Three-component reactions of tetranitromethane with olefins

Article abstract of DOI:10.1023/B:RUJO.0000034936.03355.d1

Three-component reactions of tetranitromethane with two different olefins taken in equimolar amounts are procedures fit for preparation of 3,3-dinitroisoxalidines of a mixed composition.

Full text of DOI:10.1023/B:RUJO.0000034936.03355.d1

Russian Journal of Organic Chemistry, Vol. 40, No. 2, 2004, pp. 162-173. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 2, 2004,
pp. 186-198.
Original Russian Text Copyright Ó 2004 by Averina, Budynina, Ivanova, Grishin, Gerdov, Kuznetsova, Zefirov.
Three-component Reactions of Tetranitromethane with Olefins
E. B.Averina, E. M. Budynina, O.A. Ivanova, Yu. K. Grishin, S.M. Gerdov,
T. S. Kuznetsova, and N. S. Zefirov
Moscow State University, Moscow, 119899 Russia
e-mail: elaver@org.chem.msu.ru
Received July 8, 2003
Abstract—Three-component reactions of tetranitromethane with two different olefins taken in equimolar amounts
are procedures fit for preparation of 3,3-dinitroisoxalidines of a mixed composition.
A significant position among diverse transformations
of nitro compounds hold reactions resulting in forma-
tion of heterocyclic structures. From versatile hetero-
cyclizations involving nitro compounds of the most
interest are reactions of tetranitromethane (TNM) and
its derivatives with alkenes that underlie procedures for
syntheses of heterocyclic compounds containing
nitrogen and oxygen [1].
initial olefin formed various classes of organic com-
pounds among which were mentioned arylnitro-
alkenes [3, 11], a-nitroketones [3–5, 12, 13], tetra-
nitroalkanes [4, 6–9, 11] etc. However the high and
specific TNM reactivity toward alkenes makes these
reactions first and foremost a convenient synthetic
procedure for substituted dinitroisoxazolidines [2–
4, 5, 7, 14–17].
The principal rules governing the reactions of
TNM with alkenes were established in nineteen
seventies by the research of K.V.Altukhov,
V.V.Perekalin, V.A.Tartakovskii, and their col-
laborators [2–10]. It was demonstrated that depending
on the reaction conditions and the structure of the
We showed formerly investigating the reactions
between tetranitromethane and olefins containing small
rings that the main direction of the process was formation
of 3,3-dinitroisoxazolidines of cyclobutane and cyclo-
propane series [18, 19]. However sometimes, mainly with
olefin containing three-membered rings a formation of
Scheme 1.
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1070-4280/04/4002-0162Ó2004 MAIK “Nauka/Interperiodica”

THREE-COMPONENT REACTIONS OF TETRANITROMETHANE WITH OLEFINS
163
Scheme 2.
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II, III: R = R = R = H (a) [18]; R = R = CH CH , R = H (b); R = R = H, R = CN (c) [18]. IV, V: R = R = R = R = H (a);
2
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R =cyclopropyl, R =R =R =H (b); R = R = H, R = R = CO Et (c); R = Me, R = isopropenyl, R = R = H (d).
2
tetranitropropanes or rearrangement products was ob-
served [19].
1, A, Scheme 1) and at the stage of cyclization (alkene 2,
B, Scheme 1).
Taking into account the published data and also our
own results we can present the general pattern of the
TNM reaction with olefins as follows.
The fundamental possibility to synthesize isoxazo-
lidines of mixed composition was demonstrated formerly
by an example or reaction between 1-phenylcyclohexene
TNM in solution of another sterically unhindered and
alkene taken in a 10-fold excess [10]. However this
procedure is not promising for preparative methods.
According to Scheme 1 the reaction of alkenes with
TNM proceeds via nitro carbocation formation. The latter
depending on the degree of positive charge delocalization
reacts further with trinitromethyl anion either at the
oxygen atom (O-alkylation, A), or at the carbon site
In this study we investigated heterocyclization of a
wide range of alkenes effected by TNM. The reaction
was carried out at equimolar quantities of the reagents.
As a result of studies a method was developed for the
synthesis of 3,3-dinitroisoxazolidines of a mixed
composition. We believed that for the generation of
nitronic ester tri- and tetrasubstituted olefins with a
nucleophilic double bond should be used for they actively
reacted with TNM but were poor 1,3-dipolarophiles due
to steric factors. Three-component reactions of TNM
with polysubstituted alkenes were studied by examples
of tetramethylethylene, bicyclobutylidene, 1-phenyl-
substituted cyclopentene and cyclohexene, and also
(
C-alkylation, C), or undergoes rearrangements (D, A).
Depending on the structure of the olefin substrate or, to
lesser extent, on the reaction conditions any of the
processes designated on the scheme can come true.
The synthetic prospects of TNM reaction with olefins
where two molecules of the same alkene build up with
TNM a molecule of 3,3-dinitroisoxazolidine are limited
by a condition that it can be successfully carried out only
with sterically unhindered alkenes with a sufficiently
nucleophilic double bond [7, 19]. The general scheme
suggests that isoxazolidines formation occurs in a tandem
process which can be represented as a sequence of two
stages. The first stage involves a generation of nitronic
ester of type 3, that is a 1,3-dipole. The second stage
consist in [2+3]-cycloaddition of nitronic ester of type 3
to the olefin giving a product of type 4. Since the sterical
and electronic requirements with respect to alkene are
different in the first and second stages of hetero-
cyclization it is possible to extend the opportunities of
reaction between TNM and olefins applying different
alkenes at the stage of nitronic ester formation (alkene
1
-methylcyclobutene. The structure of compounds
obtained was established with the use of unidimensional
1
13
and two-dimensional H and C NMR spectroscopy and
of mass spectrometry. The spectral parameters of
compounds synthesized are compiled in Tables 1-3 and
in EXPERIMENTAL.
We established that the universal olefin for nitronic
ester generation was bicyclobutylidene I for this olefin
reacted with TNM even at 0°C forming first apparently
a charge-transfer complex and then the nitronic ester of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

164
AVERINAet al.
1
Table 1. H NMR spectra of isoxazolidines (IIIb, Va–Vd, VIIIc, VIIIe, VIIIi,VIII j), d, ppm. (J, Hz) in CDCl
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b
c
d
Here and hereinafter the fragment of isoxazolidine ring (ONO)C(NO ) is designated as C(NO ) .
2
2
2 3
The product was separated in two fractions each containing two diastereomers.
The signals of diastereomer B of compound (VIIIe) were not assigned due to overlapping with the signals of the major diastereomer.
type 3 (Scheme 1) that at cooling (0–5°C) was not further
involved into the 1,3-dipolar cycloaddition with the second
molecule of the initial olefin I. A subsequent addition to
the mixture of TNM and olefin I of 1 equiv of some
other alkene resulted in formation of mixed isoxazolidines.
It is known that in 1,3-dipolar cycloaddition of
N-oxides to 1,1-disubstituted olefins the oxygen atom is
bound to the more substituted carbon of the double bond
[20]. A similar regioselectivity was also observed in the
reactions under study, It is in particular confirmed by
NMR data (Tables 1 and 2). The isoxazolidine ring of
compounds III, V appears as characteristic NMR signals.
The methylene groups protons have signals in the range
d 2.9–3.5 and 3.4–3.9 ppm. [AB-systems for compounds
IIIa–c, Vb, d or AB-part of ABX-systems for compounds
We found that the reaction of TNM and
bicyclobutylidene I with methylenecyclobutanes IIa–c
and vinylcyclopropanes IVa–d occurred regioselectively
and furnished the corresponding isoxazolidines of mixed
composition IIIa–c, Va–d in high yields (Scheme 2).
2
13
Va, b, J 15–16 Hz]. In the
C NMR spectrum
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

THREE-COMPONENT REACTIONS OF TETRANITROMETHANE WITH OLEFINS
165
1
3
1
Table 2. C NMR spectra of isoxazolidines IIIb, Va–d, VIIIc, f, i, j of general formula shown below (d, ppm [ J (CH), Hz] in
CDCl3)
'
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RPHUꢁ
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QRꢀꢁ
&ꢁ
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&ꢁ
& &ꢁ
ꢁ
2WKHUꢁFDUERQꢁDWRPVꢁ
ꢀ
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&+ꢈꢁF\FORꢂ%Xꢌꢁꢆꢋꢀꢊꢐꢈꢁꢆꢋꢀꢎꢑꢈꢁꢆꢅꢀꢋꢅꢈꢁꢆꢊꢀꢆꢊꢈꢁꢋꢊꢀꢆꢍꢈꢁꢋꢉꢀꢅꢎꢈꢁꢋꢐꢀꢐꢊꢈꢁ
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ꢎꢋꢀꢆꢎꢈꢁ
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&+ꢈꢁF\FORꢂ3Uꢌꢁꢇꢀꢐꢑꢁꢃꢆꢑꢋꢄꢈꢁꢎꢀꢅꢉꢁꢃꢆꢑꢋꢄꢈꢁꢆꢍꢀꢅꢋꢁꢃîꢋꢈꢁꢆꢑꢅꢄꢒꢁ
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ꢐꢎꢀꢇꢋꢈꢁ &+ꢈꢁF\FORꢂ%XꢌꢁꢆꢅꢀꢇꢉꢈꢁꢆꢊꢀꢆꢎꢈꢁꢋꢑꢀꢐꢉꢈꢁꢋꢐꢀꢍꢍꢈꢁꢋꢐꢀꢋꢎꢈꢁꢅꢍꢀꢍꢑꢒꢁF\FORꢂ3Uꢈꢁ
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ꢎꢆꢀꢍꢆꢁ &+ꢈꢁF\FORꢂ%XꢌꢁꢆꢅꢀꢉꢎꢈꢁꢆꢊꢀꢆꢐꢈꢁꢋꢇꢀꢐꢉꢈꢁꢋꢇꢀꢎꢎꢈꢁꢋꢐꢀꢑꢑꢈꢁꢋꢐꢀꢐꢇꢒꢁF\FORꢂ3Uꢈꢁ
+ꢌꢁꢅꢀꢅꢆꢈꢁꢊꢀꢅꢐꢒꢁ ꢌꢁꢆꢑꢀꢆꢆꢁ
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+ꢌꢁꢍꢀꢆꢆꢈꢁꢆꢀꢅꢆꢈꢁꢅꢀꢍꢆꢈꢁꢅꢀꢆꢊꢒꢁ ꢌꢁꢆꢑꢀꢋꢅꢈꢁꢋꢍꢀꢍꢍꢁ
&
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ꢁ
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ꢀ
ꢆꢋꢐꢀꢊꢋꢁꢐꢊꢀꢋꢍꢁꢎꢍꢀꢋꢆꢈꢁꢎꢍꢀꢎꢑꢁꢆꢎꢀꢅꢇꢈꢁ&+ꢌꢁꢋꢇꢀꢅꢍꢈꢁ ꢌꢁꢅꢅꢀꢊꢊꢒꢁ
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%ꢀꢀ
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ꢁ
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&+ꢌꢁꢆꢎꢀꢑꢐꢒꢁ&+ꢌꢁꢆꢎꢀꢑꢐꢒꢁ ꢌꢁꢅꢊꢀꢍꢍꢒꢁ
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ꢀ$ꢁ ꢅꢎꢀꢅꢍꢁꢃꢆꢊꢍꢄꢁꢆꢋꢐꢀꢆꢎꢁꢐꢍꢀꢎꢊꢁꢐꢎꢀꢐꢐꢈꢁꢎꢍꢀꢎꢎꢁ&+ꢈꢁF\FORꢂ%Xꢌꢁꢆꢅꢀꢊꢎꢁꢃꢆꢊꢊꢄꢈꢁꢆꢊꢀꢅꢑꢁꢃꢆꢅꢎꢄꢈꢁꢋꢇꢀꢐꢇꢈꢁꢋꢐꢀꢍꢉꢈꢁꢋꢐꢀꢐꢅꢈꢁ
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ꢀ
ꢐꢋꢀꢊꢑꢁ
ꢃꢆꢉꢇꢄꢁ
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ꢆꢑꢑꢀꢐꢊꢈꢁꢆꢑꢐꢀꢐꢉꢁ
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ꢀ
%ꢁꢁ
&
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ꢀꢀ9Gꢁ
$ꢀ ꢊꢊꢀꢍꢇꢁꢃꢆꢅꢎꢄꢁꢆꢋꢎꢀꢐꢊꢁꢁꢎꢅꢀꢐꢎꢁꢎꢍꢀꢆꢊꢈꢁꢎꢍꢀꢐꢎꢁ&+ꢈꢁF\FORꢂ%XꢌꢁꢆꢅꢀꢉꢅꢈꢁꢆꢊꢀꢋꢇꢈꢁꢋꢇꢀꢑꢐꢈꢁꢋꢇꢀꢎꢊꢈꢁꢋꢐꢀꢊꢇꢈꢁꢋꢐꢀꢎꢇꢒꢁF\FORꢂ3Uꢈꢁ
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ꢁ
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&+ ꢌꢁꢆꢆꢐꢀꢊꢑꢁꢃꢆꢉꢑꢄꢒꢁ& ꢌꢁꢆꢊꢉꢀꢋꢇꢁ
ꢌꢁꢋꢋꢀꢇꢆꢁꢃꢆꢋꢑꢄꢈꢁꢋꢇꢀꢆꢆꢒꢁ
ꢀ
%ꢁ ꢊꢆꢀꢆꢑꢁꢃꢆꢊꢆꢄꢁ
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ꢃꢆꢉꢍꢄꢒꢁ& ꢌꢁꢆꢊꢊꢀꢎꢐꢁ
&
ꢀꢀ9,,,Fꢀ $ꢀꢀ%ꢁ ꢅꢉꢀꢍꢋꢁꢅꢋꢀꢅꢐꢁꢆꢋꢇꢀꢅꢇꢁꢁꢐꢊꢀꢉꢉꢁꢎꢍꢀꢊꢍꢈꢁꢎꢆꢀꢆꢊꢁ&+ꢈꢁF\FORꢂ%Xꢌꢁꢆꢅꢀꢑꢍꢈꢁꢆꢊꢀꢆꢇꢈꢁꢋꢑꢀꢑꢎꢈꢁꢋꢇꢀꢐꢋꢈꢁꢋꢐꢀꢆꢍꢈꢁꢅꢍꢀꢍꢍꢒꢁ&+ ꢌꢁ
ꢁ
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&+ꢈꢁF\FORꢂ%Xꢌꢁꢆꢅꢀꢆꢑꢈꢁꢆꢊꢀꢉꢍꢈꢁꢋꢇꢀꢑꢇꢈꢁꢋꢇꢀꢇꢅꢈꢁꢋꢐꢀꢆꢐꢈꢁꢋꢎꢀꢋꢍꢒꢁ&+ ꢌꢁ
ꢋꢉꢀꢑꢇꢒꢁ& ꢌꢁꢋꢍꢆꢀꢇꢇꢁ
ꢀꢀ9,,,Hꢀ $ꢀꢀ%ꢁ ꢊꢋꢀꢅꢋꢁꢊꢊꢀꢐꢐꢁꢆꢋꢇꢀꢐꢋꢁꢁꢐꢍꢀꢅꢎꢁꢎꢍꢀꢍꢎꢈꢁꢎꢆꢀꢆꢎꢁ&+ꢈꢁF\FORꢂ%Xꢌꢁꢆꢅꢀꢆꢋꢈꢁꢆꢊꢀꢋꢍꢈꢁꢋꢑꢀꢐꢇꢈꢁꢋꢐꢀꢆꢍꢈꢁꢋꢐꢀꢆꢐꢈꢁꢋꢎꢀꢑꢆꢒꢁ&+&Oꢌꢁ
ꢁ
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&+&Oꢌꢁꢅꢇꢀꢊꢊꢁ
ꢁ
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

166
AVERINAet al.
Table 2. (Contd.)
'
VWHUHꢂꢁ
RPHUꢁ
LDꢂ
&
RPSGꢀꢁ
QRꢀꢁ
& ꢁ
& ꢁ
& ꢁ
& & ꢁ
2WKHUꢁFDUERQꢁDWRPVꢁ
ꢀꢀ9,,,Iꢀ $ꢀꢀ%ꢁ ꢃꢄꢀꢃꢅꢁꢃꢆꢀꢇꢈꢁ ꢇꢉꢄꢀꢈꢊꢁꢁꢄꢌꢀꢌꢆꢁ ꢌꢊꢀꢇꢅꢍꢁꢌꢊꢀꢇꢌꢁꢁ&+ ꢎꢁꢇꢃꢀꢈꢌꢍꢁꢇꢋꢀꢇꢇꢍꢁꢉꢅꢀꢌꢇꢍꢁꢉꢆꢀꢇꢇꢍꢁꢉꢆꢀꢉꢇꢍꢁꢉꢌꢀꢅꢇꢍꢁꢃꢊꢀꢊꢌꢁ
ꢁ
ꢇꢉꢄꢀꢋꢊꢁ ꢆꢉꢀꢌꢋꢁ ꢌꢊꢀꢈꢅꢍꢁꢌꢊꢀꢌꢈꢁꢁ&+ ꢎꢁꢇꢃꢀꢋꢄꢍꢁꢇꢋꢀꢉꢃꢍꢁꢉꢄꢀꢄꢇꢍꢁꢉꢄꢀꢌꢈꢍꢁꢉꢆꢀꢅꢃꢍꢁꢉꢆꢀꢅꢄꢍꢁꢃꢉꢀꢉꢋꢁ
ꢀ
ꢁ
ꢀ9,,,Lꢀꢀ
ꢁ
ꢁ
ꢃꢄꢀꢌꢌꢁ ꢇꢉꢆꢀꢇꢃꢁ ꢄꢉꢀꢋꢅꢁ ꢌꢊꢀꢅꢌꢍꢁꢌꢇꢀꢇꢉꢁ&+ ꢍꢁF\FORꢂ%Xꢎꢁꢇꢃꢀꢅꢅꢍꢁꢇꢋꢀꢇꢊꢍꢁꢉꢅꢀꢆꢋꢍꢁꢉꢆꢀꢇꢅꢁꢏîꢉꢐꢍꢁꢉꢌꢀꢆꢆꢑꢁ&ꢎꢁꢇꢊꢄꢀꢈꢌꢑꢁ
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ꢀꢀ9,,,Mꢁ
ꢁꢋꢇꢀꢃꢉꢁ
ꢁ
ꢁꢆꢉꢀꢈꢄꢁ ꢁꢌꢊꢀꢉꢋꢍꢁꢌꢇꢀꢉꢅꢁꢁ&+ ꢍꢁF\FORꢂ%Xꢎꢁꢇꢃꢀꢅꢅꢍꢁꢇꢋꢀꢇꢈꢍꢁꢉꢅꢀꢌꢉꢍꢁꢉꢆꢀꢉꢊꢍꢁꢉꢆꢀꢉꢃꢍꢁꢉꢌꢀꢄꢈꢑꢁ&+ꢍꢁ3Kꢎꢁ
ꢇꢉꢆꢀꢈꢆꢁꢏîꢉꢐꢍꢁꢇꢃꢉꢀꢉꢉꢁꢏîꢉꢐꢑꢁ&ꢍꢁ3Kꢎꢁꢇꢉꢆꢀꢌꢌꢍꢁꢇꢃꢃꢀꢃꢇꢁ
a
ꢁ
No signals observed.
(
Table 2) the carbon signal of the same CH group is
can be considerably extended by using as alkene 2
(Scheme 1) a series of olefins with electron-acceptor,
aromatic, and heterocyclic substituents VIIa–j. Inasmuch
the olefins with electron-withdrawing substituents do not
directly react with TNM but being dipolarophiles they
react with nitronic esters of type 3 (B, Scheme 1), the
general procedure of mixed heterocyclization consists
in a simple mixing of all the three components in 1:1:1
ratio in petroleum ether at 0g20°C. Mixed 3,3-dinitro-
isoxazolidines VIIIa–j were in all cases isolated in good
yield.
2
observed in the region d 38–44 ppm. Spiro carbons in
heterocycles IIIa–c and the corresponding methine or
quaternary carbons of compounds Va–d appear as
downfield signals at d 81–93 ppm. The carbons of
C(NO ) groups are strongly deshielded (d 127–
1
2
2
29 ppm), and their resonance lines are broadened.
Since in the isoxazolidine molecule alongside an
asymmetric nitrogen atom arises a new asymmetric
carbon center compounds IIIc, Va–d form as mixture
of stereoisomers present in various ratios (Tables 1 and
2
). It is known [21–23] that N-alkoxysubstituted isoxazo-
12
12
lidines possessing bulky substituents are characterized
by relatively high barriers to inversion of the nitrogen in
the five-membered heterocycle with the values in the
2 1
2 1
2
1
1
2 1
1
2
2
2
2
-
1
range from 60 to 120 kJ mol . The presence of an
asymmetric carbon center in the isoxazolidines
molecules alongside the hindered inversion of nitrogen
atom results in conformational diastereomerism.
,
;DꢀꢁE
VII, VIII: R = Me, R' = CO Me (a); R = H, R' = CN (b); R =
2
H, R' = COMe (c); R = H, R' = CH(OEt) (d); R = H, R' =
2
12
CH Cl (e); R = H, R' = CH Br (f) R = H, R' = Ph (g); R = H,
7
10
2
2
,
ꢀ
9D ꢀ
R' = Py (h); R = H, R' = C F (i); R = H, R' = p-Br-C H (j).
6
5
6 4
&
ꢀ12 ꢁ
As demonstrated by H and 13C NMR spectra the
1
,
9E
9,
reaction of TNM with olefins I and VII occurred like
in the above cited case in highly regioselective fashion
providing single regioisomers of isoxazolidines VIIIa–
j (Tables 1 and 2). The formation of two regioisomers
IXa, b in equal amount as a result of reaction of indene
with TNM and bicyclobutylidene is an exception.
It turned out that reaction of 1,1-dicyclo-propylethyl-
ene IVb with TNM and olefin I alongside 3,3-dinitroiso-
xazolidine Vb afforded tetranitropropane VI in 1:1 ratio.
Here presumably nitrocarbocations from olefins I and
IVb at treatment with TNM form with comparable rate,
and the subsequent C-addition of trinitromethylanion to
dicyclopropylcation (C, Scheme 1) results in adduct VI.
We formerly obtained tetranitropropane VI as individual
product in the two-component reaction of TNM with
dicyclopropylethylene [19].
We found that olefins with two electron-withdrawing
substituents attached to the double bond did not react
with nitronic ester of type 3, and the mixed isoxazolidines
do not form. Thus in reactions of TNM and bicyclo-
butylidene I with dimethyl maleate, 4-cyclo-hexene-1,2-
dicarbonitrile, coumarin, b-nitrostyrene, and 3,5-di-
methylphenylmaleimide we isolated the initial alkenes and
We demonstrated that the synthetic prospects of the
three-component reactions between TNM and alkenes
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

THREE-COMPONENT REACTIONS OF TETRANITROMETHANE WITH OLEFINS
167
homoisoxazolidine formed from olefin I and TNM that
we had described before [18]. Interestingly the small
amoumts of the same homoisoxazolidine arose also in
the three-component reaction between bicyclobutylidene,
acrylonitrile, and TNM from olefin (I) and TNM.All the
other reagents afforded mixed isoxazolidines as the only
isolated reaction products.
of nitronic ester formation from tetramethylethylene and
methylenecyclobutane become comparable.
The application of three-substituted olefins proved to
be more feasible. Phenylcyclohexene was involved into
mixed heterocyclization with TNM and olefins containing
both electron-donor and electron-acceptor substituents
using the ratio of initial reagent 1:1:1. The corresponding
isoxazolidines of mixed composition XIIIa, XIIIb and
XIVa, XIVb were thus obtained.
12
2
1
2
1
7
10
1
The characteristic features of NMR parameters
mentioned above provided a possibility of unambiguous
structural assignment of compounds XIII and XIV. NMR
spectra of compounds XIIIa, XIIIb, XIVa, XIVb
evidence that heterocyclization with participation of
phenylcyclo-hexene like that with bicyclobutylidene
occurred regioselectively furnishing diastereomers in
different ratios (Table 3) because of the presence in the
structures under discussion of asymmetric carbon atoms
and asymmetric nitrogen whose inversion is hampered.
Inasmuch as the number of diastereomers is less than
possible we believe that in the course of the reaction
certain stereocenters arise in a definite relative configura-
tion, and thus the process is diastereoselective.
ꢀ
2
2
,
1
,D
2
;
12
2
1
2 1
2
1
2 1
1
1
ꢀ
ꢀ
2
2
2
2
;
,
;,,
We investigated the possibility of application in the
three-component reactions of TNM with alkenes of the
other polysubstituted olefins beside the bicyclobutylidene
that could be involved in formation of nitronic ester of
type 3 (A, Scheme 1).
The more strained homolog of 1-phenylcyclohexene,
1-phenylcyclopentene, reacted with TNM and olefins IIa,
b to furnish a mixture of adducts of the mixed composition
XVa, b and tetranitro derivative XVI.
We found that an equimolar mixture of
tetramethylethylene and methylenecyclobutane IIa
reacted with TNM giving mainly the expected mixed
isoxazolidine X alongside two homoisoxazolidines XI [18]
and XII [5] in a ratio 3:1:1.
1
2
2
1
3
K
5 5ꢀ
5
5
ꢀ
2 1
3K
710
1
ꢂ
2
2
1
2
5
2
1
5
ꢀ
,
,DꢀꢁE
;9DꢀꢁE
2
1
3K
ꢀ
3K
,,DꢁꢂE
1
3+
&ꢁ12 ꢂ
710
2
2
ꢂ
12
;
,,,DꢁꢂE
;
9,
12
2
1
II, XV: R = R' = H (a); R, R' = CH CH (b).
2
1
2
2
3K
1
5
,9Dꢁꢂ9,,F
As show NMR data isoxazolidines XV were obtained
as a mixture of two XVa and four XVb diastereomers in
the ratios 6:5 and 10:8:5:4 respectively. Similar chemical
shifts of protons and carbons in the same fragments of
isomers XVa, b evidence that a single regioisomer is
produced by heterocyclization.
2
2
5ꢀ
;
,9DꢁꢂE
II, XII: R = R' = H (a); R, R' = CH CH (b). IV, XIV: R =
2
2
Me, R' = cyclopropyl (a). VIIc, XIVb: R = H, R'=Ac.
As already mentioned, in the three-component reac-
tion with phenylcyclopentene in contrast to the process
with phenylcyclohexene beside the principal products
XVa, b formed tetranitro derivative XVI. This version of
reaction proved to be the dominant when with TNM and
The low selectivity of the heterocyclization here may
be due to poor reactivity toward TNM of the double bond
in the tetramethylethylene caused by domination of the
steric factors over electronic ones. As a result the rates
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

168
AVERINAet al.
12
isoxazolidine. Otherwise the process is directed to the
tetranitro derivative formation [24].
2
1
2
3
K
2
1
3
K
1
We investigated as olefin 1 (Scheme 1) in reactions
with TNM a cyclic alkene with a strained double bond,
namely 1-methylcyclobutene XVIII. The reaction of
TNM with olefin XVIII at the initial reagents ratio 1:2
provided homoisoxazolidine XIX as a mixture of six
isomers in a ratio 10:9:2:1:1:1. Note that the two main
isomers are 5,5-disubstituted isoxazolidines: thus the
reaction of TNM with methylcyclobutene as in all the
other instances proceeded with a high regioselectivity.
The number of isomers is apparently due to the presence
of several asymmetric centers in the molecule of
isoxazolidine XIX. Only signals of major isomers in the
NMR spectra were attributed for those of the minor
isomers were weak and partially overlapped with the
stronger signals of the main components (Table 3).
ꢀ
;9,
2
2
2
;
9,,
&1
ꢀ
710
;9,
phenylcyclopentene were used olefins containing electron-
withdrawing substituents. For instance, bringing into the
reaction methyl vinyl ketone resulted in a mixture of
products where according to spectral data only 30%
consisted of mixed isoxazolidine XVII and the main
component was tetranitro derivative XVI. The latter
compound was the only product of the reaction with
acrylonitrile
We failed to isolate individual isoxazolidine XVII, and
Under conditions of three-component reaction olefin
XVIII reacted with TNM and olefins IIa, c in an expected
manner affording mixed isoxazolidines XXa, b. A
specific feature of these reactions is the formation of a
little (8%) levulinaldehyde, a product of oxidative
cleavage of methylcyclobutene XVIII under the action
of TNM.
therefore it was characterized only by spectral methods.
1
In the H NMR spectrum of compound XVII appeared
a double set of signals in the ratio 5:4, the protons of the
CH group in the isoxazolidine ring were observed as
2
2
two doublets of doublets at d 3.58 and 3.92 ppm ( J 15.3
Hz) and d 3.51 and 3.97 ppm ( J 15.4 Hz), and the proton
2
signals of the CH fragment gave resonances as doublets
According to NMR data (Table 3) mixed isoxazo-
lidines XXa, b form regioselectively and contain two
stereoisomers each. The stereoisomerism is caused by
formation during the heterocyclization of three asym-
metric centers (taking into account the asymmetric
nitrogen atom characterized by the hampered inversion).
The reciprocal cis-position of the methyl group and the
3
3
of doublets at d 4.38 ppm ( J 5.9 Hz, J 9.0 Hz) and d
3
3
4
.68 ppm ( J 5.9 Hz, J 9.0 Hz) respectively.
Note that the reaction of phenylcycloalkenes proper
with TNM in the ratio 2:1 furnished the corresponding
tetranitro derivatives [2]. This fact and the analysis of
our results shows that in the reaction of TNM with these
olefins compete two processes: kinetically controlled fast
formation of nitronic ester and thermodynamically
controlled formation of tetranitro derivative. When the
nitronic ester is rapidly removed from the reaction mixture
through the cycloaddition to an olefin, the product is
proton from the CHNO was proved by Overhauser
2
effect. Thus TNM adds stereoselectively across the
double bond of the methylcyclobutene, and the
asymmetric centers arising in the course of reaction
acquire a definite relative configuration.
1
2
Alkenes possessing strong electron-withdrawing
substituents (acrylonitrile, methyl methacrylate) were not
involved into heterocyclization with TNM and olefin
XVIII, and these reactions yielded as the main product
homoisoxazolidine XIX.
2
1
0
H
2
1
0
H
2
1
ꢀ
710
2
0H
;
,;
;9,,,
Thus in this study we developed a convenient
preparative procedure for alkoxy-substituted 3,3-dinitro-
isoxazolidines of a mixed composition based on a three-
component reaction of TNM with two different olefins.
1
2
2
1
2
2
1
+
,
,DꢁꢂF
0H
1
ꢀ
2
5
2
EXPERIMENTAL
2
;
;DꢁꢂF
1H and 13C NMR spectra were registered from
II, XX: R = H (a); IIc, XXb: R = CN
solutions of compounds in CDCl on spectrometers
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

THREE-COMPONENT REACTIONS OF TETRANITROMETHANE WITH OLEFINS
169
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

170
AVERINAet al.
Varian VXR-400 at operating frequencies 400 and 100
MHz respectively and Bruker DPX-300 at operating
frequencies 300 and 75 MHz respectively. The chlo-
(100), 55 (87).
7
,7-Dinitro-6-[1'-nitro-1,1'-bi(cyclobutyl)-1-
yloxy]-2-cyano-5-oxa-6-aza­spiro­[3.4]octane (IIIc).
(b)Yield 0.65 g (66%) (mixture of two diastereomers, A/
B = 4:1), mp 86–90°C, Rf 0.20 (CHCl3). Found, %:
C 45.49; H 4.85; N 17.38. C H N O . Calculated,
roform signals were used as internal standards (d 7.24,
H
dC 77.10 ppm). Mass spectra on Varian MAT-311A in-
strument at ionizing electrons energy 70 eV were mea-
sured.
1
5
19
5
8
%: C 45.34; H 4.79; N 17.63.
TNM was prepared from acetic anhydride and con-
3
,3-Dinitro-2-[1'-nitro-1,1'-bi(cyclobutyl)-1-
2
0
centrated HNO (d 1.5) by procedure [25]. Initial ole-
3
4
yloxy]-5-cyclopropylisoxazolidine (Va). (a) Yield 0.87
g (68%) (mixture of two diastereomers, A/B = 5:1), mp
2–69°C, R 0.60 (CHCl ). Found, %: C 45.46; H
fins were synthesized by the following known methods:
vinylcyclopropane, [26]; 1,1-dicyclopropyl-ethylene, [27];
6
5
5
f 3
1
,1-diisopropenylcyclopropane, [28]; diethyl -2-vinylcyclo-
propane-1,1-dicarboxylate, [29]; tetramethyl-ethylene,
30]; 1-methylcyclobut-1-ene, [31]. Besides the commer-
cial samples of bicyclo-butylidene, methylenecyclobutane,
-methylenespiro-[2.3]hexane, 1-phenyl-1-cyclopentene,
.52; N 15.45. C H N O . Calculated, %: C 45.16; H
1
4
20
4
8
.38; N 15.05.
,3-Dinitro-2-[1'-nitro-1,1'-bi(cyclobutyl)-1-
yloxy]-5,5-dicyclopropylisoxazolidine (Vb). (a) Yield
.26 g (25%), R 0.77 (CHCl ). Found, %: C 49.41;
[
3
4
0
f
3
and 1-phenyl-1-cyclohexene were applied.
H 6.28; N 13.59. C H N O . Calculated, %: C 49.51;
1
7
24
4
8
General procedure for preparation of isoxazo-
lidines of a mixed composition. (a) With a prelimi-
nary nitronic ester generation. To a solution of TNM
H 5.83; N 13.59.
Diethyl 2-{3,3-dinitro-2-[1'-nitro-1,1'-bi(cyclo-
butyl)-1-yloxy]isoxazolidine-5-yl}-cyclopropane-1,1-
dicarboxylate (Vc). (b) Yield 0.52 g (43%) (mixture of
four diastereomers). After chromatographic separation
two fractions were obtained containing two diastereomers
each: oily substance with R 0.57 (CHCl ), and crystal-
(2.5 mmol) in 5 ml of hexane cooled to 0°C was added
within 30 min at stirring a solution of olefin 1 (2.5 mmol)
in 5 ml of hexane. The mixture was stirred for 30 min
more at 0°C, and a solution was added within 30 min of
olefin 2 (2.5 mmol) in 5 ml of hexane. The reaction mix-
ture was stored at room temperature for 24–48 h. Then
the solvent was evaporated, the residue was dissolved in
f
3
line compound with R 0.36 (CHCl ), mp 94–98°C. Found,
f
3
%
: C 46.30; H 5.41. C H N O . Calculated, %:
20 28 4 12
C 46.51; H 5.43.
1
ml CHCl . The products were isolated by column chro-
3
5
-(1-Isopropenylcyclopropyl)-5-methyl-3,3-
matography (eluent chloroform).
b) One-pot synthesis. To a solution of olefin 2
2.5 mmol) and TNM (2.5 mmol) in 7 ml of hexane cooled
dinitro-2-[1'-nitro-1,1'-bi(cyclobutyl)-1-yl-oxy]iso-
xazolidine (Vd). (a) Yield 0.35 g (33%) (mixture of two
diastereomers, A/B = 3:1), R 0.66 (CHCl ). Found, %:
(
(
f
3
to 0°C was added within 1.5 h at stirring a solution of
olefin 1 (2.5 mmol) in 7 ml of hexane. The reaction mix-
ture was stored at room temperature for 24–48 h and
then worked up as in procedure (a).
C 50.73; H 6.13. C H N O . Calculated, %: C 50.70;
H 6.10.
18 26 4 8
Methyl 5-methyl-3,3-dinitro-2-[1'-nitro-1,1'-
bi(cyclobutyl)-1-yloxy]isoxazolidine-5-carboxylate
(VIIIa). (b) Yield 0.60 g (59%) (mixture of two diastere-
omers, A/B = 2:1), Rf 0.65 (CHCl3). Found, %: C 41.92;
H 4.92. C14H20N4O10. Calculated, %: C 41.58; H 4.95.
7
,7-Dinitro-6-[1'-nitro-1,1'-bi(cyclobutyl)-1-
yloxy]-5-oxa-6-aza­spiro­[3.4]­octane (IIIa). (a) Yield
.43 g (46%), mp 41–42°C, R 0.43 (CHCl ). Found, %:
0
f
3
C 45.07; H 5.07. C H N O . Calculated, %: C 45.16;
3,3-Dinitro-2-[1'-nitro-1,1'-bi(cyclobutyl)-1-
1
4
20
4
8
H 5.38.
,9-Dinitro-8-[1'-nitro-1,1'-bi(cyclobutyl)-1-
yloxy]-7-oxa-8-azadispiro­[2.2.4.0]decane (IIIb).
a) Yield 0.66 g (67%) (mixture of two diastereomers,
yloxy]-5-cyanoisoxazolidine (VIIIb). (b) Yield 0.32 g
(
1
56%) (mixture of two diastereomers, A/B = 3:1), mp
9
1
13
16–117°C, R 0.17 (CHCl ). H and C NMR spectra
f 3
were registered from solution of compound VIIIb in
CDCl – DMSO-d . Found, %: C 40.01; H 3.76; N 20.07.
(
*
A/B = 6:5), R 0.71 (CHCl ). Mass spectrum, m/z (I
3
6
f
3
rel
+
C H N O . Calculated, %: C 40.34; H 4.20; N 19.61.
%
): 352 (1) [M – NO ] , 228 (5), 182 (16), 170 (31), 154
12 15 5 8
2
(
30), 140 (37), 124 (73), 107 (55), 96 (69), 81 (70), 68
5-Acetyl-3,3-dinitro-2-[1'-nitro-1,1'- bi(cyclo-
butyl)-1-yloxy]isoxazolidine (VIIIc). (a) Yield 0.61 g
(65%) (mixture of two diastereomers, A/B = 3:2), mp
83–85°C (EtOH). Found, %: C 42.22; H 4.58; N 14.67.
*
1
Isomers ratio here and hereinafter was determined by H NMR
spectroscopy.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

THREE-COMPONENT REACTIONS OF TETRANITROMETHANE WITH OLEFINS
171
C H N O . Calculated, %: C 41.71; H 4.81; N 14.97.
bi(cyclobutyl)-1-yloxy]-3,3a,8,8a-tetrahydrO-2H-
1
3
18
4
9
indeno[1,2-d]isoxazole (IXb). (a) Yield 0.53 g (50%)
5
-Diethoxymethyl-3,3-dinitro-2-[1'-nitro-1,1'-
bi(cyclobutyl)-1-yloxy]isoxazolidine (VIIId). (a) Yield
.56 g (52%) (mixture of two diastereomers, A/B = 15:1),
mp 47–48°C, R 0.63 (CHCl ). Found, %: C 44.46; H
(
(
mixture of two regioisomers in a ratio 1:1), R 0.90
f
1
CHCl ). H NMR spectrum, d, ppm (J, Hz), of the mix-
0
3
ture of two isomers: 1.30–3.40 m (13H + 14H), 3.39 d.d
f
3
2
3
[
1H, CH CHC(NO ) , J 17.5, J 9.7, 14a], 4.72 m [H,
6
.09. C H N O . Calculated, %: C 44.24; H 5.99.
2 2 3
1
6
26
4
10
3
CHC(NO ) , 14a], 5.44 d [1H, CHC(NO ) , J 6.9, 14b],
.56 m (1H, CHO, 14b), 6.08 d (1H, CHO, J 6.9, 14a),
.20–7.44 m (4H + 4H, Ph). C NMR spectrum, d, ppm,
2
3
2 3
3
,3-Dinitro-2-[1'-nitro-1,1'-bi(cyclobutyl)-1-
yloxy]-5-chloromethylisoxazolidine (VIIIe). (a) Yield
.37 g (39%) (mixture of two diastereomers, A/B = 3:1);
R 0.33 (CHCl ). Mass spectrum, m/z (I , %): 306, 304
3
5
7
1
3
0
of the mixture of two isomers: 14.82, 14.97, 15.52 (2´),
f
3
rel.
2
8.37, 28.53, 29.30, 29.50 (2´), 29.89, 30.52, 31.11 (CH2,
+
(
(
5) [M – NO –NO] , 226 (7), 210 (16), 180 (30), 164
28), 140 (22), 124 (68), 115 (58), 95 (62), 81 (74), 70
69), 55 (100). Found, %: C 37.32; H 4.55. C H ClN O .
Calculated, %: C 37.82; H 4.47.
2
cyclo-Bu), 34.21 (CH Ph), 36.90 (CH Ph), 50.73
2
2
[
CHC(NO ) ], 58.75 [CHC(NO ) ], 89.16 (CHO), 91.14,
2 3 2 3
(
12
17
4 8
9
1
1
1
1
1.30 (C, cyclo-Bu), 92.61 (2´C, cyclo-Bu), 93.45 (CHO),
26.40 (CH, Ph), 126.81 (CH, Ph), 127.21 (2´ CH, Ph),
29.20 (CH, Ph), 129.31 (CH, Ph), 131.46 (CH, Ph),
32.20 (CH, Ph), 133.08 [C(NO ) ], 133.63 [C(NO ) ],
5
-Bromomethyl-3,3-dinitro-2-[1'-nitro-1,1'-
bi(cyclobutyl)-1-yloxy]isoxazolidine (VIIIf). (a) Yield
.53 g (50%) (mixture of two diastereomers, A/B = 4:1),
R 0.31 (CHCl ). Mass spectrum, m/z (I , %): 348, 350
2
3
2 3
0
34.28 (C, Ph), 136.81 (C, Ph), 142.65 (C, Ph), 143.37
+
f
3
rel
(C, Ph). Mass spectrum, m/z (I , %): 374 (2) [M – NO ] ,
344 (14) [M – NO –NO] , 250 (13), 204 (61), 158 (70),
rel.
2
+
+
(
5) [M – NO –NO] , 205, 207 (11), 192, 194 (22), 147,
2
2
149 (31), 147, 149 (78), 123 (100), 102 (41).
143 (84), 128 (82), 116 (74), 103 (76), 96 (70), 77 (61), 55
(
100). Found, %: C 51.34; H 4.96; N 12.98. C H N O .
3
,3-Dinitro-2-[1'-nitro-1,1'-bi(cyclobutyl)-1-
18 20 4 8
Calculated, %: C 51.43; H 4.76; N 13.33.
yloxy]-5-phenyl­isoxazolidine (VIIIg). (a) Yield 0.51
g (50%) (mixture of two diastereomers, A/B = 6:1), Rf
.68 (CHCl ). Found, %: C 49.95; H 4.90. C H N O .
7,7-Dinitro-6-(2-nitro-1-phenylcyclo-hexyloxy)-
5-oxa-6-azaspiro[3.4]octane (XIIIa). (a) Yield 0.47 g
(45%) (mixture of two diastereomers, A/B = 7:5), mp
113–114°C (EtOH). H NMR spectrum of isomer mix-
ture, d, ppm (J, Hz): 1.50–2.82 m (14H + 14H, cyclo-Bu,
cyclo-Hex), 3.28 d [1H, CH C(NO ) , J 14.9, B], 3.29
d [1H, CH C(NO ) , J 14.9, A), 3.82 br.d [1H + 1H,
CH C(NO ) , J 14.9), 5.38 m (1H, CHNO , B), 5.68 m
0
3 17 20 4 8
Calculated, %: C 50.00; H 4.90. 3,3-Dinitro-2-[1'-nitro-
,1'-bi(cyclobutyl)-1-yloxy]-5-(4-pyridyl)isoxazolidine
VIIIh).
b)Yield 0.25 g (24%) (mixture of two diastereomers,
1
1
(
2
(
2
2 3
2
A/B = 8:1), R 0.68 (CHCl ). Mass spectrum, m/z (I ,
): 362 (1) [M – HNO ] , 348 (1) [M – HNO –CH ] ,
2
2 3
f
3
rel.
+
2
+
%
3
(
2 2 3 2
2
2
2
(1H, CHNO , A), 7.32–7.37, 7.39–7.43, 7.48–7.75 m (5H
33 (4), 288 (4), 193 (7), 170 (13), 146 (24), 123 (92), 106
100), 96 (68), 78 (86), 55 (98).
,3-Dinitro-2-[1'-nitro-1,1'-bi(cyclobutyl)-1-
2
+
5H, Ph). Found, %: C 51.30; H 5.45. C H N O .
18 22 4 8
Calculated, %: C 51.18; H 5.21.
3
9
,9-Dinitro-8-(2-nitro-1-phenylcyclohexyloxy)-
-oxa-8-azadispiro[2.2.4.0]decane (XIIIb). (a) Yield
0.23 g (21%) (mixture of four diastereomers, A/B/C/D =
yloxy]-5-pentafluorophenylisoxazolidine (VIIIi). (a)
Yield 0.43 g (35%), mp 95–96°C, R 0.30 (CHCl ).
MaCC-Cïåêtð, m/z (I , %): 405 (2) [M – 2NO –H] ,
28 (6), 299 (31), 239 (34), 195 (60), 181 (42), 168 (43),
43 (49), 123 (72), 88 (100), 69 (87), 55 (94), 46 (77).
Found, %: C 43.47; H 3.80; N 10.87. C H F N O .
7
f
3
+
rel.
2
1
1
6:9:6:2); mp 143–144°C (EtOH). H NMR spectrum of
3
1
isomer mixture, d, ppm (J, Hz): 0.08–0.92 m (4H + 4H +
4
1
1
H + 4H, cyclo-Pr), 1.50–2.75 m (12H + 12H + 12H +
1
7
15
5
4
8
2
2H, cyclo-Bu, cyclo-Hex), 3.21 d [1H, CH C(NO ) , J
2
2 3
Calculated, %: C 40.96; H 3.01; N 11.24.
-(4-Bromophenyl)-3,3-dinitro-2-[1'-nitro-1,1'-
bi(cyclobutyl)-1-yloxy]­isoxazolidine (VIIIj). (a)Yield
2
5.1, B], 3.23 d [1H, CH C(NO ) , J 15.2 A], 3.25 [AB-
2
2 3
5
2
system, 1H, CH C(NO ) , J 15.3 C], 3.26 [AB-system,
2
2 3
2
1
H, CH C(NO ) , J 15.1, D], 3.45 d [1H, CH C(NO ) ,
2 2 3 2 2 3
0
3
.8 g (66%), R 0.30 (CHCl ). Found, %: C 41.13; H
.67. C H BrN O . Calculated, %: C 41.89; H 3.90.
2
2
f
3
J 15.1, B), 3.54 d [1H, CH C(NO ) , J 15.1, D], 3.83 d
2 2 3
2
1
7
19
4
8
[1H, CH C(NO ) , J15.2, A], 3.84 d [1H, CH C(NO ) ,
2 2 3 2 2 3
2
3
,3-Dinitro-2-[1'-nitro-1,1'-bi(cyclobutyl)-1-
J 15.3, C], 5.33 m (1H, CHNO , A), 5.43 m (1H,
2
yloxy]-3,3a,4,8b-tetrahydro-2H-indeno[2,1-d]-
isoxazole (IXa) and 3,3-dinitro-2-[1'-nitro-1,1'-
CHNO , D), 5.58 m (1H, CHNO , B), 5.74 m (1H,
2 2
CHNO , C), 7.27–7.52 m (5H + 5H + 5H + 5H, Ph).
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

172
AVERINAet al.
Found, %: C 53.57; H 5.40; N 12.31. C H N O . Cal-
C 50.12; H 4.85; N 13.48. C H N O . Calculated, %:
17 20 4 8
2
0
24
4
8
culated, %: C 53.57; H 5.36; N 12.50.
C 50.00; H 4.90; N 13.73.
5
-Methyl-3,3-dinitro-2-(2-nitro-1-phenylcyclo-
9
,9-Dinitro-8-(2-nitro-1-phenylcyclopentyloxy)-
hexyloxy)-5-cyclopropyl­cycloxazolidine (XIVa). (a)
Yield 0.49 g (45%) (mixture of two diastereomers, A/B =
:1), mp 129–130°C (EtOH). H NMR spectrum of
isomer mixture, d, ppm (J, Hz): 0.30–0.95 m (5H + 5H,
cyclo-Pr), 0.98 C (3H, CH ), 1.20–1.48 m (1H + 1H),
.50 c (3H, CH ), 1.54–1.90 m (3H + 3H), 2.10–2.80 m
4H + 4H), 2.94 d [1H, CH C(NO ) , J 15.3, A], 3.12 d
1H, CH C(NO ) , J15.3, B], 3.63 d [1H, CH C(NO ) ,
J15.3, B], 3.65 d [1H, CH C(NO ) , J 15.3, A], 5.44 m
1H, CHNO , A), 5.83 m (1H, CHNO , B), 7.35, 7.41,
.52 m (5H + 5H, Ph). Found, %: C 52.54; H 5.44;
N 12.80. C H N O . Calculated, %: C 52.41; H 5.29;
7
0
1
-oxa-8-azadispiro[2.2.4.0]decane (XVb). (a) Yield
.44 g (41%) (mixture of four diastereomers, A/B/C/D =
0:8:5:4), R 0.64 (CHCl ). H NMR spectrum of isomer
mixture, d, ppm (J, Hz): 0.05–0.90 m (4H + 4H + 4H +
H, cyclo-Pr), 1.50–3.20 m (10H + 10H + 10H + 10H),
.24 d [1H, CH C(NO ) , J 15.4, A], 3.26 d [1H,
1
1
1
f
3
3
4
3
1
(
2
3
2
2
2 3
2
2
2 3
CH C(NO ) , J 14.9, D], 3.33 d [1H, CH C(NO ) ,
2
2
3
2
2 3
2
[
2
2
2
2 3
2
2 3
J 15.5, B], 3.33 d [1H, CH C(NO ) , J 14.9, C], 3.55 d
[1H, CH C(NO ) , J14.9, C], 3.57 d [1H, CH C(NO ) ,
J 14.9, D], 3.82 d [1H, CH C(NO ) , J 15.5, B], 3.84 d
1H, CH C(NO ) , J 15.4, A], 5.50 m (1H, CHNO , A),
2 2 3
2
2
2
2
2 3
2
2 3
2
2 3
(
7
2
2
2
2
2 2 3
2
[
2
2
3
2
1
9
24
4
8
5.55 m (1H, CHNO , B), 5.98 m (1H, CHNO , C),
2
2
N 12.87.
-Acetyl-3,3-dinitro-2-(2-nitro-1-phenylcyclo-
hexyloxy)isoxazolidine (XIVb). (a) Yield 0.40 g (38%)
mixture of four diastereomers, A/B/C/D = 10:9:2:1),
6
.24 m (1H, CHNO , D), 7.25–7.50 m (5H + 5H +5H +
2
5
5H, Ph). Mass spectrum, m/z (I , %): 387 (1) [M –
NO –H] , 341 (2) [M – 2NO –H] , 340 (15) [M – 2NO –
rel.
+
+
2
2
2
+
+
2H] , 293 (1) [M – 3NO –3H] , 264 (8), 189 (42), 170
(
2
1
(52), 157 (62), 143 (81), 128 (78), 105 (100), 68 (100), 55
87).
R 0.70 (CHCl ). H NMR spectrum of isomer mixture,
f
3
(
d, ppm (J, Hz): 1.50–3.05 m (8H + 8H + 8H + 8H, iso-
Hex), 1.75 C (3H, CH , A), 1.96 C (3H, CH , D), 2.01 C
3
3
1-Methyl-3-(1-methyl-2-nitrocyclobutoxy)-4,4-
(
3H, CH , C), 2.06 C (3H, CH , B), 3.23 d.d [1H,
dinitro-2-oxa-3-azabicyclo[3.2.0]heptane (XIX)
(mixture of diastereomers 10:9:2:1:1:1). Yield 0.75 g
(45%), mp 88–95°C, R 0.40. H NMR spectrum of the
mixture of two main isomers, d, ppm: 1.44, 1.33, 1.59,
1.63 s (CH ), 1.8–2.50 m (cyclo-Bu), 3.83, 3.92 m [1H +
1H, CHC(NO ) ], 5.45 m (1H + 1H, CHNO ). Found,
%: C 39.90; H 4.83. C11H16N4O8. Calculated , %:
3
3
2
3
CHCH C(NO ) , J 15.2, J 7.9, C], 3.30 d.d [1H,
CHCH C(NO ) , J 15.4, J 8.4, D], 3.33 d.d [1H,
CHCH C(NO ) , J 15.5, J 5.8, A)], 3.38 d.d [1H,
CHCH C(NO ) , J 15.5, J 5.9, B], 3.82 d.d [1H,
CHCH C(NO ) , J 15.5, J 8.9, A], 3.85 d.d [1H,
CHCH C(NO ) , J 15.5, J 9.0, B], 4.18 d.d [1H,
CHCH C(NO ) , J 15.4, J 7.1, D], 4.20 d.d [1H,
CHCH C(NO ) , J 15.2, J 8.0, C], 4.49 d.d [1H,
CHCH C(NO ) , J 8.4, J 7.1, D], 4.52 d.d [1H,
CHCH C(NO ) , J 7.9, J 8.0, C], 4.73 d.d [1H,
CHCH C(NO ) , J 5.8, J 8.9, A], 5.09 d.d [1H,
CHCH C(NO ) , J 5.9, 9.0, B], 5.30 m (1H, CHNO ,
2
2 3
2
3
1
2
2 3
f
2
3
2
2 3
2
3
2
2 3
3
2
3
2
2 3
2 3
2
2
3
2
2 3
2
3
C 39.76; H 4.82.
2
2 3
2
3
6-(1-Methyl-2-nitrocyclobutoxy)-7,7-dinitro-5-
2
2 3
3
3
oxa-6-azaspiro[3.4]octane (XXa). (a) Yield 0.23 g
2
2 3
3
3
(28%) (mixture of two diastereomers, A/B = 2/1), R 0.55.
2
2 3
f
3
3
1
H NMR spectrum of isomer mixture, d, ppm (J, Hz):
2
2 3
3
1.55–2.61 m (10H + 10H, cyclo-Bu), 1.18 s (3H, CH3,
2
2 3
2
B), 5.39 m (1H, CHNO , C), 5.49 m (1H, CHNO , A),
A), 1.29 s (3H, CH
J 15.7, B], 3.36 d [1H, CH C(NO ) , J 15.7, A], 3.81
3
, B), 3.32 d [1H, CH
2
C(NO
2 3
) ,
2
2
2
2
5
5
.52 m (1H, CHNO , D), 7.30–7.60 m (5H+ 5H + 5H +
H, Ph).
2
2 3
2
2
[AB-system, 1H, CH C(NO ) , J 15.7, A], 3.85 [AB-
2 2 3
2
system, 1H, CH C(NO ) , J 15.7, B], 5.18 t (1H,
2
2 3
3
3
7
,7-Dinitro-6-(2-nitro-1-phenylcyclo-pentyloxy)-
CHNO , J 9.3, B), 5.48 t (1H, CHNO , J 9.3, A).
2
2
5
-oxa-6-azaspiro[3.4]octane (XVa). (a) Yield 0.45 g
Found, %: C 39.33; H 5.14. C H N O . Calculated,
11 16 4 8
(
1
45%) (mixture of two diastereomers, A/B = 6:5), mp
46–147°C (EtOH). H NMR spectrum of isomer
%: C 39.76; H 4.82.
-(1-Methyl-2-nitrocyclobutoxy)-7,7-dinitro-2-
cyano-5-oxa-6-azaspiro[3.4]octane (XXb). (a) Yield
.30 g (34%) (mixture of four isomers, A/B/C/D =
1
6
mixture, d, ppm (J, Hz): 1.55–3.05 m (12H + 12H), 3.27
d [1H, CH C(NO ) , J 15.1, A], 3.28 d [1H,
CH C(NO ) , J 15.1, B], 3.78 d [1H, CH C(NO ) ,
1
2
0
2
2 3
2
2
1
J
14:6:5:3), mp 112–113°C (EtOH), R 0.16. H NMR
2
2 3
2
2 3
f
2
5.1, B], 3.79 d [1H, CH C(NO ) , J 15.1, A], 5.55 d.d
spectrum of isomer mixture, d, ppm (J, Hz): 1.72–2.85 m
2
2 3
2
3
[
1H, CHNO , J 3.1, J 7.6, B], 5.68 br.d [1H, CHNO ,
(9H + 9H + 9H +9H, cyclo-Bu), 1.15 s (3H, CH , A),
2
2
3
3
J 7.1, A], 7.20–7.50 m (5H + 5H, Ph). Found, %:
1.17, 1.25, 1.28 s (3H, CH , B, C, D), 3.41 d [1H,
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

THREE-COMPONENT REACTIONS OF TETRANITROMETHANE WITH OLEFINS
173
2
CH C(NO ) , J 15.8, C], 3.52 d [1H, CH C(NO ) ,
Chem. Soc., 1968, vol. 90, p. 2174.
12. Rathore, R., Lin, Z., and Kochi, J.K., Tetrahedron Lett.,
993, vol. 34, p. 1859.
13. Rathore, R. and Kochi, J.K., J. Org. Chem., 1996, vol. 61,
p. 627.
2
2 3
2
2 3
2
2
J 16.0, A], 3.54 d [1H, CH C(NO ) , J 15.7, B], 3.78 d
2
2 3
2
1
[
1H, CH C(NO ) , J15.7, B], 3.84 d [1H, CH C(NO ) ,
2 2 3 2 2 3
2
2
J 15.8, D], 3.86 d [1H, CH C(NO ) , J 15.2, C], 3.87 d
2
2 3
2
[
1H, CH C(NO ) , J 15.7, A], 5.12 t (1H, CHNO ,
2 2 3 2
3
3
14. Shveikhgeimer, G.A., Sobtsova, N.I., and Baran’ski, A.,
Roczn. Chem., 1972, vol. 46, p. 1741.
J 9.0, B), 5.15 t (1H, CHNO , J 9.0, C), 5.41 t (1H,
CHNO , J 9.0, D), 5.43 t (1H, CHNO , J 9.0, A).
Found, %: C 40.74; H 4.10; N 19.83. C H N O .
Calculated, %: C 40.34; H 4.20; N 19.61.
2
3
3
2
2
1
5. Eberson, L., Hartshorn, M.P., and Persson, O., Acta Chem.
Scand., 1998, vol. 52, p. 745.
1
2
15
5
8
1
6. Eberson, L., Hartshorn, M.P., and Persson, O., Acta Chem.
Scand., 1998, vol. 52, p. 751.
The study was carried out under financial support of
ISTC (grant not 1151B).
17. Berg, U., Butts, C.P., Eberson, L., Hartshorn, M.P., and
Persson, O., Acta Chem. Scand., 1998, vol. 52, p. 761.
1
1
8.Averina, E.B., Ivanova, O.A., Grishin, Yu.K., Kuznetso-
va, T.S., and Zefirov, N.S., Zh. Org. Khim., 2000, vol.
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1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004