Mechanism of replacement of the nitro group and fluorine atom in meta-substituted nitrobenzenes by phenols in the presence of potassium carbonate

Article abstract of DOI:10.1007/s11178-005-0280-1

The relative mobilities of the nitro group and fluorine atom in 1,3-dinitrobenzene and 1-fluoro-3-nitrobenzene by the action of phenols in the presence of potassium carbonate in dimethylformamide at 95-125°C were studied by the competing reaction method. The rate constant ratios k(NO ₂)/k(F) were correlated with the differences between the corresponding activation parameters (ΔΔH^≠ and ΔΔS^≠). The greater mobility of the nitro group was found to be determined by the entropy control of the reactivity of arenes. The activation parameters (ΔH^≠ and ΔS^≠) were calculated, and the enthalpy-entropy compensation effect was revealed. The reaction mechanism is discussed.

Full text of DOI:10.1007/s11178-005-0280-1

Russian Journal of Organic Chemistry, Vol. 41, No. 7, 2005, pp. 978–983. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005,
pp. 999–1005.
Original Russian Text Copyright © 2005 by Khalfina, Vlasov.
Mechanism of Replacement of the Nitro Group and Fluorine
Atom in meta-Substituted Nitrobenzenes by Phenols
in the Presence of Potassium Carbonate
I. A. Khalfina and V. M. Vlasov
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
Received May 29, 2004
Abstract—The relative mobilities of the nitro group and fluorine atom in 1,3-dinitrobenzene and 1-fluoro-
3-nitrobenzene by the action of phenols in the presence of potassium carbonate in dimethylformamide at 95–
125°C were studied by the competing reaction method. The rate constant ratios k(NO2)/k(F) were correlated
with the differences between the corresponding activation parameters (ΔΔH≠ and ΔΔS≠). The greater mobility
of the nitro group was found to be determined by the entropy control of the reactivity of arenes. The activation
parameters (ΔH≠ and ΔS≠) were calculated, and the enthalpy–entropy compensation effect was revealed. The
reaction mechanism is discussed.
Nucleophilic aromatic substitution still remains
an extensively developing field of organic chemistry
[1, 2] due to diversity of mechanisms of these reactions
[1–4] and their wide synthetic potential [5–7]. Nucleo-
philic substitution of hydrogen (SNH) in arenes provides
an effective tool for their functionalization [1, 2, 8, 9],
though replacement of a nucleofugal group in aromatic
compounds is equally important. The latter process
makes it possible to obtain not only ortho or para
isomers but also meta-substituted derivatives with
high regioselectivity [1]. meta-Substituted arenes are
formed most readily by replacement of a halogen atom
(Cl, Br, I) in copper- and palladium-catalyzed reactions
[10] or of another readily departing group (such as
nitro group or fluorine atom) by nucleophilic species
generated in situ [11–13]. Systematic studies on such
reactions were initiated relatively recently [11–13] due
to wide prospects in further functionalization of the
substrates [11, 14].
energy parameters of the reaction, which provide some
information on the reaction mechanism, we studied the
relative mobilities of the nitro group in 1,3-dinitro-
benzene (I) and fluorine atom in 1-fluoro-3-nitroben-
zene (II) in reactions with phenols III–VI in DMF in
the presence of potassium carbonate (Scheme 1) at
different temperatures.
Scheme 1.
ArOH (III–VI), K2CO3
DMF, 95–125°C
O2N
X
O2N
OAr
I, II
VII–X
I, X = NO2; II, X = F; III, VII, Ar = 4-MeC6H4; IV, VIII,
Ar = Ph; V, IX, Ar = 4-ClC6H4; VI, X, Ar = 3-O2NC6H4.
We found that in the temperature range from 95 to
125°C the ratio of the rate constants for replacement
of the nitro group and fluorine atom k(NO2)/k(F) is
greater than unity and that it increases with rise in both
temperature and acidity of phenols (Table 1). For each
phenol III–VI, log[k(NO2)/k(F)] values are linearly
related to the reciprocal temperature 1/T (r ≥ 0.998,
Fig. 1). Using these relations we calculated the dif-
ferences between the apparent activation parameters
ΔΔH≠ and ΔΔS≠ according to the modified Eyring equa-
tion (Table 1). The ΔΔH≠ and ΔΔS≠ values are positive
and are linearly related to each other (r = 0.999). This
Studies on the kinetics of nucleophilic replacement
in meta-substituted nitrobenzenes by the action of
phenols in the presence of potassium carbonate have
shown that the dependences of the rate constant on the
temperature, reagent nature, and nucleofugality of the
leaving group differ considerably [12, 13, 15, 16] from
those found for analogous reactions with potassium
phenoxides [17–20]. With the goal of elucidating the
general relations between the reactant structure and
1070-4280/05/4107-0978 © 2005 Pleiades Publishing, Inc.

MECHANISM OF REPLACEMENT OF THE NITRO GROUP
979
Table 1. Rate constant ratios k(NO2)/k(F) for the replacement of nitro group and fluorine atom and differences in the
activation parameters for competing reactions of compounds I and II with phenols III–VI in the presence of K2CO3 in DMF
k(NO2)/k(F)a
Compound
ΔΔH≠,b kJ/mol
ΔΔS≠,b, c J mol–1 K–1
no.
98°C
110°C
120°C
125°C
1.06±0.02
1.08±0.01
1.12±0.04
1.90e, f
1.16±0.01
1.21±0.01
1.27±0.02
g1.79±0.01g
1.23±0.01
1.31±0.01
1.40±0.01
1.54±0.02
d1.03±0.01d
1.36±0.01
1.48±0.01
1.66±0.02
08.5±0.1
10.5±0.1
12.6±0.4
16.3±0.2
23.5±0.3
28.9±0.3
34.8±1.1
45.0±0.5
III
IV
V
VI
a
Average value from no less than two parallel runs.
b
ΔΔH≠ = ΔH≠(NO2) – ΔH≠(F); ΔΔS≠ = ΔS≠(NO2) – ΔS≠(F); calculated by the modified Eyring equation: log[k(NO2)/k(F)] = (–ΔΔH≠/T +
ΔΔS≠)/4.576.
At 98°C.
At 95°C.
At 137°C.
Data of [21].
At 132°C.
c
d
e
f
g
suggests that replacement of the nitro group in I by
each phenol is favored by the entropy factor and that
replacement of the fluorine atom in II is favored by the
enthalpy factor. As follows from Fig. 1, all competing
reactions with phenols III–VI are entropy-controlled
(ΔΔH≠ < TΔΔS≠) at a temperature exceeding 90°C.
It is known that isoselective relationship exists
when the isokinetic temperatures for two reaction
series are equal [26]. Therefore, the replacement of
both nitro group in I and fluorine atom in II by the
action of phenols III–VI in the presence of K2CO3
gives rise to isokinetic relationship with β = 361 K.
Insofar as an isokinetic series is characterized by the
equation [27]
Comparison of these results with those obtained
previously while studying competing reactions of 3,5-
dinitrobenzotrifluoride (XI) and 3-fluoro-5-nitrobenzo-
trifluoride (XII) with the same phenols (III–VI) in the
presence of K2CO3 in DMF [16] allowed us to estimate
the effect of the substrate electrophilicity on the rela-
tive mobilities of the nitro group and fluorine atom.
Analysis of the dependences log[k(NO2)/k(F)]—1/T
(Fig. 1) indicates similarity in the relations observed
for meta-substituted nitrobenzenes I and II, on the one
hand, and 3-nitrobenzotrifluorides XI and XII, on the
other. However, the sensitivity of log[k(NO2)/k(F)] to
temperature and reagent structure considerably in-
creases as the substrate electrophilicity rises.
–2.303RTρσ = (β – T)δΔS≠ = (1 – T/β)δΔH≠,
the activation parameters are linearly related to the
substituent constants σ in ArOH:
log[k(NO2)/k(F)]
VI
0.6
V
0.4
VI
IV
V
IV
III
III
0.2
0.0
As with compounds XI and XII [16], the com-
peting reactions of nitrobenzenes I and II with phenols
III–VI fit the Hammett and Brønsted dependences
log[k(NO2)/k(F)]—σ(pKa) (Table 2). Here, the positive
differences in the ρ values, Δρ = ρ(NO2) – ρ(F), and
negative differences in the Brønsted coefficients,
ρβNu = βNu(NO2) – βNu(F), are linear in 1/T (Table 3).
The data in Table 3 show that the isokinetic tem-
peratures β calculated from different dependences fall
into a narrow range; therefore, reactions of phenols
III–VI with compounds I and II can be regarded as
a reaction series for which isoselective relationship is
fulfilled [25].
–0.2
2.4
2.6
2.8
3.0
1/T×103, K–1
Fig. 1. Plots of log[k(NO2)/k(F)] versus 1/T for competing
reactions of compounds I and II with phenols III–VI in the
presence of K2CO3 in DMF (solid lines). For comparison,
analogous plots are given for competing reactions of com-
pounds XI and XII with the same phenols in the presence of
K2CO3 in DMF [16] (dashed lines).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 7 2005

KHALFINA, VLASOV
980
δΔS≠ = cσ and δΔH≠ = βcσ,
Table 2. Parameters of the Hammett and Brønsted equa-
tions log[k(NO2)/k(F)] = Δρσ + a and log[k(NO2)/k(F)] =
ΔβNu pKa + b for competing reactions of compounds I and II
with phenols III–VI in the presence of K2CO3 in DMFa
where c = –2.303RTρ/(β – T). Using our results and
previously reported data [15, 16] we can calculate
the parameters c and βc for each substrate in the
reaction with phenols III–VI in the presence of K2CO3
(Table 4). As follows from Table 4, these parameters
have large negative values reflecting a high sensitivity
of ∆H≠ and ∆S≠ to the substituent nature in ArOH; they
also depend on the nature of the leaving group and
substrate electrophilicity.
Using the activation parameters ∆H≠ and ∆S≠ deter-
mined previously for the reaction of compound I with
3,4-dimethylphenol (XIII) in DMF in the presence of
K2CO3 [15] and the values of c and βc (Table 4), we
calculated ∆H≠ and ∆S≠ for the reactions of I with
phenols III–VI (Table 5). The obtained data together
with the ∆∆H≠ and ∆∆S≠ values (Table 1) were then
used to determine the corresponding values for the
reactions of 1-fluoro-3-nitrobenzene (II) with the same
phenols (Table 5). Table 5 also contains the activation
parameters for the reactions of compounds XI and
XII with phenols III–VI in DMF in the presence of
K2CO3, which were calculated as described above
from ∆H≠ and ∆S≠ for the reaction of XII with
4-chlorophenol (V).
Temperature, °C
Parameter
98
110
120
125
0.129
0.133
0.993
0.005
–0.026–
0.627
0.995
0.004
Δρ
0.041
0.034
0.973
0.008
0.075
0.081
0.989
0.007
0.108
0.114
0.990
0.006
a
r
s
ΔβNu
–0.008– –0.015– –0.022–
0.191
0.978
0.008
0.369
0.992
0.006
0.531
0.993
0.005
b
r
s
The ratios k(NO2)/k(F) were taken from Table 1; σp– = –0.17
(4-Me), 0 (H), 0.19 (4-Cl), σm = 0.71 (3-NO2) [22]; pKa of
phenols in DMSO: 18.9 (III), 18.0 (IV), 16.75 (V), 14.4 (VI)
[23]; pKa values of phenols in DMF are related to pKa in DMSO
by the formula: pKa(DMF) = 1.56 + 0.96pKa(DMSO) [24].
a
Table 3. Isokinetic temperatures β calculated from different
dependencesa
Dependence
ΔΔH≠ = f(ΔΔS≠)
log[k(NO2)/k(F)] = f(1/T)
Δρ = f(1/T)
β, K
r
s
362±1
359±3
361±2
361±2
0.999
0.024
Our results are sufficiently reliable, as follows from
comparison of the calculated (Table 5) and experi-
mental [28] relative rate constants of the competing
reactions of compounds I and XI with 4-bromophenol
(XIV) in DMF in the presence of K2CO3 at 100°C:
k(XI)/k(I) = 148 and 151, respectively.
0.996
0.997
0.004
0.001
ΔβNu = f(1/T)
a
The values of ΔΔH≠ and ΔΔS≠ were taken from Table 1, and Δρ
and ΔβNu, from Table 2.
The observed general relations between structural
factors and activation parameters (Tables 1, 5) led us to
conclude that under the given conditions (β < T) the
kinetics of each reaction, as well as the effect of sub-
stituent in the substrate, are determined by the enthalpy
factors and that the effects of the leaving group in the
substrate and of the substituent in the reagent are deter-
mined by the entropy factors.
Table 4. Parameters of the δΔH≠ = βcσ and δΔS≠ = cσ
dependences for replacement of the nitro group in com-
pounds I and XI and fluorine atom in II and XII by the
action of phenols III–VI in the presence of K2CO3 in DMF
Parameter
c, J mol–1 K–1 βc, kJ/mol
Comp.
no.
ρ (tempera-
ture, K)
β, K
–1.638a (423) 361
–1.835b (423)
–0.675c (343) d322d
–0.809e (343)
–214
–240
–211
–253
–77
–87
–68
–81
I
The enthalpy and entropy of activation in the
replacement of nitro group and fluorine atom in meta-
substituted nitrobenzenes I, II, XI, and XII by the
action of phenols III–VI in the presence of K2CO3
range from 126 to 233 kJ/mol and from –18 to
255 J mol–1 K–1, respectively (Table 5). These data
contradict the concept involving formation of a σ-com-
plex in the framework of the classical SNAr mech-
anism [17]. On the other hand, the Gibbs energies
of activation for all the examined reactions (120–
II
XI
XII
a
Data of [15].
b
ρ(F) = ρ(NO2) – Δρ; Δρ = 0.197 at 423 K; calculated from the
dependence Δρ = f(1/T) (Table 3).
Data of this work.
ρ(F) = ρ(NO2) – Δρ; Δρ = 0.134 at 343 K [16].
Data of [16].
c
d
e
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 7 2005

MECHANISM OF REPLACEMENT OF THE NITRO GROUP
981
Scheme 2.
Fast
ArOH
+
K2CO3
ArOH·K2CO3
(1)
(2)
XV
XV
+
Ar'X
[ArOH·K2CO3]·Ar'X
A
A
[TS1]=/
R
–KHCO3
K+
ArOAr'
+
KX
X
(3)
O2N
[ArO– K+ ·KHCO3]·Ar'X
[TS2]=/
OAr
–KHCO3
σ-Complex
140 kJ/mol) approach the ∆G≠ range typical of SN
reactions of weakly activated arenes with charged O-
nucleophiles [17]. Figure 2 shows two compensation
(isokinetic) dependences, one of which corresponds to
the reactions with compounds I and II, and the other,
to the reactions with XI and XII.
ity between SN reactions of meta-substituted arenes
with phenols in the presence of K2CO3 and hetero-
geneous or enzymatic processes.
The existence of an isoselective relationship in-
dicates that the structure of complex A depends on the
substrate electrophilicity rather than on the nature of
the leaving group. In this case, the isotope effect, i.e.,
the dependence of the substitution selectivity in com-
peting reactions of compounds XI and XII with
phenols III and VI in the presence of K2CO3 at
70°C on the isotope composition of the reagent SH/SD
(Table 6), is controlled by stage (3).
It should be emphasized that anomalously broad
ranges of variation of the enthalpy and entropy of
activation, for which isokinetic relationship is fulfilled,
are typical of complex heterogeneous and enzymatic
catalytic reactions [29]. Therefore, we propose a re-
fined scheme for SN reactions of meta-substituted
arenes with phenols in the presence of K2CO3
(Scheme 2, cf. [16]). The first stage [reaction (1)] is
fast formation of complex XV [16] which then reacts
with substrate to give complex A via intermolecular
interactions [reaction (2)] (cf. [30]). Complex A under-
goes intramolecular transformation (either in a syn-
chronous mode through transition state TS1 or in
a stepwise mode through transition state TS2) leading
to σ-complex [reaction (3)]. According to the proposed
kinetic scheme, the apparent rate constant charac-
terizes the stage of formation of σ-complex and the
preceding stage. Taking into account the calculated
isokinetic temperatures which are typical of equilib-
rium formation of complexes like A [31], we presume
that the high sensitivity of the activation parameters to
the reagent structure is determined mainly by reaction
(2). Obviously, a necessary condition is the possibility
for complex XV to considerably change its geometry
upon interaction with Ar'X. We previously showed
[32] that reactions of phenols with potassium carbo-
nate in dipolar aprotic solvents give at least two types
of complexes, including (2ArOH)·K2CO3 for which
equilibrium structures were determined [32]. Presum-
ably, just the ability of the (2ArOH)·K2CO3 complex
to change its structure is responsible for some similar-
Thus analysis of empirical correlations found for
SN reactions of meta-substituted nitrobenzenes with
ΔH≠, kJ/mol
220
200
1
180
2
160
140
120
–50
0
50
100
150
200
250
ΔS≠, J mol–1 K–1
Fig. 2. Isokinetic relationships (ΔH≠ versus ΔS≠) for (1) nu-
cleophilic replacement of the nitro group in compound I and
fluorine atom in II (ΔH≠ = 0.36ΔS≠ + 141, r = 0.999, n = 8,
s = 0.3) and (2) analogous reactions of compounds XI and
XII (ΔH≠ = 0.32ΔS≠ + 132, r = 0.999, n = 8, s = 0.7) with
phenols III–VI in the presence of K2CO3 in DMF (the ΔH≠
and ΔS≠ values were taken from Table 5).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 7 2005

KHALFINA, VLASOV
982
Table 5. Activation parameters for replacement of the nitro
group in compounds I and XI and fluorine atom in II and
XII by the action of phenols III–VI, XIII, and XIV in the
presence of K2CO3 in DMF
phenols in the presence of K2CO3 revealed crucial role
of molecular organization of the reagents under the
conditions of nucleophile generation in situ (cf. [33]).
ΔH≠, kJ/mol ΔS≠, J mol–1 K–1
EXPERIMENTAL
Substrate
Phenol
Ia
233
228
215
200
160
195
220
205
187
144
212
201
190
154
184
197
183
168
126
255
240
204
163
052
150
217
175
128
007
250
215
178
066
162
205
162
114
0–18–
XIII
III
IV
The reaction mixtures were analyzed by GLC on
an LKhM-72 chromatograph equipped with a thermal
conductivity detector; 4000×4-mm column, stationary
phase 15% of SKTFT-803 on Chromaton-W; linear
oven temperature programming from 70 to 270°C at
a rate of 10 deg/min; carrier gas helium. The com-
ponents were quantitated by absolute calibration using
calibration curves and were identified by adding
authentic samples.
V
VI
XIV
III
IV
IIb
V
Commercial dimethylformamide was dried over
4-Å molecular sieves and was distilled over calcium
hydride under reduced pressure. Commercial phenols
III–VI were purified by standard procedures. Com-
mercial potassium carbonate of analytical grade was
dehydrated by heating in a muffle furnace for 3 h at
400°C, finely ground, and additionally dried by heat-
ing for 2 h at 150°C under reduced pressure (~5 mm).
Commercial 1,3-dinitrobenzene (I) and 1-fluoro-3-
nitrobenzene (II) were purified by standard proce-
dures. 3,5-Dinitrobenzotrifluoride (XI), mp 47–48°C,
and 3-fluoro-5-nitrobenzotrifluoride (XII), bp 67–
68°C (4 mm), were synthesized as described in [34];
their physical constants were in agreement with pub-
lished data. Deuterated phenols ArOD (III and VI)
were prepared by the procedure reported in [35]. Com-
pounds VII–X used as authentic samples were syn-
thesized as described in [21].
VI
XIc
III
IV
V
VI
XIVf
IIId
IVd
Ve
XII
VId
The ΔH≠ and ΔS≠ values for the reactions with 1,3-dinitro-
benzene (I) were calculated by the equations ΔH≠ = 233 – βcΔσ
and ΔS≠ = 255 – cΔσ, where 233 J/mol and 255 J mol–1 K–1 are
the corresponding activation parameters for the reaction of I with
3,4-dimethylphenol (XIII) [15], and Δσ is the difference between
the substituent constants in 3,4-dimethylphenol and phenols
III–VI [22].
a
The ΔH≠ and ΔS≠ values for the reactions with 1-fluoro-3-nitro-
benzene (II) were determined from the corresponding parameters
for compound I and ΔΔH≠ and ΔΔS≠ values (Table 1).
The ΔH≠ and ΔS≠ values for the reactions with compound XI
were determined from the sum of the activation parameters for
the reactions with XII and ΔΔH≠ and ΔΔS≠ values for competing
reactions of compounds XI and XII [16].
b
c
The general procedures for carrying out competing
reactions and treatment of the results were reported
previously [16, 28]. The data obtained for competing
reactions of compounds I and II with phenols III–VI
in DMF in the presence of DMF at 95–125°C are
given in Table 1. From the data obtained for competing
reactions of phenols III–VI with compound XI in the
presence of K2CO3 in DMF at 70°C [k(III)/k(IV) =
1.26±0.05, k(V)/k(IV) = 0.81±0.03, k(VI)/k(IV) =
0.32±0.02] we calculated ρ(NO2) = –0.675. From the
data obtained for competing reactions of compounds
II and XII with 4-chlorophenol (V) in the presence of
K2CO3 in DMF at 130–145°C [k(XII)/k(II) = 55±2,
130°C; 50±1, 135°C; 47±2, 140°C; 45±1, 145°C]
we calculated the differences in the enthalpies and
entropies of activation: δΔH≠ = ΔH≠(XII) – ΔH≠(II) =
–19 kJ/mol and δΔS≠ = ΔS≠(XII) – ΔS≠(II) =
–14 J mol–1 K–1. The data obtained for competing
The ΔH≠ and ΔS≠ values for the reactions of compound XII with
phenols III, IV, and VI were calculated by the equations ΔH≠ =
168 + βcΔσ and ΔS≠ = 114 + cΔσ, where 168 kJ/mol and
114 J mol–1 K–1 are the corresponding activation parameters for
the reaction of XII with phenol V, and Δσ is the difference
between the substituent constants in 4-chlorophenol (V) and
phenols III, IV, and VI.
d
The ΔH≠ and ΔS≠ values for the reaction of compound XII with
phenol V were determined from the sum of the activation param-
eters for the reaction with II and δΔH≠ and δΔS≠ values (see
Experimental).
e
f
The ΔH≠ and ΔS≠ values for the reaction of compound XI with
4-bromophenol (XIV) were extrapolated from the dependences
ΔH≠ = f(σ) and ΔS≠ = f(σ) for the reactions of XI with phenols
III–VI.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 7 2005

MECHANISM OF REPLACEMENT OF THE NITRO GROUP
983
Table 6. Isotope effect on the selectivity of replacement of
the nitro group and fluorine atom (SH/SD) in reactions of
compounds XI and XII with phenols III and VI in the
presence of K2CO3 at 70°C in DMF
15. Dorogov, M.V., Doctoral (Chem.) Dissertation,
Yaroslavl, 1998.
16. Khalfina, I.A. and Vlasov, V.M., Russ. J. Org. Chem.,
2002, vol. 38, p. 47.
Comp.
no.
17. Miller, J., Aromatic Nucleophilic Substitution, Am-
sterdam: Elsevier, 1968; Gomes, P.C.B., Vichi, E.J.S.,
Moran, P.J.S., Neto, A., Maroso, M.L., and Miller, J.,
Organometallics, 1996, vol. 15, p. 3198.
SH = kH(NO2)/kH(F)a SD = kD(NO2)/kD(F)b SH/SD
1.05±0.05
1.38±0.02
0.84±0.01
1.26±0.03
1.25
1.10
III
VI
18. Bazzano, F., Mencarelli, P., and Stegel, F., J. Org.
Chem., 1984, vol. 49, p. 2375.
a
Data of [16].
Average value from at least two parallel runs.
b
19. Takeda, M., Karatsuma, I., Tao, K., and Manabe, O.,
Nippon Kagaku Kaishi, 1991, p. 139; Chem. Abstr.,
1991, vol. 114, no. 142406.
reactions of compounds XI and XII with deuterated
phenols ArOD (III, VI) in the presence of K2CO3 in
DMF are given in Table 6.
20. El-Bardan, A.A., J. Phys. Org. Chem., 1999, vol. 12,
p. 347.
21. Khalfina, I.A. and Vlasov, V.M., Russ. J. Org. Chem.,
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