Kinetics and thermochemistry of the [2π+2σ+2σ]-cycloaddition of quadricyclane with 2,3-dicyano-1,4-benzoquinone

Article abstract of DOI:10.1002/kin.21264

Two-stage [2π+2σ+2σ]-cycloaddition of quadricyclane (2) with 2,3-dicyano-1,4-benzoquinone (1) with a huge difference in the activity of two reaction centers has been studied. In the first stage (kinetic control), the cycloaddition of 2 takes place on the activated С₂=С₃ bond of 1 to form the monoadduct 3, and in the second stage the cycloaddition of 2 on the С₅=С₆ bond of the monoadduct 3 occurs by 6 orders of magnitude lower with the formation of bisadduct 4. The structures of adducts 3 and 4 have been proved by NMR data and the X-Ray method, respectively. The kinetics of the first and second stages, the enthalpy of dissolution of 1 in the π-donor solvents, and the enthalpy of the reaction 1+2→3 have been measured.

Full text of DOI:10.1002/kin.21264

Received: 29 December 2018
DOI: 10.1002/kin.21264
Accepted: 6 March 2019
A R T I C L E
Kinetics and thermochemistry of the [2ꢀ+2ꢁ+2ꢁ]-cycloaddition
of quadricyclane with 2,3-dicyano-1,4-benzoquinone
Dmitry A. Kornilov1
Oleg V. Anikin1
Anastasia O. Kolesnikova1
Maxim V. Bermeshev2
Aidar T. Gubaidullin3
Vladimir D. Kiselev1
1Butlerov Institute of Chemistry, Kazan
Federal University, Kazan, Russia
Abstract
Two-stage [2ꢀ+2ꢁ+2ꢁ]-cycloaddition of quadricyclane (2) with 2,3-dicyano-1,4-
benzoquinone (1) with a huge difference in the activity of two reaction centers has
been studied. In the first stage (kinetic control), the cycloaddition of 2 takes place on
the activated С2=С3 bond of 1 to form the monoadduct 3, and in the second stage
the cycloaddition of 2 on the С5=С6 bond of the monoadduct 3 occurs by 6 orders of
magnitude lower with the formation of bisadduct 4. The structures of adducts 3 and 4
have been proved by NMR data and the X-Ray method, respectively. The kinetics of
the first and second stages, the enthalpy of dissolution of 1 in the ꢀ-donor solvents,
and the enthalpy of the reaction 1+2→3 have been measured.
2Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences,
Moscow, Russia
3Arbuzov Institute of Organic and Physical
Chemistry, FRC Kazan Scientific Center of
RAS, Kazan, Russia
Correspondence
Vladimir D. Kiselev, ButlerovInstituteof
Chemistry, KazanFederal University, Kazan
420008, Russia.
Email:vkiselev.ksu@gmail.com
K E Y W O R D S
[2ꢀ+2ꢁ+2ꢁ]-cycloaddition, quadricyclane,2,3-dicyano-1,4-benzoquinone, rate constant, reaction heat
1,2,4-triazoline-3,5-dione (8) (–255.1 kJ⋅mol−1) in compar-
1
INTRODUCTION
ison with all known cycloaddition reactions.9,10 So we can
The unusual combination of the high strain energy (328
expect a sufficiently high stability of monoadduct 3 in the
reaction 1+2→3.
kJ⋅mol−11)1 of quadricyclane (2) (tetracyclo[3.2.0.02,704,6]-
−6
heptane) and its high thermal stability (k
= 9.6 × 10
In this paper, we have established that the cycloaddition of
quadricyclane (2) to 2,3-dicyanobenzoquinone (1) is a two-
stage process: in the first stage, the cycloaddition 1+2→3 pro-
ceeds very fast at С2=С3 reaction center of dienophile 1. Fur-
ther, very slow addition of 2 at inactivated С5=С6 bond of
monoadduct, 3+2→4, takes place (Scheme 1). The structures
of adducts 3 and 4 have been proved by NMR data and the X-
Ray method, respectively. The kinetic data of the first and sec-
ond stages, the enthalpy of reaction 1+2→3, and ꢀ-acceptor
properties of 1 have been studied.
dec.
−1
о
s
at 140 С2)2 has attracted the attention of researchers.
A large amount of data on the synthesis of [2ꢀ+2ꢁ+2ꢁ]
adducts of quadricyclane with a wide range of dienophiles
have been accumulated,3–7 but only few quantitative kinetic
and thermochemical measurements were carried out for the
reactions involving 2 and no data were available for the
reactions involving 1. Quadricyclane has a low ionization
potential (7.40 eV),8 which promotes the fast formation of
adducts with strong ꢀ-acceptor dienophiles in the cycloaddi-
tion reactions.9,10 For 2,3-dicyano-1,4-benzoquinone, a high
ꢀ-acceptor property should be expected. A huge difference
in the enthalpy of C7H8 isomers formation, quadricyclane
(339.1), norbornadiene (247.6), and cycloheptatriene (183.7
kJ⋅mol−1)7, indicate an increased strain energy in quadricy-
clane, which should be released significantly by opening of
two cyclopropane moieties in 2 during the adduct formation.
This is the reason of a record enthalpy of the reactions of
2 with tetracyanoethylene (5) (–236.1) and with 4-phenyl-
2
EXPERIMENTAL
2.1 Materials
Quadricyclane 2 was synthesized from norbornadiene by
the known method,11 dried with metallic sodium and dis-
tilled twice under reduced pressure (600 Pa). Its purity was
Int J Chem Kinet. 2019;1–7.
wileyonlinelibrary.com/journal/kin
© 2019 Wiley Periodicals, Inc.
1

2
KORNILOV ET AL.
SCHEME 1 Two stage reaction of quadricyclane (2) with 2,3-dicyanobenzoquione (1) with the formation of mono- (3) and bisadduct (4)
× 0.47 × 0.67 mm3, M = 391.86, monoclinic, a = 6.5182(5)
determined at the titration by known concentration of a red
solution of tetracyanoethylene (5) in toluene. The rate con-
stant of norbornadiene as the possible admixture in reac-
◦
˚
˚
˚
A, b = 23.8420(18) A, c = 11.7391(9) A, 훽 = 94.061(5) ,
3
˚
V = 1819.8(2) A , T = 100(2) K, space group P21/n, Z = 4,
−5
−1 12
tion with tetracyanoethylene (1.3 × 10 L⋅mol−1⋅s
)
is
휇(Mo K훼) = 0.233 mm−1, 휌 = 1.430 g⋅cm–3, F(000) = 820,
calc
◦
7 orders of magnitude lower than the rate constant of reac-
tion (2+5) (104.4 L⋅mol−1⋅s−1),10 therefore only quadricy-
clane participates in titration. The purity of 2 was 97
0.5%. 2,3-Dicyano-1,4-benzoquinone (1) was obtained by
oxidation of 2,3-dicyanohydroquinone (98%; Sigma-Aldrich,
theta range for data collection 3.42–27.09 , 23,372 reflections
measured, 3815 independent reflections (Rint = 0.0772), 259
parameters, two restraints. Final indices: R = 0.0444, wR =
1
2
2
0.0895 (2284 reflections with I > 2ꢁI), R = 0.0999, wR =
1
0.1097 (all data), GoF = 0.986, largest difference in peak and
◦
–3
˚
Steinheim, Germany) with nitrogen oxide at 0 C. Quinone 1,
hole (0.255 and –0.267 eA ).
◦
◦
◦
m.p. 181–183 C (182–183 C),13 was sublimed (110 C, 10
Pa) before the measurements. All solvents were purified by
known methods.14
Crystallographic data for the structure 4 has been deposited
in the Cambridge Crystallographic Data Centre as supple-
mentary publication number CCDC 1878601. Copies of the
data can be obtained free of charge upon application to CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (fax: 44(0)1223
336033 or e-mail: deposit@ccdc.cam.ac.uk).
Monoadduct 3, 4,7-dioxotetracyclo[8.2.17,1002,903,8]tride-
cene-3,8-dicarbonitrile, was obtained as white crystals from
benzene, m.p. 242–243 C (with decomposition). 1H and 13
C
◦
NMR spectra were recorded on a spectrometer Bruker Avance
1
о
400. H NMR spectrum (400 MHz, CDCl3, 25 C), 훿, ppm:
2.2 Kinetic measurements
2
2
1.84 (d, J
= 11.6 Hz, 1H); 2.38 (s, 2H); 2.47 (d, J
= 11.6 Hz,H1HH); 3.33 (s, 2H); 6.16 (br s, 2H); 7.01 (s, 2H).
HH
The rate of the fast reaction 1+2→3 was measured by
the stopped flow method (spectrophotometer Cary 50 Bio
with RX 2000 attachment) in 1,2-dichloroethane at 25.0 and
13C NMR spectrum (100 MHz, CDCl3, 25 C), 훿, ppm: 42.19;
о
43.62; 44.42; 45.99; 112.83; 136.76; 139.95; 185.04.
Bisadduct 4, 4,13-dioxoheptacyclo[14.2.1.17,1002,1503,14
05,1206,11] icosa-8,17-diene-3,14-dicarbonitrile, was obtained
◦
44.4 C. The reaction was monitored by a change in absorp-
tion of 2,3-dicyano-1,4-benzoquinone (1) at 440 nm, where
compounds 2 and 3 are optically transparent. The initial con-
◦
as colorless crystals from benzene, m.p. 330 C (with decom-
−2
−2
position). The X-ray diffraction data of adduct 4 were col-
lected on a Bruker Kappa Apex II CCD diffractometer in
the 휔 and 휑-scan modes using graphite monochromated Mo
centrations of 1 and 2 were 2.57 × 10 and 4.47 × 10
mol⋅L−1, respectively. The slow reaction rate of 2+3→4 was
◦
measured in 1,2-dichloroethane at 25 and 45 C (spectropho-
˚
K훼 (휆 = 0.71073 A) radiation at 100(2) K. Data were cor-
tometer Hitachi U-2900). The course of the reaction was mon-
rected for the absorption effect using the SADABS program.15
The structure was solved by the direct method and refined
by the full matrix least-squares using SHELXTL16 and
WinGX17 programs. All non-hydrogen atoms were refined
anisotropically. The hydrogen atoms were inserted at calcu-
lated positions and refined using a “riding” model. Data col-
lections: images were indexed, integrated, and scaled using
the APEX218 data reduction package. Analysis of the inter-
molecular interactions was performed using the program
PLATON19. Mercury program20 package was used for fig-
ures’ preparation.
itored by the change of monoadduct 3 absorption at 368 nm,
where the compounds 2 and 4 are optically transparent. The
−1
initial concentrations of 2 and 3 were 2.0 and 0.075 mol⋅L
,
respectively. The relative standard errors of the rate constants
did not exceed 3%.
2.3 Calorimetric measurements
To estimate the ꢀ-acceptor properties of 1, the enthalpies of
◦
dissolution of 1 were determined at 25 C in ꢀ-donor solvents,
chlorobenzene, benzene, toluene, and o-xylene using a differ-
ential calorimeter as described earlier.21 The sample of 1 was
placed in a small stainless steel cylinder, the base and top of
Crystallographic data for compound 4: C22H18N2O2,
*0.5(C2H4Cl2), (C23H20ClN2O2), colorless prism, size 0.07

KORNILOV ET AL.
3
F I G U R E 1 Two projections of bisadduct 4 molecule in the crystal with a partial atomic numbering scheme. Non-hydrogen atoms are
represented by thermal vibration ellipsoids (p = 50%), hydrogen atoms are spheres of arbitrary radius (A) and (B) omitted for clarity. Some of bond
lengths in the molecule: C21 N21 1.150(3), C22 N22 1.144(3), C4 O4 1.204(3), C13 O13 1.207(3), C2 C15 1.554(3), C2 C3 1.574(3), C3 C21
˚
1.455(3), C3 C4 1.540(3), C4 C5 1.500(3), C5 C6 1.547(3), C6 C7 1.547(3), C7 C8 1.521(3), C7 C20 1.545(3), C8 C9 1.326(3) A. [Color figure can
be viewed at wileyonlinelibrary.com]
which were closed with the thin (0.1 mm) round Teflon gas-
kets and tightly screwed onto the lid. After achieving thermal
equilibrium, the Teflon films were cut out with a razor blade.
Three measurements of enthalpy of dissolution were made for
formally possesses 12 chiral centers, and the analysis of their
relative configuration by the PLATON program led to the fol-
lowing configuration of the molecule: C1 – S, C2 – R, C3 –
S, C5 – S, C6 – R, C7 – S, C10 – R, C11 – S, C12 – R, C14
– R, C15 – S, and C16 – R. Given that the compound 4 crys-
tallizes in the centrosymmetric space group P21/n, it should
be borne in mind that the crystal also contains the molecules
with reverse configuration of chiral centers.
each solvent. The relative error of the dissolution enthalpy was
−1
less than 1.0 kJ⋅mol
.
The heat of reaction 1+2→3 was determined by adding
crystals of 1 to a solution of excess 2 in toluene. The enthalpy
of the reaction in toluene (–182.2 1.0 kJ⋅mol−1) was deter-
mined taking into account the dissolution enthalpy of 1 in
toluene (6.3 1.0 kJ⋅mol−1).
In the absence of classical hydrogen bonds, the main types
of the structure-forming interactions in the crystal of 4 are pre-
sented by the intermolecular C–H⋅⋅⋅O and C–H⋅⋅⋅N hydrogen
bonds, the combined effect of which leads to the formation
of two-dimensional supramolecular structures—corrugated
H-layers of molecules lying in the crystallographic plane
0ac (Figure 2A). Parallel stacking of such two-dimensional
structures along the crystallographic direction 0b is car-
ried out in such a way that only Van der Waals interac-
tions are carried out between them (Figure 2B). Solvate
molecules of dichloroethane are located in the linear pseudo-
cavities, formed of fragments of four neighboring bisadduct
4 molecules in a checkerboard pattern (Figure 2C), with the
3
RESULTS AND DISCUSSION
3.1 X-Ray diffraction data
The structure of 4,13-dioxoheptacyclo[14.2.1.17,1002,1503,14
05,1206,11]icosa-8,17-diene-3,14-dicarbonitrile 4 was unam-
biguously confirmed by the single-crystal X-ray experiments.
According to the data obtained, the molecule 4 is symmetric
and has its own plane of symmetry, but loses it in the crys-
tal and is in the general position of the monoclinic unit cell
(Figure 1). On the contrary, solvated dichloroethane molecule
is located at the center of symmetry, so that in the indepen-
dent part of the unit cell one bisadduct 4 molecule and half of
the dichloroethane molecule are located. Bond lengths in the
molecule 4 are in the range of standard values of bond lengths,
and no significant deviations from them are observed, with the
exception, perhaps, of three C–C bonds: C6–C11, C5–C12,
and C3–C14, the values of which are 1.567(3), 1.580(3), and
˚
distances 4.1 A between centers of Cl atoms of neighboring
solvate molecules.
With such mutual packing of the molecules in the crystal,
there are practically no voids potentially accessible for the sol-
vent, and calculated packing index of the molecules, equal
to 0.727, approaches to the upper limit of the range charac-
teristic of crystals of organic compounds (0.65–0.75).22 We
emphasize that the structure-forming interactions lead to the
formation of two-dimensional layer structures located along
the two shortest distances of the unit cell. The absence of sig-
nificant interactions along the third direction seems to imply
the least stable direction in the crystal, along which we should
expect the destruction of the crystal at the initial stages of this
process.
˚
1.607(3)A—this is noticeably higher than the standard C–C
single bond for sp3-hybridized atoms. One of the reasons for
the observed values can be a rather stressed state of atoms
in the rigid carbon frame formed. A bisadduct 4 molecule

4
KORNILOV ET AL.
F I G U R E 2 Three projections of the crystal packing in 4: (A) H-layers, view along 0b, solvent molecules omitted for clarity, C–H⋅⋅⋅O,
C–H⋅⋅⋅N interactions are shown by dashed lines; (B) crystal packing view along 0c axis; (C) view along 0a axis. Solvent molecules are shown in the
“space-fill” model. Some of bisadduct 4 molecules, belonging to the same H-layers, are shown in “ball-and-stick” or “space-fill” model styles.
[Color figure can be viewed at wileyonlinelibrary.com]
SCHEME 2 ꢀ-Acceptors used in the calorimetric analysis
TA B L E 1 Comparison of the enthalpy of dissolution (ΔHdissol, kJ⋅mol−1) of some ꢀ-acceptors in ꢀ-donor solvents at 25 C
◦
ꢀ-Acceptor
o-Xylene
1.4
Toluene
9.7
Benzene
14.9
10.3
16.7
9.6
Chlorobenzene
Tetracyanoethylene (5)
23.0
15.7
18.0
10.9
21.8
18.4
17.6
2,3-Dicyano-1,4-benzoquinone (1)a
Tetrachloro-1,4-benzoquinone (6)
1,3,5-Trinitrobenzene (7)
2.1
6.3
9.2
12.6
7.5
5.9
4-Phenyl-1,2,4-triazoline-3,5-dione (8)
Maleic anhydride (9)
18.0
15.1
16.3
18.3
16.4
16.4
20.6
16.9
17.1
1,4-Benzoquinone (10)
aData of this work, the others from Ref. 23.
2,3-dicyano-1,4-benzoquinone (1) is 휆
575 nm, E 2.15
3.2 Calorimetric data
max
c.t.
eV, and with tetracyanoethylene (5) is 휆max 538 nm, Ec.t. 2.30
eV, both in 1,2-dichloroethane. These data predict the greater
ꢀ-acceptor property and activity of dienophile 1. The dif-
ference in the interaction energy of ꢀ,ꢀ-complexes can be
determined independently. The obtained values of dissolution
enthalpy of ꢀ-acceptors 1, 5–10 (Scheme 2) are presented in
Table 1.
Very high reactivity of tetracyanoethylene (5) in the cycload-
dition reactions12,23–26 can be explained by the high ꢀ-
acceptor value of 5 (EA = 2.88 eV [Ref. 27]). The ꢀ-acceptor
properties of dienophiles can be estimated by the difference of
the charge transfer energy of ꢀ,ꢀ-complexes with a convenient
ꢀ-donor, such as hexamethylbenzene28 or by the difference
of interaction energy with ꢀ-donors, obtained from the dis-
solution heat of dienophiles in ꢀ-donor aromatic solvents.23
The observed value of a maxima of the charge transfer
absorption bands of the hexamethylbenzene complex with
The change in the heat of dissolution of ꢀ-acceptors in
the studied series of ꢀ-donor solvents corresponds to the dif-
ference in enthalpies of the ꢀ,ꢀ-complexes in the following

KORNILOV ET AL.
5
1,2,4-triazoline-3,5-dione (8), 19%, r = 0.942; maleic anhy-
dride (9), 15%, r = 0.995; 1,4-benzoquinone (10), 6%, r =
0.948.
3.2 Rate constants of
[2ꢀ+2ꢁ+2ꢁ]-cycloaddition
The values of the rate constants of some fast and very slow
reactions are prsented in Table 2.
The reaction rate constants (ln k ) of a quadricyclane
2
(2) with tetracyanoethylene (2+5) (4.65), 2,3-dicyano-1,4-
benzoquinone (2+1) (3.61), 4-phenyl-1,2,4-triazoline-3,5-
dione (2+8) (–1.27), and with 1,4-benzoquinone (2+10) (–
12.6) change in the same order of ꢀ-acceptor properties that
follows from the data in Figure 3 (100, 64, 19, and 6%).
The rate constant of the reaction 1+2→3 at the 2,3-reaction
center is 2.7 × 106 times higher than that of 2 with the
monoadduct 3. This corresponds to a much higher elec-
trophilicity of С2=С3 carbon atoms in dienophile 1 com-
pared to С5=С6. Note, that 2 reacts only 20 times faster with
monoadduct 3 compared with 1,4-benzoquinone (10). The
stronger donor–acceptor pair, 9,10-dimethylanthracene (11)
(IP = 7.04 eV)29 and tetracyanoethylene (5) (EA = 2.88 eV)27
reacts faster than 2 (IP = 7.40 eV8)8 with 5 despite the huge
loss in the enthalpy of reaction (148 kJ⋅mol−1, Table 2). It can
be noted that the enthalpy and entropy of activations of the
reactions [2ꢀ+2ꢁ+2ꢁ]- (1+2) and [4ꢀ+2ꢀ]-cycloaddition
(1+11) are very close (Table 2).
F I G U R E 3 Correlations of the relative enthalpy of the
tetracyanoethylene (5) solvation [훿Hsolv(5) = ∆Hsolut.(5)/Si –
∆Hsolut.(5)/o-xylene] with that of 2,3-dicyano-1,4-benzoquinone (1),
tetrachloro-1,4-benzoquinone (6), 1,3,5-trinitrobenzene (7),
4-phenyl-1,2,4-triazoline-3,5-dione (8), maleic anhydride (9), and
1,4-benzoquinone (10). [Color figure can be viewed at
wileyonlinelibrary.com]
order (Figure 3): tetracyanoethylene (5), blank, 100%, corre-
lation coefficient, r = 1; 2,3-dicyano-1,4-benzoquinone (1),
64%, r = 0.997; tetrachloro-1,4-benzoquinone (6), 43%, r =
0.970; 1,3,5-trinitrobenzene (7), 24%, r = 0.986; 4-phenyl-
3.3 Enthalpies of [2ꢀ+2ꢁ+2ꢁ]-cycloaddition
Highly exothermic reactions often, but not always,29 go
faster. Typically, the enthalpies of the Diels–Alder reac-
TA B L E 2 The rate constants (k , L⋅mol−1⋅s−1), enthalpy (ΔH≠, kJ⋅mol−1) and entropy activation (ΔS≠, J⋅mol−1⋅K−1), and enthalpy (ΔH
,
r-n
2
kJ⋅mol−1) of some cycloaddition reactions
о
Reaction
k2 (Т/ С), solvent
∆H≠
−∆S≠
−∆Hr-n
(1+2)
36.9 (25), S1
10.5 1.2
179.7 4.0
182.2 0.8,
50.8 (44.4), S1
S2
−5
a
(3+2)
1.35 × 10 (25.0), S1
63.0 2.0
126.7 6.7
−5
7.11 × 10 (45.0), S1
−6
a
(10+2)
(1+11)b
3.41 × 10 (45.0), S1
–
–
235.0 (25.0), S1
7.9 1.3
172.9 4.3
–
304.1 (317.75 K), S1
(5+2)c
104.4 (293.15 K), S2
18.0 1.1
145.0 4.0
236.6 1.0,
S3
(5+11)d
(5+11)e
2810 (298.15), S2
92700 (24.9), S1
11.9
138.0
178.8
–
−8.7
88.3f
Solvents: S1, 1,2-dichloroethane; S2, toluene; S3, 1,4-dioxane; S4, dichloromethane
aVery low rate for the measurements of the reaction heat.
bReaction of 1 with 9,10-dimethylanthracene (11).
cFrom Ref. 10.
dFrom Ref. 29.
eFrom Ref. 26.
fFrom Refs. 24 and 29.

6
KORNILOV ET AL.
TA B L E 3 The enthalpy of reactions (ΔHr-n, kJ⋅mol−1) of
2,3-dicyano-1,4-benzoquinone (1), tetracyanoethylene (5) and
4-phenyl-1,2,4-triazoline-3,5-dione (8) with quadricyclane (2),
9,10-dimethylanthracene (11) and cyclopentadiene (12)
ACKNOWLEDGMENTS
This work was supported by the Russian Foundation for Basic
Research (Projects No 16-03-00071 and No 18-33-00063),
the Ministry of Education and Science of Russian Federa-
tion (Project No 4.6223.2017/9.10), and the research grant of
Kazan Federal University.
−∆Hr-n
ꢀ-Donor reagents
1
5
8
2
11
12
182.2
236.6a
88.3c
113c
255.1a
117.8c
134c
(∼50 5)b
(∼60 5)b
CONFLICT OF INTEREST
The authors hereby confirm they have no conflicts of interest.
aFrom Ref. 10.
bEstimated values.
cFrom Ref. 23.
ORCID
Vladimir D. Kiselev
https://orcid.org/0000-0002-2039-3265
−1 23,29
tion lie in the range from –50 to –200 kJ⋅mol
.
It
is useful to compare the enthalpy of the reactions of 2,3-
dicyano-1,4-benzoquinone (1), tetracyanoethylene (5), and 4-
phenyl-1,2,4-triazoline-3,5-dione (8) with the quadricyclane
(2), 9,10-dimethylanthracene (11), and cyclopentadiene (12)
(Table 3).
REFERENCES
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Since the difference in the reaction enthalpy of dienophiles
with common diene depends little on the nature of the
diene,23,30 we can estimate the reactions enthalpy of
2,3-dicyano-1,4-benzoquinone with 9,10-dimethylanthracene
2. Hammond GS, Turro NJ, Fischer A. Photosensitized cycloaddition
reactions1. J Am Chem Soc. 1961;83:4674–4675.
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Chem Soc. 1966;88:4273–4274.
(1+11) (∼–50
5) and with cyclopentadiene (1+12) (∼–
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60 5 kJ⋅mol−1). The exothermicity of the reaction (2+1)
−1
is 54 kJ⋅mol lower than that of reaction (2+5) and 72.9
−1
kJ⋅mol than that of reaction (2+8). So, the kinetic activ-
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4
CONCLUSION
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The difference in the energy of the charge transfer band in
ꢀ,ꢀ-complexes of hexamethylbenzene with 1 (휆 575 nm,
max
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E
2.15 eV) and with 5 (휆
538 nm, E 2.30 eV) in
max
1,2-dichloroethane corresponds to a lower lce.vt.el of LUMO
in 2,3-dicyano-1,4-benzoquinone than in tetracyanoethylene.
However, from the difference in the heat of dissolution in ꢀ-
donor solvents, it is necessary to conclude that 2,3-dicyano-
1,4-benzoquinone is inferior to tetracyanoethylene in the spe-
cific interaction with ꢀ-donors. This fact is confirmed by the
values of the rate constants of the reactions of tetracyanoethy-
lene and 2,3-dicyano-1,4-benzoquinone with strong electron
donors quadricyclane and 9,10-dimethylanthracene. The data
obtained make it possible to recommend quadricyclane for
carrying out the Diels–Alder reactions with C=C bonds of the
low-active and very high conjugated dienophiles. Similarly, to
conduct the reactions with the low-active and high conjugated
dienes, the most convenient partner should be 4-phenyl-1,2,4-
triazoline-3,5-dione.
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How to cite this article: Kornilov DA, Anikin OV,
Kolesnikova AO, Bermeshev MV, Gubaidullin AT,
Kiselev VD. Kinetics and thermochemistry of the
[2ꢀ+2ꢁ+2ꢁ]-cycloaddition of quadricyclane with 2,3-
dicyano-1,4-benzoquinone. Int J Chem Kinet. 2019;1–
7. https://doi.org/10.1002/kin.21264
24. (a) Kiselev VD, Konovalov AI, Kashaeva EA, Ustugov AN.
Heat of Diels-Alder reaction and reactivity of substituted
anthracenes in reaction with tetracyanoethylene. Russ J Org Chem.
1978;14:128–134; (b) Russ J Org Chem, Engl Transl. 1978;14:
128–134.