S. Takano et al. / Reactive & Functional Polymers 71 (2011) 195–203
197
dichloromethane followed by a mixture of ethyl acetate and dichlo-
romethane (1:2), was collected. From the eluate solution, solvent
was evaporated under high vacuum to leave 1 as a colorless oil
d, J = 8.0 Hz, 19-H, 19’-H), 7.39 (1H, t, J = 6.0 Hz, 15-H), 7.52 (1H,
d, J = 8.0 Hz, 13-H), 7.65 (2H, d, J = 8.0 Hz, 20-H, 20’-H), 7.92
(1H, t, J = 7.2 Hz, 14-H), 8.66 (1H, d, J = 4.6 Hz, 16-H); 13C NMR
(DMF d-7) d: 20.5 (C-17), 28.8 (C-3), 29.0 (C-10), 36.1 (C-11),
42.5 (C-4), 43.0 (C-1), 49.3 (C-7), 63.4 (C-9), 122.4 (C-15), 124.1
(C-13), 126.0 (C-20,20’), 128.2 (C-19,19 ), 132.3 (C-6), 137.4 (C-5),
138.2 (C-18), 138.4(C-14), 146.2 (C-21), 150.8 (C-16), 161.5 (C-
12), 174.0 (C-8).
(
1.63 g, 44% yield). Elemental analysis calc. for C16
2
H19NO : C,
7
v
1
2
5
4.68; H, 7.44; N, 5.44. Found: C, 74.06; H, 7.41; N, 5.33%. IR (neat)
max/cm : 1731 (C@O). 1H NMR (DMF d-7) d: 1.31 (2H, m, 7-H),
ꢁ
1
0
.86 (2H, m, 3-H), 2.01 (2H, m, 10-H), 2.83 (1H, t, J = 7.4 Hz, 4-H),
.99–3.02 (3H, m, 1-H, 11-H), 3.14 (1H, s, 2-H), 4.03 (2H, m, 9-H),
.92 (1H, dd, J
= 2.9 Hz, 5-H), 7.19 (1H, t, J = 6.0 Hz, 15-H), 7.28 (1H, d,
J = 7.4 Hz, 13-H), 7.70 (1H, t, J = 7.4 Hz, 14-H), 8.50 (1H, d,
1 2 1
= 5.2, J = 2.9 Hz, 6-H), 6.14 (1H, dd, J = 5.2,
J
2
2.5. Reaction of 2 with Ag(PTS)
1
3
J = 4.0 Hz, 16-H). C NMR (DMF d-7) d: 28.5 (C-3), 28.8 (C-10),
Monomer 2 (0.11 g, 0.43 mmol) in DMF (1 ml) and Ag(PTS)
3
9
1
4.3 (C-11), 42.5 (C-4), 43.0 (C-1), 45.7 (C-2), 49.4 (C-7), 63.5 (C-
), 121.4 (C-15), 122.9 (C-13), 132.6 (C-6), 136.5 (C-5), 137.7 (C-
4), 149.4 (C-16), 161.2 (C-12), 174.0 (C-8).
(
0.12 g, 0.43 mmol) in DMF (2 ml) were mixed. After the mixture
was stirred at room temperature overnight, the solvent was re-
moved under high vacuum and the remaining heavy oil of 2-Ag
was subjected to spectral characterization. IR(KBr)
1
1
2
7
7
7
ꢁ1
v
max/cm
:
1
2.3. Preparation of norbornene derivative 2
694 (C@O); H NMR (DMF d-7) d: 1.61 (2H, m, 7-H), 2.28 (3H, s,
7-H), 3.29 (2H, s, 1-H, 4-H), 3.50 (2H, dd, J = 2.87, J = 1.72 Hz,
1
2
2
-(Aminomethyl)pyridine (6.7 g, 62 mmol) was slowly added to
-H, 3-H), 4.68 (2H, s, 10-H), 6.07 (2H, t, J = 2.29 Hz, 5-H, 6-H),
a
solution of 5-norbornene-endo-2.3-dicarboxylic anhydride
0
.12 (2H, d, J = 7.4 Hz, 19-H, 19 -H), 7.32 (1H, d, J = 7.4 Hz, 13-H),
(
10.3 g, 62 mmol) in 1,2-dichloroethane (150 ml). A white precipi-
.37 (1H, t, J = 6.0 Hz, 15-H), 7.65 (2H, d, J = 8.0 Hz, 20-H, 20’-H),
.87 (1H, t, J = 7.2 Hz, 14-H), 8.59 (1H, d, J = 4.6 Hz, 16-H); 13
C
tate formed immediately. The suspension was heated at 60 °C with
stirring for two days, during which time the precipitate gradually
disappeared. The solvent was evaporated and the remaining red
NMR (DMF d-7) d: 20.5 (C-17), 43.9 (C-10), 44.9 (C-1,4), 46.0 (C-
0
2
1
1
, 3), 52.1 (C-7), 122.3 (C-13), 123.2 (C-15), 126.0 (C-20, 20 ),
oily residue was chromatographed on
a
silica-gel column
0
28.2 (C-19, 19 ), 134.8 (C-5, 6), 138.0 (C-14), 138.2 (C-18),
(
3 ꢀ 15 cm). A colorless fraction eluted with dichloromethane/
46.3, (C-21), 150.3 (C-16), 155.9 (C-12), 177.5 (C-8, 9).
THF (1:1) was collected. Evaporation of the solvent gave 2 as color-
less crystals (13 g, 82% yield) [18]. M.p. 121–122 °C; elemental
2
.6. Polymerization of 1
analysis calc. for C15
C, 70.72; H, 5.59; N, 11.02. IR(KBr)
NMR (DMF d-7) d: 1.61 (2H, t, J = 1.72 Hz, 7-H), 3.28 (2H, m, 1-H,
14 2 2
H N O : C, 70.85; H, 5.55; N, 11.02. Found:
ꢁ1
1
v
max/cm : 1699 (C@O); H
To a stirred solution of monomer 1 (0.92 g, 3.58 mmol)) in DMF
(
7 ml), complex G2 (3.5 lmol in 3 ml DMF) at room temperature
4
1
1
-H), 3.49 (2H, dd, J
0-H), 6.09 (2H, t, J = 1.72 Hz, 5-H, 6-H), 7.21–7.26 (2H, m, 13-H,
5-H), 7.74 (1H, td, J = 7.7, J = 1.1 Hz, 14-H), 8.46 (1H, d,
1 2
= 2.87, J = 1.72 Hz, 2-H, 3-H), 4.56 (2H, s,
was added. After 1 h, ethyl vinyl ether (1 ml) was added and the
stirring was continued for 1 h. The reaction mixture was concen-
trated under reduced pressure to ca. 1/3 of the original volume
and poured into a large amount of methanol to precipitate the
polymer (poly(1)) in 64% yield. IR(THF)
1
2
1
3
J = 4.0 Hz, 16-H); C NMR (DMF d-7) d: 43.1 (C-10), 44.9 (C-1,
C-4), 46.0 (C-2, C-3), 52.1 (C-7), 121.3 (C-13), 122.5 (C-15), 134.8
max/cm : (C@O); 1
ꢁ1
v
H
(
C-5, C-6), 136.8 (C-14), 149.2 (C-16), 155.8 (C-12), 177.4 (C-8,
C-9).
Using a similar reaction of 4-(2-aminoethyl)pyridine with
NMR (DMF d-7) d: 1.10–1.46 (1H, br-m), 1.58–2.17 (5H, br-m),
.38–3.08 (5H, br-m, partly overlapped by DMF peak), 3.97–4.26
2H, br-s, –CO CH
2
(
2
2
–), 5.13–5.61 (2H, br-m, HAC'), 7.15 (1H, s,
0
5
-norbornene-endo-2.3-dicarboxylic anhydride, 2 was obtained
as colorless crystals. M. p. 148–152 °C; elemental analysis calc.
for C16 : C, 71.62; H, 6.01; N, 10.44. Found: C, 71.52; H,
.08; N, 11.68. IR(KBr)
d-7) d: 1.54 (2H, m, 7-H), 2.76 (2H, t, J = 7.16 Hz, 11-H), 3.20 (2H,
m, 1-H, 4-H), 3.33 (2H, dd, J = 2.87, J = 1.72 Hz, 2-H, 3-H), 3.57
2H, t, J = 7.4 Hz, 10-H), 5.89 (2H, t, J = 1.72 Hz, 5-H, 6-H), 7.23
2H, d, J = 5.2 Hz, 13-H, 16-H), 8.47 (2H, d, J = 5.2 Hz, 14-H,
py-H), 7.23 (1H, s, py-H), 7.65 (1H, s, py-H), 8.48 (1H, s, py-H);
13
C NMR (DMF d-7) d: 28.5, 63.5, 121.3, 122.8, 136.4, 149.3,
61.2 (py-ipso), 174.1(–CO
16 2 2
H N O
1
2
–). Other polymerizations of 1 shown
ꢁ
1
6
v
max/cm : 1687 (C@O); 1H NMR (DMF
in Table 1 were performed similarly.
1
2
2.7. Polymerization of 2 and film preparation
(
(
1
1
3
To a stirred solution of monomer 2 (0.50 g, 2.0 mmol) in 1,2-
5-H); C NMR (DMF d-7) d: 32.6 (C-11), 37.9 (C-10), 44.7
dichloroethane (4 ml), a 1,2-dichloroethane solution (1 ml) con-
taining complex G2 (0.66 mol) was added, and the mixture was
stirred at room temperature. After 5 h, ethyl vinyl ether was added
and the mixture was stirred for 1 h. The reaction mixture was
poured into a large volume of methanol to precipitate the polymer
(
1
C-1,4), 45.6 (C-2,3), 51.8 (C-7), 124.4 (C-13,16), 134.5 (C-5,6),
47.4 (C-12), 149.9 (C-14,15), 177.4 (C-8,9).
l
2.4. Reaction of 1 with Ag(PTS)
A DMF solution (4 ml) containing 1 (0.38 g, 1.47 mmol) and a
solution of Ag(PTS) (silver p-toluenesulfonate, 0.49 g, 1.76 mmol)
in DMF (10 ml) were mixed and stirred at room temperature. After
Table 1
a
Typical ROMP of 1 catalyzed by the ruthenium complex G2.
1
8 h, about half of the solvent was evaporated and the white pre-
cipitate of the resulting 1-Ag was separated by filtration
0.312 g, 40% yield). M.p. 138–146 °C (decomp.); elemental analy-
sis calc. for C23 26AgNSO : C, 51.50; H, 4.85; N, 2.61. Found: C,
0.95; H, 4.86; N, 2.89. IR(KBr)
DMF d-7) d: 1.28 (2H, dd, J = 17.8, J
-H), 2.06 (2H, m, 10-H), 2.28 (3H, s, 17-H), 2.84 (1H, s, 4-H),
.98–3.01 (3H, m, 1-H, 11-H), 3.12 (1H, s, 2-H), 4.05 (2H, ddd,
= 23.1, = 10.7, = 6.4 Hz, 9-H), 5.90 (1H, dd, = 5.2,
= 2.9 Hz, 6-H), 6.15 (1H, dd, J = 5.2, J = 2.9 Hz, 5-H), 7.12 (2H,
Run
Reaction time (m)
Yield (%)
Mn (GPC)b
Mw/Mnb
1
2
3
4
2
30
60
28
40
64
77
31,500
54,200
56,300
40,700
2.41
2.11
2.72
2.37
(
H
5
ꢁ
1
1
5
(
3
2
v
max/cm : 1732 (C@O); H NMR
= 7.4 Hz, 7-H), 1.85 (2H, m,
300
1
2
a
Polymerizations were performed in DMF (10 ml) at room temperature with
initial [1] /[G2] ratio of 1000. [1] = 1.0 g (3.6 mmol).
Mn(GPC) and Mw/Mn are the relative number-averaged molecular weight and
the polydispersity index, respectively, determined by GPC and calibrated with
polystyrene standards.
0
0
b
J
J
1
J
2
J
3
J
1
2
1
2