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washed by sat. NaHCO aq., and brine. The organic layer was
and 1.53 (1H, dd, J 5 4.8, 7.6 and 5.6, 6.8 Hz, CH (trans to
3
dried over Na SO , flittered, and evaporated. The residue
vinyl)), 0.95-0.81 (12H, m, CH(CH
m/z 410.2417, calcd. for C15
3
)
O
2
3 2): HRMS (EI): found
; M : 410.2417.
2
4
1
was fractionated by flash silica-gel column chromatography
eluent: ethyl acetate and hexane), and the fraction contain-
H
22
N
2
6
(
According to the typical procedure, DCAVCP and L-phenylala-
ing 1a were collected, evaporated, and dried under vacuum
1
nine methyl ester hydrochloride were condensed to obtain
to obtain 1a (1.19 g, 3.99 mmol, 63%): H NMR (CDCl ): d
3
1
1
f (1.07 g, 2.2 mmol, 60%): H NMR (CDCl ): d 7.69, 7.40
3
7
.87 (1H, br t, J 5 6.0 Hz, NH anti to vinyl), 7.16 (1H, br t,
J 5 6.0 Hz, NH syn to vinyl), 5.53–5.44 (1H, m, CH@CH2),
.31 (1H, d, J 5 15.6 Hz, C@CH (trans)), 5.14 (1H, d, J 5 7.8
(
(
1H 1 1H, d, J 5 8.0 Hz, NH anti to vinyl 3 2), 7.29-7.11
10H, m, aromatic) 6.87, 6.81 (1H 1 1H, d, J 5 7.2, NH syn to
5
vinyl 3 2), 5.20-5.09, 5.02–4.99, 4.91-4.88 (4H 1 1H 1 1H,
Hz, C@CH (cis)), 4.25 and 4.15 (1H 1 1H, dd, J 5 6.4, 18.4 Hz,
NACH 3 2), 3.96 and 3.89 (1H 1 1H, dd, J 5 5.2, 18.4 Hz,
NACH 3 2), 3.77 and 3.75 (3H 1 3H, s, OCH3 3 2), 2.48–
m, CH@CH 3 2), 4.89-4.73 (4H, m, N-CH 3 4), 3.76, 3.73,
2
3.70, 3.69 (each 3H, s, OCH3 3 4), 3.23-3.11, 3.07-2.96
(
4H 1 4H, m, CH -phenyl), 2.35-2.30, 2.11-2.05 (1H 1 1H, m,
2
242 (1H, m, C@CACH 3 2), 1.76 (1H, dd, J 5 6.4, 18.0 Hz,
C@CACH 3 2), 1.69, 1.49, 1.31 (1H 1 2H 1 1H, m, CH (cis to
vinyl) 3 2 1 CH (trans to vinyl) 3 2). HRMS (EI): found m/z
CH trans to vinyl), 1.61 (1H, dd, J 5 5.2, 18.0 Hz, CH cis to
vinyl); HRMS (EI): found m/z 298.1165, calcd. for
1
1
478.2105, calcd. for C27
H
N
30
2
O
6
; M : 478.2104.
C H N O ; M : 298.1165.
1
5 22 2 6
2
3
Radical ROP of Vinylcyclopropanes 1
Typical procedure
1
b was Synthesized by Previously Reported Method.
According to the typical procedure, DCAVCP and L-valine
methyl ester hydrochloride were condensed to obtain 1c
Vinylcyclopropane 1a (150.0 mg, 503 mmol) and AIBN
(2.4 mg, 15.1 mmol, 3 mol% to 1a) were dissolved in 0.5 mL
of distilled DMF. The solution was degassed by three freeze-
thaw cycles, sealed, and heated at 60 8C. After 20 h, the solu-
tion was diluted with chloroform (5 mL) and added to
diethyl ether (300 mL). The resulting white precipitates
were collected by filtration with suction and dried under
1
(
(
(
5
3
2.47 g, 6.47 mmol, 68%): H NMR (CDCl ): d 7.66 and 7.53
1H 1 1H, d, J 5 8.0 Hz, NH anti to vinyl 3 2), 7.00 and 6.80
1H 1 1H, d, J 5 7.6, NH syn to vinyl 3 2), 5.63-5.54, 5.47-
.39 (1H, m, CH@CH 3 2), 5.35-5.28 (2H, m, C@CH (trans)
2), 5.20-5.11 (2H, m, C@CH (cis) 3 2), 4.53-4.45 (4H, m,
NACH 3 4), 3.76, 3.74 , 3.74 , 3.73 (each 3H, s, OCH 3 4),
.51-2.45, 2.36-2.30 (1H 1 1H, m, C@CACH 3 2), 2.28-2.15
4H, m, CH(CH ) 3 4), 1.83, 1.70 (1H 1 1H, dd, J 5 5.2, 9.2
3
2
9
5
3
1
vacuum to obtain polymer 2a (101.1 mg, 67%): H NMR
2
(
(
CDCl ): d 7.65 (2H, brs, NH 3 2), 5.54 (2H, brs, CH@CH),
3
3
2
3
2
1
.99 (4H, d, J 5 4.4 Hz, NACH 3 2), 3.72 (6H, brs, OCH 3
2 3
Hz, CH (cis to vinyl) 3 2), 1.65, 1.55 (1H 1 1H, dd, J 5 5.2,
.8 Hz, CH (trans to vinyl)), 0.983-0.918 (12H, m, CH(CH3)2
2): HRMS (EI): found m/z 382.2105, calcd. for
1
3
), 2.56 (4H, brs, CH ACH@CHACH ); C NMR (CDCl ): d
2
2
3
6
3
72.66, 170.70, 129.44, 56.81, 52.40, 41.59, 39.05; IR (ATR):
E 3351 (NH), 1742 (C@O ester), 1662 (C@O amide), 978
C@CH trans).
1
C H N O ; M : 382.2104.
1
5 22 2 6
(
According to the typical procedure, DCAVCP and L-leucine
According to the typical procedure, 1c was polymerized in
toluene to obtain polymer 2c (285.6 mg, 53%): H NMR
methyl ester hydrochloride were condensed to obtain 1d
1
1
(
(
(
2.34 g, 5.71 mmol, 85%): H NMR (CDCl ): d 7.87, 7.40
3
(
CDCl ): d 7.46 (2H, brd, J 5 7.6 Hz, NH 3 2), 5.52 (2H, brs,
3
1H 1 1H, d, J 5 7.2 Hz, NH anti to vinyl 3 2), 7.04, 7.01
1H 1 1H, d, J 5 7.2, NH syn to vinyl 3 2), 5.62-5.53 (1H, m,
CH@CH), 4.43 (2H, dd, J 5 5.2, 7.6 Hz, NACH 3 2), 3.73 (6H,
brs, OCH 3 2), 2.55 (4H, brs, CH ACH@CHACH ), 2.20-2.12
3
2
2
CH@CH ), 5.39-5.26 (3H, m, CH@CH 1 CH@CH (trans) 3 2),
2
2
(
3 2 3
2H, m, CH(CH ) 3 2), 0.90 (12H, t, J 5 6.0Hz, CH 3 4);
5
.16-5.07 (2H, m, CH@CH (cis) 3 2), 4.62-4.52 (4H, m,
NACH 3 4), 3.76, 3.75, 3.74, 3.73 (each 3H, s, OCH3 3 4),
.61-2.55, 2.35-2.29 (1H 1 1H, m, C@CACH 3 2), 1.80-1.60
15H, m, C@CACHACH 3 3 1 CH CH(CH ) 3 4), 1.48 (1H,
13
C NMR (CDCl ): d 172.01, 171.75, 129.69, 57.84, 56.81,
3
5
1
2.17, 39.78, 30.61, 19.05, 18.06; IR (ATR): E 3358 (NH),
740 (C@O ester), 1663 (C@O amide), 993 (C@CH trans).
2
(
2
3 2
dd, J 5 5.2, 7.2 Hz, CH (trans to vinyl)), 0.96-0.90 (12H, m,
According to the typical procedure, 1d was polymerized in
toluene to obtain polymer 2d (259.3 mg, 45%): H NMR
1
CH(CH3)2 3 2); HRMS (EI): found m/z 410.2416, calcd. for
1
C H N O ; M : 410.2417.
(CDCl ): d 7.32 (2H, br d, J 5 6.8 Hz, NH 3 2), 5.51 (2H, brs,
1
5
22
2
6
3
CH@CH), 4.50 (2H, br t, J 5 6.8 Hz, NACH 3 2), 3.72 (6H, br
s, OCH3 3 2), 2.51 (4H, brs, CH ACH@CHACH ), 1.60 (6H,
According to the typical procedure, DCAVCP and L-isoleucine
2
2
methyl ester hydrochloride were condensed to obtain 1e
brs, CH CH(CH ) 3 2), 0.92 (12H, t, J 5 4.0Hz, CH3 3 4);
2
3 2
1
(
(
(
2.80 g, 6.83 mmol, 87%): H NMR (CDCl ): d 7.70, 7.53
13
3
C NMR (CDCl ): d 173.65, 171.93, 129.62, 56.98, 52.36,
3
1H 1 1H, d, J 5 7.6 Hz, NH anti to vinyl 3 2), 7.00, 6.84
1H 1 1H, d, J 5 8.0 Hz, NH syn to vinyl 3 2), 5.56-5.51 (1H,
51.347, 40.167, 39.57, 24.91, 22.94, 21.48; IR (ATR): E 3349
(NH), 1740 (C@O ester), 1668 (C@O amide), 981 (C@CH
m, CH@CH ), 5.46-5.37 (1H, m, CH@CH ), 5.34-5.27 (2H, m,
2
2
trans).
C@CH (trans) 3 2), 5.19-5.10 (2H, m, CH@CH (cis) 3 2),
4
3
.57-4.46 (4H, m, NACH 3 4), 3.76, 3.74, 3.74, 3.73 (each
H, s, OCH3 4), 2.49–242, 2.35-2.29 (1H 1 1H, m,
According to the typical procedure, 1e was polymerized in
toluene to obtain polymer 2e (639.3 mg, 71%). H NMR
1
3
C@CACH 3 2), 2.01-1.86 (4H, m, CH(CH )CH 3 4) 1.81,
(CDCl ): d 7.46 (2H, br d, J 5 6.8 Hz, NH 3 2), 5.52 (2H, br
3
2
3
1.69 (1H 1 1H, dd, J 5 5.2, 8.8 Hz, CH (cis to vinyl) 3 2) 1.62
s, CH@CH), 4.47 (2H, br t, J 5 6.0 Hz, NACH 3 2), 3.73 (6H,
6
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2017, 00, 000–000