BIS(2-CHLOROETHYL) ETHENYLPHOSPHONATE
875
Commercial vinylphosphonate I was used in all
reactions.
tetrachloride, 0.5 g of a mixture of starting vinylphos-
phonate I and oxanonbornenes VIa and VIb was
isolated. Repeated chromatography of the mixture
of compounds I, VIa, and VIb gave 0.27 g (43%) of a
mixture of isomers VIa and VIb (eluent benzene), Rf
0.21 and 0.25.
Bis(2-chloroethyl) (3,4-dimethylcyclohex-3-en-1-
yl)phosphonate (II). To a solution of 1.5 g of bis(2-
chloroethyl) ethenylphosphonate (I) in 5 ml of an-
hydrous benzene, 0.1 g of hydroquinone and 1.53 ml
of 2,3-dimethylbuta-1,3-diene were added. The reac-
tion mixture was refluxed for 20 h. The solvent was
removed on a rotary evaporator, and the residue was
subjected to chromatography on silica gel to obtain
1.7 g of a mixture of starting alkene I and cyclo-
hexenylphosphonate II (eluent chloroform) in a 1:4
ratio. Repeated chromatography of the mixture gave
1.29 g (64%) of cyclohexene II (eluent chloroform)
as a dark brown oil, Rf 0.38, nD 1.5041 (published
data [5]: nD 1.5051, yield 36%).
Bis(2-chloroethyl) [bicyclo[2.2.2]oct-5-en-2-yl]-
phosphonate (VIIa, VIIb). To a solution of 1.8 g of
vinylphosphonate I in 5 ml of absolute p-xylene, 0.1 g
of hydroquinone and 1.23 g of 1,3-cyclohexadiene
were added. The reaction mixture was refluxed for
76 h. The solvent was removed on a rotary evaporator,
and the residue was subjected to chromatography on
silica gel. From the fraction washed out with carbon
tetrachloride, 1.5 g of a mixture of starting vinylphos-
phonate I and bicyclooctenes VIIa and VIIb was
isolated. Repeated chromatography of the mixture of
compounds I, VIIa, and VIIb gave 1.09 g (45%) of a
mixture of isomers VIIa and VIIb (eluent carbon
tetrachloride) as an oil, Rf 0.47 and 0.52.
Bis(2-chloroethyl) [3(4)-methylcyclohex-3-en-1-
yl]phosphonate (IIIa, IIIb) and bis(2-chloroethyl)
[3(4)-methylphenyl]phosphonates (IVa, IVb). To a
solution of 0.56 g of bis(2-chloroethyl) ethenylphos-
phonate (I) in 5 ml of anhydrous p-xylene, 0.1 g of
hydroquinone and 0.63 g of 3-methyl-3-thiolene 1,1-
dioxide were added; the reaction mixture was refluxed
with stirring for 20 h. The solvent was then removed
on a rotary evaporator, and the residue was subjected
to chromatography on silica gel to obtain 0.17 g
(30%) of starting vinylphosphonate I (eluent benzene),
0.40 g (55%) of cyclohexenylphosphonates IIIa and
IIIb (eluent chloroform) as a brown oil, Rf 0.67 and
0.84, and 0.11 g (15%) of arylphosphonates IVa and
IVb (eluent ether) as a brown oil with Rf 0.32 and
0.39.
Bis(2-chloroethyl) (9,10-dihydro-9,10-ethano-
anthracen-11-yl)phosphonate (VIII). To a solution
of 0.5 g of vinylphosphonate I in 5 ml of anhydrous
toluene, 0.1 g of hydroquinone and 0.37 g of anthra-
cene were added. The reaction mixture was refluxed
for 30 h. The solvent was removed on a rotary eva-
porator, and the residue was subjected to chromato-
graphy on silica gel to isolate 0.70 g of a mixture of
starting vinylphosphonate I and ethanoanthracene
VIII (eluent chloroform) in a 1:5 ratio. Repeated
chromatography of the mixture of compounds I and
VIII gave 0.41 g (48%) of compound VIII as a dark
1
brown oil, Rf 0.38. H NMR spectrum (CDCl3), ,
Bis(2-chloroethyl) [bicyclo[2.2.1]hept-5-en-2-yl]-
phosphonates (Va, Vb). To a solution of 1.5 g of bis-
(2-chloroethyl) ethenylphosphonate (I) in 5 ml of an-
hydrous benzene, 0.1 g of hydroquinone and 0.86 g
of cyclopentadiene were added. The reaction mixture
was refluxed for 10 h. The solvent was removed on a
rotary evaporator, and the residual oil was subjected
to chromatography on silica gel to obtain 1.65 g of a
mixture of vinylphosphonate I and isomeric nonbo-
rnenes Va and Vb (eluent benzene) (I:Va,Vb ratio
1:5). Repeated chromatography of the mixture of
compounds I and Va, Vb gave 1.18 g (62%) of a
mixture of diastereomers Va and Vb (eluent chloro-
form) as an oil, Rf 0.62 and 0.57.
ppm: 4.65 (1H, H10, J10,11 4.0, JPH 12.0 Hz), 3.50
10
(1H, H11, J10,11 4.0, JPH 18.0, J11,12 4.0 Hz), 3.30
11
(2H, H12, J11,12 4.0, J9,12 5.1, JPH 16.0 Hz), 4.00
12
(1H, H9, J9,12 5.1 Hz), 7.1 8.1 m (8H, H1 4, H5 8),
4.28 (4H, OCH2), 3.70 (4H, CH2C1). 31P NMR spec-
rum (CDCl3), , ppm: 35.0. IR spectrum (CHCl3), ,
1
cm : 1248 (P=O), 1028, 1081 (P O C).
REFERENCES
1. Baranov, G.M. and Perekalin, V.V., Zh. Obshch.
Khim., 1987, vol. 57, no. 4, p. 793.
2. Botata, Zh.E., Deiko, L.I., Kostina, T.K., Bara-
nov, G.M., and Berestovitskaya, V.M., Zh. Obshch.
Khim., 1995, vol. 65, no. 1, p. 160.
Bis(2-chloroethyl) [7-oxabicyclo[2.2.1]hept-5-
en-2-yl]phosphonates (VIa, VIb). To a solution of
0.5 g of vinylphosphonate I in 5 ml of acetonitrile,
0.28 g of furan was added. The reaction mixture was
heated for 10 h at 30 35 C, the solvent was removed,
and the residue was subjected to chromatography on
alumina. From the fraction washed out with carbon
3. Pudovik, A.N. and Imaev, M.G., Izv. Akad. Nauk
SSSR, 1965, no. 5, p. 916.
4. Daniewski, W.M. and Griffin, C.E., J. Org. Chem.,
1966, vol. 31, no. 10, p. 3236.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 5 2007