S
R
Br
LDA/THF
-40
o
C
S
R
Br
Li
MgBr 2 OEt 2
-40
o
C
S
R
Br
BrMg
Ni(dppp)Cl 2
S
R
S
R
n
a McCullough method
b Rieke method
S
R
Br
Zn*/THF
-78
o
C
S
R
Br
BrZn
S
R
ZnBr
Br
Ni(dppe)Cl 2
Br
+
S
R
S
R
n
R= C 4 H 9 , C 6 H 13 , C 8 H 17 , C 12 H 25
R= C 4 H 9 , C 6 H 13 , C 8 H 17 , C 10 H 21 , C 12 H 25 , C 14 H 27
Scheme 2 McCullough method and Rieke method for the synthesis of regioregular P3AT
Fig. 5
1
H NMR spectrum of the aromatic region of highly regioregular P3HT [76]. Reprinted
with permission from Chen and Rieke [76]. Copyright (1992) American Chemical Society
S
R
Br
S
R
Br
BrMg
S
R
MgBr
Br
Ni(dppp)Cl 2
S
R
S
R
n
GRIM method
Br
RMgBr
THF
Scheme 3 GRIM method for the synthesis of regioregular P3ATs
Progress in the Synthesis of Poly(3-hexylthiophene)
9