Chemistry Reference
In-Depth Information
6
-p-EtOC
6
H
4
Me)][PF
6
]
Treatment of
[FeCp(
Z
[87] with allyl bromide gave
<
>
6
-p-triallylmethylphenate), which was decomplexed in MeCN
using a Hg lamp affording the desired
(50%)
[FeCp(
Z
<
p-tris(allyl)methylphenol, HOC
6
H
4
C-
(CH
2
CH
¼
CH
2
)
3
[88,89]. The HC
CCH
2
OC
6
H
4
C(CH
2
CH
¼
CH
2
)
3
was prepared
from HOC
6
H
4
C(CH
2
CH
¼
CH
2
)
3
with HC
CCH
2
Br with base [90,91]. The
HOC
6
H
4
C(CH
2
CH
CH
2
)
3
can be coated with azide moieties by treatment of
the polyolefin with HSiMe
2
CH
2
Cl and Karstedt catalyst, followed by NaN
3
[92],
then via a click reaction with HC
¼
CCH
2
OC
6
H
4
C(CH
2
CH
¼
CH
2
)
3
the next tier
can be generated. The reaction of HOC
6
H
4
C(CH
2
CH
CH
2
)
3
with HSiMe
2
CH
2
Cl
generated HOC
6
H
4
C[(CH
2
)
3
SiMe
2
Cl]
3
[93] that was extended (K
2
CO
3
,DMF)
with
¼
CHC
6
H
4
CH
2
OC
6
H
4
C[(CH
2
)
3
Si-
Me
2
Cl]
3
then subjected to AIBN-induced radical polymerization, followed by
conversion to (CH
2
¼
p-iodomethylstyrene
affording CH
2
¼
CH)
n
C
6
H
4
CH
2
OC
6
H
4
C[(CH
2
)
3
SiMe
2
CH
2
N
3
]
3
[94], which
is set up for the click reaction [95,96]. The nucleophilic displacement of chloride
from the terminal R-SiMe
2
Cl with the triallylmethylphenoxide was catalyzed
with NaI
CH
2
)
3
with HSi-
Me
2
CH
2
Cl was catalyzed to give HOC
6
H
4
C[(CH
2
)
3
SiMe
2
CH
2
Cl]
3
,whichcan
be converted (NaI, butanone) to the related HOC
6
H
4
C[(CH
2
)
3
SiMe
2
CH
2
I]
3
.
Another monomer in this family is the protected EtCO
2
C
6
H
4
C[(CH
2
)
3
I]
3
[97]
and the
in DMF [88,89]; whereas HOC
6
H
4
C(CH
2
CH
¼
related sulfide
reagents were
also derived from MeSC
6
H
4
C-
(CH
2
CH
¼
CH
2
)
3
[98].
3.2.7 Tetraphenylmethane-Based
4-[2-(4-Formylphenyl)ethynyl]phenyl-tris[4-[2-(4-pyridinyl)ethynyl]phenyl]-
methane was prepared by the treatment [Pd(PPh
3
)
2
Cl
2
/CuI]oftetrakis(4-iodo-
phenyl)methane with 4-ethynylbenzaldehyde to generate (38%) OHCC
6
H
4
C
CC
6
H
4
C(C
6
H
4
I)
3
, which with 4-ethynylpyridine under similar conditions gave
(54%) the desired OHCC
6
H
4
C
CC
6
H
4
C(C
6
H
4
C
CC
5
H
4
N)
3
[99].
