Synthesis of phosphorylated nitrocyclohexenes and nitronorbornenes [2]

Full text of DOI:10.1023/A:1023360322616

Russian Journal of General Chemistry, Vol. 72, No. 10, 2002, pp. 1652 1653. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 10, 2002,
pp. 1752 1753.
Original Russian Text Copyright
2002 by Kuzhaeva, Berestovitskaya, Deiko, Anisimova, Berkova.
LETTERS
TO THE EDITOR
Synthesis of Phosphorylated Nitrocyclohexenes
and Nitronorbornenes
A. A. Kuzhaeva, V. M. Berestovitskaya, L. I. Deiko, N. A. Anisimova, and G. A. Berkova
Gertsen Russian State Pedagogical University, St. Petersburg, Russia
Received December 25, 2001
Due to the presence of an activated multiple bond,
conjugated nitroalkenes are widely used as dieno-
philes in the Diels Alder reaction and hold promise
as synthetic blocks for designing natural and biolo-
gically active compounds [1 3].
diene synthesis involving the former compounds has
been reported [8].
We showed that nitroethenylphosphonates II and
III react with 2,3-dimethyl-1,3-butadiene and cyclo-
pentene under rather mild conditions (refluxing in
benzene for 1 2 h). The reagent ratio was 1:3 for
nitroalkene and 2,3-dimethyl-1,3-butadiene and 1:2
for nitroalkene and cyclopentadiene. The reactions
gave phosphorylated nitrocyclohexenes III and IV
and nitronorbornenes V and VI.
Highly reactive nitro- and gem-halonitroethenyl-
phosphonates [4 7] present undoubted interest for
the diene synthesis of functionalized cyclic systems
with a preset arrangement of substituents. Only one
HF
O
O
O
HA
1
HD
CH2
CH2
6
5
H3C
H3C
HD
HE
HD
2 P(OR)2
P(OR)2
H
HGC7HI
(RO)2P
3
H3C
C
C
2
1
HA
6
H3C4
NO2
3 X(HB)
NO2
5
X(HB)
X
4
HC
NO2
HC
HC
III, IV
I, II
Va, Vb, VI
R = CH2CH2Cl (I VI); X = H (I, III, Va, Vb), Br (II, IV, VI).
Compounds IV VI were isolated by column
chromatography on SiO2 as viscous yellowish oils.
Nitronorbornene VI crystallized on handling. Decreas-
ing the reflux time from 8 [8] to 1 h in the case of
compound V improved the total yield from 40 [8] to
80%; therewith, the product was isolated as a mixture
of the endo and exo isomers (6:1). The composition
of compounds III VI was confirmed by elemental
analysis, and their structure was established by means
Bis(2-chloroethyl) (3,4-dimethyl-6-nitro-3-
cyclohexene-1-yl)phosphonate (III). Yield 90%, mp
86 87 C (from hexane benzene, 5:1), beige crystals.
1H NMR spectrum (CDCl3), , ppm: 2.96 m (1H, HA,
3
3
3
2JPA 17.6 Hz, JAB 8.8 Hz, JAD 8.8 Hz, JAD
3
3
6.8 Hz), 4.85 m (1H, HB, JPB 7.3 Hz, JAB 8.8 Hz,
3JBC 7.3 Hz, JBC 5.8 Hz), 2.14 m (2H, HD , HD ),
3
2.66 m (2H, HC , HC ), 1.65 s (6H, CH3, CH3), 4.30 m
(4H, OCH2), 3.70 t (4H, CH2Cl). 31P NMR spectrum
1
of H and 31P NMR spectroscopy. The endo:exo ratio
(CDCl3),
27.50 ppm. Found, %: C 39.81, 39.85;
P
was determined on the basis of the Alder rule [2] and
the integral intensities of signals in the H NMR
spectra.
H 5.73, 5.75; N 3.94, 3.95; P 8.33, 8.33. C12H20Cl2
NO5P. Calculated, %: C 40.00; H 5.55; N 3.89;
P 8.61.
1
2-Nitro- and 2-bromo-2-nitroethenylphosphonates
I and II were synthesized as described in [9, 10].
Bis(2-chloroethyl) (6-bromo-3,4-dimethyl-6-
nitro-3-cyclohexen-1-yl)phosphonate (IV). Yield
1070-3632/02/7210-1652$27.00 2002 MAIK Nauka/Interperiodica

SYNTHESIS OF PHOSPHORYLATED NITROCYCLOHEXENES
1653
1
1
68%, oil, Rf 0.46. H NMR spectrum (CDCl3),
,
The H and 31P NMR spectra were recorded on a
Bruker AC-200 spectrometer (200 MHz). The 31P
NMR spectra were measured against 85% phosphoric
acid. The Rf values were obtained on Silufol plates,
eluent hexane acetone, 3:2.
2
3
ppm: 3.41 m (1H, HA, JPA 19.5 Hz, JAD 8.5 Hz,
3JAD 7.1 Hz), 2.40 m, 2.54 m (2H, HD , HD ), 2.90 d,
3.20 d (2H, HC , HC ), 1.48 s, 1.60 s (6H, CH3, CH3),
4.26 m (4H, OCH2), 3.67 t (4H, CH2Cl). 31P NMR
spectrum (CDCl3):
23.40 ppm. Found,%: C 32.76,
P
32.75; H 4.38, 4.39; N 3.19, 3.20; P 7.21, 7.16.
C12H19BrCl2NO5P. Calculated,%: C 32.80; H 4.33;
N 3.78; P 7.06.
REFERENCES
1. Perekalin, V.V., Lipina, E.S., Berestovitskaya, V.M.,
and Efremov, D.A., Nitroalkenes, London: Wiley,
1994, pp. 131 168.
2. The Chemistry of the Nitro and Nitroso Groups,
Feuer, H., Ed., New York: Wiley Interscience, 1970,
part 2. Translated under the title Khimiya nito- i
nitrozogrupp, Moscow: Mir, 1973, vol. 2, pp. 117
121.
3. Novikov, S.S., Shvehgeimer, G.A., Sevostyano-
va, V.V., and Shlyapochnikov, V.A., Khimiya alifa-
ticheskikh i aromaticheskikh nitrosoedinenii (Che-
mistry of Aliphatic and Aromatic Nitro Compounds),
Moscow: Khimiya, 1974, pp. 239 244.
4. Deiko, L.I., Botata, Zh. E., Paperno, T.Ya., and Beres-
tovitskaya, V.M., Zh. Obshch, Khim., 1995, vol. 65,
no. 6, pp. 1052 1053.
5. Botata, Zh.E., Deiko, L.I., Berkova, G.A., Kosti-
na, T.K., Baranov, G.M., and Berestovitskaya, V.M.,
Zh. Obshch. Khim., 1995, vol. 65, no. 6, pp. 1050
1051.
6. Berestovitskaya, V.M., Deiko, L.I., Botata, Zh.E., and
Berkova, G.A., Zh. Obshch. Khim., 1998, vol. 68,
no. 1, pp. 160 161.
7. Berestovitskaya, V.M., Deiko, L.I., Sarkisyan, Z.M.,
and Berkova, G.A., Zh. Obshch. Khim., 2001, vol. 5,
pp. 864 865.
8. Kostina, T.K., Baranov, G.M., and Perekalin, V.V.,
Zh. Obshch. Khim., 1981, vol. 51, no. 3, pp. 712 714.
9. Baranov, G.M. and Perekalin, V.V., Zh. Obshch.
Khim., 1987, vol. 57, no. 3, pp. 793 798.
Bis(2-chloroethyl) (3-nitro-5-norbornen-2-yl)-
phosphonate (Va, Vb). Yield 80%, Rf 0.36. Isomer
1
Va (endo-NO2). H NMR spectrum (CDCl3), , ppm:
3
3
3
2.48 m (1H, HF, JPF 18.0 Hz, JFE 18.0 Hz, JFE
3
3
5.0 Hz), 3.65 m (1H, HA, JAB 4.5 Hz, JAF 2.5 Hz,
2JPA 5.0 Hz), 5.22 m (1H, HB, JBC 3.0 Hz), 3.24 m
3
3
3
(1H, HC, JCB 3.0 Hz, JCD 2.5 Hz), 6.44 d.d (1H, HD,
3
3
3JDE 5.0 Hz, JDC 2.5 Hz), 5.96 m (1H, HE, JED
3
4
5.0 Hz, JEF 5.0 Hz, JPE 4.5 Hz), 1.52 m (1H, HG,
2JGI 9.5 Hz), 1.92 m (1H, HI, JIG 9.5 Hz), 4.29 m
2
(4H, OCH2), 3.65 m (4H, CH2Cl). 31P (CDCl3):
P
1
28.50 ppm. Isomer Vb (exo-NO2). H NMR spectrum
(CDCl3), , ppm: 3.10 m (1H, HF), 3.65 m (1H, HA),
4.50 m (1H, HB), 3.47 m (1H, HC), 6.35 d.d (1H, HD),
6.10 m (1H, HE), 1.62 m (1H, HG), 1.90 m (1H, HI),
4.29 m (4H, OCH2), 3.65 (4H, CH2Cl). 31P NMR
spectrum (CDCl3): P 27.80 ppm. Found, % C 38.48,
38.44; H 4.74, 4.77; N 4.20, 4.19; P 9.03, 9.11.
C11H17Cl2NO5P. Calculated, %: C 38.37; H 4.65;
N 4.06; P 9.01.
Bis(2-chloroethyl) (3-bromo-3-nitro-5-norbor-
nen-2-yl)phosphonate (VI). Yield 85%, mp 86 C
(from hexane benzene), beige crystals. 1H NMR
3
spectrum (CDCl3), , ppm: 3.18 d.d (1H, HF, JPF
3
3
23.7 Hz, JFE 5.5 Hz), 3.75 (1H, HA, JAE 3.0 Hz),
3
3
3.37 m (1H, HC JCD 2.5 Hz), 6.55 d.d (1H, HD, JDE
4
2
5.0 Hz, JPE 4.6 Hz), 1.90 d (1H, HG, JGI 9.2 Hz),
2
2.50 d (1H, HI, JIG 9.2 Hz), 4.45 (4H, CH2O), 3.75
(4H, CH2Cl). 31P NMR spectrum:
22.50 ppm.
P
Found, %: C 31.31, 31.33; H 3.56, 3.57; N 3.40, 3.40; 10. Botata, Zh.E., Deiko, L.I., Kostina, T.K., Baran-
P 7.37, 7.40. C11H16C12BrNO5. Calculated, %: C
31.21; H 3.55; N 3.31; P 7.33.
ov, G.M., and Berestovitskaya, V.M., Zh. Obshch.
Khim., 1995, vol. 65, no. 1, p. 160.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 10 2002