Polymer Journal, Vol. 21, No.
8,
pp
669-671
(1989)
SHORT
COMMUNICATIONS
New Polymeric Catalyst for the Addition Reaction
of
Active Ester with Epoxy Compound
Tadatomi
NISHIKUBO,t
Tetsuya
KATO,
Masao
TOMOI,*
and Satoshi
ISHIGAKI*
Department
of
Applied Chemistry, Faculty
of
Engineering,
Kanagawa University, Yokohama 221, Japan
* Department
of
Applied Chemistry, Faculty
of
Engineering,
Yokohama National University, Yokohama 240, Japan
(Received December
13,
1988)
KEY
WORDS
Polymeric Catalyst / Polymer-Supported Base / Pendant
4-
(N,N-Dimethylamino)pyridine / Pendant N-Methylimidazole / Addition
Reaction / 4-(N,N-dimethylamino)pyridine / Active Ester / Epoxy Com-
pound/
It
is
well known1
-s
that
polystyrene-
supported catalysts containing pendant
4-
(N,N-dimethylamino )pyridine, 4-pyrrolidino-
pyridine
or
N-methylimidazole moieties are
useful catalysts for the acylation
of
alcohols,
phospholipid synthesis, and acyl rearrange-
ments. However, the activity
of
all these
polymer-supported catalysts has mostly been
comparable to
or
slightly lower than
that
of
the corresponding low molecular weight cat-
alysts also used.
Recently,
we
found6 that regioselective ad-
dition reaction
of
active ester with epoxy com-
pound and the addition reaction
7
of
cyclic
ester with epoxy compound are effectively
catalyzed by insoluble polymer-supported cat-
alyst containing pendant quaternary phos-
phonium
or
ammonium salts,
and
these poly-
meric catalysts have higher activity
than
the
corresponding low molecular weight catalyst.
In this communication,
we
report new cata-
lytic activity
of
polymer-supported bases for
the regioselective addition reaction
of
active
ester with epoxy compound.
Polymer-supported catalysts
1-5
were pre-
1
To
whom correspondence should be addressed.
0-@
c~
(CH
2
)rtl---\Q,;•
1-3
4
Scheme I.
pared using the methods previously report-
ed.1-5 A typical addition reaction was carried
out as follows: S-phenyl thioacetate (PTA)
[0.61
g (4mmol)] and 0.60g (4mmol)
of
phenyl
glycidyl ether (PGE) were dissolved in
2ml
of
chlorobenzene, and then 0.15 g (0.2 mmol as
base)
of
the catalyst 1 having a pendant 4-
(N,N-dimethylamino)pyridine
(DMAP)
moie-
ty was added to the solution. The mixture was
stirred
at
90°C for
24
h, and the yield
of
1-
phenoxy-3-thiophenoxy-2-propyl acetate (6a)
was monitored by gas chromatography.
Although the reaction
of
PTA with
PGE
was expected to produce two isomers due to
rx-
and /3-cleavage
of
the oxirane ring using the
polymer-supported catalysts
1-5,
or
the cor-
responding low molecular weight (LMW) cat-
669
