Synthesis and structure of phosphorylated nitrocyclohexenes

Article abstract of DOI:10.1134/S1070363207010045

Diene condensations of 2-nitro-and 2-bromo-2-nitroethenylphosphonates with 2,3-dimethyl-1,3-butadiene, as well as with 2,4-dihydro-and 3-methyl-2,4- dihydrothiophene 1,1-dioxides that generate 1,3-butadiene and isoprene under the reaction conditions were

Full text of DOI:10.1134/S1070363207010045

ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 1, pp. 25 35.
Pleiades Publishing, Ltd., 2007.
Original Russian Text V.M. Berestovitskaya, N.A. Anisimova, A.A. Kuzhaeva, G.A. Berkova, L.I. Deiko, 2007, published in Zhurnal Obshchei Khimii,
2007, Vol. 77, No. 1, pp. 29 40.
Synthesis and Structure of Phosphorylated Nitrocyclohexenes
V. M. Berestovitskaya, N. A. Anisimova, A. A. Kuzhaeva, G. A. Berkova, and L. I. Deiko
Hertsen Russian State Pedagogical University,
nab. r. Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
Received September 28, 2006
Abstract Diene condensations of 2-nitro- and 2-bromo-2-nitroethenylphosphonates with 2,3-dimethyl-1,3-
butadiene, as well as with 2,4-dihydro- and 3-methyl-2,4-dihydrothiophene 1,1-dioxides that generate 1,3-buta-
diene and isoprene under the reaction conditions were effected. (6-Nitrocyclohex-3-en-1-yl)phosphonates and
their dehydrogenation and/or dehydrohalogenation products, namely nitrocyclohexadienyl- and nitrophenyl-
1
phosphonates were prepared. The structure of the obtained compounds was proved by IR and H and 31P
NMR spectroscopy, and independent synthesis.
DOI: 10.1134/S1070363207010045
It is known that a lot of natural compounds, such
as vitamins, terpenes, hormones, alkaloids, etc.,
contain the cyclohexane ring in their structures [1, 2].
For this reason, there is unrelenting interest of organic
chemists in improving methods of synthesis of fun-
ctionally substituted six-membered rings. One of these
methods is the Diels Alder reaction. The use of ali-
phatic dienes in this reaction allows formation of a
six-membered ring, while the use of vicinal substi-
tuted nitroalkenes as dienophiles allows easily modi-
fied functional groups, such as NO2, CO2R, SO2Ph,
and others, to be introduced in the ring [3, 4]. Cyclo-
hexenes with such functional groups hold promise as
convenient reagents in the synthesis of biologically
active compounds. Thus, for example, preparation of
nitrocyclohexenes (or nitrocyclohexadienes) is the key
stage in the synthesis of a natural analgesic epibati-
dine [5, 6], non-narcotic alkaloid mesembrane [7, 8],
estrogenic hormones [9], morphine derivatives [10],
and conduritols [11] which are important starting
reagents for the design of anti-AIDS drugs.
Earlier we successfully reacted 2-nitroethenylphos-
phonates with some open-chain [15] and cyclic dienes
[16 20]. In the present work we investigated reactions
of nitroethenylphosphonates I III with typical acyclic
dienes, namely divinyl, isoprene, and 2,3-dimethyl-
buta-1,3-diene.
The reactions of nitroethenylphosphonates I, II
with 2,3-dimethylbuta-1,3-diene were performed by
refluxing the starting reagents in benzene for 1 2 h to
obtain phosphorylated nitrocyclohexenes IV, V in
90 98% yields (Table 1).
Nitroalkene III containing a methyl group at the
C1 atom and an isopropoxy group at phosphorus failed
to react with 2,3-dimethylbuta-1,3-diene under the
same conditions. The reaction required more rigid
conditions to occur: Refluxing in toluene for 10 h in
the presence of aluminum chloride. The reaction was
accompanied by dehydrogenation and gave 22% of
phosphorylated nitrocyclohexane VI and 45% of
nitrocyclohexadiene VII.
According to published data, nitroalkenes generally
enter diene condensation with alkadienes under rigid
conditions (prolonged heating in autoclave) [12-14].
Introduction of the second electron-acceptor substi-
The formation of compound VII is probably fa-
vored by increased reaction temperature and duration
[21, 22]. The much lower activity of the sterically
shielded double bond is explained by heavy demands
the Diels Alder reaction imposes on mutual orienta-
tion of the starting reagents [23, 24].
tuent (CO2R, CCl3, or SO2Ph) in the
position of
nitroalkenes favors milder reaction conditions [3, 4].
X
H3C
H3C
CH2
CH2
(RO)2(O)P
Y
X
CH3
P(O)(OR)2
NO2
, C6H6
toluene
H3C
H3C
H3C
H3C
C
C
C
C
2
5
6
3
P(O)(OR)2
NO2
Y
1
2
3
4
1
6
5
4
+
+
NO2
I III
IV VI
VII
R = CH2CH2Cl, X = Y = H (I, IV), X = H, Y = Br (II, V); R = C3H7-i, X = CH3, Y = H (III, VI).
25

26
BERESTOVITSKAYA et al.
Table 1. Yields, melting points, Rf, and elemental analyses of phosphorylated nitrocyclohexenes IV VI, VIII, XIII, XVa,
and XVIa, nitrocyclohexadienes VII and XXIV, and nitroarenes X, XI, and XXV
Found, %
Calculated, %
Comp. Yield,
mp,
(Rf)
C
Formula
no.
%
C
H
N
P
C
H
N
P
IV
90
98
22
45
38
37
45
80
36
50
39
80
86 87
(0.46)
(0.66)
(0.59)
60 62
0.24
39.81
39.85
32.76
32.75
54.15
54.19
54.45
54.49
36.14
36.21
36.50
36.52
36.50
36.55
28.99
29.01
38.21
38.33
31.21
31.22
40.45
40.50
40.27
40.35
5.73
5.75
4.38
4.39
8.33
8.35
7.93
7.95
5.00
5.01
4.21
4.25
3.21
3.25
3.87
3.88
5.16
5.24
4.02
4.07
5.21
5.25
5.10
5.11
3.94
3.95
3.19
3.20
4.38
4.39
4.38
4.39
4.19
4.20
4.30
4.31
4.30
4.31
3.53
3.54
4.09
4.11
3.15
3.19
3.80
3.81
3.80
3.81
8.53 C12H20Cl2NO5P
8.55
7.21 C12H19BrCl2NO5P
7.16
9.25 C15H28NO5P
9.28
9.25 C15H26NO5P
9.28
9.10 C10H16Cl2NO5P
9.08
9.22 C10H14Cl2NO5P
9.28
9.58 C10H12Cl2NO5P
9.28
7.90 C10H15BrCl2NO5P
7.93
9.00 C11H18Cl2NO5P
9.17
7.34 C11H17BrCl2NO5P
7.38
8.58 C12H18Cl2NO5P
8.62
8.58 C12H16Cl2NO5P
8.28
40.00
32.80
54.05
54.38
36.14
36.36
36.58
29.20
38.15
31.06
40.22
40.44
5.55
4.33
8.41
7.85
4.82
4.24
3.66
3.65
5.20
4.00
5.03
4.49
3.89
3.18
4.20
4.23
4.22
4.24
4.27
3.41
4.05
3.29
3.91
3.93
8.61
7.06
9.31
9.37
9.34
9.39
9.45
7.54
8.96
7.29
8.66
8.71
V
VI
VII
VIII
X
XI
(0.38)
(0.46)
0.67
XIII
XVa
XVIa
XXIV
XXV
0.45
(0.42)
90 100
The condensation of nitroalkenes I, II with 2,4-di-
hydrothiophene 1,1-dioxides, synthetic precursors of
aliphatic alka-1,3-dienes (divinyl, isoprene), required
still more rigid conditions (refluxing in p-xylene for
18 34 h), because desulfonylation to generate dienes
proceeds at an elevated temperature.
nitroalkenes with hydrogen eliminated from the reac-
tion product has also been reported by Itoh et al. [25].
gem-Bromonitroethenylphosphonate II reacted with
2,4-dihydrothiophene 1,1-dioxide by the same route
to give, along with cyclohexene XIII (yield 80%),
isomeric cyclohexa-1,4- and cyclohexa-2,4-dienes IX,
X, nitrophenylphosphonate XI, and bis(2-chloroethyl)
(2-bromo-2-nitroethyl)phosphonate (XIV).
The reaction of nitroalkene I with unsubstituted
2,4-dihydrothiophene 1,1-dioxide leads to formation
of bis(2-chloroethyl) (6-nitrocyclohex-3-en-1-yl)phos-
phonate (VIII). Therewith, like in the previous reac-
tion, rigid reaction conditions favored dehydrogena-
tion of cyclohexene VIII to form phosphorylated
cyclohexa-1,4- and cyclohexa-2,4-dienes IX, X, as
well as 2-nitrophenylphosphonate XI.
It is known that nitroalkenes react with 2-substi-
tuted 1,3-dienes, yielding, as a rule, a mixture of para-
and meta-substituted cyclohexenes [3, 4, 26, 27]. In
our case, an unsymmetrical diene, isoprene, formed
in situ from 3-methyl-2,4-dihydrothiophene 1,1-di-
oxide reacted with nitroalkenes I, II to form a mixture
of regioisomers with the methyl group para or meta
to the nitro group in the cyclohexene ring. The reac-
tion was carried out at 140 C in p-xylene for 13 24 h
and resulted in formation of mixtures of structural
isomers XVa, XVb and XVIa, XVIb in total yields
of 48 and 67%, respectively.
Along with the mentioned compounds, nitroethyl-
phosphonate XII was isolated. Its formation can be
explained by hydrogenation at the C C bond of nitro-
ethenylphosphonate I that had no time to react with
2,4-dihydrothiophene 1,1-dioxide (or formed as a
result of the retro process). The hydrogenation of
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SYNTHESIS AND STRUCTURE OF PHOSPHORYLATED NITROCYCLOHEXENES
27
O
O
O
O
R2
R2
P(OR1)2
P(OR1)2
P(OR1)2
P(OR1)2
Y
2
5
2
5
, 13 34 h
3
4
3
4
H2C1
O2N
1
6
1
6
+
C=C
+
+
C2H
Y
Y
Y
p-xylene
O2N
H
R2
SO2
NO2
NO2
I II
VIII, XIII
XII, XIV
meta-XVb, XVIb
para-XVa, XVIa
O
O
O
P(OR1)2
P(OR1)2
P(OR1)2
R2
R2
R2
1
2
6
3
6
6
1
5
4
5
4
1
2
5
4
3
2
3
NO2
NO2
NO2
IX
X
XI
para-XXI
para-XVII
para-XVIII
meta-XXII
meta-XX
meta-XIX
R1 = CH2CH2Cl, Y = H (I, XII), Br (II, XIV); Y = H, R2 = H (VIII), CH3 (XVa, XVb); Y = Br, R2 = H (XIII), CH3
(XVIa, XVIb); R2= H (IX XI), CH3 (XVII XXII).
The formation of regioisomers is evidenced by
teristics of structurally related compounds, reported
in [4, 38. 39].
1
doubled ring and methyl proton signals in the H
NMR spectra and phosphorus signals in the 31P NMR
1
The IR spectra of nitrocyclohexenylphosphonates,
IV VI, VIII, XIII, XV, XVI contain characteristic
bands of all proposed functional groups. The phos-
phonate group gives strong stretching vibration bands
in the ranges 1250 1240 (P=O), 1075 1110, and
spectra. The para/meta ratios determined by H and
31P NMR spectroscopy were equal to 4:1 (XVa/XVb)
and 3:1 (XVIa/XVIb). By column chromatography
we isolated individual para isomers XVa and XVIa
only.
1
1035 1010 cm (P O C). Two bands (medium and
Rigid conditions of the condensation of isoprene
with nitroalkenes I, II favor, like with divinyl, intra-
molecular transformation of nitrocyclohexenes XVa,
strong) correspond to symmetrical and unsymmetrical
vibrations of the nitro group ( 1375 1320 and
1570 1560 cm ). The weak band at 1610 cm in the
spectrum of compound XVa corresponds to the
double bond of the cyclohexene ring; for the majority
of compounds of this series, especially those with a
symmetrical C=C bond, this band is lacking.
s
as
1
1
1
XVb, XVIa, XVIb. The H and 31P NMR spectra of
the reaction mixtures showed, together with signals of
compounds XVa, XVb, XVIa, XVIb, signals of other
unsaturated cyclic systems, namely conjugated and
nonconjugated cyclohexadienes and benzene deriva-
tives. Moreover, the reaction with isoprene is com-
plicated by the fact that each nitrocyclohexene regio-
isomer undergoes intramolecular transformation, i.e.
para and meta isomers each produce their correspond-
ing pairs of nitrocyclohexadienes and nitroarenes.
Thus, the reaction of nitroalkene I with isoprene
(formed from 3-methyl-2,4-dihydrothiophene 1,1-di-
oxide) results in formation of not only phosphorylated
nitrocyclohexenes XVa, XVb, but also of their de-
hydrogenation (nitrocyclohexadienylphosphonates
XVII, XVIII, XIX, XX) and aromatization products
(2-nitrophenylphosphonates XXI, XXII).
1
The H and 31P NMR spectra (Table 2, Fig. 1)
demonstrate steric homogeneity of compounds IV VI,
VIII, XIII, Va, XVIa (their phosphorus signals are
detected in the range 23.0 27.6 ppm). The formation
of couples of para regioisomers XVa, XVIa and meta
regioisomers XVb, XVIb is confirmed by doubled
proton signals of the methyl group (1.70 and
1.75 ppm) and ring protons H1 (3.0 and 3.58 ppm for
para isomers XVa, XVIa and 3.25 and 3.50 ppm for
the meta isomers, respectively) and H6 (4.88 ppm for
para isomer XVa and 4.70 ppm for meta isomer
XVb). The methylene protons at C2 in nitrocyclo-
hexenes IV, VI, VIII, XVa, XVb appear as multiplets
in the range 1.90 2.59 ppm. The nitro group affects
the chemical shifts of the H5 methylene proton signals,
and they are observed downfield (2.32 2.78 ppm)
from those of H2 (2.50 2.59 ppm). These chemical
The structure of nitrocyclohexenes IV VI, VIII,
XIII, XVa, XVb, XVIa, XVIb was evidenced by IR,
1H, and 31P NMR spectroscopy (Table 2) and by com-
parison of their spectral data with the spectral charac-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 1 2007

28
BERESTOVITSKAYA et al.
Table 2. 1H and 31P NMR spectral data for 6-nitrocyclohexenylphosphonates
H H
H(Me)
(H)Me
P(O)(OR1)2
NO2
(H)Me
H(Br)
H H
IV VI, VIII, XIII, XVa, XVb, XVIa, XVIb
NMR spectra, , ppm (CDCl3), J, Hz
Comp.
no.
1H
Me
C2H2
C5H2
H1
H6
CH2Cl
(OCH)
PCH2 31P
(Me)
(H3, H4)
IV
1.52 s
1.62 s JH H 13.6, JH
2.30 m, 2.40 m
2.66 m
2.96 m
4.85 m
3.70 m 4.30 m 27.5
2
2
2
6
5
6
5
1 6
H1
10.2 JH H 7.3, JH H 5.8
JH H 8.8
JH P 17.6, JH P 7.3,
JH H 8.8 JH H 11.8
JHP 6.3 JHP
JHH 7.2
0
1
6
1
2
1 2
V
1.48 s
2.46 m, 2.41 m
3.19 m, 2.90 m
3.41
3.67 m 4.26 m 23.0
2
2
2
1
5
5
1
1 2
1.60 s JH H 9.7, JH H 5.4,
JH H 17.6
JH P 19.2 JH H 5.4 JHP 6.5 JHP 0
2
1 2
JH H 8.3
H1
JH
8.3
JHH 7.1
(4.61) (1.15)
JHH 7.0
JHP 6.5 JHP 1.2
3.72 m 4.35 m
JHH 7.2
VI
1.58 s
1.98 m, 1.90 m
2.42 m, 2.32 m
4.86 m
6 5
JH H 5.0
26.0
27.0
2
2
2
5
5
5
6
6
1.58 s JH H 12.6, JH P 4.5, JH H 16.6, JH H 5.0, JH P 9.8
2
5
6 5
JH H 5.0
3.00 4.90
P
H6
JH
5.6
JH
5.0
VIII
(5.72 m)
2.59 m, 2.50 m
2.78 m
2
2
1
2
1 6
JH H 7.5
JH H 11.2, JH H 6.7,
1
2
2
1
2
6
5
JH H 7.5, JH P 3.0,
JH H 6.7, JH H 6.3, JHP 6.3 JHP
JH H 7.5, JH H 7.3,
JH P 17.5 JH P 6.7
0
2
1
2
6 5
JH
3.7
P
1
6
XIII
XVa
(5.65 m,
5.85 m)
1.70 s
2.70 m
3.25 m
2.73 m
3.50
3.75 m 4.30 m 24.0
2.50 m, 2.43 m
3.00
JH H 7.2
4.88
3.67 m 4.26 m 27.0
2
2
1
2
6
5
6
5
1 6
(5.38 m) JH H 11.2, JH H 8.0, JH H 4.0, JH H 6.0
JHH 7.2
1
2
2
1
6
JH H 6.5, JH P 4.5,
JH P 17.8,
JH P 7.1, JHP 6.3
JHP 0
2
1
2
1 2
JH
5.3
JH H 8.0 JH H 6.5
P
XVb
1.75 s
(5.30 m)
2.55 m
3.10 m
2.62 m
2.70 m
2.90 m
3.20 m
3.25 m
3.58 m
3.50 m
4.70 m
3.67 m 4.26 m 27.5
JHH 7.2
JHP 6.3
JHP 0
XVIa 1.70 s
3.71 m 4.32 m 23.0
(5.32 m)
JHH 7.1
JHP 6.3 JHP
0
XVIb
1.75 s
3.71 m 4.32 m 23.5
(5.48 m)
JHH 7.1 JHP 6.3
shifts are fairly close to published data for related
compounds [4].
spectra of compounds IV, VIII, XV appear as a multi-
plet in the range 2.96 3.25 ppm, but in the case of
compounds V, XIII, XVI bromine shifts this signal
downfield to 3.41 3.58 ppm. The multiplet at 4.7
4.9 ppm in the spectra of compounds IV, VI, VIII,
XV corresponds to H6. The ring olefin protons in
compounds VIII, XIII, XV, XVI give singlets
The bromine atom in the gem position to NO2 in
V, XIII, XVIa, XVIb contributes to the downfield
shift of the H2 and H5 methylene proton signals
0.5 ppm on average. The H1 methine protons in the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 1 2007

SYNTHESIS AND STRUCTURE OF PHOSPHORYLATED NITROCYCLOHEXENES
29
CH3
CH2Cl
31P {1H}
H3C
O
H
H
P(OC2H4Cl)2
H
NO2
OCH2
2
1
6
3
4
5
H
H
H
para-
H5
H5
2 H2
H
H4
H6
H1
28.0 26.0 6.0
5.0
4.0
3.0
2.0
1.0
, ppm
1
31
Fig. 1. H and P NMR spectra of bis(2-chloroethyl) (para-3-methyl-6-nitrocyclohex-3-en-1-yl)phosphonate (XVa) in CDCl .
3
and multiplets at 5.30 5.85 ppm. The H3 and H4 sig-
nals of compound VIII overlap (5.72 ppm), whereas
in compound XIII these proton signals are resolved:
5.65 (H3) and 5.85 ppm (H4). The chemical shifts of
methyl protons vary depending on the position of the
methyl group. Thus, the methyl groups at saturated
carbon atoms and isopropyl methyl groups in com-
pound VI appear at 1.25 ppm, while the methyl
groups at the ring C=C bond in compounds IV VI,
X, XV, at 1.48 1.75 ppm.
[30, 31]. Hence, the six-membered ring in compounds
IV, VIII, XV has a half-chair conformation with
equatorial arrangement of bulky substituents [NO2 and
P(O)(OR)2] and anti orientation of the vicinal protons
along the C1 C6 bond in the Newman projection.
For elucidation of the structure of nitrocyclohexa-
dienyl- and nitroarylphosphonates isolated from the
mixture of the Diels Alder reaction products, we tried
to synthesize these compounds directly from bromo-
nitrocyclohexanes V, XIII, XXIa, XXIb by dehydro-
halogenation. In was found that halonitrocyclohexene
V, when refluxed in benzene in the presence of tri-
ethylamine, splits off HBr to form a mixture of nitro-
cyclohexa-1,4- and -1,2-dienes XXIII and XXIV. The
use of pyridine as dehydrohalogenating agent and
prolonged (48 h) heating in benzene induced forma-
tion of aromatic derivative XXV, along with cyclo-
hexadienes XXIII, XXIV.
H6
O
H6
O2N
(RO)2P
O2N
6
H
H
4
5
2
(3)
4
5
( )
1
|
|3
H
H
H
2
6
1
H
P(OR)2
H1
H1
O
To establish mutual arrangement of the nitro and
phosphonate groups and conformational character-
istics of the six-membered ring in nitrocyclohexenyl-
phosphonates, we used as analytical criterion the
value of the spin-spin coupling constant of the vicinal
protons H1 and H6. For the investigated compounds
The splitting off of HBr from bromonitrocyclo-
hexene XIII (under reflux in benzene for 48 h in the
presence of pyridine) also gave a mixture of nitro-
cyclohexadienylphosphonates IX, X and nitrophenyl-
phosphonate XI.
3
the J1.6 values span the range 7.2 8.8 Hz, which
corresponds to the dihedral angle between the vicinal
protons of about 180 or to their axial arrangement
Dehydrobromination of cyclohexenes XVIa, XVIb
1
occurred in a more intricate fashion. The H and 31P
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30
BERESTOVITSKAYA et al.
O
O
O
O
P(OR)2
6
3
R1
R2
R1
5
4
R1
1
(1) pyridine
(2) triethylamine
R1
R2
1
5
5
P(OR)2
P(OR)2
P(OR)2
6
6
H
1
+
+
Br
3
HBr
R2
4
2 NO2
R2
4
2 NO2
2 NO2
NO2
3
V, XIII, XVIa, XVIb
IX, XVII, XIX, XXIII X, XVIII, XX, XXIV XI, XXI, XXII, XXV
R1 = R2 = CH3 (V, XXIII XXV); R1 = R2 = H (XIII, IX XI); R1 = CH3, R2 = H (XVI XVIII, XXI); R1 = H, R2 = CH3
(XIX, XX, XXII).
NMR spectra of the reaction mixture after 46-h re-
fluxing in toluene in the presence of pyridine revealed
formation of regioisomeric para- and meta-non-
conjugated XVII, XIX and conjugated XVIII, XX
cyclohexadienes and corresponding arenes XXI, XXII.
However, we failed to isolate individual compounds
from this multicomponent mixture.
The structure of nitroaromatic compounds XI, XXI,
XXII, XXV was elucidated on the basis of their spec-
1
tral characteristics (Table 3). For example, in the H
1
Table 3. H and 31P NMR spectral data for nitrocyclohexadienylphosphonates VII, IX, X, XVII XXIV and nitroaryl-
phosphonates XI, XXI, XXII, XXV
O
O
O
6
3
R3
R2
5
4
R3
R2
1
R3
R2
1
5
4
5
4
P(OR)2
P(OR)2
X
P(OR)2
6
6
1
3
2 NO2
2 NO2
2 NO2
3
IX, XVII, XIX, XXIII VII, X, XVIII,
XX, XXIV
XI, XXI, XXII, XXV
NMR spectra, , ppm (CDCl3), J, Hz
Comp.
no.
31P
C1H, (CH3)
3.50 m
C5H
C4H, (CH3) C5H, (CH3)
C6H
CH2Cl, (CH3) OCH2, (OCH)
Nitrocyclohexadienylphosphonates
IX
12
2.70 m
2.45 m
2.41 m
2.50 m
7.50
6.40 m
5.50 m
(1.78 s)
(1.68 s)
(2.30 s)
5.40 m
(1.75 s)
5.45 m
(1.63 s)
(2.22 s)
2.50 m
2.40 m
2.45 m
2.40 m
3.75,
3.72 m
3.70 m
3.70 m
3.70 m
(1.33 m)
4.30 m
4.35 m
4.45 m
4.45 m
(4.75 m)
XVII
XIX
XXIII
VIIa
15.5
17.5
13
(1.33)
3
JCH P 17
JH P 16.5
JCH P 16
2.520 m
2.50 m
2.55 m
3
X
XVIII
XX
28
27
24
8.00 m
8.02 m
7.80
7.10 m
7.40 m
(2.42 s)
7.30 m
(2.32 s)
7.50 m
3.71 m
3.68 m
3.70 m
4.38 m
4.35 m
4.38 m
3.50
3.50 m
3
JH P 8.00
XXIV
23
3.60 m
7.80
(2.38 s)
(2.30 s)
2.50 m
3.70 m
4.30 m
3
JH P 8.00
Nitroarylphosphonates
XI
XXI
XXII
15
14
15
8.20 m
8.15 m
8.00
7.35 m
7.15 m
(2.50 s)
7.50 m
(2.25 s)
7.20 m
6.31 m
6.30 m
6.50 m
3.71 m
3.70 m
3.71 m
4.40 m
4.45 m
4.38 m
3
JH P 9.00
XXV
17
8.12
(2.42 s)
(2.30 s)
6.18
3.71
JHH 7.20,
JHP 1.20
4.38
JHP 6.80
3
6
JH P 15.8
JH P 6.00
a
1
1
In compound VII, R = i-C H and X = CH ; in the other compounds, R = CH CH Cl and X = H.
3
7
3
2
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 1 2007

SYNTHESIS AND STRUCTURE OF PHOSPHORYLATED NITROCYCLOHEXENES
31
31P {1H}
H3C
H3C
CH3
O
CH3
P(OCH2CH2Cl)2
6
CH3
1
2
5
4
CH2Cl
3
NO2
O
OCH2
H3C
P(OC3H7-i)2
H3C
H3C
6
1
2
3
5
4
NO2
CH3
CH3
H3
H6
OCH H6
H3
18.0 15.0
8.0 7.0 6.0 5.0 4.0 3.0 2.0
, ppm
8.0
7.0
6.0
5.0
4.0
3.0
2.0 1.0
, ppm
1
31
1
Fig. 2. H and P NMR spectra of bis(2-chloroethyl)
Fig. 3. H NMR spectra of diisopropyl (1,4,5-trimethyl-
2-nitrocyclohexa-2,4-dien-1-yl)phosphonate (VII) in
(4,5-dimethyl-2-nitrophenyl)phosphonate
(XXV)
in
CDCl .
3
CDCl .
3
NMR spectrum of compound XXV the H6 signal is at
6.18 ppm and the H3 signal, due to the action of the
electron-acceptor NO2 group, is shifted downfield to
8.12 ppm. Both signals are doublets (Fig. 2), on ac-
count of the spin spin coupling of H3 and H6 with
phosphorus.
the corresponding parameters of structurally related
compounds [4, 33].
The two conjugated C=C bonds in the six-mem-
bered ring causes a downfield shift of the methylene
and olefin proton signals compared to the respective
signals of the starting cyclohexenes and nonconju-
gated cyclohexadienes [33] (Tables 2, 3). Thus, in the
1H NMR spectra of cyclohexadiene VII the H3 olefin
proton gives a doublet at 7.5 ppm, and ring methylene
protons, a signal at 3.7 ppm (Fig. 3).
The same pattern of benzene proton signals is ob-
1
served in the H NMR spectra of compounds XI,
XXI, XXII, which allows these compounds, too,
to be related to aromatic derivatives. The phosphorus
signals of compounds XI, XXI, XXII, XXV are in the
range 14.0 17.0 ppm. The IR spectra of nitroaryl-
phosphonate XXV contain characteristic absorption
bands of the functional groups present in the molecule:
Compounds X, XVIII, XX, XXIV show similar
1H NMR spectral pictures, which allows these com-
pounds to be related to conjugated cyclohexadienes
(Table 3).
The phosphonate group gives three bands at 1250
1
(
P=O) and 1085 and 1025 cm
( P O C), and the
An important criterion in the structural analysis of
the investigated compounds is the value of the chem-
ical shift of methyl protons. The signals of the methyl
group at C1 and isopropoxy methyl groups in com-
pound VII almost coincide and occur at 1.33
1.35 ppm. The signals of the CH3 group at the C=C
bond in nonconjugated dienes XVII, XIX, XXIII are
detected in the range 1.63 1.74 ppm, but the respec-
tive signals of conjugated VI, XVIII, XX, XXIV and
aromatic XXI, XXII, XXV structures are shifted
downfield (2.22 2.50 ppm).
conjugated nitro group, two bands at 1550 and
1
1360 cm .
The assignment of nitrocyclohexadienylphospho-
nates to conjugated (VII, X, XVIII, XX, XXIV) and
nonconjugated (IX, XVII, XIX, XXIII) systems was
1
carried out by analysis of their H and 31P NMR spec-
tral characteristics and comparison with the corres-
ponding characteristics of model nitrocyclohexadienes
[4]. Nonconjugated cyclohexadienes IX, XVII, XIX,
1
XXIII are characterized by the presence in the H
NMR spectra of signals of methylene protons at C3
and C6 (2.40 2.40 ppm) and olefin protons at an iso-
lated C=C bond (5.45 5.50 ppm), in accordance with
The position of methyl proton signals was used to
identify the para and meta isomers of nitrocyclohexa-
dienes. The downfield CH3 signal at 2.42 ppm cor-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 1 2007

32
BERESTOVITSKAYA et al.
enes provides a convenient synthetic route to nitro-
31P {1H}
cyclohexenylphosphonates, nitro precursors of po-
tentially biologically active compounds [32], speci-
fically -aminophosphonic acids of the cyclohexane
series. The synthesis of one of such compounds we
described in [34].
O
CH2Cl
2
1
O2N CH CH2 P(OC2H4Cl)2
OCH2
Br
CH2
EXPERIMENTAL
The IR spectra were recorded on an Infra-LYUM
CH
FT-02 spectrometer in chloroform (c 0.1 0.001 M).
1
The H and 31P NMR spectra were registered on a
Brucker AC-200 spectrometer (200 MHz) in CDCl3
against external HMDS (1H; accuracy 0.5 Hz,
scale) or external 85% phosphoric acid (31P). Indivi-
dual compounds were isolated by column chromato-
graphy on silica gel (Chemapol 100/200). Purity and
reaction control was performed TLC on Silufol-254
plates, eluent hexane acetone (3:2), developer iodine
17.0 15.0
6.0
5.0
4.0 , ppm
1
31
Fig. 4. H and P NMR spectra of bis(2-chloroethyl)
(2-bromo-2-nitroethyl)phosphonate (XIV) in CDCl .
3
responds to proximate arrangement of the methyl and
nitro groups in meta isomer XX. At the same time,
the CH3 group in para isomer XVIII experiences a
weaker effect from the electron-acceptor nitro group,
and, as a result, its signal is shifted upfield (2.32 ppm).
1
vapor. Compound ratios were determined by H and
31P NMR spectroscopy after column chromatography.
The starting nitro- and gem-bromonitroethenyl-
phosphonates I III were prepared by published
procedures [35 37].
The phosphorus signals of conjugated dienes VII,
X, XVIII, XX, XXIV appear at 23.0 28.0 ppm and
those of nonconjugated dienes IX, XVII, XIX, XXIII
and aromatic structures XI, XXI, XXII, XXV, at 12.0
17.5 ppm, providing evidence showing that the phos-
phonate group is located at the sp3- and sp2-carbon
atoms, respectively.
Bis(2-chloroethyl) (3,4-dimethyl-6-nitrocyclo-
hex-3-en-1-yl)phosphonate (IV). To a solution of
1.10 g of bis(2-chloroethyl) 2-nitroethenylphospho-
nate (I) in 6 ml of absolute benzene, 1.50 ml of 2,3-
dimethylbuta-1,3-diene in 1 ml of anhydrous benzene
was added, and the reaction mixture was heated under
reflux for 1 h. The solvent was then removed on a
rotary evaporator to give 1.25 g (90%) of compound
IV, mp 86 87 C (from hexane benzene, 5:1).
The IR and H and 31P NMR spectral character-
1
istics of nitro- and bromonitroethylphosphonates XII,
XIV completely correspond to the proposed structures.
Thus, the methylene proton signals of compound XII
are at 4.69 (C1H2) and 4.88 ppm (C2H2). The bromine
atom in compound XIV contributes to the downfield
shift of the C1H2 signals to 4.82 ppm, and the C2H
methine proton resonates at 6.05 ppm (Fig. 4). The
phosphorus signals are singlets in the range of 16.0
20.0 ppm.
Bis(2-chloroethyl) (6-bromo-3,4-dimethyl-6-
nitrocyclohex-3-en-1-yl)phosphonate (V). To a solu-
tion of 1.00 g of bis(2-chloroethyl) 2-bromo-2-nitro-
ethenylphosphonate (II) in 5 ml of anhydrous benze-
ne, 0.90 ml of 2,3-dimethylbuta-1,3-diene in 1 ml of
absolute benzene was added, and the reaction mixture
was refluxed for 1 h. The solvent was then removed
on a rotary evaporator. The residual yellow oil was
purified by chromatography on silicic acid, eluent
benzene, to obtain 1.20 g (98%) of compound V as an
oil, Rf 0.46.
Thus, we developed conditions for the reaction of
2-nitro- and 2-bromo-2- nitroethenylphosphonates
with 2,3-dimethylbuta-1,3-diene, as well as with 2,4-
dihydrothiophene and 3-methyl-2,4-dihydrothiophene
1,1-dioxides, synthetic precursors of alka-1,3-dienes.
We found that nitro- phosphorylated cycloadducts
show enhanced tendency for intermolecular transfor-
mations under their preparation conditions (dehydro-
bromination, dehydrogenation, and aromatization),
and the highest reactivity is characteristic of bromine-
containing nitrocycloalkenylphosphonates.
Diisopropyl (6-nitro-1,3,4-trimethylcyclohex-3-
en-1-yl)phosphonate (VI) and diisopropyl (2-nitro-
1,4,5-trimethylcyclohexa-2,4-dien-1-yl)phosphonate
(VII). To a solution of 0.80 g of diisopropyl 1-me-
thyl-2-nitroethenylphosphonate (III) in 6 ml of to-
luene, 0.05 g of aluminum chloride and 2.55 ml of
2,3-dimethylbuta-1,3-diene were added. The reaction
mixture was heated under reflux for 10 h and held for
We found that the Diels-Alder reactions with
2-nitroethenylphosphonates and acyclic alka-1,3-di-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 1 2007

SYNTHESIS AND STRUCTURE OF PHOSPHORYLATED NITROCYCLOHEXENES
33
3 days at 20 C. Aluminum chloride was filtered off,
the solvent was removed on a rotary evaporator, and
the oily residue was purified by chromatography on
alumina. From the benzene fraction, 0.45 g (45%) of
compound VII was isolated as a light yellow oil, Rf
0.59. From the ether fraction, 0.22 g (22%) of com-
pound VI was isolated as a light yellow oil, Rf 0.66.
the ether fraction after repeated chromatography,
0.09 g (10%) of compound XIV was isolated as an
oil crystallizing on storage, mp 51 53 C. IR spectrum
1
(CHCl3), , cm : 1570, 1375 (NO2), 1270 (P=O),
1
1025, 1080 (P O C). H NMR spectrum (CDCl3), ,
ppm (J, Hz): 4.82 m (2H, CH2P(O)(OR)2) (3JHH 3.24,
JH P 3.5); 6.05 m (1H, CHBrNO2) (3JHH 3.24, JH P
2.00); 3.70 m (4H, 2CH2Cl), 4.40 m (4H, 2OCH2).
31P NMR spectrum (CDCl3), P, ppm: 16.00. Found
%: C 20.25, 20.27; H 4.18, 4.20; N 4.18, 4.20.; P
8.40, 8.48. C6H11BrCl2NO5P. Calculated %: C 20.05;
H 3.06; N 3.90; P 8.64.
1
2
Bis(2-chloroethyl) (6-nitrocyclohex-3-en-1-yl)-
phosphonate (VIII), bis(2-chloroethyl) (2-nitro-
cyclohexa-1,4-dien-1-yl)phosphonate (IX), bis-
(2-chloroethyl) (2-nitrocyclohexa-2,4-dien-1-yl)-
phosphonate (X), bis(2-chloroethyl) 2-nitrophenyl-
phosphonate (XI), and bis(2-chloroethyl) 2-nitro-
ethylphosphonate (XII). To a solution of 1.52 g of
bis(2-chloroethyl) 2-nitroethenylphosphonate (I) in
10 ml of p-xylene, 0.78 g of 2,4-dihydrothiophene
1,1-dioxide was added, and the reaction mixture was
refluxed for 34 h. The solvent was removed on a
rotary evaporator, and the residual oil was subjected
to chromatography on silica gel. From the first ben-
zene fraction (ca. 200 ml), 0.69 g (38%) of compound
VIII was isolated, mp 60 62 C. From the second
benzene portion (ca. 200 ml), 0.20 g of a mixture of
compounds IX, X, and XI (1:3:1) was isolated as a
yellow oil. From the ether fraction, 0.22 g of a mix-
ture of compounds XI and XII (1:10) was isolated as
a yellow oil. The latter mixture was subjected to
repeated chromatography to isolate, from the ether
fraction, 0.20 g (13%) of compound XII as an oil
crystallizing on storage, mp 80 81 C. IR spectrum
Bis(2-chloroethyl) [3(4)-methyl-6-nitrocyclohex-
3-en-1-yl]phosphonates (XVa, XVb), bis(2-chloro-
ethyl) [5(4)-methyl-2-nitrocyclohexa-1,4-dien-1-yl]-
phosphonates (XVII, XIX), bis(2-chloroethyl) [5(4)-
methyl-2-nitrocyclohexa-2,4-dien-1-yl]phosphona-
tes (XVIII, XX), bis(2-chloroethyl) [5(4)-methyl-2-
nitrophenyl]phosphonates (XXI, XXII), and bis(2-
chloroethyl) 2-nitroethylphosphonate (XII). To a
solution of 1.00 g of bis(2-chloroethyl) 2-nitroethen-
ylphosphonate (I) in 10 ml of p-xylene, 1.32 g of
3-methyl-2,4-dihydrothiophene 1,1-dioxide was added,
and the reaction mixture was heated under reflux for
24 h. The solvent was removed on a rotary evaporator,
and the residue was subjected to chromatography on
silica gel. From the first benzene fraction (ca. 100 ml),
0.14 g of a mixture of compounds XVII, XIX, and
XXI (2:1:1) was isolated as a yellow oil, and from
the second benzene fraction (ca. 100 ml), 0.22 g of a
mixture of compounds XVII, XX, and XXII (2:1:2)
as a yellow oil. From the chloroform fraction, 0.6 g
(48%) of compound XV as a mixture of structural
isomers XVa and XVb (4:1), Rf 0.67 and 0.55, respec-
tively. From the ether fraction, 0.15 g (15%) of com-
pound XII was isolated as an oil crystallizing on
storage, mp 80 81 C. Repeated chromatography of
the mixture of isomers XVa and XVb, eluent chloro-
form, gave 0.45 g (36%) of para isomer XVa, Rf 0.67.
1
(CHCl3), , cm : 1560, 1375 (NO2), 1220 (P=O),
1
1030, 1090 (P O C). H NMR spectrum, (CDCl3), ,
ppm (J, Hz): 4.69 m (2H, CH2P(O)(OR)2) (3JHH 5.8,
JH P 3.4); 4.88 m (2H, CH2NO2) (3JHH 5.8, JH P 6.8);
1
2
3.75 m (4H, 2CH2Cl), 4.43 m (4H, 2OCH2). 31P NMR
spectrum (CDCl3), P, ppm: 20.00. Found, %: C 25.79,
25.71; H 4.45, 4.38; N 5.04, 5.16; P 11.12, 11.28.
C6H12Cl2NO5P. Calculated, %: C 25.71; H 4.28; N
5.00; P 11.07.
Bis(2-chloroethyl) [6-bromo-3(4)-methyl-6-ni-
trocyclohex-3-en-1-yl]phosphonate (XVIa, XVIb),
bis(2-chloroethyl) [5(4)-methyl-2-nitrocyclohexa-
1,4-dien-1-yl]phosphonates (XVII, XIX), bis(2-
chloroethyl) [5(4)-methyl-2-nitrocyclohexa-2,4-di-
en-1-yl]phosphonates (XVIII, XX), bis(2-chloro-
ethyl) [5(4)-methyl-2-nitrophenyl]phosphonates
(XXI, XXII), and bis(2-chloroethyl) 2-bromo-2-
nitroethylphosphonate (XIV). To a solution of
1.00 g of bis(2-chloroethyl) 2-bromo-2-nitroethenyl-
phosphonate (II) in 10 ml of p-xylene, 1.11 g of
3-methyl-2,4-dihydrothiophene 1,1-dioxide was added,
and the reaction mixture was refluxed for 13 h. The
solvent was removed on a rotary evaporator, and the
residue was subjected to chromatography on silica gel.
Bis(2-chloroethyl) (6-bromo-6-nitrocyclohex-3-
en-1-yl)phosphonate (XIII), bis(2-chloroethyl)
2-nitrophenylphosphonate (XI), and bis(2-chloro-
ethyl) 2-bromo-2-nitroethylphosphonate (XIV). To
a solution of 1.00 g of bis(2-chloroethyl) 2-bromo-2-
nitroethenylphosphonate (II) in 10 ml of p-xylene,
0.40 g of 2,4-dihydrothiophene 1,1-dioxide was added,
and the reaction mixture was refluxed for 18 h. The
solvent was removed on a rotary evaporator, and the
residual oil was subjected to chromatography on silica
gel. From the chloroform fraction, 0.92 g (80%) of
compound XIII was isolated as an oil, Rf 0.46. From
the ether fraction, 0.17 g of a mixture of compounds
XIV and XI (1:1) was isolated as a yellow oil. From
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 1 2007

34
BERESTOVITSKAYA et al.
From the first benzene fraction (ca. 100 ml), 0.08 g
of a mixture of compounds XVII, XIX, and XXII
(3:1:1) was isolated as a yellow oil. From the second
benzene fraction (ca. 100 ml), 0.06 g of a mixture of
compounds XVIII, XX, and XXI (1:0.5:1) was iso-
lated as a yellow oil. From the chloroform fraction,
0.80 g (67%) of compound XVI as a mixture of struc-
tural isomers XVIa and XVIb (3:1), Rf 0.45 and 0.32,
respectively, was isolated. From the ether fraction,
0.10 g (10%) of compound XVI was isolated as an
oil crystallizing on storage, mp 51 53 C. Repeated
column chromatography of the mixture of isomers
XVIa and XVIb, eluent chloroform, gave 0.6 g (50%)
of para isomer XVIa, Rf 0.45.
of anhydrous benzene, 0.48 ml of pyridine was added,
and the reaction mixture was refluxed for 48 h. The
pyridine hydrobromide formed was filtered off, the
filtrate was evaporated on a rotary evaporator, and the
residue was subjected to chromatography on a silica
gel. From the benzene fraction, 0.20 g of a mixture of
compounds IX and X (1:6) was isolated as a yellow
oil. From the methanol fraction, 0.18 g (45%) of
compound XI was isolated as a yellow oil, Rf 0.38.
Repeated chromatography of the mixture of com-
pounds IX and X gave 0.15 g (37%) of compound X
as a yellow oil, Rf 0.24.
Bis(2-chloroethyl) [5(4)-methyl-2-nitrocyclo-
hexa-1,4-dien-1-yl]phosphonates ( XVII, XIX), bis-
(2-chloroethyl) [5(4)-methyl-2-nitrocyclohexa-2,4-
dien-1-yl]phosphonates (XVIII, XX), and bis(2-
chloroethyl) (5-methyl-2-nitrophenyl)phosphonate
(XXI). a. To a solution of 0.48 g of bis(2-chloroethyl)
[6-bromo-3(4)-methyl-6-nitrocyclohex-3-en-1-yl]-
phosphonates (XVIa, XVIb) in 4 ml of absolute to-
luene, 0.45 ml of pyridine was added, and the reaction
mixture was refluxed for 46 h. The pyridine hydro-
bromide formed was filtered off, the filtrate was
evaporated on a rotary evaporator, and the residue was
subjected to chromatography on silica gel. From the
chloroform fraction, 0.30 g of a mixture of com-
pounds XVII and XIX (3:1) was isolated as a yellow
oil. From the methanol fraction, 0.12 g of a mixture
of compounds XVIII, XX, and XXI (2:1:3) was
isolated as a yellow oil.
Bis(2-chloroethyl) (4,5-dimethyl-2-nitrocyclo-
hexa-1,4-dien-1-yl)phosphonate (XXIII), bis(2-
chloroethyl) (4,5-dimethyl-2-nitrocyclohexa-2,4-
dien-1-yl)phosphonate (XXIV), and bis(2-chloro-
ethyl) (4,5-dimethyl-2-nitrophenyl)phosphonate
(XXV). a. To a solution of 0.50 g of bis(2-chloro-
ethyl) (6-bromo-3,4-dimethyl-6-nitrocyclohex-3-en-1-
yl)phosphonate (V) in 4 ml of anhydrous benzene,
0.16 ml of triethylamine was added, and the reaction
mixture was refluxed for 4 h. After cooling, the tri-
ethylamine hydrobromide formed was filtered off,
20 ml of benzene was added to the filtrate, and the
resulting solution was washed with water. The ben-
zene solution was separated, dried over magnesium
sulfate, and the solvent was removed on a rotary
evaporator. The residue was subjected to chromato-
graphy on silica gel. From the ether fraction, 0.15 g
(39%) of compound XXIV was isolated as an oil, Rf
0.42. From the methanol fraction, 0.12 g of a mixture
of compounds XXIII and XXIV (2:5) was isolated as
a yellow oil, Rf 0.68 and 0.42.
b. To a solution of 0.60 g of bis(2-chloroethyl)
[6-bromo-3(4)-methyl-6-nitrocyclohex-3-en-1-yl]-
phosphonates (XVIa, XVIb) in 10 ml of anhydrous
benzene, 0.58 ml of pyridine was added, and the reac-
tion mixture was heated under reflux for 84 h. The
pyridine hydrobromide formed was filtered off, the
filtrate was evaporated on a rotary evaporator, and the
residue was subjected to chromatography on silica gel.
From the first chloroform fraction (ca. 100 ml), 0.20 g
of a mixture of compounds XVII and XIX (3:1) was
isolated as a yellow oil. From the second chloroform
fraction (ca. 100 ml), 0.35 g of a mixture of com-
pounds XVIII, XX, and XXI (2:1:5) was isolated as
a yellow oil.
b. To a solution of 0.50 g of compound V in 4 ml
of anhydrous benzene, 1.00 ml of pyridine was added,
and the reaction mixture was refluxed for 48 h. After
cooling, the pyridine hydrobromide formed was fil-
tered off, and the filtrate was evaporated on a rotary
evaporator. The residue was extracted with ether, and
the solvent was removed to obtain 0.32 g (80%) of
compound XXV, mp 99 100 C (from CCl4). The
residue after extraction with ether was subjected to
repeated chromatography. From the methanol fraction,
0.06 g of a mixture of compounds XXIII and XXIV
(1:3) was isolated, Rf 0.68 and 0.42, respectively.
Bis(2-chloroethyl) (2-nitrocyclohexa-1,4-dien-1-
yl)phosphonate (IX), bis(2-chloroethyl) (2-nitro-
cyclohexa-2,4-dien-1-yl)phosphonate (X), and bis-
(2-chloroethyl) 2-nitrophenylphosphonate (XI). To
a solution of 0.50 g of bis(2-chloroethyl) (6-bromo-6-
nitrocyclohex-3-en-1-yl)phosphonate (XIII) in 10 ml
ACKNOWLEDGMENTS
The work was financially supported by the Mi-
nistry of Education of the Russian Federation (grant
no. E 02-5.0-138).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 1 2007

SYNTHESIS AND STRUCTURE OF PHOSPHORYLATED NITROCYCLOHEXENES
35
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