Chemistry Reference
In-Depth Information
Ph
O
Ph
+
Ph
S
Br
Ph
S
N
N
Ac
2
O
then
Et
3
N, heat
65%
N
S
N
O
Ph
S
Ph
+
Ph
Ph
Br
Scheme 68 The synthesis of hole transport materials from thioamides and 2-bromoketones [
111
]
Ar
OTMS
N
H
H
O
CO
2
Me
H
O
CO
2
Me
Ar
H
O
TsNHOTs, NaOAc, PhMe
+
TsN
+
n
-Hex
TsHN
91%; 96% ee
NMe
2
S
NMe
2
S
Ar = 3,5-(CF
3
)
2
C
6
H
3
n
-Hex
n
-Hex
-
CO
2
Me
O
H
H
O
CO
2
Me
H
CO
2
Me
+H
+
-H
+
,-H
2
O
n
-Hex
n
-Hex
NMe
2
n
-Hex
TsHN
S
NMe
2
S
NMe
2
+
S
TsHN
TsHN
Scheme 69 The synthesis of 2-aminothiophenes from thioamides and an
N
-tosylaziridin-2-yl-
aldehyde [
112
]
Br
Ph
+
Br
-
NMe
2
NMe
2
NMe
2
O
Et
3
N
CH
2
Cl
2
,0°
C
LR, CH
2
Cl
2
Ph
S
Ar
O
Ar
S
Ar
O
+
NR
2
Br
-
Me
2
N
Ph
Ph
-
Ar
Ph
-H
+
S
S
S
Ar
-Me
2
NH
OMe
O
O
76%
from vinylogous amide
O
Scheme 70 The synthesis of 2-acylthiophenes from vinylogous thioamides [
113
]
with a 2-halo-ketone producing a salt, and 46 deprotonation (
47) and then ring
closure and aromatisation follow. Scheme
71
details some typical examples.
In a related work, it was found preferable to protect (Ac or Boc) the nitrogen of
the 3-amino-thioacrylamide before reaction with the 2-halo-carbonyl component:
!
