15 π-Conjugated Polymers Incorporating Naphthalene-Based …
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NBS
N
X
N
N
X
N
NOz-Br2 (X = O)
NTz-Br2 (X = S)
NSz-Br2 (X = Se)
Br
Br
NOz (X = O)
NTz (X = S)
NSz (X = Se)
N
X
N
N
X
N
(d)
Ir[(OMe)(COD)] 2 , DTBPY
N
S
N
N
S
N
NTz-Bpin2
B
B
NTz
N
S
N
N
S
N
O
O
O
O
B B
O
O
O
O
(a)
70– 80%
Cyclohexane
70%
H 2 SO 4
TZNT-Br2
TZNT
Zn
N
N
N
N
N
N
Br
Br
N
N
N
N
N
N
(b)
AcOH,
Dioxane, EtOH
R
R
R
R
N
S
N
N
S
N
Br
Br
Br
Br
Br
Br
Br 2
78%
HBr aq.
H 2 N
NH 2
H 2 N
NH 2
O
O
R
R
80% in two steps
(c)
NTz-Br2
NTz-Br2
N
N
N
N
R
R
R
R
Scheme 15.2 Synthesis of naphthalene-based nitrogen-containing heteroaromatics with reactive
groups
example, NTz-Br2 can be cross-coupled with stannylated alkylthiophene to give
NTz2T, which can then be brominated into NTz2T-Br2. NTz2T-Br2 can be copolymerized with distannylated bithiophene (5) to yield a π-conjugated polymer
(PNTz4T) (Scheme 15.4). As such, brominated and boronated naphthalene-based