REACTION OF DI-2-CHLOROETHYL 2-CHLOROETHANEPHOSPHONATE
739
Esters derived from di-2-chloroethyl 2-chloroethane-
phosphonate and potassium methacrylate were prepared
at the initial component ratios of 1 : 1, 1 : 2, and 1 : 3.
at δ 5.57 and 5.94 ppm correspond to nonequivalent
protons in the methacrylate moiety. The intensity of the
proton signals from the unsaturated fragment exceeds
the intensity of the proton signals from the methyl group
of the methacrylate. This fact can be attributed to the
formation of ethenephosphonate along with phosphorus-
containing methacrylate, which is confirmed by the
1
: 1 ratio. A four-necked reactor equipped with
a stirrer,arefluxcondenser,athermometer,anda calcium
chloride tube was charged with 40 g (0.074 mol) of
di-2-chloroethyl 2-chloroethanephosphonate, 18.4 g
1
presence in the H NMR spectrum of the typical ABX
(0.074 mol) of vacuum-dried potassium methacrylate,
pattern from protons H , H , and H , with the coupling
A
B
X
2
5 ml of dimethylformamide (DMF), and 0.01 g of
constants JAB 2.2, JAХ 17.9, and JBХ 11.4 Hz.Appearance
of signals corresponding to vinyl group protons (δ 6.15
and 6.25 ppm) and a sharp decrease in the signal from
methylene protons of the chloroethyl group bonded to
the P atom (δ 2.2 ppm) indicate that the methacrylate
formation is accompanied by dehydrochlorination with
the formation of the ethenephosphonate. It should also
be noted that the signal at δ 4.18 ppm, corresponding
to protons of methylene groups in the ester fragments
of the phosphorus-containing methacrylate, increases
relative to the signal from chloromethyl protons (δ
hydroquinone. The synthesis was performed at 130°С
for 4 h. The KCl precipitate was filtered off on a glass
frit. DMF was distilled off from the filtrate in a vacuum
at 86°С. The reaction product was a light yellow
viscous oil readily soluble in toluene, chloroform, and
acetone. Yield of the phosphorus-containing product
4
6.5 g (98.5%).
: 2 ratio. The reaction was performed as described
above, with 10 g (0.037 mol) of di-2-chloroethyl
-chloroethanephosphonate and 9.18 g (0.074 mol)
1
2
of potassium methacrylate. Yield of the phosphorus-
containing product 13.09 g (95.7%).
3
2
.4 ppm). This fact confirms that di-2-chloroethyl
-chloroethanephosphonate reacts with potassium
1
: 3 ratio. The reaction was performed as
methacrylate via chlorine atom.
described above with 80 g (0.296 mol) of di-2-
chloroethyl 2-chloroethanephosphonate and 110.3 g
At 1 : 2 molar ratio of the isomerization product and
potassium methacrylate, some specific features were
revealed. In the range δ 5.5–6.5 ppm, two additional
signals appear. They correspond in the intesity to the
signals at δ 5.57 and 5.94 ppm, which confirms the
formation of di-2-methacryloylethyl ethenephosphonate
IIIb, the major product in this case. In addition, a weak
signal remains at δ 3.64 ppm. This signal corresponds to
protons of the chloromethyl group, which is confirmed
by the 9.6% content of chlorine, determined analytically
These data are indicative of the formation of di-2-
methacryloylethyl 2-chloroethanephosphonate IVb.
(0.888 mol) of potassium methacrylate. Yield of the
phosphorus-containing product 97.08 g (88.5%).
The physicochemical properties of the phosphorus-
containing methacrylates prepared at various molar
ratios of di-2-chloroethyl 2-chloroethanephosphonate
and potassium methacrylate are given in the table.
1
The Н NMR spectrum of products IIIa and IVa
(see scheme) obtained at equimolar product ratio
contains signals at δ 1.80 and 1.84 ppm, corresponding
to protons of the methyl group of the methacrylate
2
moiety, and four singlets from protons bonded to the sp -
When the reaction was peformed at 1 : 3 molar ratio
of the isomerization product to potassium methacrylate,
hybridized carbon atom at δ 5.5–6.25 ppm. The signals
Physicomechanical properties of phosphorus-containing methacrylates
2
4
0
Found, %/Calculated, %
Molar ratio
I : II
Molecular
weight M
Reduced
viscosity ν, St
Refractive
index nD
Density d , g
2
0
–3
cm
С
Н
Сl
P
3
3
5.8
6.1
4.8
5.0
33.0
22.2
9.4
9.7
1:1
1:2
1:3
382
356
332
30.2
28.4
24.7
1.4681
1.4660
1.4750
1.2548
1.2405
1.2446
3
3
9.4
8.7
5.8
5.2
9.6
8.8
7.8
8.1
5
5
1.5
0.3
7.2
6.6
1.2
–
7.9
7.3
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 4 2010