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dichloromethane (30 mL) were introduced in a round-bot-
tomed flask. Then dihydropyrane (2.5 mL, 27.6 mmol, 1 eq.)
was added and the mixture was stirred for 3 h at room tem-
perature. The crude product was washed with distilled water
together with 4-dimethylamino pyridine (80.0 mg, 0.7 mmol)
and redistilled triethylamine (2.9 mL, 21.0 mmol, 1.1 eq.).
Then methacrylic anhydride was introduced (2.3 mL, 15.4
mmol). After 6 h at room temperature, water was added and
the product was extracted. The organic layer was dried over
magnesium sulfate and the crude product was purified by
flash chromatography (eluent: ethyl acetate) providing
Monomer 4 (3.7 g, 11.4 mmol) as a colorless oil.
(
50 mL). The organic layer was dried with magnesium sulfate
and concentrated under reduced pressure. A bulb to bulb dis-
ꢃꢃ
tillation under reduced pressure (180 C, 0.1 mbar) provided
the pure product (6.5 g, 20.2 mmol) as a colorless oil.
1
1
3
Yield: 89%. H NMR (CDCl , 400.1 MHz, d): 1.33–1.91 (m,
Yield: 81%. H NMR(CDCl , 400.1 MHz, d): 1.29–1.33 [t, J
3 HH
3
3
1
4H, H
2
–H
5
, and H
8
–H10), 3.39–3.42 (t,
J
HH ¼ 5.2 Hz, 2H,
¼ 7.2 Hz, 3H, CH
3 2
(OEt)], 1.34–1.48 (m, 2H, CH ), 1.50–1.78
H ), 3.36–3.53 (m, 2H, H ), 3.70–3.89 (m, 2H, H ), 4.57 (t,
(m, 8H, CH ), 1.93 (m, 3H, H ), 4.06–4.14 [m, 6H, H , and
1
6
8
2
9
6
3
13
13
JHH ¼ 3.6 Hz, 2H, H ). C NMR (CDCl , 100.6 MHz, d): 19.9
CH (OEt)], 5.54 (m, 1H, H ), 6.08 (m, 1H, H ). C NMR
2 8a 8b
7
3
3
(
s, C ), 25.6 (s, CH ), 25.6 (s, CH ), 28.2 (s, CH ), 29.7 (s,
(CDCl3, 100.6 MHz, d): 16.4 [d, JCP ¼ 5.9 Hz, CH (OEt)],
1
0
2
2
2
3
2
CH ), 30.9 (s, CH ), 32.9 (s, CH ), 34.0 (s, C ), 62.6 (s, C ),
7.6 (s, C ), 99.1 (s, C ). HRMS (m/z): calcd for C H BrO ,
87.0623; found, 287.0623 [M þ Na] .
Diethyl 6-(tetrahydropyran-2-yloxy)hexylphosphonate
A mixture of triethylphosphite (6.2 mL, 35.8 mmol, 2.5 eq.)
and 2-(6-bromohexyloxy)tetrahydro-2H-pyran (3.8 g, 14.3
mmol) was heated at 150 C for 15 h. Excess triethylphos-
18.3 (s, C ), 22.3 (d, J ¼ 5.1 Hz, C ), 25.5 (s, C ), 25.6 (d,
2
2
2
1
6
10
CP
2
4
1
3
6
2
JCP ¼ 140.7 Hz, C ), 28.3 (s, C ), 30.1 (d,
J
CP
¼ 16.8 Hz,
8
7
11 21
2
1
5
þ
2
C
3
), 61.4 [d, JCP ¼ 6.5 Hz, CH
2 6
(OEt)] ; 64.5 (s, C ), 125.1 (s,
3
1
C ), 136.4 (s, C ), 167.4 (s, C ). P NMR (CDCl , 162.0 MHz,
9
8
7
3
d): 32.3. HRMS (m/z): calcd for C H O P, 307.1670; found,
07.1674 [M þ H] .
1
4 27 5
þ
3
ꢃꢃ
6-(Methacryloyloxy)hexylphosphonic acid (Monomer 3)
Under inert conditions, a solution of diethyl 6-(methacryloy-
loxy)hexylphosphonate 4 (1.9 g, 5.3 mmol) in anhydrous
dichloromethane (15 mL) was introduced in a round-bot-
tomed flask. Then TMsBr (2.1 mL, 15.9 mmol, 3.0 eq.) was
added dropwise. After stirring for 3 h at room temperature,
the mixture was concentrated under reduced pressure and
methanol (10 mL) was added. The mixture was stirred for
h and the solvent was evaporated. The product was dried
to a constant weight under vacuum. The phosphonic acid
Monomer 3 (1.6 g, 5.3 mmol) was isolated with a quantita-
tive yield as yellowish oil.
phite and by-products were removed under reduced pres-
ꢃꢃ
sure (P ¼ 0.1 mbar, T ¼ 180 C). The phosphonate (3.6 g,
1
1.2 mmol) was obtained as a colorless liquid.
1
Yield: 79%. H NMR (CDCl , 400,1 MHz, d): 1.26–1.29 [t,
3
3
JHH ¼ 6.8 Hz, 3H, CH (OEt)], 1.30–1.41 (m, 2H, CH ), 1.41–
3
2
1
.72 (m, 6H, CH ), 3.30–3.47 (m, 2H, H ), 3.65–3.69 (m, 2H,
2 1
3
H ), 4.02–4.11 [m, 4H, CH (OEt)], 4.51–4.53 (t, JHH ¼ 3.6
6
2
1
1
3
3
Hz, 1H, H7). C NMR (CDCl , 100.6 MHz, d): 16.6 [d, J
¼
3
CP
2
6
2
(
.0 Hz, CH
3
(OEt)], 19.8 (s, C10), 22.5 (d, JCP ¼ 5.2 Hz, C
2
),
1
5.1 (s; C ), 25.6 (s, C ), 25.8 (d, J ¼ 140.6 Hz, C ), 29.6
4
9
CP
1
3
2
s, C ), 30.6 (d, J ¼ 17.0 Hz, C ), 30.9 (s, C ), 61.5 [d, J
5
CP
3
11
CP
1
¼
6.5 Hz, CH (OEt)], 62.5 (s, C ), 67.6 (s, C ), 99.0 (s, C ).
Yield: 100%. H NMR (D
2
O, 400.1 MHz, d): 1.36–1.82 (m, 10H,
2
6
8
7
3
1
3
P NMR (CDCl , 162.0 MHz, d): 32.4. HRMS (m/z): calcd for
C H O P, 323.1987; found, 323.1978 [M þ H] .
Diethyl 6-hydroxyhexylphosphonate
Diethyl 6-(tetrahydropyran-2-yloxy)hexylphosphonate
0.70 g, 2.3 mmol) and Amberlyst H15 (8 mg) were intro-
H
1
–H
5
), 1.93 (s, 1H, H10), 4.21 (t, JHH ¼ 6.4 Hz, 2H, H
), 5.70
6
3
þ
13
(s, 1H, H9a), 6.12 (s, 1H, H9b), 8.30 (sl, 2H, OH). C NMR
1
5 31 5
2
(
2
CDCl , 100.6 MHz, d): 18.4 (s, C ), 23.8 (d, J ¼ 4.8 Hz, C ),
3
10
CP
2
1
3
5.1 (s, C ), 25.2 (d, J ¼ 147.7 Hz, C ), 28.7 (d, J ¼ 17.9
4
CP
1
CP
2
Hz, C ), 29.6 (s, C ), 65.8 (s, C ), 125.9 (s, C ), 137.9 (C ),
3
5
6
9
8
(
31
1
68.9 (s, C7). P NMR (D O, 162.0 MHz, d): 32.3. HRMS (m/
z): calcd for C H O P, 249.0892; found, 249.0889 [M ꢀ H] .
2
duced in a round-bottomed flask with methanol (5 mL). The
reaction was heated at 45 C under reflux for 1 h. After fil-
ꢀ
1
0 19 5
ꢃꢃ
tration and concentration under reduced pressure, diethyl 6-
hydroxydecylphosphonate was obtained (0.54 g, 2.3 mmol)
with a quantitative yield as a colorless oil.
RESULTS AND DISCUSSION
Copolymerization of Monomer 5 with Monomers 1–4
To understand the effect on the kinetics of the copolymeriza-
tion of phosphonic acid based monomers with the acrylam-
ide moiety without overlaying the effect of the formation of
a crosslinked network, we first studied the copolymerization
of monovinyl phosphonic acid monomers, Monomers 1–4
with the monoacrylamide Monomer 5. Mixtures of Monomer
5 with Monomers 1–4 were prepared in a 0.95/0.05 (i.e.,
1.8/0.1) molar ratio so as to be consistent with our previous
study of the copolymerization of difunctional DEBAAP and
monofuctional acrylamide phosphonic acids where we used
a 0.9/0.1 monomer ratio and thus a 1.8/0.1 or 0.9/0.05
molar ratio of acrylamide units.
1
3
Yield: 100%. H NMR (CDCl , 400.1 MHz, d): 1.33–1.37 [t, J
3
HH
¼
5.6 Hz, 3H, CH (OEt)], 1.31–1.41 (m, 2H, CH ), 1.49–1.74
3 2
3
(
m, 8H, CH ), 3.14 (sl, 1H, OH), 3.58–3.61 (t, J ¼ 6.4 Hz,
2
HH
13
H ), 4.03–4.08 [m, 4H, CH (OEt)]. C NMR (CDCl , 100.6
6
2
3
3
2
MHz, d): 16.7 [d, JCP ¼ 6.0 Hz, CH
3
(OEt)], 22.5 (d, JCP ¼ 5.0
1
3
Hz, C
2
), 25.3 (s, C
4
), 25.0 (d, JCP ¼ 141.0 Hz, C
1
), 30.3 (d, JCP
2
¼
16.4 Hz, C ), 32.6 (s, C ), 61.6 [d, J ¼ 6.5 Hz, CH (OEt)],
3
5
CP
2
3
1
6
2.9 (s, C6). P NMR (CDCl , 162.0 MHz, d): 32.5. HRMS (m/
3
þ
z): calcd for C H O P, 239.1412; found, 239.1419 [M þ H] .
1
0 23 4
Diethyl 6-(methacryloyloxy)hexylphosphonate
Monomer 4)
(
A solution of diethyl 6-hydroxyhexylphosphonate (3.3 g, 14.0
mmol) in anhydrous dichloromethane (60 mL) was mixed
Figure 2 shows the copolymerization rate of monoacrylamide
Monomer
5
with the acrylamide phosphonate ester
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