Cyclopropyl- and allyl-substituted arenes in reaction with dinitrogen tetroxide. Effect of substrate oxidation potential on reaction direction

Article abstract of DOI:10.1023/B:RUJO.0000045888.43245.d7

A correlation was found between oxidation potentials of acylcyclopropanes in solution (in CH₂Cl₂ and CH₃CN) and their HOMO energies calculated by semiempirical (AM1) and nonempirical (HF/6-31G and HF/6-31G**) methods. The

Full text of DOI:10.1023/B:RUJO.0000045888.43245.d7

Russian Journal of Organic Chemistry, Vol. 40, No. 8, 2004, pp. 1098 -1112. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 8, 2004,
pp. 1146-1160.
Original Russian Text Copyright Ó 2004 by Mochalov, Gazzaeva, Fedotov, Trofimova, Trushkov, Zefirov.
Cyclopropyl- and Allyl-substituted Arenes
in Reaction with Dinitrogen Tetroxide.
Effect of Substrate Oxidation Potential on Reaction Direction
S.S. Mochalov1, R.A. Gazzaeva2, A.N. Fedotov1, E.V. Trofimova1,
I.V. Trushkov1, and N.S. Zefirov1
1Lomonosov Moscow State University, Moscow, 119234 Russia
e-mail: ssmoch @ org.chem.msu.ru
2Khetagurov North-Osetia State University, Russia
Received December 12 , 2003
Abstract—A correlation was found between oxidation potentials of acylcyclopropanes in solution (in CH2Cl2
and CH3CN) and their HOMO energies calculated by semiempirical (AM1) and nonempirical (HF/6-31G and
HF/6-31G**) methods. The correlation provides a possibility to forecast the reaction direction of the mentioned
substrates and N2O4. The correlation possesses a general character. It was established for instance that arylcyclo-
propanes, cyclopropylmethyl- and allylbenzenes oxidized at more positive potentials than reduction potential of
NO+ and having more positive eHOMO than –9.0 eV (AM1), –8.4 eV (HF/6-31G), and –8.3 eV (HF/6-31 G**)
reacted with N2O4 following the mechanism “electron transfer – radical pair recombination” affording nitroaromatic
derivatives retaining the cyclopropane (or allyl) fragments. Substrates of the same type where the electron transfer
to NO+ should be endothermic process and whose HOMO values are less than the above critical numbers react
with N2O4 by the mechanism of electrophilic cyclopropane ring opening (with aryl and benzylcyclopropanes) or
by electrophilic addition across the double C=C bond (with allylbenzenes).
It was shown previously that reaction with dinitrogen
tetroxide (N2O4) of phenylcyclopropane and its para-
alkyl- or para-bromo-substituted analogs in dichloro-
methane occurred solely at the three-membered carbon
ring [1, 2]. On the contrary 6-cyclopropyl-1,4-benzodi-
oxane and its 7-bromo-substituted analog under the same
conditions reacted with N2O4 at the aromatic ring with
conservation of the cyclopropane moiety [2, 3].
to electron transfer, and also to apply the data obtained
to performing new syntheses.
It was shown recently [4] that the nitrosyl cation
having reduction potential Ered 1.48 V (with respect to
saturated calomel electrode, normal electrode) efficiently
oxidized in dichloromethane aromatic compounds
possessing oxidation potential below 1.45 V, but with
substrates having oxidation potential over 1.60 V it only
formed charge-transfer complexes. From these data we
presumed that cyclopropyl-substituted substrates with an
oxidation potential below 1.48 V would be oxidized with
dinitrogen tetroxide into the corresponding cation-radical
that further through ion-radical reaction with ·NO2 would
furnish a product of substitution in the aromatic ring.
This difference in behavior of arylated cyclopropanes
was rationalized [1–3] as dissimilar relation of the initial
substrates with respect to nitrozyl cation initiating the
reaction. It was implied that in the first case the nitrosyl
cation played the role of an electrophilic agent reacting
with the three-carbon ring along the standard electrophilic
addition route, whereas in the second instance the nitrosyl
cation functioned as oxidant initiating the nitration of
the aromatic ring by one-electron transfer mechanism.
The data on oxidation potentials of arylcyclopropanes
are scanty up till now. Nonetheless, the available
experimental data confirm our assumption. For instance,
it was established experimentally that phenylcyclo-
propane and 4-methylphenylcyclopropane (oxidation
potentials 1.78 and 1.60 V respectively) (Table 1), react
with N2O4 only with the opening of the cyclopropane
We attempted in this study to test this assumption, to
determine the frontier criteria where we should expect
the alteration in the reaction pathway originating from
the change in its mechanism from electrophilic addition
1070-4280/04/4008-1098Ó2004 MAIK “Nauka/Interperiodica”

CYCLOPROPYL- AND ALLYL-SUBSTITUTED ARENES
1099
Table 1. Calculated values of HOMO energies of arylcyclopropanes I–V, experimental values of their oxidation potentials in
dichloromethane and acetonitrile, and of their ionization potentials
±H
ꢀ H9ꢁꢁ
(
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$0ꢃꢁ
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&1ꢁ
ꢁ
ring. In contrast, 4-anisylcycloprpoane having oxidation
potential of 1.35 V (Table 1) reacted with N2O4 with
conservation of the three-memberd ring [2].
Interestingly both equations give consistent results:
oxidation potential of arylcyclopropane would be below
1.48 V if the –eHOMO value calculated byAM1 procedure
be smaller than 9.0 eV [8.9 and 8.96 eV according to
equations (1) and (2) respectively]. At the use of the
calculations by HF/6-31G and HF/6-31G** methods the
corresponding frontier values equal approximately to 8.4
and 8.3 eV. For comparison we mention the values of
–eLUMO(NO+) calculated by procedures HF/6-31G
(8.36 eV) and MP2/6-31G** (8.31 eV).
Aiming at developing criteria for distinguishing
between cyclopropyl-containing substrates capable of
one-electron oxidation to furnish products of nitration
into the aromatic ring or those capable of electrophilic
opening of the cyclopropyl ring we planned to use
quantum-chemical calculation of various cyclopropyl-
benzenes properties in comparison with available
experimental data on their oxidation potentials in
solution. The quantum-chemical calculations were
carried out with the use of software package GAUSSIAN
98 [5] applying three procedures: semiempirical method
AM1 [6] and ab initio method in the basis HF/6-31G
with accounting for polarization functions and without
it [7, 8].
The correlation analysis performed suggests that
arylcyclopropanes whose ionization potential calculated
by methodsAM1, HF/6-31G, and HF/6-31G** is below
respectively 9.0, 8.4, and 8.3 eV should react with N2O4
according to electron transfer mechanism, retaining the
cyclopropane fragment and giving products of nitration
into the aromatic ring, whereas the compounds with
larger value of the calculated ionization potentials should
react along the electrophilic mechanism of the cyclo-
propane ring opening.
As seen from Table 1, experimental values of
ionization potentials of arylcycloprppanes are in good
agreement with the eHOMO values calculated by
nonempirical procedure with the use of HF/6-31G**
basis. On the other hand a better correlation with the
oxidation potentials in solution is observed at the use of
semiempiricalAM1 procedure for calculation of HOMO
energy (which according to Kupmans theorem [13]
correspond to ionization potentials of the compound):
To prove these conclusions we first calculated the
energy of the frontier orbitals for cyclopropylarenes
whose behaviour in reactions with dinitrogen tetroxide
had been already studied before.
The data of Table 2 show that the calculated HOMO
energies of these substrates really conform to our
suggestion: 4-bromophenylcyclopropane (VI) having
ionization potential higher than the frontier value reacts
with N2O4 with the opening of cyclopropane ring (as
shown in [1]), and 6-cyclopropyl-1,4-benzodioxane (VII)
(1)
(2)
E
OX (MeCN) –0.838eHOMO – 5.97, r 0.978
OX (CH2Cl2) –1.06eHOMO – 8.02, r 0.988
E
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

1100
MOCHALOV et al.
Table 2. Calculated values of HOMO energy for
arylcyclopropanes VI–IX
nitrated by dinitrogen tetroxide into the benzene ring
without opening of the cyclopropane ring. To prove this
conclusion 3,4-dimethoxyphenylcyclopropare was
prepared, and its reaction with N2O4 was investigated.
±H
H9ꢁꢁ
&RPSGꢂꢁ
QRꢂꢁ
$0ꢃꢁ
+)ꢄꢅꢆꢇꢃ*ꢁ
+)ꢄꢅꢆꢇꢃ*ꢈꢈꢁ
It turned out really that compound IX reacted with
N2O4 in dichloromethane to yield exclusively 4,5-di-
methoxy-2-nitrophenylcyclopropane (X). Interestingly
that unlike reaction of 4-methoxyphenylcyclopropane (I)
with N2O4 occurring by SET-mechanism with the rupture
of the ether O–Me bond, in this case no demethylation
product was obtained. Apparently in reaction of com-
pound I the electron transfer from substrate to nitro-
sonium ion leads to formation of a cation-radical species
Ia (Scheme 1) where the radical site is localized mainly
of the carbon atoms attached to methoxy and cyclopropyl
substituents (as confirmed by our own and published [15]
nonempirical calculations of such cation-radicals). The
subsequent ipso-attack of NO2-radical on the C1 carbon
results in benzolonium ions of Ic type that are known to
be responsible for formation of nitrophenols XI and XII
at 4-anisylcyclopropane (I) nitration with nitric acid in
acetic anhydride. In the case of dimethoxy derivative IX
the arising cation-radical IXa is characterized by higher
degree of delocalization of the charge as well as spin
density.As a result the attack of ·NO2 on the ipso-position
competes with its addition to C6 carbon. Whereas the
arising ipso-s-complex IXb has relatively longer lifetim,
and its formation is reversible, s-complex IXc eliminates
proton rapidly and irreversibly affording the final product
of aromatic substitution X.
9,ꢀ
ꢌꢂꢇꢌꢁ
ꢊꢂꢍꢋꢁ
ꢊꢂꢌꢍꢁ
ꢊꢂꢎꢌꢁ
ꢊꢂꢌꢉꢁ
ꢊꢂꢋꢍꢁ
ꢊꢂꢎꢏꢁ
ꢏꢂꢊꢏꢁ
ꢊꢂꢏꢎꢁ
ꢊꢂꢉꢋꢁ
ꢊꢂꢃꢌꢁ
ꢏꢂꢏꢋꢁ
9,,ꢀ
9,,,ꢀ
,;ꢀ
ꢁ
Table 3. Calculated values of HOMO energy for substituted
benzylcyclopropanes XIV–XXIV
±H
H9ꢁꢁ
&RPSGꢂꢁ
QRꢂꢁ
$0ꢃꢁ
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;;,,ꢀ
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;;,9ꢀ
a
ꢁ
6-Bromo-7-cyclopropylmethyl-1,4-benzodioxane.
b 1,1-Dichloro-2-benzylcyclopropane.
with the ionization potential below the frontier value
affords product of benzene ring nitration [3, 14]. 6-
Bromo-7-cyclopropyl-1,4-benzodioxane (VIII) is an
intermediate case: its HOMO energy turned out to be
larger than the frontier value when calculated by
procedure HF/6-31G, but both other calculation methods
give figures slightly lower than the frontier value
permitting the occurrence of one-electron transfer.
Inasmuch as the experiment demonstrated [3, 14] that
under the chosen conditions the reaction afforded the
product nitrated into the aromatic ring, it was possible
to conclude that the results of calculation by AM1 or
HF/6-31G** methods possess better power for forcasting
the reaction direction than the data of HF/6-31G
calculations. Nonetheless we use further all the three
calculation procedures.
So far the correlation of eHOMO for cyclopropyl-
substituted substrate with the pathway taken by their
reaction with N2O4 was limited to arylcyclopropanes
where the small ring is conjugated with the benzene one.
We anticipated that if the calculated eHOMO values of
cyclopropylmethylbenzenes would fit to criteria
governing the cyclopropyl ring conservation in
phenylcyclopropane reactions with N2O4, then the similar
reactions of benzylcyclopropanes also would proceed
with retention of the cyclopropane moiety,
notwithstanding the fact that here the cyclopropyl ring
removed from the benzene one by one methylene group
was more capable to open under the action of
electrophilic reagents [17]. Therefore we performed
quantum-chemical calculations of frontier orbitals for a
series of benzylcyclopropanes, both substituted in the
aromatic and cyclopropane rings (Table 3).
In Table 2 the calculated HOMO values are also
presented for 3,4-dimethoxyphenylcyclopropane whose
reaction with N2O4 has not been previously studied. On
comparison of these energies with the frontier values
that determine the direction of arylcyclopropane reactions
with N2O4 we concluded that compound IX would be
The calculation results show that the eHOMO values
exceeding the limit permitting the reaction of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

CYCLOPROPYL- AND ALLYL-SUBSTITUTED ARENES
1101
Scheme 1.
12
12
12
12
12
20H
20H
20H
20H
,D
,E
,
12
12
+
12
12
12
2 1
12
2+
20H
;,,,ꢀꢁꢂꢃ
2+
20H
2+
;,,ꢀꢁꢄꢅꢃ
;,ꢀꢁꢆꢇꢃ
12
12
20H
20H
20H
,;
20H
,;D
12
12
ꢀ
ꢁ
12
12
12
IDVW
20H
20H
0H2
0H2
20H
2+
20H
,;F
20H
,;E
;
opening.As to compounds XVIII, XXI, and XXIII, their
eHOMO values fall into the frontier region, and these
compounds may presumably react with N2O4 along both
possible routes.
cyclopropyl-containing substrates with N2O4 to proceed
through SET-mechanism correspond to compounds XV–
XVIII, and XXII. Unlike that, the eHOMO value of
benzylcyclopropane (XIV) and those of compounds XIX,
XX, and XXIV lie below the indicated frontier values,
and these compounds should react with dinitrogen
tetroxide following the ionic mechanism and
consequently yielding products of cyclopropane ring
To test our assumption we synthesized a series of
substituted benzylcyclopropanes whose reaction with
N2O4 was expected to take the route “electron transfer-
recombination of the radical pair”, and also some
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

1102
MOCHALOV et al.
the predicted pathway. Therewith the trends observed in
Scheme 2.
the reaction of phenylcyclopropyl substrates with N2O4
by SET-mechanism were also valid for their structural
analogs from the benzylcyclopropane series although
with some distinctions. For instance, the common feature
of reactions between N2O4 and 4-anisylcyclopropane (I)
and 4-methoxybenzylcyclopropane (XV) possessing
virtually identical ionization potentials (Tables 1 and 3)
is the process proceeding through the stage of an ipso-s-
complexes Ib (Scheme 1) and XVb (Scheme 4)
formation. However the further transformation of these
s-complexes is different. Thus as shown in [2] the ipso-
benzolonium ions arising in the reaction of 4-anisyl-
cyclopropane (I) with N2O4 were converted under the
reaction conditions into cyclopropyl-substituted nitro-
and dinitrophenols XI and XII (Scheme 1), whereas the
ipso-benzolonium ions XVb inevitably forming under
the same conditions from 4-methoxybenzylcyclopropane
(XV) transformed mainly into products of intramolecular
cyclopropylation and nitration into the aromatic ring
XXVIII and XXIX (Scheme 4) as was demonstrated in
this study.
Y
7ꢀ
`
ꢁ ꢂꢃHtꢄꢃr‡urꢀ
Y
ꢁ!ꢂꢃ8C 28C8C 8y
`
;;9 ;;9,,
Y
8C8y
IhPCꢄ
@‡ 7I 8y
`
8y 8y
;;, ;;,,,
Y
`
Ihꢅ8C PC
6i†ꢆꢃr‡urꢀ
;9 ;9,,
Interestingly the 2-(4-methoxybenzyl)-1,1-dichloro-
cyclopropane (XXI) possessing ionization potential
(eHOMO) corresponding to the frontier region reacted with
N2O4 under the given conditions still by the SET-
mechanism affording in contrast to the nonchlorinated
analog XV only nitro-substituted benzylcyclopropanes
XXXII and XXXIII (Scheme 5).
X = H, Y = MeO (XV, XXI, XXV); X = Y = MeO (XVI,
XXII, XXVI); X, Y = OCH2CH2O (XVII, XXIII,
XXVII).
Scheme 3.
2
It is interesting to note that although the reaction of
compound XXI with N2O4 [like that of 4-methoxy-
benzylcyclopropane (XV)] proceeded through ipso-s-
complexes XXIc as shows nitrophenol XXXIII
formationb no tricyclic compounds, like XXXIV, were
obtained similar to those arising in the process with
nonchlorinated analog XV (Scheme 3).
2
;
;
;9,,ꢀꢁ;;,,,
;
2
2
+12
$F 2
;
12
;,;ꢀꢁ;;,9
As we anticipated, unsubstituted benzylcyclopropane
(XIV) having eHOMO value significantly smaller than the
HOMO energy of, e.g., 4-methoxybenzylcyclopropane
(XV) reacted with N2O4 solely at the three-membered
ring furnishing a multicomponent mixture of highly labile
addition products.
X = H (XVII, XIX), X = Cl (XXIII, XXIV).
benzylcyclopropanes where the electron transfer would
be thermodynamically unfavorable. The synthesis of
model compounds was carried out along Schemes 2
and 3.
The study of reaction of dinitrogen tetroxide with
substituted benzylcyclopropanes whose calculated eHOMO
values (Table 3) suggested that the process would proceed
by the mechanism “electron transfer-recombination of
the radical pair” demonstrated that the conversion of
these cyclopropane substrates actually occurred along
Interestingly, compounds XIX, XX, and XXIV with
HOMO situated deeper than that of benzylcyclopropane
(XIV) (Table 3) under the given conditions do not react
with N2O4 and are quantitatively recovered from the
reaction mixture.At the same time benzylcyclopropanes
XVII, XXII, and XXIII whose calculated eHOMO values
we close to those of eHOMO for 3,4-dimethoxy-phenyl-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

CYCLOPROPYL- AND ALLYL-SUBSTITUTED ARENES
1103
Scheme 4.
2 1
0H2
2 1
;;9,,,ꢃꢀꢄꢅꢆꢅꢇ
12
1 2
&+ &O ꢀ ꢁꢂ &
20H
20H
;9E
20H
;9
;9D
12
+2
ꢀ
ꢀ
ꢀ
ꢀ
2 1
12
12
20H
;;;ꢃꢀꢉꢈꢆꢊꢇ
20H
aꢉꢇ
2+
;;,;ꢁꢀꢁꢆꢈꢇ
;;;,ꢃꢀꢄꢆꢋꢇ
Scheme 5.
8y
8y
HrP
P I
;;;,9
8y
8y
8y
8y
8y
8y
I P
8C 8y ꢃ "ꢇ 8
PHr
;;,D
PHr
PHr
;;,
8y
8y
IP
ꢀ
ꢁ
8y
8y
8y
8y
8y
8y
P I
C
IP
IP
IP
PHr
PHr
;;,E
PC
;;;,,,ꢄꢃ!%!
PHr
;;;,,ꢄꢃ&#!
;;,F
IP
IP
IP
;;,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

1104
MOCHALOV et al.
Scheme 6.
;
<
5
;
<
5
1 2
&+ &O ꢀꢁ &
;9,,Dꢀꢁ;;,,Dꢀꢁ;;,,,D
;9,,ꢀꢁ;;,,ꢀꢁ;;,,,
;
5
;
5
12
+
<
12
<
12
;9,,Eꢀꢁ;;,,Eꢀꢁ;;,,,E
;,;ꢀꢁ;;,9ꢀꢁ;;;9
X, Y = OCH2CH2O, R = cyclopropylmethyl (XVII, XVIIa, XIX); X = Y = OMe, R = 2,2-dichlorocyclopropylmethyl
(XXII, XXIIa, XXXV); X, Y = OCH2CH2O, R = 2,2-dichlorocyclopropylmethyl (XXIII, XXIIIa, XXIV).
Scheme 7.
1 2
&+ &O ꢀ ꢁꢂ &
0H2
0H2
0H2
20H
20H
20H
;9,E
;9,
;9,D
E 12
D
12
0H2
0H2
2 1
+
2 1
12
;;;9,,ꢀ ꢃꢄꢅꢆꢇ
12
ꢁ
12
0H2
0H2
0H2
20H
;;;9,ꢈꢀꢉꢉꢇ
20H
;9,G
20H
;9,F
0H2
0H2
;;;9,,,ꢈꢀꢃꢅꢆꢇ
cyclopropane (IX) and 6-cyclopropyl-1,4-benzodioxane
(VII) (Tables 2 and 3) behaved in the reaction under
consideration as expected completely identical to IX and
VII: in high yields only the corresponding 2-nitro-
substituted benzylcyclopropanes XIX, XXIV, and
XXXV are obtained (Scheme 6).
In contrast to compounds VII, IX, XVII, XXII, and
XXIII 3,4-dimethoxtbenzylcyclopropane whose eHOMO
value suggested that reaction with N2O4 should have
occurred by the mechanism “electron transfer-
recombination of the radical pair” reacted actually
ambiguously: apart from the main product corresponding
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

CYCLOPROPYL- AND ALLYL-SUBSTITUTED ARENES
1105
Table 4. Calculated values of HOMO energy for allylbenzenes
XXV–XXVII, and XXXIX
to the general trends of the reaction, 4,5-dimethoxy-2-
nitrobenzylcyclopropane (XXXVI), we identified in the
reaction mixture also 3,4-dimethoxy-5-nitro-1,1a,6,6a-
tetrahydrocyclopropa[a]indene (XXXVII) and its 2-nitro
isomer XXXVIII (Scheme 7).
±H
H9ꢁꢁ
&RPSGꢂꢁ
QRꢂꢁ
$0ꢃꢁ
+)ꢄꢅꢆꢇꢃ*ꢁ
+)ꢄꢅꢆꢇꢃ*ꢈꢈꢁ
;;9ꢀ
;;9,ꢀ
;;9,,ꢀ
ꢊꢂꢊꢅꢁ
ꢊꢂꢍꢋꢁ
ꢊꢂꢊꢇꢁ
ꢊꢂꢋꢃꢁ
ꢏꢂꢊꢅꢁ
ꢊꢂꢇꢉꢁ
ꢊꢂꢉꢊꢁ
ꢏꢂꢏꢎꢁ
ꢊꢂꢉꢏꢁ
The formation of cyclopropaindenes XXVIII and
XXIX in reaction of 4-methoxybenzylcyclopropane (XV)
and cyclopropaindenes XXXVII and XXXVIII in
reaction of 3,4-dimethoxybenzylcyclopropane (XVI)
evidences by and large the general character of the
intramolecular cyclopropylation process in the series of
benzylcyclopropanes. For generation of these tricyclic
compounds may be responsible the corresponding ipso-
s-complexes of XVb or XVIc type (Schemes 4 and 7).
The latter assumption is confirmed, e.g., by the fact that
the yield of cyclization products XXXVII and XXXVIII
in the reaction of 3,4-dimethoxybenzylcyclopropane
(XVI) is considerably smaller than the yield of their
analog XXVIII in the reaction of 4-methoxybenzyl-
cyclopropane (XV).Apparently in the process involving
3,4-dimethoxybenzylcyclopropane (XVI) the recombina-
tion of the ion-radical pair follows preferably the pathway
b than the path a (Scheme 7). Consequently ipso-s-
complexes XVIc necessary for the substrate transforma-
tion into cyclopropa[a]indenes XXXVII and XXXVIII
are formed in a lesser amount.
;;;,;ꢀ
ꢌꢂꢎꢋꢁ
ꢊꢂꢏꢊꢁ
ꢊꢂꢏꢃꢁ
ꢁ
eHOMO values of the substrates in question. To test the
validity of this assumption we calculated eHOMO for some
substituted allylbenzenes (Table 4), compared the
calculated eHOMO values with the corresponding data for
cyclopropane analogs, and studied the behavior in
reaction with N2O4 of unsaturated compounds whose
eHOMO values were close to those of the respective
benzylcyclopropanes reacting with dinitrogen tetroxide
by the SET-mechanism.
As seen from Tables 3 and 4 the eHOMO values for 4-
methoxybenzylcyclopropane (XV) and 4-methoxyallyl-
benzane (XXV) calculated, for instance, by ab initio
calculations in the HF/6-31G basis are practically equal
(–8.17 and –8.21 eV respectively). It proved that the
behavior of substrates XV and XXV under conditions of
the staudy was also similar. Although the reaction of 4-
methoxyallylbenzane (XXV) with N2O4 unlike that of
compound XV was more complicated, and a considerable
part of the substrate still was converted into labile
products of addition to the double bond, yet three com-
pounds XL–XLII were isolated in an overall yield of
~35% with structures unambiguously demonstrating that
allylbenzenes also can react with dinitrogen tetroxide
along the SET-mechanism to afford nitroaromatic com-
pounds with the retained allyl substituent (Scheme 8).
This is essentially the first example of aromatic nitra-
tion of alkenylbenzenes effected by N2O4 occurring with
retention of the electron-donor double bond in the side
chain. It was important that we failed to identify in the
reaction mixture obtained from 3,4-dimethoxyallyl-
benzene and N2O4 any products which could have formed
via ipso-s-complexes of XXVId type (Scheme 9).
Apparently in contrast to reaction of 3,4-dimethoxy-
benzylcyclopropane (XVI) the second reaction stage
(radical pair recombination) with 3,4-dimethoxy-
allylbenzene (XXVI) proceeded rather along path a
(Scheme 9) than path b.An alternative possibility consists
in reduction of the demethylation rate of ipso-s-complex
XXVId as compared to XXVb induced by the presence
of the second methoxy group, and therefore the main
The results obtained give convincible proof of the
possibility to retain the susceptible to electrophilic attack
cyclopropyl ring of benzylcyclopropanes in reactions
following the mechanism “electron transfer-recombina-
tion of the radical pair” that can be achieved when eHOMO
of the initial substrates has values necessary for reactions
taking this pathway (i.e., the HOMO must be situated
higher than the mentioned critical values).
It is known [18], that styrene and its alkyl-substituted
analogs in reaction with dinitrogen tetroxide afford only
products of the electrophilic addition to the double bond.
Taking into consideration these data it was presumable
that the reaction between N2O4 and allylbenzenes should
also give addition products at the double bond, and the
reaction should go as easily as with alkylenes [19-21]
since the vinyl moiety was not conjugated with the
benzene ring. At the same time we have demonstrated in
this study that the cyclopropyl ring of benzylcyclo-
propanes prone to reactions of electrophilic addition can
be conserved in the reaction with N2O4 when the eHOMO
of the initial substrates fits in the range of values ensuring
reaction occurring via mechanism “electron transfer-
recombination of the radical pair”.
We suggested that the direction of allylbenzenes
reaction with N2O4 would also depend first of all on the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

1106
MOCHALOV et al.
Scheme 8.
2 1
12
1 2
&+ &O ꢀ ꢁꢂ &
12
20H
20H
20H
20H
;;9E
;;9
;;9D
12
12
12
2+
;/,,
20H
20H
;/,
;/
Scheme 9.
1 2
&+ &O ꢀ ꢀꢁ &
;
;
<
<
<
;;9,Eꢀꢁ;;9,,E
;;9,Dꢀꢁ;;9,,D
;;9,ꢀꢁ;;9,,
D
E
2 1
+
12
12
;
;
;
<
<
<
;;9,Gꢀꢁ;;9,,G
;/9ꢀꢁꢃꢄꢅꢆ
;/9,ꢀꢁꢇꢃꢅ
;;9,Fꢀꢁ;;9,,F
12
;
<
X = Y = OMe (XXVI, XXVIa–d, XLV); X, Y = OCH2CH2O (XXVII, XXVIIa–d, XLVI).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

CYCLOPROPYL- AND ALLYL-SUBSTITUTED ARENES
1107
transformation route of the former leads to isomeric
s-complex XXVIId and to the final product of aromatic
nitration at C6 atom. Similar difference was found in
behavior of 4-methoxy- and 3,4-dimethoxyphenyl-
cyclopropanes (I and IX) (Scheme 1).
4-Allylanisole (XXVI) was prepared as described in
[24], yield 91%, bp 122–124°C (22 mm Hg), nD20 1.5210.
4-Allyl-1,2-dimethoxybenzene (XXV) was prepared
as described in [25], yield 79%, bp 128–130°C (10 mm
Hg), nD20 1.5344.
Hence in this study we demonstrated that application
of relatively simple quantum-chemical calculations
of the frontier orbitals energy permitted forecasting
of direction in N2O4 reactions with cyclopropyl-,
cyclopropylmethyl-, and allylbenzenes in solvents of
low polarity, like dichloromethane. In particular,
substrates possessing more positive calculated eHOMO
values than –9.0 eV (method AM1), –8.4 eV (method
HF/6-31G), and –8.3 eV (method HF/6-31G**)
should react with N2O4 via mechanism “electron
transfer-recombination of the radical pair” with
subsequent stabilization of the adduct of ion-radical
recombination.
6-Allyl-1,4-benzodioxane (XXVII). To a solution of
Grignard reagent prepared from 4.1 g of Mg and 32.5 g
(0.151 mol) of 6-bromo-1,4-benzodioxane in 70 ml of
ether at 10°C while stirring was added dropwise a cooled
solution of 19.6 g (0.162 mol) of allyl bromide in 30 ml
of ether. The mixture was warmed to 20°C and then
heated at reflux for 3 h. Then the reaction mixture was
poured on a mixture of 100 g of ice and 50 ml of 2 N
HCl, the ether layer was separated, the water layer was
extracted with ether (2´30 ml). The combined ether
solution was washed with 2 N solution of K2CO3, with
water, and dried on MgSO4. The solution was evaporated,
the residue was subjected to vacuum distillation. Yield
14.1 g (53%), bp 138–139°C (14 mm Hg), nD20 1.5534.
1H NMR spectrum, d, ppm: 3.28 d (2H, CH2, J 7.8 Hz),
4.23 s (4H, OCH2CH2O), 5.08 m (2H, CH2=CH), 5.96 m
(1H, CH2 =CH), 6.64 d.d (1H, arom, JO 8.8, Jm 1.8 Hz),
6.71 d (1H, arom, Jm 1.8 Hz), 6.81 d (1H, arom, JO 8.8 Hz).
Found, %: C 74.88, 74.96; H 6.68, 6.77. C11H12O2.
Calculated, %: C 74.98; H 6.86.
EXPERIMENTAL
1H NMR spectra were registered on spectrometers
Bruker AW-300 (operating frequency 300 MHz) and
Varian BXR-400 (400 MHz) in CDC13 using TMS as
internal reference. Mass spectra were measured on
Finnigan SSQ-7000 instrument, GC-MS type equipped
with a capillary column (30 m, liquid phase DB-1, carrier
gas helium), oven temperature programmed from 50 to
300°C at a rate 10 deg/min. Ionizing electrons energy
70 eV. The preparative separation of reaction mixtures
was carried out on plates with A12O3 of the II activity
grade in a thin layer, eluent systems: A , ethyl ether–
petroleum ether (40–70°C), 1:3; B, ether–chloroform–
petroleum ether (40–70°C), 1:1:3.
Dichlorocarbenylation of allylbenzenes XXV–
XXVII. Standard procedure: To a solution of 0.1 mol of
allylbenzene XXV–XXVII and 0.5 g of Et3BnNCl in
70 ml of CHC13 was gradually added at stirring 60 ml
of 50% NaOH solution, the mixture was stirred for
3 h and poured into 200 ml of H2O. The organic
layer was separated, the water layer was extracted with
CHC13 (3 ´ 5 0 ml), the combined organic solvents were
washed with 2 N HC1, with water, and dried on MgSO4.
On removing 2/3 of solvent the residue was passed
through a bed of A12O3 of II activity grade, eluate was
evaporated, and reaction product was subjected to
distillation.
6-Bromo-1,4-benzodioxane was prepared as
described in [22], yield 74%, bp 150–151°C (20 mm Hg),
nD20 1.5914.
3,4-Dimethoxyphenylcyclopropane (IX) was
synthesized from 3,4-dimethoxyacetophenone similarly
to a described procedure for preparation of 4-methoxy-
phenylcyclopropane [23], yield 64% (calculated with
respect toMannich base), bp 155–156°C (19 mm Hg), nD20
2-(4-Methoxybenzyl)-1,1-dichlorocyclopropane
(XXI). From 14.8 g (0.1 mol) of 4-allylanisole (XXV)
by the standard procedure was obtained 15.2 g (66%) of
compound XXI, bp 169–170°C (12 mm Hg), nD20 1.5435.
1H NMR spectrum, d, ppm: 1.22 m (1H), 1.64 m (1H)
and 1.83 m (1H): cyclopropane ring protons, 2.72 d.d
(1H, CH2Ar, J1 14.4, J2 14.4 Hz), 2.93 d.d (1H, CH2Ar,
J1 14.4, J2 7.7 Hz), 3.81 s (3H, OCH3), 6.88 d (2H, arom,
JO 8.8 Hz), 7.21 d (2H, arom, JO 8.8 Hz). Found, %:
C 57.04, 57.11; H 5.19, 5.10. C11H12C12O. Calculated,
%: C 57.16; H 5.23.
1
1.5485. H NMR spectrum, d, ppm: 0.66 m (2H), 0.93 m
(2H) and 1.87 m (1H): cyclopropane ring protons, 3.83 s
(3H, OCH3), 3.86 s (3H, OCH3), 6.62 d.d (1H, ArH6,
Jo 8.0, Jm 2 Hz), 6.64 d (1H, ArH2, Jm 2 Hz), 6.76 d
(1H, ArH5, J 8.0 Hz). Found, %: C 73.99, 74.02;
H 7.77, 7.83. C11H14O2. Calculated, %: C 74.13;
H 7.92.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

1108
MOCHALOV et al.
8.6). Found, %: C 81.22, 81.31; H 8.61, 8.65. C11H14O.
2-(3,4-Dimethoxybenzyl)-1,1-dichlorocyclo-
Calculated, %: C 81.44; H 8.70.
propane (XXII). Likewise from 17.8 g (0.1 mol) of
3,4-dimethoxyallylbenzene (XXVI) was obtained 18.1 g
(69%) of compound XXII, bp 193–195°C (13 mm Hg),
3,4-Dimethoxybenzylcyclopropane (XVI). From
26.1 g (0.1 mol) of compound XXII we obtained 14.1 g
(73%) of compound XVI, bp 162–164°C (20 mm Hg),
nD20 1.5354. 1H NMR spectrum, d, ppm: 0.21 m (2H),
0.53 m (2H), 0.98 m (1H): cyclopropane ring protons,
2.54 d (2H, CH2Ar, J 9.8 Hz), 3.87 s (3H, OCH3), 3.92 s
(3H, OCH3), 6.82 m (3H, arom). Found, %: C 74.81,
74.93; H 8.14, 8.35. C12H16O2. Calculated, %: C 74.96;
H 8.39.
nD20 1.5526. H NMR spectrum, d, ppm: 1.23 m (1H),
1
1.65 m (1H) and 1.89 m (1H): cyclopropane ring protons,
2.78 d.d (1H, CH2Ar, J1 15.2, J2 6.0 Hz), 2.95 d.d (1H,
CH2Ar, J1 15.2, J2 7.6), 3.86 s (3H, OCH3) and 3.91 s
(3H, OCH3), 6.86 m (3H, arom). Found, %: C 54.92,
55.12; H 5.23, 5.32. C12H14C12O2. Calculated, %:
C 55.19; H 5.40.
6-Cyclopropylmethyl-1,4-benzodioxane (XVII).
From 25.9 g (0.1 mol) of dichloride XXIII we obtained
11.8 g (62%) of compound XVII, bp 144–146°C (14 mm
Hg), nD20 1.5503. 1H NMR spectrum, d, ppm: 0.14 m
(2H), 0.48 m (2H), 0.92 m (1H): cyclopropane ring
protons, 2.41 d (2H, CH2Ar, J 10.2 Hz), 4.18 s (4H,
OCH2CH2O), 6.61 m (3H, arom). Found, %: C 75.70,
75.72; H 7.16, 7.38. C12H14O2. Calculated, %: C 75.57;
H 7.42.
6-(2,2-Dichlorocyclopropylmethyl)-1,4-benzo-
dioxane (XXIII). Likewise from 17.8 g (0.1 mol) of
6-allyl-1,4-benzodioxane (XXVII) was obtained 16.1 g
(62%) of dichlorocyclopropane XXIII, bp 193–194°C
(15 mm pò.Cò), nD20 1.5645. H NMR spectrum, d, ppm:
1
1.19 d.d (1H, J1 7.2, J2 7.3 Hz), 1.63 d.d (1H, J1 7.2, J2
10.6 Hz), 1.81 m (1H): cyclopropane ring protons,
2.65 d.d (1H, CH2Ar, J1 14.8, J2 7.3 Hz), 2.87 d.d (1H,
CH2Ar, J1 14.8, J2 9.9 Hz), 4.40 m (4H, OCH2CH2O),
6.73 d.d (1H, ArH7, JO 8.8, Jm 2.1 Hz), 6.79 d (1H,
ArH5, Jm 2.1 Hz), 6.81 d (1H, ArH8, JO 8.8 Hz).
Found, %: C 55.57, 55.36; H 4.39, 4.41. C12H12C12O2.
Calculated, %: C 55.62; H 4.67.
6-Nitro-7-cyclopropylmethyl-1,4-benzodioxane
(XIX). To 15 ml of acetic anhydride at –50°C was added
1.3 ml of HNO3 (d420 1.51), at the same temperature was
added dropwise a solution of 1.9 g (0.01 mol) of com-
pound XVII in 3 ml of acetic anhydride. The reaction
mixture was stirred for 2 h at –50°C and then poured
into 150 ml of warm water. On cooling the precipitated
oily product crystallized. The crystals were filtered off,
washed with water, and recrystallized from ethanol. Yield
1.7 g (72%), mp 87°C (EtOH). 1H NMR spectrum, d,
ppm: 0.21 m (2H), 0.49 m (2H), 1.01 m (1H): cyclo-
propane ring protons, 2.71 d (2H, CH2Ar, J 7.6 Hz), 4.46
m (4H, OCH2CH2O), 7.08 s (1H, ArH5), 7.53 s (1H,
ArH8). Found, %: C 61.01, 61.17; H 5.41, 5.48; N 5.71,
6.06. C12H13NO4. Calculated, %: C 61.27; H 5.57;
N 5.95.
Reduction of gem-dichlorocyclopropanes XXI–
XXIII. To a suspension of 18.4 g (0.8 mol) of finely
dispersed sodium in 200 ml of anhydrous ether was added
dropwise at vigorous stirring 0.1 mol of an appropriate
gem-dichlorocyclopropane XXI–XXIII in a mixture of
31 ml of methanol and 20 ml of anhydrous ether. The
rate of addition was so controlled that the ether steadily
boiled. After the completion of dichloride addition 12 ml
of methanol was added dropwise to the reaction mixture,
and it was stirred for 3 h. Into the reaction mixture that
became thick was added first 100 ml of moist ether, and
then gradually water till a transparent two-phase system
arose. The ether layer was separated, the water layer was
extracted with ether (2´50 ml), the combined ethereal
solutions were washed with water till neutral washings,
and dried on MgSO4. .The solvent was distilled off, the
residue was subjected to distillation.
6-(2,2-Dichlorocyclopropylmethyl)-7-nitro-1,4-
benzodioxane (XXIV). Nitration of compound XXIII
was carried out as described above but at –30°C. From
2.6 g (0.01 mol) of dichloride XXIII we obtained 2.47 g
(81%) of nitro compound XXIV, mp 81–82°C (EtOH).
1H NMR spectrum, d, ppm: 1.23 d.d (1H, J1 7.2,
J2 7.3 Hz), 1.64 d.d (1H, J1 7.2, J2 10.6 Hz), 1.97 m
(1H): cyclopropane ring protons, 3.15 d.d (1H, CH2Ar,
J1 7.3, J2 14.7 Hz), 3.24 d.d (1H, CH2Ar, J1 8.3,
J2 14.7 Hz), 4.31 m (2H, OCH2CH2O), 4.39 m (2H,
OCH2CH2O), 6.97 s (1H, ArH5), 7.69 C (1H, ArH8).
Found, %: C 47.24, 47.31; H 3.47, 3.53; N 4.31, 4.54.
C12H11NC12O4. Calculated, %: C 47.39; H 3.65; N 4.61.
4-Methoxybenzylcyclopropane (XV). From 23.1 g
(0.1 mol) of compound XXI by the above procedure was
obtained 11.5 g (71%) of compound XV, bp 112–113°C
(12 mm Hg), nD20 1.5348. 1H NMR spectrum, d, ppm:
0.29 m (2H), 0.62 m (2H), 1.02 m (1H): cyclopropane
ring protons, 2.61 d (2H, CH2Ar, J 7.7 Hz), 3.91 s (3H,
OCH3), 6.92 d (2H, arom, JO 8.6), 7.26 d (2H, arom, JO
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

CYCLOPROPYL- AND ALLYL-SUBSTITUTED ARENES
1109
Reaction of substrates IX, XV–XVII, XIX, XXI–
XXIII, XXV–XXVII with dinitrogen tetroxide. To a
solution of 2.8 g (0.03 mol) of N2O4 in 30 ml of anhydrous
CH2C12 cooled to –30°C was added dropwise at this
temperature a solution of 0.015 mol of an appropriate
substrate in 15 ml of the same solvent. The reaction
mixture was stirred for 1 h at –30°C, poured into 100 ml
of water, the organic layer was separated, washed with
3% NaHCO3 solution, with water, and dried with MgSO4.
on evaporating the solvent the target compounds were
isolated: 1) by column chromatography on silica gel, 40/
100, eluent ether–petroleum ether (40–70°C), 1:5; 2)
by thin-layer chromatography on A12O3 of II activity
grade, eluent ether–chloroform–petroleum ether, 1:1:3.
73°C (EtOH). 1H NMR spectrum, d, ppm: 0.07 d.t (1H,
H1', J1 4.5, J2 3.4 Hz), 1.14 d.ò (1H, H1', J1 4.5, J2
8.0 Hz), 1.94 m (1H, H6a), 2.33 m (1H, H1a), 2.84 d (1H,
H6', J1 16.8 Hz), 3.07 d.d (1H, H6'', J1 16.8, J2 6.7 Hz),
3.88 s (3H, OCH3), 6.97 s(1H,ArH2), 7.58 s (1H,ArH5).
13C NMR spectrum, d, ppm: 17.14 (C1), 17.89 (C6a),
24.46 (C1a), 34.26 (C6), 108.40 (C5), 122.55 (C2), 133.18
(C3), 137.0 (C6a), 152.6 (C4), 155.0 (C1b). Mass spectrum,
m/z (Irel, %): 205 (45.6) M+, 158 (34.2), 144 (11.3), 129
(40.5), 128 (100), 127 (43.3), 115 (73.4), 114 (24.0), 103
(13.7), 91 (13.5), 89 (13.4), 77 (14.2), 65 (6.3), 63 (15.8),
51 (10.1). Found, %: C 64.41, 64.12; H 5.32, 5.29;
N 6.68, 6.83. C11H11NO3. Calculated, %: C 64.38; H 5.40;
N 6.83;
0.11 g of a mixture of 3-hydroxy-4-nitro-1,1a,6,6a-
tetrahydrocyclopropa[a]indene (XXIX) and 4-
hydroxy-3-nitrobenzylcyclopropane (XXXI) in 1:1.2
ratio as shown by a chromatogram obtained in the study
of the reaction mixture by GC-MS method. Mass
spectrum of compound XXIX, m/z (Irel, %): 191 (35.4)
M+, 145 (27.2), 144 (18.9), 127 (6.3), 115 (100), 114
(22.8), 103 (6.3), 91 (16.2), 89 (11.4), 77 (13.3), 65 (6.2),
63 (11.3), 51 (10.1); of compound XXXI, m/z (Irel, %):
193 (8.9) M+, 165 (70.9), 152 (100), 119 (6.2), 106 (36.7),
91 (21.5), 77 (31.6), 65 (10.1), 51 (22.8), 39 (12.6).
From 2.67 g (0.015 mol) of 3,4-dimethoxyphenyl-
cyclopropane (IX) and N2O4 with subsequent perform-
ance of column chromatography of the reaction mixture
we obtained 3.07 g (92%) of 4,5-dimethoxy-2-
nitrophenylcyclopropane (XIII), mp 56–57°C (EtOH).
1H NMR spectrum, d, ppm: 0.63 m (2H), 1.08 m (2H),
2.54 m (1H): cyclopropane ring protons, 3.93 s (3H,
OCH3), 3.95 s (3H, OCH3), 6.62 s (1H, ArH6), 7.57 C
(1H, ArH3). Mass spectrum, m/z, (Irel, %): 223 (31.1) M+
, 206 (7.7), 189 (11.0), 162 (10.5), 151 (18.6), 136 (100),
119 (14.2), 108 (19.9), 103 (12.2), 91 (20.5), 77 (19.2),
65 (16.7), 51 (10.9). Found, %: C 58.98, 59.23; H 5.71,
5.82; N 6.03, 6.11. C11H13NO4. Calculated, %: C 59.18;
H 5.87; N 6.27.
Reaction of 1,1-dichloro-2-(4-methoxybenzyl)-
cyclopropane (XXI) with N2O4. In reaction of 3.5 g
(0.015 mol) of compound XXI with N2O4 carried out
under standard conditions and followed by separation
of the reaction mixture on plates withAl2O3 we obtained
2.7 g (78%) of initial compound XXI, 0.71 g (74%)** of
2-(4-methoxy-3-1,1-dichloronitrobenzyl)cyclo-
Reaction of 4-methoxybenzylcyclopropane (XV)
with N2O4 was carried out as described above. From
2.45 g (0.015 mol) of compound XV we obtained 2.63 g
of reaction mixture. Chromatography on a plate with
A12O3 furnished 1.24 g (51%) of the initial reagent, 0.26
g (16.8%)* of 4-methoxy-3-nitrobenzyl-cyclopropane
1
propane (XXXII), viscous oily substance. H NMR
spectrum, d, ppm: 1.29 m (1H), 1.72 m (1H), 1.88 m
(1H): cyclopropane ring protons, 2.86 d.d (1H, CH2Ar,
J1 17.2, J2 6.8 Hz), 2.96 d.d (1H, CH2Ar, J1 17.2, J2 8.8
Hz), 3.97 s (3H, OCH3), 7.04 d (1H, ArH5, JO 8.3 Hz),
7.46 d.d (1H, ArH6, JO 8.4, Jm 2.2 Hz), 7.72 d (1H,ArH2,
Jm 2.2 Hz). Mass spectrum, m/z (Irel, %): 277 (5.1) 1[M]+,
1
(XXX), viscous oily substance. H NMR spectrum, d,
ppm: 0.22 m (2H), 0.58 (2H), 0.94 (1H): cyclopropane
ring protons, 2.55 d (2H, CH2Ar, J 5.7 Hz), 3.98 s (3H,
OCH3), 7.03 d (1H,ArH5, JO 8.8 Hz), 7.44 d.d (1H,ArH6,
JO 8.8, Jm 2.4 Hz), 7.75 d (1H, ArH2, Jm 2.4 Hz). Mass
spectrum, m/z (Irel, %): 207 (14.9) M+ , 190 (3.2), 179
(18.9), 166 (100), 161 (20.9), 146 (6.8), 135 (13.1), 132
(12.6), 115 (21.5), 103 (30.4), 91 (43.0), 90 (68,3), 89
(31.6), 77 (27.8), 63 (13.4), 51 (17.1). Found, %: C 63.41,
63.48; H 6.32, 6.39; N 6.38, 6.71. C11H13NO3. Calculated,
%: C 63.75; H 6.32; N 6.76;
2
275 (8.3) [M]+, 236 (3.5), 234 (5.8), 179 (57.2), 166
(100), 132 (18.6), 119 (13.5), 103 (24.3), 90 (37.2), 77
(20.2), 63 (8.2), 51 (12.7). Found, %: C 7.62, 47.79;
H 3.89, 3.97; N 4.94, 4.98. C11H11CI2NO3. Calculated,
%: C 47.84, H 4.02, N 5.07;
0.22 g (26%)* of 2-(3-nitro-4-hydroxybenzyl)-1,1-
dichlorocyclopropane (XXXIII), viscous oily
substance. 1H NMR spectrum, d, ppm: 1.24 m (1H), 1.71
0.69 g (45.5%)* of 3-methoxy-4-nitro-1,1a,6,6a-
tetrahydrocyclopropa-[a]indene (XXVIII), mp 72–
** Calculated on the reacted compound XXI.
* Calculated on the reacted compound XV.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

1110
MOCHALOV et al.
m (1H), 1.82 m (1H): cyclopropane ring protons, 2.84
d.d (1H, CH2Ar, J1 17.6, J2 10.6 Hz), 7.14 d (1H, ArH5,
Jo 9.0), 7.54 d.d (1H, ArH6, JO 9.0, Jm 2.22), 8.03 d (1H,
ArH3, Jm 2.2 Hz). Mass spectrum, m/z (Irel, %): 263 (4.0)
1[M]+ , 261 (6.4) 2[M]+, 165 (83.3), 152 (100), 115 (9.4),
106 (19.2), 91 (10.9), 77 (14.1), 63 (7.4), 51 (11.9).
dimethoxy-2-nitro-1,1a,6,6a-tetrahydrocyclopropa-
[a]indene (XXXVIII), light-yellow crystals. 1H NMR
spectrum, d, ppm: 0.87 m (1H, H'1), 1.29 m (1H, H''1),
1.64 m (1H, H6a), 2.53 m (1H, H1a), 2.96 d (1H, H'6, J
17.8 Hz), 3.19 d.d (1H, H''6, J1 17.8, J2 7.1 Hz), 3.94 s
(3H, OCH3), 4.01 s (3H, OCH3), 7.33 s (1H,ArH2). Mass
spectrum, m/z (Irel, %): 235 M+ . Found, %: C 60.94,
61.07; H 5.34, 5.47; N 5.69, 5.90. C12H13NO4.
Calculated, %: C 61.27; H 5.57; N 5.95;
Reaction of 6-cyclopropylmethyl-1,4-benzo-
dioxane (XVII) with N2O4. From 2.85 g (0.015 mol) of
compound XVII and two equiv of N2O4 under standard
conditions followed by column chromatography on silica
gel (40/100) we obtained 3.27 g (93%) of 6-nitro-7-
cyclopropylmethyl-1,4-benzodioxane (XIX), mp 87°C
0.73 g (12.5%) of 3,4-dimethoxy-5-nitro-1,1a,6,6a-
tetrahydrocyclo-propa[a]indene (XXXVII), mp 99°C
1
(EtOH). H NMR spectrum, d, ppm: 0.18 m (1H, H'1),
1
1.21 m (1H, H''1), 1.99 m (1H, H6a), 2.59 m (1H, H1a),
3.43 d (1H, H'6, J 19.2), 3.52 d.d (1H, H''6, J1 9.2, J2 6.6
Hz), 3.92 s (3H, OCH3), 4.07 s (3H, OCH3), 7.55 s (1H,
ArH2). Mass spectrum, m/z (Irel, %): 235 (13.4) M+, 218
(100), 188 (24.8), 173 (14.7), 159 (9.2), 145 (10.4), 131
(12.3), 115 (16.8), 103 (18.1), 91 (7.7), 77 (21.9), 63
(7.8), 51 (10.6). Found, %: C 60.99, 61.03; H 5.38, 5.55;
N 5.71, 5.76. C12H13NO4. Calculated, %: C 61.27; H
5.57; N 5.95;
(EtOH). H NMR spectrum was identical to that of an
authentic sample, and the sample mixed with an authentic
compound showed no melting point depression.
Reaction of 2-(3,4-dimethoxybenzyl)-1,1-dichloro-
cyclopropane (XXII) with N2O4. Reaction of 3.9 g
(0.015 mol) of compound XXII under standard
conditions followed by column chromatography afforded
4.3 g (95%) of 2-(4,5-dimethoxy-2-nitrobenzyl)-1,1-
dichlorocyclopropanea (XXXV), mp 52–53°C (EtOH).
1H NMR spectrum, d, ppm: 1.34 ò (1H), 1.75 d.d (1H, J1
14.4, J2 3.4 Hz), 1.99 m (1H): cyclopropane ring protons,
3.12 d.d (1H, CH2Ar, J1 19.8, J2 6.8 Hz), 3.14 d.d (1H,
CH2Ar, J1 19.8, J2 5.4 Hz), 3.98 s (3H, OCH3), 4.04 s
(3H, OCH3), 7.04 s (1H, ArH6), 7.69 s (1H, ArH3). Mass
spectrum, m/z (Irel, %): 307 (9.9) 1[M]+, 305 (16.1) 2[M]+,
270 (15.9), 240 (18.2), 206 (17.2), 192 (53.2), 181 (32.1),
180 (100), 166 (98.1), 150 (43.6), 138 (33.3), 136 (33.2),
121 (16.0), 109 (19.5), 107 (18.6), 92 (18.5), 77 (36.5),
63 (23.2), 51 (24.9), 39 (14,6). Found, %: C 46.87, 47.01;
H 4.08, 4.13; N 4.31, 4.49. C12H13Cl2NO4. Calculated,
%: C 47.08; H 4.28; N 4.57.
4.55 g (77%) of 4,5-dimethoxy-2-nitrobenzylcyclo-
propane (XXXVI), mp 75–76°C (EtOH). 1H NMR
spectrum, d, ppm: 0.24 m (1H), 0.55 m (1H), 1.11 m
(1H): cyclopropane ring protons, 2.89 d (2H, CH2Ar, J
6.8), 3.92 s (3H, OCH3), 3.99 s (3H, OCH3), 6.98 s (1H,
ArH6), 7.62 s (1H, ArH3). Mass spectrum, m/z (Irel, %):
237 (39.7) M+, 220 (80.1), 190 (22.4), 176 (24.3), 165
(100), 148 (19.3), 136 (25.51), 121 (16.1), 115 (30.7),
103 (21.1), 91 (29.7), 77 (55.7), 69 (47.7), 63 (23.1), 51
(28.2), 39 (24.9). Found, %: C 60.46, 60.48; H 6.21,
6.30; N 5.71, 5.79. C12H15NO4. Calculated, %: C 60.75;
H 6.37; N 5.90.
Reaction of 4-allylanisole (XXV) with N2O4.
Reaction of 2.96 g (0.02 mol) of compound XXV with
3.7 g (0.04 mol) of N2O4 was carried out by standard
procedure. The separation of the reaction mixture on
plates withAl2O3 afforded 1.69 g(57%) of initial 4-allyl-
anisole (XXV) identified by 1H and mass spectra; 0.1 g
(6.1%) of 4-allyl-3-nitroanisole (XLI), oily substance.
1H NMR spectrum, d, ppm: 3.43 d (2H, CH2Ar, J
6.2 Hz), 3.99 s (3H, OCH3), 5.12 m (2H, CH2=CH), 5.95
m (1H, CH2=CH), 6.92 d (1H, ArH5, Jo 9.2 Hz), 8.06 d
(1H, ArH2, Jm 2.5 Hz), 8.14 d.d (1H, ArH6, Jo 9.2, Jm
2.5 Hz). Mass spectrum, m/z (Irel, %): 193 (71.8) M+,
146 (12.4), 133 (15.4), 115 (100), 103 (39.7), 91 (75.6),
77 (39.1), 63 (18.6), 51 (25.1), 39 (15.5); 0.76 g (45.5%)
Reaction of 6-(2,2-dichlorocyclopropylmethyl)-
1,4-benzodioxane (XXIII) with N2O4. Reaction of
3.9 g (0.015 mol) of compound XXIII with two equiv of
N2O4 followed by column chromatography furnished
4.25 g (93%) of nitro compound XXIV, mp 81–82°C
(EtOH). 1H NMR spectrum was identical to that of a
sample obtained by nitration of compound XXIII with
nitric acid in acetic anhydride.
Reaction of 3,4-dimethoxybenzylcyclopropane
(XVI) with N2O4. Reaction of 4.8 g (0.025 mol) of
cyclopropane XVI with 4.6 g (0.05 mol) N2O4 in 60 ml
of CH2Cl2 at –30°C after standard workup of the reaction
mixture followed by separation of the reaction mixture
on plates with Al2O3 afforded 0.08 g (1.5%) of 3,4-
1
of 4-allyl-2-nitroanisole (XL), oily substance. H NMR
spectrum, d, ppm: 3.38 d (2H, CH2Ar, J 6.0 Hz), 3.95 s
* Calculated on the reacted compound XXI.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

CYCLOPROPYL- AND ALLYL-SUBSTITUTED ARENES
1111
(3H, OCH3), 5.14 m (2H, CH2=CH), 5.93 m (1H,
CH2=CH), 7.03 d (1H, ArH6, Jo 8.8 Hz), 7.37 d.d (1H,
ArH5, Jo 8.8, Jm 2.2 Hz), 7.67 d (1H, ArH3, Jm 2.2 Hz).
Mass spectrum, m/z (Irel, %): 193 (100) M+, 164 (6.4),
147 (17.3), 132 (47.3), 131 (46.7), 118 (37.8), 115 (39.1),
103 (41.1), 91 (39.2), 77 (33.9), 63 (16.1), 51 (18.6), 39
(10.2). Found, %: C 61.93, 62.07; H 5.59, 5.62; N 7.01,
7.11. C10H11NO3. Calculated, %: C 62.16; H 5.74; N 7.25;
va, E.V., Gazzaeva, R.A., Shabarov, Yu.S., and Zefi-
rov, N.S., Zh. Org. Khim., 1998, vol. 34, p. 1379.
3. Mochalov, S.S., Gazzaeva, R.A., Atanov, V.N., Fedo-
tov,A.N., and Zefirov, N.S., Khim. Geterotsikl. Soed., 1999,
p. 324.
4. Rosokha, S.V. and Kochi, J.K., J. Am. Chem. Soc., 2001,
vol. 123, p. 8985.
5. Gaussian, 98, Revision, A.7; Frisch, M.J., Trucks, G.W.,
Schiegei, H.B., Scuseria, G.E., Robb, M.A., Cheese-
man, J.R., Zakrzewski, V.G., Montgomery, J.A., Jr.,
Stratmann, R.E., Burant, J.C., Dapprich, S., Millan, J.M.,
Daniels, A.D., Kudin, K.N. Strain, M.C., Farkas, O.,
Tomasi, J., Barone, V., Cossi, M., Cammi, R., Mennuc-
ci, B., Pomelli, C., Adamo, C., Cllifford, S., Ochterski, J.,
Petersson, G.A., Ayaia, P.Y., Cui, Q., Morokuma, K.,
Malick, D.K., Rabuck, A.D., Raghavachari, K., Fores-
man, J.B., Cioslowski, J., Ortis, J.V., Baboul, A.G.,
Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P.,
Komaromi, I., Gomperts, R., Martin, R.L., Fox, D.J.,
Keith, T., AI-Laham, M.A., Peng, C.Y., Nanayakkara, A.,
Gonzalez, C., Challacombe, M., Gill, P.M.W., John-
son, B., Chen, W., Wong, W., Andres, J.L., Gonzalez, C.,
Head-Gordon, M., Repiogie, E.S., and Pople, J.A.,
Gaussian, Inc., Pittsburgh, PA, 1998.
6. Dewar, M.J.S., Zoebisch, E.G., and Healy, E.F., J. Am.
Chem. Soc., 1985, vol. 107, p. 3902.
7. Ditchfield, R., Hehre, W.J., and Pople, J.A., J. Chem. Phys.,
1971, vol. 54, p. 724.
8. Petersson, G.A., Bennett, A., Tensfeldt, T.G., Al-Laham,
M.A., Shirley, W.A., and Mantzaris, J., J. Chem. Phys.,
1988, vol. 89, p. 2193.
9. Somich, C., Mazzocchi, P., Edwards, M., Morgan, T., and
Ammon, H.L., J. Org. Chem., 1990, vol. 55, p. 2624.
10. Takahashi, Y., Ohaku, H., Nishioka, N., Ikeda, H., Miya-
shi, T., Gormin, D.A., and Hilinski, E.F., J. Chem. Soc.,
Perkin, Trans. II, 1997, p. 303.
0.37 g (24.5%) of 4-allyl-2-nitrophenol (XLII), oily
substance. 1H NMR spectrum, d, ppm: 3.35 d (2H,
CH2Ar, J 6.8 Hz), 5.19 m (2H, CH2=CH), 5.92 m (1H,
CH2=CH), 7.11 d (1H, ArH6, JO 8.6 Hz), 7.44 d.d (1H,
ArH5, Jo 8.6, Jm 2.4 Hz), 7.94 d (1H, ArH3, Jm 2.4 Hz),
10.51 s (1H, OH). Mass spectrum, m/z (Irel, %): 179 (100)
M+, 162 (13.6), 133 (49.6), 116 (6.2), 103 (38.8), 91
(15.3), 84 (21.9), 77 (44.2), 63 (5.8), 51 (29.3), 49 (30.9),
39 (9.9).
Reaction of allyl-1,2-dimethoxybenzene (XXVI)
with N2O4. From 2.67 g (0.015 mol) of compound XXVI
we obtained 3.12 g (94%) of 4-allyl 1,2-dimethoxy-5-
1
nitrobenzene (XLIII), mp 36–37°C (EtOH). H NMR
spectrum, d, ppm: 3.64 d (2H, CH2Ar, J 7.1), 3.87 s (3H,
OCH3), 3.89 s (3H, OCH3), 5.04 m (2H, CH2=CH),
5.91 m (1H, CH2=CH), 6.65 s (1H, ArH3), 7.51 s (1H,
ArH6). Mass spectrum, m/z (Irel, %): 223 (19.2) M+, 206
(100), 189 (72.4), 176 (21.1), 162 (33.9), 147 (21.1),
133 (21.2), 118 (18.6), 103 (21.9), 91 (30.8), 77 (31.1),
65 (27.6), 63 (20.5), 55 (45.1), 51 (16.1), 39 (17.1).
Found, %: C 58.96, 58.99; H 5.71, 5.84; N 6.03, 6.11.
C11H13NO4. Calculated, % : C 59.18; H 5.87; N 6.27 .
Reaction of 6-allyl-1,4-benzodioxane (XXVII) with
N2O4. Reaction of 2.64 g (0.015 mol) of compound
XXVII under standard conditions followed by separation
of the reaction mixture by column chromatography on
silica gel (40/100 mm) afforded 2.25 g (68%) of 6-allyl-
7-nitro-1,4-benzodioxane (XLIV), mp 40–42°C
11. Prins, I., Verhoeven, J.W., de, Boer, Th.J., and Worrell, C.,
Tetrahedron, 1977, vol. 33, p. 127.
12. Shudo, K., Kobayashi, T., and Utsunomiya, C.,
Tetrahedron, 1977, vol. 33, p. 1721.
13. Clark, T., A Handbook of Computational Chemistry, New
York:Wiley, 1985.
14. Samodov, A.A., Mochalov, S.S., and Shchapin, I.Yu.,
Abstract of Papers, Int. Conf. “Reaction Mechanisms and
Organic Intermediates”, St. Petersburg, Russia, 2001,
p. 137.
1
(EtOH). H NMR spectrum, d, ppm: 3.59 d (2H, CH2Ar,
J 7.6 Hz), 4.33 m (4H, OCH2CH2O), 5.06 m (2H,
CH2=CH), 5.91 m (1H, CH2=CH), 6.88 s (1H, ArH5),
7.52 s (1H, ArH8). Found, %: C 59.41, 59.67; H 4.88,
4.93; N 6.12, 6.27. C11H11NO4. Calculated, % : C 59.72;
H 5.01; N 6.33 .
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