and even than tetracya-
noethylene (1) (λmax = 538 nm, Ec.t. 2.30 eV). However,
we prefer to estimate the energy of intermolecular inter-
action of π-acceptors from the data on the difference in
the enthalpy of their dissolution in the series of π-donor
solvents, alkylbenzenes. The enthalpy of dissolution of a
π-acceptor (ΔHsol) in this series of solvents can be repre-
sented as the sum of the enthalpy of vaporization (ΔHvap),
values were ∆Hr-n = −116.8 and −117.4 kJ mol−1, ∆ꢀ
̄
117.1 1.0 kJ mol−1. To assess the π-acceptor propertiesro-nf
dienophiles, the enthalpies of dissolution were determined
at 25◦C in π-donor solvents (Table 1). Three measurements
of dissolution enthalpy of π-acceptor were carried out
for each solvent. The relative error in the enthalpy of
dissolution did not exceed 1.0 kJ mol−1. The order of the
heat measurements was described earlier.30
3
RESULTS AND DISCUSSION
From the analysis of accumulated experimental data,
it follows that the change in the DAR rate is mainly
caused by the difference in the donor–acceptor prop-

4
KISELEV et al.
S C H E M E 2 Reactions of cyclopentadiene (4) and 9,10-dimethylanthracene (6a) with 2,3-dicyano-1,4-benzoquinone (10) and
N-phenylimide-1,4-benzoquinone-2,3-dicarboxylic acid (11)
TA B L E 1 Enthalpies of dissolution (ΔHsol) of several π-acceptors in a series of π-donor solvents and differences in their enthalpies of
solvation with respect to o-xylene, δHsol/kJ mol−1 s
а
ΔHsol/δHsol
π-Acceptors
Tetracyanoethylene
2,3-Dicyano-1,4-benzoquinone
Tetrachloro-1,4-benzoquinone
N-phenylimide 1,4-
benzoquinone-2,3-dicarboxylic
acid
o-Xylene
1.4/0
2.1/0
9.2/0
6.4/0
Toluene
9.7/8.3
6.3/4.2
12.6/3.4
9.9/3.5
Benzene
14.9/13.5
10.3/8.2
16.7/7.5
Chlorobenzene
23.0/21.6
15.7/13.6
18.0/8.8
12.7/6.3
10.7/4.3
1,3,5-Trinitrobenzene
4-Phenyl-1,2,4-triazoline-3,5-
dione
5.9/0
18.0/0
7.5/1.6
18.3/0.3
9.6/3.7
20.6/2.6
10.9/5.0
21.8/3.8
Maleic anhydride
1,4-Benzoquinone
15.1/0
16.3/0
16.4/1.3
16.4/0.1
16.9/1.8
17.1/0.8
18.4/3.3
17.6/1.3
аThe data for 10, 11 were obtained in this work, the rest are taken from Ref. 29.
enthalpy of nonspecific (ΔHnonsp) and specific (ΔHsp) sol-
It can be expected that the energy of nonspecific solva-
tion of a compound in the series of alkylbenzenes differs
insignificantly.31 The enthalpy of vaporization of the π-
acceptor is a constant for a series of data taken at the same
vation (Equation 1):
Δꢀsol = Δꢀvap + Δꢀnonsp + Δꢀsp
(1)

KISELEV et al.
5
F I G U R E 1 Comparison of changes in the enthalpies of dissolution (δHsol = δHsp) of π-acceptors with changes in the enthalpies of
dissolution of tetracyanoethylene (line 8, R2 = 1.000): 2,3-dicyano-1,4-benzoquinone (line 7, R2 = 0.997); tetrachloro-1,4-benzoquinone (line 6,
R2 = 0.970); N-phenylimide-1,4-benzoquinone-2,3-dicarboxylic acid (line 5, R2 = 0.982); 1,3,5-trinitrobenzene (line 4, R2 = 0.986);
4-phenyl-1,2,4-triazoline-3,5-dione (line 3, R2 = 0.942); maleic anhydride (line 2, R2 = 0.995); 1,4-benzoquinone (line 1, R2 = 0.948)
temperature. Therefore, the relative change in the energy
Hence, it follows that the introduction of the imide
of specific interaction (δHsp) can be determined from
group in (11) instead of two cyano groups in (10) leads to
the change in the enthalpy of dissolution (δHsol = ΔHsol
,
a more than twofold decrease in the energy of the donor–
acceptor interaction in (11) as compared with dienophile
10.
S-ΔHsol So
,
= δHsp) of the π-acceptor in these π-donor
solvents. ΔHsol So is the enthalpy of dissolution of π-
,
acceptor in o-xylene, ΔHsol,S is the enthalpy of dissolution
of π-acceptor in π-donor solvents (o-xylene, toluene, ben-
zene, chlorobenzene). The data on the heat of dissolution
of π-acceptors in a series of substituted benzenes are
collected in Table 1. This table shows both the absolute
enthalpies of dissolution (ΔHsol), and the value relative
to that measured in o-xylene, which, as discussed above,
can equivalently be identified as the change in the energy
of specific interaction of the π-acceptor with the solvent
(δHsol).
3.1
Kinetics of reactions involving
2,3-dicyano-1,4-benzoquinone and
N-phenylimide-1,4-benzoquinone-2,3-
dicarboxylic
acid
The obtained kinetic parameters for the DAR of some
dienes with dienophiles 10 and 11 are collected in
Table 2.
An enormous rate of cycloaddition at the C2═C3 bond
of dienophile 10 is observed in reactions with quadricy-
clane (7) (36.9), 9,10-dimethylanthracene (6a) (235), and
cyclopentadiene (4) (457 L mol−1 s−1, Table 2).
It was shown that the reaction rate of the quadricy-
clane at the activated C2═C3 bond of the highly acceptor
dienophile 10 (entry 4, Table 2) is 2.7 × 106 times higher
than at the remaining С5═С6 bond in the monoadduct.
From Table 2, it follows that the enthalpy of activation in
the reaction of cyclopentadiene at С5═С6 of the bond of
the monoadduct (entry 2) (34.5 kJ mol−1) is close to the
The data of Table 1 are plotted in Figure 1, which shows
the relative interaction energies of the various π-acceptors
when normalized to those obtained for tetracyanoethy-
lene. Taking the value for tetracyanoethylene as 100%,
the changes in the enthalpy of dissolution of π-acceptors
in the studied series of π-donor solvents are arranged in
terms of the interaction energy in the following order:
tetracyanoethylene, 100%; 2,3-dicyano-1,4-benzoquinone,
64%; tetrachloro-1,4-benzoquinone, 43%; N-phenylimide-
1,4-benzoquinone-2,3-dicarboxylic acid, 28%; 1,3,5-
trinitrobenzene, 24%; 4-phenyl-1,2,4-triazoline-3,5-dione,
19%; maleic anhydride, 15%; 1,4-benzoquinone, 6%.

6
KISELEV et al.
TA B L E 2 Rate constants (k2/L mol−1 s−1), enthalpy (∆H≠/kJ mol−1), entropy (∆S≠/J mol−1 K−1), and free activation energies (∆G≠/kJ
mol−1) of the Diels–Alder reaction of some dienes with 2,3-dicyano-1,4-benzoquinone (10) and N-phenylimide
1,4-benzoquinone-2,3-dicarboxylic acid (11) in 1,2-dichloroethane at 25◦C
N
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
Reaction
4+10
k2 (оС)
457/25
0.0103/15
0.0119/25
36.9/25
0.16/25
235/25
24/25
5.5 × 104/25
104.3/20
2810/25
92,700/25
∆H≠
5.1
34.5
38.1
10.5
−∆S≠
∆G≠
57.9
83
84.3
66.8
507/35
0.0185/25
–
–
554/45
0.0280/35
177
163
155
4+14a
4+933
7+1032
6b+10
6a+10
6b+11
6a+11
7+123
50.8/44.4
304/45
189
–
7.9
173
59.4
5.4 × 104/35
5.4 × 104/45
−0.8
18.0
11.9
170
145
138
179
49.0
61.2
55.4
44.6
–
–
–
–
–
–
6a+119
6a+119
−8.7
aReaction with formation of bisadduct.
enthalpy of activation in the reaction of cyclopentadiene
with 1,4-benzoquinone (9) (35 kJ mol−1).33 The compari-
son of the activity of dienophiles 10 and 11 is of particu-
lar interest. Despite the fact that the energy of the donor–
new bonds. The stabilization energy during the interaction
of reagent orbitals lowers this barrier.1 Therefore, with
moderate π-acceptor properties of dienophile 11 (Table 1),
its increased activity (Table 2) can be explained by the
easier rupture of the strained C2=C3 π-bond in bicyclic
dienophile 11. If this assumption is true, then the increased
structural tension should manifest itself in a difference
enthalpy of DAR of cyclopentadiene (4) with monocyclic
(10) and bicyclic dienophile (11) (Equations 2–4).
acceptor interaction of dienophile 11 with π-donors was
low (Figure 1), the reaction rate (6a+11) was determined
by the stopped-flow method only at low reagent concen-
trations (∼10−4 M), (entry 8, Table 2). The rate constant
of the reaction 6а+11 by С2═С3 bond of the dienophile
(5.5 × 104) turned out to be 255 times greater than in the
reaction by С2═С3 bond of dienophile 10 (235 L mol−1 s−1).
A similar ratio of these rate constants (150) was obtained
for the reactions of quinones 10 and 11 with anthracene
(6b) (Table 2). It can be noted that for reaction 6а+11 the
energy of partial breaking of π-bonds in the activated com-
plex is completely compensated by the energy of partial
formation of new σ-bonds and by the contribution of the
energy of orbital interaction, leading to a zero value of the
activation enthalpy and with the normal value of the acti-
vation entropy (Table 2).
Δꢀr−n 4+11 = ꢁp 11 + ꢁp 4 − 2ꢁC−C
(2)
(3)
(4)
(
)
(
)
( )
Δꢀr−n 4+10 = ꢁp 10 + ꢁp 4 − 2ꢁC−C
(
)
(
)
( )
ΔΔꢀr−n ≈ ꢁC=C 10 − ꢁC=C(11) ≈ ꢁp 10 − ꢁp 11
(
)
(
)
(
)
The data of our calorimetric measurements of the
reactions confirm that the exothermicity of the reaction
4+11→16 (−117 kJ mol−1) is significantly higher than for
the reaction 4+10→14 (−79.4 kJ mol−1). It can be assumed
that the rupture energy of Eπ(11) is 37 kJ mol−1 less than of
E
π(10). The data obtained allow us to assert that in the case
3.2
Calorimetry of reactions of
of DAR with dienophiles 10 and 11 the difference in the
reaction rates is controlled by the difference in the cleav-
age energy of π-bonds.
2,3-dicyano-1,4-benzoquinone and
N-phenylimide-1,4-benzoquinone-2,3-
dicarboxylic acid with
cyclopentadiene
4
CONCLUSION
Evans and Polanyi suggested that the activation barrier is
formed by the balance of the energy of breaking old bonds
and the formation of new ones.34 Usually, the contribution
of the bond breaking energy in the value of the activation
energy is greater than the subsequent formation energy of
The work clearly shows that the reagents, even with
reduced energy of donor–acceptor interaction, can exhibit
a sharply increased activity in the DAR due to the easier

KISELEV et al.
7
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breaking of π-bonds entering into the reaction. This differ-
ence can be estimated from the difference in the enthalpy
of reactions of monocyclic 2,3-dicyano-p-benzoquinone
(10) (−79.4 kJ mol−1
)
and bicyclic dienophile,
N-phenylimide-1,4-benzoquinone-2,3-dicarboxylic acid
(−117.1 kJ mol−1) with the same diene, cyclopentadiene.
The cleavage energy of the π-bond of dienophile 11 is
reduced by 37.7 kJ mol−1 in comparison with dienophile
10 and this is the main reason for their unusual kinetic
behavior.
AC K N OW L E D G M E N T
This work was funded by the subsidy allocated to Kazan
Federal University for the state assignment in the sphere
of scientific activities, grant No. 0671-2020-0061.
C O N F L I C T O F I N T E R E S T
The authors declare no conflict of interest.
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DATA AVA I L A B I L I T Y S TAT E M E N T
Research data are not shared.
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Vladimir D. Kiselev https://orcid.org/0000-0002-2039-
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How to cite this article: Kiselev VD, Kolesnikova
AO, Shulyatiev AA, Dinikaev IF, Kornilov DA.
Sharp difference in the rate of formation and
stability of the Diels-Alder reaction adducts with
2,3-dicyano-1,4-benzoquinone and
N-phenylimide-1,4-benzoquinone-2,3-dicarboxylic
acid. Int J Chem Kinet. 2021;1-8.
https://doi.org/10.1002/kin.21534