U.S. patent application number 10/554546 was filed with the patent office on 2007-04-26 for heterogeneous catalyst and process for producing oxirane compound with the catalyst.
This patent application is currently assigned to Nissan Chemical Industries, Ltd.. Invention is credited to Kowichiro Saruhashi, Hisayuki Watanabe.
Application Number | 20070093667 10/554546 |
Document ID | / |
Family ID | 33424783 |
Filed Date | 2007-04-26 |
United States Patent
Application |
20070093667 |
Kind Code |
A1 |
Watanabe; Hisayuki ; et
al. |
April 26, 2007 |
Heterogeneous catalyst and process for producing oxirane compound
with the catalyst
Abstract
There is provided a process for producing oxirane compound
comprising treating with hydrogen peroxide in the presence of
either an olefin oxidation catalyst prepared from an organic
compound or a polymer compound of formula (1) ##STR1## a tungstic
acid compound, a phosphoric acid, hydrogen peroxide and a
quaternary ammonium salt of formula (2) or (3) ##STR2## or an
olefin oxidation catalyst prepared from an organic compound or a
polymer compound of formula (1), a tungsten compound and a
quaternary ammonium salt of formula (2) or (3). The process is
useful especially industrially.
Inventors: |
Watanabe; Hisayuki;
(Funabashi-shi, JP) ; Saruhashi; Kowichiro;
(Funabashi-shi, JP) |
Correspondence
Address: |
OLIFF & BERRIDGE, PLC
P.O. BOX 19928
ALEXANDRIA
VA
22320
US
|
Assignee: |
Nissan Chemical Industries,
Ltd.
Tokyo
JP
101-0054
|
Family ID: |
33424783 |
Appl. No.: |
10/554546 |
Filed: |
April 21, 2004 |
PCT Filed: |
April 21, 2004 |
PCT NO: |
PCT/JP04/05723 |
371 Date: |
October 27, 2005 |
Current U.S.
Class: |
549/533 ;
525/432 |
Current CPC
Class: |
Y02P 20/52 20151101;
B01J 23/30 20130101; C07D 301/12 20130101; B01J 31/0247 20130101;
B01J 2231/72 20130101; B01J 27/16 20130101; B01J 31/0239
20130101 |
Class at
Publication: |
549/533 ;
525/432 |
International
Class: |
C07D 301/06 20060101
C07D301/06; C08L 77/00 20060101 C08L077/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 28, 2003 |
JP |
2003-123694 |
Jul 24, 2003 |
JP |
2003-279438 |
Feb 20, 2004 |
JP |
2004-044040 |
Claims
1. An olefin oxidation catalyst, prepared from an organic compound
or a polymer compound of formula (1) ##STR20## wherein R.sup.11,
R.sup.12 and R.sup.13 are independently of one another hydrogen
atom, C.sub.1-10alkyl group (the C.sub.1-10alkyl group may be
substituted by C.sub.6-10aryl group), C.sub.3-10cycloalkyl group,
C.sub.6-10aryl group, C.sub.1-6alkylcarbonyl group (the
C.sub.1-6alkylcarbonyl group may be substituted by C.sub.6-10aryl
group) or C.sub.6-10arylcarbonyl group; a tungstic acid compound; a
phosphoric acid; hydrogen peroxide; and a quaternary ammonium salt
of formula (2) or (3) ##STR21## wherein R.sup.5, R.sup.6, R.sup.7,
R.sup.8 and R.sup.9 are independently of one another hydrogen atom,
a halogen atom, cyano group, C.sub.1-10alkyl group (the
C.sub.1-10alkyl group may be substituted by C.sub.6-10aryl group,
C.sub.1-10alkoxy group or benzyloxy group), C.sub.1-10alkoxy group,
benzyloxy group or phenyl group, or any two of R.sup.5, R.sup.6,
R.sup.7, R.sup.8 and R.sup.9 together may form 1 or 2 fused benzene
rings, R.sup.10, R.sup.14, R.sup.15, R.sup.16 and R.sup.17 are
independently of one another C.sub.1-20alkyl group, and X is a
halogen atom.
2. An olefin oxidation catalyst, prepared from an organic compound
or a polymer compound of formula (1) ##STR22## wherein R.sup.11,
R.sup.12 and R.sup.13 are independently of one another hydrogen
atom, C.sub.1-10alkyl group (the C.sub.1-10alkyl group may be
substituted by C.sub.6-10aryl group), C.sub.3-10cycloalkyl group,
C.sub.6-10aryl group, C.sub.1-6alkylcarbonyl group (the
C.sub.1-6alkylcarbonyl group may be substituted by C.sub.6-10aryl
group) or C.sub.6-10arylcarbonyl group; a tungsten compound; and a
quaternary ammonium salt of formula (2) or (3) ##STR23## wherein
R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently of
one another hydrogen atom, a halogen atom, cyano group,
C.sub.1-10alkyl group (the C.sub.1-10alkyl group may be arbitrarily
substituted by C.sub.6-10aryl group, C.sub.1-10alkoxy group or
benzyloxy group), C.sub.1-10alkoxy group, benzyloxy group or phenyl
group, or any two of R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9
together may form 1 or 2 fused benzene rings, R.sup.10, R.sup.14,
R.sup.15, R.sup.16 and R.sup.17 are independently of one another
C.sub.1-20alkyl group, and X is a halogen atom.
3. The olefin oxidation catalyst according to claim 1, wherein the
polymer compound is composed of a repeating unit of formula (8)
##STR24## wherein R.sup.18 is a tetravalent organic group derived
from tetracarboxylic acid, and R.sup.19 is a divalent organic group
derived from diamine, and is a polyimide having a number average
molecular weight of 5.times.10.sup.3 or more.
4. The olefin oxidation catalyst according to claim 1, wherein the
quaternary ammonium salt is a compound of formula (2) ##STR25##
wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are
independently of one another hydrogen atom, a halogen atom, cyano
group, C.sub.1-10alkyl group (the C.sub.1-10alkyl group may be
substituted by C.sub.6-10aryl group, C.sub.1-10alkoxy group or
benzyloxy group), C.sub.1-10alkoxy group, benzyloxy group or phenyl
group, or any two of R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9
together may form 1 or 2 fused benzene rings, R.sup.10 is
C.sub.1-20alkyl group, and X is a halogen atom.
5. The olefin oxidation catalyst according to claim 4, wherein the
quaternary ammonium salt of formula (2) in which R.sup.5, R.sup.6,
R.sup.7, R.sup.8 and R.sup.9 are hydrogen atom is used.
6. A process for producing oxirane compound of formula (5)
##STR26## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently of one another hydrogen atom, phenyl group,
C.sub.1-10alkyl group, C.sub.3-10cycloalkyl group (the
C.sub.1-10alkyl group and C.sub.3-10cycloalkyl group may be
substituted by a halogen atom, phenyl group, hydroxy group or
C.sub.1-6alkoxy group), carboxyl group, C.sub.1-6alkylcarbonyl
group, C.sub.1-6alkoxycarbonyl group (the C.sub.1-6alkylcarbonyl
group and C.sub.1-6alkoxycarbonyl group may be substituted by a
halogen atom, phenyl group, hydroxy group or C.sub.1-6alkoxy group)
or phenoxycarbonyl group (the phenoxycarbonyl group may be
substituted by a halogen atom, phenyl group, C.sub.1-6alkyl group
or C.sub.1-6alkoxy group), or any two of R.sup.1, R.sup.2, R.sup.3
and R.sup.4 together are --(CH.sub.2).sub.m-- wherein m is 3, 4 or
5, --CO.sub.2(CH.sub.2).sub.n-- wherein n is 1, 2 or 3,
--CO(CH.sub.2).sub.o-- wherein o is 2, 3 or 4,
--(CH.sub.2).sub.p--O--(CH.sub.2).sub.q-- wherein p and q are
independently of each other 0, 1, 2, 3 or 4, and a sum of p and q
is 2, 3 or 4, ##STR27## wherein R.sup.20 and R.sup.21 are
independently of one another hydrogen atom or C.sub.1-6alkoxy group
(the C.sub.1-6alkoxy group may be substituted by C.sub.2-4alkenyl
group or phenyl group (the phenyl group may be substituted by a
halogen atom, C.sub.1-6alkyl group or C.sub.1-10alkoxy group)),
characterized by treating an olefin of formula (4) ##STR28##
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the same meaning
as the above, with hydrogen peroxide in the presence of the olefin
oxidation catalyst according to claim 1.
7. The olefin oxidation catalyst according to claim 2, wherein the
polymer compound is composed of a repeating unit of formula (8)
##STR29## wherein R.sup.18 is a tetravalent organic group derived
from tetracarboxylic acid, and R.sup.19 is a divalent organic group
derived from diamine, and is a polyimide having a number average
molecular weight of 5.times.10.sup.3 or more.
8. The olefin oxidation catalyst according to claim 2, wherein the
quaternary ammonium salt is a compound of formula (2) ##STR30##
wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are
independently of one another hydrogen atom, a halogen atom, cyano
group, C.sub.1-10alkyl group (the C.sub.1-10alkyl group may be
substituted by C.sub.6-10aryl group, C.sub.1-10alkoxy group or
benzyloxy group), C.sub.1-10alkoxy group, benzyloxy group or phenyl
group, or any two of R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9
together may form 1 or 2 fused benzene rings, R.sup.10 is
C.sub.1-20alkyl group, and X is a halogen atom.
9. The olefin oxidation catalyst according to claim 3, wherein the
quaternary ammonium salt is a compound of formula (2) ##STR31##
wherein R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are
independently of one another hydrogen atom, a halogen atom, cyano
group, C.sub.1-10alkyl group (the C.sub.1-10alkyl group may be
substituted by C.sub.6-10aryl group, C.sub.1-10alkoxy group or
benzyloxy group), C.sub.1-10alkoxy group, benzyloxy group or phenyl
group, or any two of R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9
together may form 1 or 2 fused benzene rings, R.sup.10 is
C.sub.1-20alkyl group, and X is a halogen atom.
10. A process for producing oxirane compound of formula (5)
##STR32## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently of one another hydrogen atom, phenyl group,
C.sub.-10alkyl group, C.sub.3-10cycloalkyl group (the
C.sub.1-10alkyl group and C.sub.3-10cycloalkyl group may be
substituted by a halogen atom, phenyl group, hydroxy group or
C.sub.1-6alkoxy group), carboxyl group, C.sub.1-6alkylcarbonyl
group, C.sub.1-6alkoxycarbonyl group (the C.sub.1-6alkylcarbonyl
group and C.sub.1-6alkoxycarbonyl group may be substituted by a
halogen atom, phenyl group, hydroxy group or C.sub.1-6alkoxy group)
or phenoxycarbonyl group (the phenoxycarbonyl group may be
substituted by a halogen atom, phenyl group, C.sub.1-6alkyl group
or C.sub.1-6alkoxy group), or any two of R.sup.1, R.sup.2, R.sup.3
and R.sup.4 together are --(CH.sub.2).sub.m-- wherein m is 3, 4 or
5, --CO.sub.2(CH.sub.2).sub.n-- wherein n is 1, 2 or 3,
--CO(CH.sub.2).sub.o-- wherein o is 2, 3 or 4,
--(CH.sub.2).sub.p--O--(CH.sub.2).sub.q-- wherein p and q are
independently of each other 0, 1, 2, 3 or 4, and a sum of p and q
is 2, 3 or 4, ##STR33## wherein R.sup.20 and R.sup.21 are
independently of one another hydrogen atom or C.sub.1-6alkoxy group
(the C.sub.1-6alkoxy group may be substituted by C.sub.2-4alkenyl
group or phenyl group (the phenyl group may be substituted by a
halogen atom, C.sub.1-6alkyl group or C.sub.1-10alkoxy group)),
characterized by treating an olefin of formula (4) ##STR34##
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the same meaning
as the above, with hydrogen peroxide in the presence of the olefin
oxidation catalyst according to claim 2.
11. A process for producing oxirane compound of formula (5)
##STR35## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently of one another hydrogen atom, phenyl group,
C.sub.1-10alkyl group, C.sub.3-10cycloalkyl group (the
C.sub.1-10alkyl group and C.sub.3-10cycloalkyl group may be
substituted by a halogen atom, phenyl group, hydroxy group or
C.sub.1-6alkoxy group), carboxyl group, C.sub.1-6alkylcarbonyl
group, C.sub.1-6alkoxycarbonyl group (the C.sub.1-6alkylcarbonyl
group and C.sub.1-6alkoxycarbonyl group may be substituted by a
halogen atom, phenyl group, hydroxy group or C.sub.1-6alkoxy group)
or phenoxycarbonyl group (the phenoxycarbonyl group may be
substituted by a halogen atom, phenyl group, C.sub.1-6alkyl group
or C.sub.1-6alkoxy group), or any two of R.sup.1, R.sup.2, R.sup.3
and R.sup.4 together are --(CH.sub.2).sub.n-- wherein m is 3, 4 or
5, --CO.sub.2(CH.sub.2).sub.n-- wherein n is 1, 2 or 3,
--CO(CH.sub.2).sub.o-- wherein o is 2, 3 or 4,
--(CH.sub.2).sub.p--O--(CH.sub.2).sub.q-- wherein p and q are
independently of each other 0, 1, 2, 3 or 4, and a sum of p and q
is 2, 3 or 4, ##STR36## wherein R.sup.20 and R.sup.21 are
independently of one another hydrogen atom or C.sub.1-6alkoxy group
(the C.sub.1-6alkoxy group may be substituted by C.sub.2-4alkenyl
group or phenyl group (the phenyl group may be substituted by a
halogen atom, C.sub.1-6alkyl group or C.sub.1-10alkoxy group)),
characterized by treating an olefin of formula (4) ##STR37##
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the same meaning
as the above, with hydrogen peroxide in the presence of the olefin
oxidation catalyst according to claim 3.
12. A process for producing oxirane compound of formula (5)
##STR38## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently of one another hydrogen atom, phenyl group,
C.sub.1-10alkyl group, C.sub.3-10cycloalkyl group (the
C.sub.1-10alkyl group and C.sub.3-10cycloalkyl group may be
substituted by a halogen atom, phenyl group, hydroxy group or
C.sub.1-6alkoxy group), carboxyl group, C.sub.1-6alkylcarbonyl
group, C.sub.1-6alkoxycarbonyl group (the C.sub.1-6alkylcarbonyl
group and C.sub.1-6alkoxycarbonyl group may be substituted by a
halogen atom, phenyl group, hydroxy group or C.sub.1-6alkoxy group)
or phenoxycarbonyl group (the phenoxycarbonyl group may be
substituted by a halogen atom, phenyl group, C.sub.1-6alkyl group
or C.sub.1-6alkoxy group), or any two of R.sup.1, R.sup.2, R.sup.3
and R.sup.4 together are --(CH.sub.2).sub.m-- wherein m is 3, 4 or
5, --CO.sub.2(CH.sub.2).sub.n-- wherein n is 1, 2 or 3,
--CO(CH.sub.2).sub.o-- wherein o is 2, 3 or 4,
--(CH.sub.2).sub.p--O--(CH.sub.2).sub.q-- wherein p and q are
independently of each other 0, 1, 2, 3 or 4, and a sum of p and q
is 2, 3 or 4, ##STR39## wherein R.sup.20 and R.sup.21 are
independently of one another hydrogen atom or C.sub.1-6alkoxy group
(the C.sub.1-6alkoxy group may be substituted by C.sub.2-4alkenyl
group or phenyl group (the phenyl group may be substituted by a
halogen atom, C.sub.1-6alkyl group or C.sub.1-10alkoxy group)),
characterized by treating an olefin of formula (4) ##STR40##
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the same meaning
as the above, with hydrogen peroxide in the presence of the olefin
oxidation catalyst according to claim 4.
13. A process for producing oxirane compound of formula (5)
##STR41## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently of one another hydrogen atom, phenyl group,
C.sub.1-10alkyl group, C.sub.3-10cycloalkyl group (the
C.sub.1-10alkyl group and C.sub.3-10cycloalkyl group may be
substituted by a halogen atom, phenyl group, hydroxy group or
C.sub.1-6alkoxy group), carboxyl group, C.sub.1-6alkylcarbonyl
group, C.sub.1-6alkoxycarbonyl group (the C.sub.1-6alkylcarbonyl
group and C.sub.1-6alkoxycarbonyl group may be substituted by a
halogen atom, phenyl group, hydroxy group or C.sub.1-6alkoxy group)
or phenoxycarbonyl group (the phenoxycarbonyl group may be
substituted by a halogen atom, phenyl group, C.sub.1-6alkyl group
or C.sub.1-6alkoxy group), or any two of R.sup.1, R.sup.2, R.sup.3
and R.sup.4 together are --(CH.sub.2).sub.m-- wherein m is 3, 4 or
5, --CO.sub.2(CH.sub.2).sub.n-- wherein n is 1, 2 or 3,
--CO(CH.sub.2).sub.o-- wherein o is 2, 3 or 4,
--(CH.sub.2).sub.p--O--(CH.sub.2).sub.q-- wherein p and q are
independently of each other 0, 1, 2, 3 or 4, and a sum of p and q
is 2, 3 or 4, ##STR42## wherein R.sup.20 and R.sup.21 are
independently of one another hydrogen atom or C.sub.1-6alkoxy group
(the C.sub.1-6alkoxy group may be substituted by C.sub.2-4alkenyl
group or phenyl group (the phenyl group may be substituted by a
halogen atom, C.sub.1-6alkyl group or C.sub.1-10alkoxy group)),
characterized by treating an olefin of formula (4) ##STR43##
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the same meaning
as the above, with hydrogen peroxide in the presence of the olefin
oxidation catalyst according to claim 5.
Description
TECHNICAL FIELD
[0001] The present invention relates to an industrial process for
producing oxirane compound useful as starting material for epoxy
resins used for adhesive or electronic material, or in
architectural field, or the like, or for heat resistant polymers,
and as an intermediate for pharmaceuticals and agrochemicals.
BACKGROUND ART
[0002] Several documents report epoxidation process with hydrogen
peroxide by using as catalyst, heteropolyacid prepared separately
and a quaternary ammonium salt being a phase transfer catalyst
(see, for example, J. Org. Chem., Vol. 53, p. 1553-1557 (1988) and
J. Org. Chem., Vol. 53, p. 3587-3595 (1988)). The epoxidation
process yields only water other than the product and therefore is a
very clean oxidation reaction.
[0003] However, the above-mentioned process is not necessarily a
satisfactory industrial production process from reason that it uses
solvents such as chloroform, dichloromethane, benzene or the like
that are not used in ordinary industrial production processes, and
the like. In addition, in the above-mentioned documents, although
oxidation catalysts are prepared by using alkyl ammonium salt such
as methyltrioctyl ammonium chloride, the oxidation catalysts have a
high partition coefficient for organic solvents, and it is
difficult to separate with products dissolved in organic solvents.
Therefore, the process has problems in the separation and re-use of
oxidation catalyst.
[0004] On the other hand, is also reported a process for making an
oxidation catalyst heterogeneous by using an inorganic compound
such as silica gel as a carrier (see, for example, JP 2001-17863 A
and JP 2001-17864 A). This process requires an expensive silane
coupling agent or the like as an auxiliary substance for
heterogenization, and therefore is not necessarily a satisfactory
process. Industrially, further preferable oxidation catalysts are
desired.
[0005] Therefore, an object of the present invention is to provide
a process for producing oxirane compounds which is clean and
industrially useful, and an olefin oxidation catalyst which is
excellent in separability from a reaction solution and
re-usability.
DISCLOSURE OF THE INVENTION
[0006] The present inventors eagerly studied in order to resolve
the problems. Consequently, they found that reactions for producing
oxirane with hydrogen peroxide proceed also in any solvent system
normally used in industrial use by preparing an olefin oxidation
catalyst from an organic compound or a polymer compound, a tungstic
acid compound, phosphoric acid, hydrogen peroxide and a quaternary
ammonium salt, and using the oxidation catalyst, or by preparing an
olefin oxidation catalyst from an organic compound or a polymer
compound, a tungsten compound and a quaternary ammonium salt, and
using the oxidation catalyst, and that the oxidation catalysts
exert heterogenization effect without using any auxiliary substance
such as silane coupling agent or the like, and can be separated
from reaction system and re-used due to a low solubility in organic
solvents and water, and they completed the present invention.
[0007] That is, the present invention relates to the following
aspects: [0008] as a first aspect, an olefin oxidation catalyst,
prepared from an organic compound or a polymer compound of formula
(1) ##STR3## [0009] wherein R.sup.11, R.sup.12 and R.sup.13 are
independently of one another hydrogen atom, C.sub.1-10alkyl group
(the C.sub.1-10alkyl group may be substituted by C.sub.6-10aryl
group), C.sub.3-10cycloalkyl group, C.sub.6-10aryl group,
C.sub.1-6alkylcarbonyl group (the C.sub.1-6alkylcarbonyl group may
be substituted by C.sub.6-10aryl group) or C.sub.6-10arylcarbonyl
group; [0010] a tungstic acid compound; [0011] a phosphoric acid;
[0012] hydrogen peroxide; and [0013] a quaternary ammonium salt of
formula (2) or (3) ##STR4## [0014] wherein R.sup.5, R.sup.6,
R.sup.7, R.sup.8 and R.sup.9 are independently of one another
hydrogen atom, a halogen atom, cyano group, C.sub.1-10alkyl group
(the C.sub.1-10alkyl group may be substituted by C.sub.6-10aryl
group, C.sub.1-10alkoxy group or benzyloxy group), C.sub.1-10alkoxy
group, benzyloxy group or phenyl group, or [0015] any two of
R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 together may form 1
or 2 fused benzene rings, [0016] R.sup.10, R.sup.14, R.sup.15,
R.sup.16 and R.sup.17 are independently of one another
C.sub.1-20alkyl group, and [0017] X is a halogen atom; [0018] as a
second aspect, an olefin oxidation catalyst, prepared from an
organic compound or a polymer compound of formula (1) ##STR5##
[0019] wherein R.sup.11, R.sup.12 and R.sup.13 are independently of
one another hydrogen atom, C.sub.1-10alkyl group (the
C.sub.1-20alkyl group may be substituted by C.sub.6-10aryl group),
C.sub.3-10cycloalkyl group, C.sub.6-10aryl group,
C.sub.1-6alkylcarbonyl group (the C.sub.1-6alkylcarbonyl group may
be substituted by C.sub.6-10aryl group) or C.sub.6-10arylcarbonyl
group; [0020] a tungsten compound; and [0021] a quaternary ammonium
salt of formula (2) or (3) ##STR6## [0022] wherein R.sup.5,
R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are independently of one
another hydrogen atom, a halogen atom, cyano group, C.sub.1-10alkyl
group (the C.sub.1-10alkyl group may be arbitrarily substituted by
C.sub.6-10aryl group, C.sub.1-10alkoxy group or benzyloxy group),
C.sub.1-10alkoxy group, benzyloxy group or phenyl group, or [0023]
any two of R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 together
may form 1 or 2 fused benzene rings, [0024] R.sup.10, R.sup.14,
R.sup.15, R.sup.16 and R.sup.17 are independently of one another
C.sub.1-20alkyl group, and [0025] X is a halogen atom; [0026] as a
third aspect, the olefin oxidation catalyst as set forth in the
first or second aspect, wherein the polymer compound is composed of
a repeating unit of formula (8) ##STR7## [0027] wherein R.sup.18 is
a tetravalent organic group derived from tetracarboxylic acid, and
[0028] R.sup.19 is a divalent organic group derived from diamine,
and is a polyimide having a number average molecular weight of
5.times.10.sup.3 or more; [0029] as a fourth aspect, the olefin
oxidation catalyst as set forth in the first, second or third
aspect, wherein the quaternary ammonium salt is a compound of
formula (2) ##STR8## [0030] wherein R.sup.5, R.sup.6, R.sup.7,
R.sup.8 and R.sup.9 are independently of one another hydrogen atom,
a halogen atom, cyano group, C.sub.1-10alkyl group (the
C.sub.1-10alkyl group may be substituted by C.sub.6-10aryl group,
C.sub.1-10alkoxy group or benzyloxy group), C.sub.1-10alkoxy group,
benzyloxy group or phenyl group, or [0031] any two of R.sup.5,
R.sup.6, R.sup.7, R.sup.8 and R.sup.9 together may form 1 or 2
fused benzene rings, [0032] R.sup.10 is C.sub.1-20alkyl group, and
[0033] X is a halogen atom; [0034] as a fifth aspect, the olefin
oxidation catalyst as set forth in the fourth aspect, [0035]
wherein the quaternary ammonium salt of formula (2) in which
R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are hydrogen atom is
used; and [0036] as a sixth aspect, a process for producing oxirane
compound of formula (5) ##STR9## [0037] wherein R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 are independently of one another hydrogen atom,
phenyl group, C.sub.1-10alkyl group, C.sub.3-10cycloalkyl group
(the C.sub.1-10alkyl group and C.sub.3-10cycloalkyl group may be
substituted by a halogen atom, phenyl group, hydroxy group or
C.sub.1-6alkoxy group), carboxyl group, C.sub.1-6alkylcarbonyl
group, C.sub.1-6alkoxycarbonyl group (the C.sub.1-6alkylcarbonyl
group and C.sub.1-6alkoxycarbonyl group may be substituted by a
halogen atom, phenyl group, hydroxy group or C.sub.1-6alkoxy group)
or phenoxycarbonyl group (the phenoxycarbonyl group may be
substituted by a halogen atom, phenyl group, C.sub.1-6alkyl group
or C.sub.1-6alkoxy group), or [0038] any two of R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 together are --(CH.sub.2).sub.m-- wherein m is
3, 4 or 5, --CO.sub.2(CH.sub.2).sub.n-- wherein n is 1, 2 or 3,
--CO(CH.sub.2).sub.o-- wherein o is 2, 3 or 4,
--(CH.sub.2).sub.p--O--(CH.sub.2).sub.q-- wherein p and q are
independently of each other 0, 1, 2, 3 or 4, and a sum of p and q
is 2, 3 or 4, ##STR10## [0039] wherein R.sup.20 and R.sup.21 are
independently of one another hydrogen atom or C.sub.1-6alkoxy group
(the C.sub.1-6alkoxy group may be substituted by C.sub.2-4alkenyl
group or phenyl group (the phenyl group may be substituted by a
halogen atom, C.sub.1-6alkyl group or C.sub.1-10alkoxy group)),
characterized by treating an olefin of formula (4) ##STR11## [0040]
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the same meaning
as the above, with hydrogen peroxide in the presence of the olefin
oxidation catalyst as set forth in the first, second, third, fourth
or fifth aspect.
BEST MODE FOR CARRYING OUT THE INVENTION
[0041] Hereinafter, the present invention will be described in
further detail.
[0042] In the meanwhile, in the present specification, "n" means
normal, "i" means iso, "s" means secondary, "t" means tertiary, and
"c" means cyclo.
[0043] First of all, the definition of each substituent of R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8,
R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20,
R.sup.21 and X will be described.
[0044] C.sub.1-6alkyl group includes methyl group, ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-butyl group,
s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl
group, 2-methyl-n-butyl group, 3-methyl-n-butyl group,
1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group,
2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group,
1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl
group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group,
1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group,
2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group,
3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl
group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl
group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl
group, etc.
[0045] C.sub.1-10alkyl group includes in addition to the above,
1-methyl-1-ethyl-n-pentyl group, 1-heptyl group, 2-heptyl group,
1-ethyl-1,2-dimethyl-n-propyl group, 1-ethyl-2,2-dimethyl-n-propyl
group, 1-octyl group, 3-octyl group, 4-methyl-3-n-heptyl group,
6-methyl-2-n-heptyl group, 2-propyl-1-n-heptyl group,
2,4,4-trimethyl-1-n-pentyl group, 1-nonyl group, 2-nonyl group,
2,6-dimethyl-4-n-heptyl group, 3-ethyl-2,2-dimethyl-3-n-pentyl
group, 3,5,5-trimethyl-1-n-hexyl group, 1-decyl group, 2-decyl
group, 4-decyl group, 3,7-dimethyl-1-n-octyl group,
3,7-dimethyl-3-n-octyl group, etc.
[0046] C.sub.1-20alkyl group includes in addition to the above,
n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl
group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group,
n-octadecyl group, n-nonadecyl group, n-eicosyl, etc.
[0047] C.sub.3-10cycloalkyl group includes c-propyl group, c-butyl
group, 1-methyl-c-propyl group, 2-methyl-c-propyl group, c-pentyl
group, 1-methyl-c-butyl group, 2-methyl-c-butyl group,
3-methyl-c-butyl group, 1,2-dimethyl-c-propyl group,
2,3-dimethyl-c-propyl group, 1-ethyl-c-propyl group,
2-ethyl-c-propyl group, c-hexyl group, 1-methyl-c-pentyl group,
2-methyl-c-pentyl group, 3-methyl-c-pentyl group, 1-ethyl-c-butyl
group, 2-ethyl-c-butyl group, 3-ethyl-c-butyl group,
1,2-dimethyl-c-butyl group, 1,3-dimethyl-c-butyl group,
2,2-dimethyl-c-butyl group, 2,3-dimethyl-c-butyl group,
2,4-dimethyl-c-butyl group, 3,3-dimethyl-c-butyl group,
1-n-propyl-c-propyl group, 2-n-propyl-c-propyl group,
1-i-propyl-c-propyl group, 2-i-propyl-c-propyl group,
1,2,2-trimethyl-c-propyl group, 1,2,3-trimethyl-c-propyl group,
2,2,3-trimethyl-c-propyl group, 1-ethyl-2-methyl-c-propyl group,
2-ethyl-1-methyl-c-propyl group, 2-ethyl-2-methyl-c-propyl group,
2-ethyl-3-methyl-c-propyl group, c-heptyl group, c-octyl group,
c-nonyl group, c-decyl group, etc.
[0048] C.sub.6-10arylcarbonyl group includes benzoyl group,
1-indenylcarbonyl group, 2-indenylcarbonyl group, 3-indenylcarbonyl
group, 4-indenylcarbonyl group, 5-indenylcarbonyl group,
6-indenylcarbonyl group, 7-indenylcarbonyl group, 1-naphthoyl
group, 2-naphthoyl group, 1-tetrahydronaphthoyl group,
2-tetrahydronaphthoyl group, 5-tetrahydronaphthoyl group,
6-tetrahydronaphthoyl group, etc.
[0049] C.sub.1-6alkoxy group includes methoxy group, ethoxy group,
n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group,
s-butoxy group, t-butoxy group, n-pentyloxy group,
1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy
group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group,
2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, 1-hexyloxy
group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group,
3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group,
1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group,
1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group,
2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group,
1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group,
1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group,
1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group,
etc.
[0050] C.sub.1-10alkoxy group includes in addition to the above,
1-methyl-1-ethyl-n-pentyloxy group, 1-heptyloxy group, 2-heptyloxy
group, 1-ethyl-1,2-dimethyl-n-propxy group,
1-ethyl-2,2-dimethyl-n-propoxy group, 1-octyloxy group, 3-octyloxy
group, 4-methyl-3-n-heptyloxy group, 6-methyl-2-n-heptyloxy group,
2-propyl-1-n-heptyloxy group, 2,4,4-trimethyl-1-n-pentyloxy group,
1-nonyloxy group, 2-nonyloxy group, 2,6-dimethyl-4-n-heptyloxy
group, 3-ethyl-2,2-dimethyl-3-n-pentyloxy group,
3,5,5-trimethyl-1-n-hexyloxy group, 1-decyloxy group, 2-decyloxy
group, 4-decyloxy group, 3,7-dimethyl-1-n-octyloxy group,
3,7-dimethyl-3-n-octyloxy group, etc.
[0051] C.sub.1-6alkylcarbonyl group includes methylcarbonyl group,
ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl
group, n-butylcarbonyl group, i-butylcarbonyl group,
s-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl
group, 1-methyl-n-butylcarbonyl group, 2-methyl-n-butylcarbonyl
group, 3-methyl-n-butylcarbonyl group,
1,1-dimethyl-n-propylcarbonyl group, 1,2-dimethyl-n-propylcarbonyl
group, 2,2-dimethyl-n-propylcarbonyl group,
1-ethyl-n-propylcarbonyl group, n-hexylcarbonyl group,
1-methyl-n-pentylcarbonyl group, 2-methyl-n-pentylcarbonyl,
3-methyl-n-pentylcarbonyl, 4-methyl-n-pentylcarbonyl,
1,1-dimethyl-n-butylcarbonyl group, 1,2-dimethyl-n-butylcarbonyl
group, 1,3-dimethyl-n-butylcarbonyl group,
2,2-dimethyl-n-butylcarbonyl group, 2,3-dimethyl-n-butylcarbonyl
group, 3,3-dimethyl-n-butylcarbonyl group, 1-ethyl-n-butylcarbonyl
group, 2-ethyl-n-butylcarbonyl group,
1,1,2-trimethyl-n-propylcarbonyl group,
1,2,2-trimethyl-n-propylcarbonyl group,
1-ethyl-1-methyl-n-propylcarbonyl group,
1-ethyl-2-methyl-n-propylcarbonyl group, etc.
[0052] C.sub.1-6alkoxycarbonyl group includes methoxycarbonyl
group, ethoxycarbonyl group, n-propoxycarbonyl group,
i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl
group, s-butoxycarbonyl group, t-butoxycarbonyl group,
n-pentyloxycarbonyl group, 1-methyl-n-butoxycarbonyl group,
2-methyl-n-butoxycarbonyl group, 3-methyl-n-butoxycarbonyl group,
1,1-dimethyl-n-propoxycarbonyl group,
1,2-dimethyl-n-propoxycarbonyl group,
2,2-dimethyl-n-propoxycarbonyl group, 1-ethyl-n-propoxycarbonyl
group, n-hexyloxycarbonyl group, 1-methyl-n-pentyloxycarbonyl
group, 2-methyl-n-pentyloxycarbonyl, 3-methyl-n-pentyloxycarbonyl,
4-methyl-n-pentyloxycarbonyl, 1,1-dimethyl-n-butoxycarbonyl group,
1,2-dimethyl-n-butoxycarbonyl group, 1,3-dimethyl-n-butoxycarbonyl
group, 2,2-dimethyl-n-butoxycarbonyl group,
2,3-dimethyl-n-butoxycarbonyl group, 3,3-dimethyl-n-butoxycarbonyl
group, 1-ethyl-n-butoxycarbonyl group, 2-ethyl-n-butoxycarbonyl
group, 1,1,2-trimethyl-n-propoxycarbonyl group,
1,2,2-trimethyl-n-propoxycarbonyl group,
1-ethyl-1-methyl-n-propoxycarbonyl group,
1-ethyl-2-methyl-n-propoxycarbonyl group, etc.
[0053] C.sub.6-10aryl group includes phenyl group, 1-indenyl group,
2-indenyl group, 3-indenyl group, 4-indenyl group, 5-indenyl group,
6-indenyl group, 7-indenyl group, 1-naphthyl group, 2-naphthyl
group, 1-tetrahydronaphthyl group, 2-tetrahydronaphthyl group,
5-tetrahydronaphthyl group, 6-tetrahydronaphthyl group, etc.
[0054] C.sub.2-4alkenyl group includes ethenyl group, 1-propenyl
group, 2-propenyl group, 1-butenyl group, 2-butenyl group,
3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl
group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group,
1-ethyl-1-ethenyl group, etc.
[0055] Halogen atom includes fluorine atom, chlorine atom, bromine
atom and iodine atom.
[0056] Then, specific examples of R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10,
R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16,
R.sup.17, R.sup.18, R.sup.19 and X will be described.
[0057] Specific examples of R.sup.1, R.sup.2, R.sup.3 and R.sup.4
include hydrogen atom, methyl group, ethyl group, n-propyl group,
i-propyl group, n-butyl group, i-butyl group, s-butyl group,
t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group,
n-octyl group, n-nonyl group, n-decyl group, c-hexyl group, phenyl
group, chloromethyl group, bromomethyl group, hydroxymethyl group,
methoxymethyl group, ethoxymethyl group, phenoxymethyl group,
carboxyl group, methylcarbonyl group, ethylcarbonyl group,
n-propylcarbonyl group, n-butylcarbonyl group, n-pentylcarbonyl
group, n-hexylcarbonyl group, methoxycarbonyl group, ethoxycarbonyl
group, n-propoxycarbonyl group, n-butoxycarbonyl group,
n-pentyloxycarbonyl group, n-hexyloxycarbonyl group,
phenoxycarbonyl group, etc.
[0058] Specific examples of groups that any two of R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 form together include groups of the
following formulae ##STR12##
[0059] Specific examples of R.sup.5, R.sup.6, R.sup.7, R.sup.8 and
R.sup.9 include hydrogen atom, fluorine atom, chlorine atom,
bromine atom, iodine atom, cyano group, methyl group, ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-butyl group,
s-butyl group, t-butyl group, n-pentyl group, n-hexyl group,
n-heptyl group, n-octyl group, n-nonyl group, n-decyl group,
methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group,
n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group,
n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy
group, n-nonyloxy group, n-decyloxy group, benzyloxy group, benzyl
group, 3-phenylpropyl group, etc., and hydrogen atom is
preferable.
[0060] Specific examples of fused benzene ring that any two of
R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 form together
include a case where R.sup.5 and R.sup.6 together form
--CH.dbd.CH--CH.dbd.CH--, a case where R.sup.6 and R.sup.7 together
form --CH.dbd.CH--CH.dbd.CH--, and a case where R.sup.5 and R.sup.6
together form --CH.dbd.CH--CH.dbd.CH-- and R.sup.8 and R.sup.9
together form --CH.dbd.CH--CH.dbd.CH--.
[0061] Specific examples of R.sup.10 include CH.sub.3--,
H(CH.sub.2).sub.2--, H(CH.sub.2).sub.3--, H(CH.sub.2).sub.4--,
H(CH.sub.2).sub.5--, H(CH.sub.2).sub.6--, H(CH.sub.2).sub.7--,
H(CH.sub.2).sub.8--, H(CH.sub.2).sub.9--, H(CH.sub.2).sub.10--,
H(CH.sub.2).sub.11--, H(CH.sub.2).sub.12--, H(CH.sub.2).sub.13--,
H(CH.sub.2).sub.14--, H(CH.sub.2).sub.15--, H(CH.sub.2).sub.16--,
H(CH.sub.2).sub.17--, H(CH.sub.2).sub.18--, H(CH.sub.2).sub.19--
and H(CH.sub.2).sub.20--, etc., and H(CH.sub.2).sub.14--,
H(CH.sub.2).sub.16--, H(CH.sub.2).sub.18-- and H(CH.sub.2).sub.20--
are preferable.
[0062] Specific examples of R.sup.11, R.sup.12 and R.sup.13 include
hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl
group, n-butyl group, i-butyl group, s-butyl group, t-butyl group,
n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group,
3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group,
1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group,
1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group,
2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl
group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group,
1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group,
2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group,
1-ethyl-n-butyl group, 2-ethyl-n-butyl group,
1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group,
1-ethyl-i-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group,
1-methyl-1-ethyl-n-pentyl group, n-heptyl group, 2-heptyl group,
1-ethyl-1,2-dimethyl-n-propyl group, 1-ethyl-2,2-dimethyl-n-propyl
group, 1-octyl group, 3-octyl group, 4-methyl-3-n-heptyl group,
6-methyl-2-n-heptyl group, 2-propyl-1-n-heptyl group,
2,4,4-trimethyl-1-n-pentyl group, 1-nonyl group, 2-nonyl group,
2,6-dimethyl-4-n-heptyl group, 3-ethyl-2,2-dimethyl-3-n-pentyl
group, 3,5,5-trimethyl-1-n-hexyl group, 1-decyl group, 2-decyl
group, 4-decyl group, 3,7-dimethyl-1-n-octyl group,
3,7-dimethyl-3-n-octyl group, c-propyl group, c-butyl group,
1-methyl-c-propyl group, 2-methyl-c-propyl group, c-pentyl group,
1-methyl-c-butyl group, 2-methyl-c-butyl group, 3-methyl-c-butyl
group, 1,2-dimethyl-c-propyl group, 2,3-dimethyl-c-propyl group,
1-ethyl-c-propyl group, 2-ethyl-c-propyl group, c-hexyl group,
1-methyl-c-pentyl group, 2-methyl-c-pentyl group, 3-methyl-c-pentyl
group, 1-ethyl-c-butyl group, 2-ethyl-c-butyl group,
3-ethyl-c-butyl group, 1,2-dimethyl-c-butyl group,
1,3-dimethyl-c-butyl group, 2,2-dimethyl-c-butyl group,
2,3-dimethyl-c-butyl group, 2,4-dimethyl-c-butyl group,
3,3-dimethyl-c-butyl group, 1-n-propyl-c-propyl group,
2-n-propyl-c-propyl group, 1-i-propyl-c-propyl group,
2-i-propyl-c-propyl group, 1,2,2-trimethyl-c-propyl group,
1,2,3-trimethyl-c-propyl group, 2,2,3-trimethyl-c-propyl group,
1-ethyl-2-methyl-c-propyl group, 2-ethyl-1-methyl-c-propyl group,
2-ethyl-2-methyl-c-propyl group, 2-ethyl-3-methyl-c-propyl group,
c-heptyl group, c-octyl group, c-nonyl group, c-decyl group, benzyl
group, phenyl group, methylcarbonyl group, ethylcarbonyl group,
n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl
group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, etc.,
and hydrogen atom, methyl group, ethyl group, n-propyl group,
i-propyl group, n-butyl group, i-butyl group and phenyl group are
preferable.
[0063] Specific examples of R.sup.14, R.sup.15, R.sup.16 and
R.sup.17 include benzyl group, CH.sub.3--, H(CH.sub.2).sub.2--,
H(CH.sub.2).sub.3--, H(CH.sub.2).sub.4--, H(CH.sub.2).sub.5--,
H(CH.sub.2).sub.6--, H(CH.sub.2).sub.7--, H(CH.sub.2).sub.8--,
H(CH.sub.2).sub.9--, H(CH.sub.2).sub.10--, H(CH.sub.2).sub.11--,
H(CH.sub.2).sub.12--, H(CH.sub.2).sub.13--, H(CH.sub.2).sub.14--,
H(CH.sub.2).sub.15--, H(CH.sub.2).sub.16--, H(CH.sub.2).sub.17--,
H(CH.sub.2).sub.18--, H(CH.sub.2).sub.19-- and
H(CH.sub.2).sub.20--, etc., and benzyl group, CH.sub.3--,
H(CH.sub.2).sub.2--, H(CH.sub.2).sub.8--, H(CH.sub.2).sub.14--,
H(CH.sub.2).sub.16--, H(CH.sub.2).sub.18-- and H(CH.sub.2).sub.20--
are preferable.
[0064] Specific examples of tetracarboxylic acid forming R.sup.18
include aromatic tetracarboxylic acids such as pyromellitic acid,
2,3,6,7-naphthalenetetracarboxylic acid,
1,2,5,6-naphthalenetetracarboxylic acid,
1,4,5,8-naphthalenetetracarboxylic acid,
2,3,6,7-anthracenetetracarboxylic acid,
1,2,5,6-anthracenetetracarboxylic acid,
3,3',4,4'-biphenyltetracarboxylic acid,
2,3,3',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)
ether, 3,3',4,4'-benzophenone tetracarboxylic acid,
bis(3,4-dicarboxyphenyl) sulfone, bis(3,4-dicarboxyphenyl) methane,
2,2-bis(3,4-dicarboxyphenyl) propane,
1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl) propane,
bis(3,4-dicarboxyphenyl) dimethylsilane, bis(3,4-dicarboxyphenyl)
diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid,
2,6-bis(3,4-dicarboxyphenyl) pyridine, etc.; alicyclic
tetracarboxylic acids such as 1,2,3,4-cyclobutane tetracarboxylic
acid, 1,2,3,4-cycloheptane tetracarboxylic acid,
2,3,4,5-tetrahydrofuran tetracarboxylic acid, 1,2,4,5-cyclohexane
tetracarboxylic acid, 5-succinic
acid-3-methyl-cyclohexene-1,2-dicarboxylic acid,
3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic acid, etc.;
aliphatic tetracarboxylic acids such as 1,2,3,4-butane
tetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic acid,
2,3,5-tricarboxy-2-cyclopentane acetic acid,
3,5,6-tricarboxy-2-norbornane acetic acid, etc., and these
compounds can be used in a mixture of two or more. Preferable
tetracarboxylic acids are 3,3',4,4'-biphenyltetracarboxylic acid,
3,3',4,4'-biphenyltetracarboxylic acid,
1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl) propane,
1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentane
tetracarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid,
5-succinic acid-3-methyl-3-cyclohexene-1,2-dicarboxylic acid,
3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic acid,
1,2,3,4-butane tetracarboxylic acid, 1,2,3,4-cyclobutane
tetracarboxylic acid, etc.
[0065] Specific examples of diamine forming R.sup.19 include
aromatic diamines such as p-phenylenediamine, m-phenylenediamine,
2,5-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminobiphenyl,
3,3'-dimethyl-4,4'-diaminobiphenyl,
3,3'-dimethoxy-4,4'-diaminobiphenyl,
3,3'-diethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 4,4'-isopropylidene bisaniline,
bis(3,5-diethyl-4-aminophenyl) methane,
4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone,
1,4-diaminonaphthalene, 1,5-diaminonaphthalene,
1,4-bis(4-aminophenoxy) benzene, 1,4-bis(4-aminophenyl) benzene,
9,10-bis(4-aminophenyl) anthracene, 1,3-bis(4-aminophenoxy)
benzene, bis[4-(4-aminophenoxy) phenyl] sulfone,
4,4'-bis(4-aminophenoxy) diphenylsulfone,
2,2-bis[4-(4-aminophenoxy) phenyl] propane, 2,2-bis(4-aminophenyl)
hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]
hexafluoropropane, etc.; alicyclic diamines such as
bis(4-aminocyclohexyl) methane, bis(4-amino-3-methylcyclohexyl)
methane, etc.; and aliphatic diamines such as 1,2-diaminoethane,
1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, etc., and
these compounds can be-used in a mixture of two or more. Preferable
diamines are p-phenylenediamine, m-phenylenediamine,
3,3'-dimethyl-4,4'-diaminobiphenyl,
3,3'-diethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, bis(3,5-diethyl-4-aminophenyl) methane,
4,4'-diaminodiphenylsulfone, 1,5-diaminonaphthalene,
1,4-bis(4-aminophenoxy) benzene, 1,3-bis(4-aminophenoxy) benzene,
bis(4-aminocyclohexyl) methane, bis(4-amino-3-methylcyclohexyl)
methane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane,
1,6-diaminohexane, etc.
[0066] Specific examples of X include fluorine atom, chlorine atom,
bromine atom and iodine atom, and chlorine atom is preferable.
[0067] Preferable organic compounds are compounds of formula (1)
wherein any two of R.sup.11, R.sup.12 and R.sup.13 are hydrogen
atom, the remaining one is methyl group, ethyl group, n-propyl
group, i-propyl group, n-butyl, i-butyl group, phenyl group,
etc.
[0068] Preferable quaternary ammonium salts of formula (2) include
the following compounds: [0069] 1) quaternary ammonium salts of
formula (2) wherein R.sup.10 is H(CH.sub.2).sub.14--,
H(CH.sub.2).sub.16--, H(CH.sub.2).sub.18-- or H(CH.sub.2).sub.20--;
[0070] 2) quaternary ammonium salts of formula (2) wherein R.sup.5,
R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are hydrogen atom; [0071] 3)
quaternary ammonium salts of formula (2) wherein R.sup.10 is
H(CH.sub.2).sub.14--, H(CH.sub.2).sub.16--, H(CH.sub.2).sub.18-- or
H(CH.sub.2).sub.20--, and R.sup.5, R.sup.6, R.sup.7, R.sup.8 and
R.sup.9 are hydrogen atom.
[0072] Preferable quaternary ammonium salts of formula (3) include
commercially available trioctylmethyl ammonium salts,
benzylcetyldimethyl ammonium salts, benzyldimethylstearyl ammonium
salts, cetyidimethylethyl ammonium salts, dimethyldistearyl
ammonium salts, stearyltrimethyl ammonium salts, etc.
[0073] Polyimides composed of a repeating unit of formula (8) are
specifically limited so far as they can heterogenize an olefin
oxidation catalyst prepared from a tungstic acid compound, a
phosphoric acid, hydrogen peroxide and a quaternary ammonium, or an
olefin oxidation catalyst prepared from a tungsten compound and a
quaternary ammonium salt, but they generally have a lower limit of
number average molecular weight of 5.times.10.sup.3, preferably
8.times.10.sup.3, and an upper limit of 2.times.10.sup.5, for
example 1.times.10.sup.5, or preferably for example
3.times.10.sup.4.
[0074] Preferable combination of tetracarboxylic acid forming
R.sup.18 with diamine forming R.sup.19 is as follows: [0075] 1)
polyimides composed of repeating unit of formula (8) in which the
tetracarboxylic acid forming R.sup.18 is pyromellitic acid,
2,3,6,7-naphthalenetetracarboxylic acid,
1,2,5,6-naphthalenetetracarboxylic acid,
1,4,5,8-naphthalenetetracarboxylic acid,
2,3,6,7-anthracenetetracarboxylic acid,
1,2,5,6-anthracenetetracarboxylic acid,
3,3',4,4'-biphenyltetracarboxylic acid,
2,3,3',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)
ether, 3,3',4,4'-benzophenone tetracarboxylic acid,
bis(3,4-dicarboxyphenyl) sulfone, bis(3,4-dicarboxyphenyl) methane,
2,2-bis(3,4-dicarboxyphenyl) propane,
1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl) propane,
bis(3,4-dicarboxyphenyl) dimethylsilane, bis(3,4-dicarboxyphenyl)
diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid,
2,6-bis(3,4-dicarboxyphenyl) pyridine, 1,2,3,4-cyclobutane
tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid,
2,3,4,5-tetrahydrofuran tetracarboxylic acid, 1,2,4,5-cyclohexane
tetracarboxylic acid, 5-succinic
acid-3-methyl-cyclohexene-1,2-dicarboxylic acid,
3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic acid,
1,2,3,4-butane tetracarboxylic acid, 1,2,3,4-cyclobutane
tetracarboxylic acid, 2,3,5-tricarboxy-2-cyclopentane acetic acid
or 3,5,6-tricarboxy-2-norbornane acetic acid, or a mixture of two
or more of these, and the diamine forming R.sup.19 is
p-phenylenediamine, m-phenylenediamine,
3,3'-dimethyl-4,4'-diaminobiphenyl,
3,3'-diethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, bis(3,5-diethyl-4-aminophenyl) methane,
4,4'-diaminodiphenylsulfone, 1,5-diaminonaphthalene,
1,4-bis(4-aminophenoxy) benzene, 1,3-bis(4-aminophenoxy) benzene,
bis(4-aminocyclohexyl) methane, bis(4-amino-3-methylcyclohexyl)
methane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane
or 1,6-diaminohexane; [0076] 2) polyimides composed of repeating
unit of formula (8) in which the tetracarboxylic acid forming
R.sup.18 is 3,3',4,4'-biphenyltetracarboxylic acid,
3,3',4,4'-biphenyltetracarboxylic acid,
1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl) propane,
1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentane
tetracarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid,
5-succinic acid-3-methyl-3-cyclohexene-1,2-dicarboxylic acid,
3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic acid,
1,2,3,4-butane tetracarboxylic acid or 1,2,3,4-cyclobutane
tetracarboxylic acid, and the diamine forming R.sup.19 is
p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene,
2,6-diaminotoluene, 4,4'-diaminobiphenyl,
3,3'-dimethyl-4,4'-diaminobiphenyl,
3,3'-dimethoxy-4,4'-diaminobiphenyl,
3,3'-diethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 4,4'-isopropylidene bisaniline,
bis(3,5-diethyl-4-aminophenyl) methane,
4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone,
1,4-diaminonaphthalene, 1,5-diaminonaphthalene,
1,4-bis(4-aminophenoxy) benzene, 1,4-bis(4-aminophenyl) benzene,
9,10-bis(4-aminophenyl) anthracene, 1,3-bis(4-aminophenoxy)
benzene, bis[4-(4-aminophenoxy) phenyl] sulfone,
4,4'-bis(4-aminophenoxy) diphenylsulfone,
2,2-bis[4-(4-aminophenoxy) phenyl] propane, 2,2-bis(4-aminophenyl)
hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]
hexafluoropropane, bis(4-aminocyclohexyl) methane,
bis(4-amino-3-methylcyclohexyl) methane, 1,2-diaminoethane,
1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane, or a
mixture of two or more of these; and [0077] 3) polyimides composed
of repeating unit of formula (8) in which the tetracarboxylic acid
forming R.sup.18 is 3,3',4,4'-biphenyltetracarboxylic acid,
3,3',4,4'-biphenyltetracarboxylic acid,
1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl) propane,
1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentane
tetracarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid,
5-succinic acid-3-methyl-3-cyclohexene-1,2-dicarboxylic acid,
3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic acid,
1,2,3,4-butane tetracarboxylic acid or 1,2,3,4-cyclobutane
tetracarboxylic acid, and the diamine forming R.sup.19 is
p-phenylenediamine, m-phenylenediamine,
3,3'-dimethyl-4,4'-diaminobiphenyl,
3,3'-diethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, bis(3,5-diethyl-4-aminophenyl) methane,
4,4'-diaminodiphenylsulfone, 1,5-diaminonaphthalene,
1,4-bis(4-aminophenoxy) benzene, 1,3-bis(4-aminophenoxy) benzene,
bis(4-aminocyclohexyl) methane, bis(4-amino-3-methylcyclohexyl)
methane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane
or 1,6-diaminohexane.
[0078] The polymer compounds in the present invention are
specifically limited so far as they can heterogenize an olefin
oxidation catalyst prepared from a tungstic acid compound, a
phosphoric acid, hydrogen peroxide and a quaternary ammonium, or an
olefin oxidation catalyst prepared from a tungsten compound and a
quaternary ammonium salt, and include for example polyimides,
acrylamides, methacrylamides, polyamides, polyurethanes, etc. The
lower limit of number average molecular weight thereof is generally
5.times.10.sup.3, preferably 8.times.10.sup.3, and the upper limit
is 2.times.10.sup.5, for example 1.times.10.sup.5, or preferably
for example 3.times.10.sup.4.
[0079] Preferable polyimides include polyimides composed of
repeating unit of formula (8).
[0080] The tungsten compound in the present invention includes
12-tungstophosphoric acid, sodium salt of 12-tungstophosphoric
acid, potassium salt of 12-tungstophosphoric acid, ammonium salt of
12-tungstophosphoric acid, etc., and 12-tungstophosphoric acid is
preferable.
[0081] In the meanwhile, the salts of 12-tungstophosphoric acid can
be easily produced from 12-tungstophosphoric acid.
[0082] The tungstic acid compound in the present invention includes
tungstic acid, sodium salt of tungstic acid, potassium of tungstic
acid, ammonium salt of tungstic acid, and tungstic acid is
preferable.
[0083] The olefin oxidation catalyst prepared from the organic
compound or polymer compound of formula (1), a tungstic acid
compound, phosphoric acid, hydrogen peroxide and the quaternary
ammonium salt of formula (2) or (3), and the olefin oxidation
catalyst prepared from the organic compound or polymer compound of
formula (1), a tungsten compound and the quaternary ammonium salt
of formula (2) or (3) can be prepared by modifying the process
described in J. Org. Chem., Vol. 53, p. 1552-1557 (1988) and J.
Org. Chem., Vol. 53, p. 3587-3593 (1988).
[0084] The olefin oxidation catalyst prepared from the organic
compound or polymer compound of formula (1), a tungstic acid
compound, phosphoric acid, hydrogen peroxide and the quaternary
ammonium salt of formula (2) or (3) according to the present
invention can be produced by adding the tungstic acid compound in
an aqueous solution of hydrogen peroxide, warming and then adding
phosphoric acid at room temperature, diluting with water to obtain
a diluted solution, dispersing the organic compound or polymer
compound of formula (1) in the diluted solution, and then adding
dropwise a solution of the quaternary ammonium salt of formula (2)
or (3) diluted with a solvent.
[0085] The used amount of the organic compound or polymer compound
of formula (1) is 1 to 200 g per 1 mmol of phosphoric acid.
[0086] As the hydrogen peroxide used, commercially available
aqueous solution can be used as such or in a diluted state, and the
used amount thereof is 2 to 50 molar equivalents, preferably 2 to
30 molar equivalents based on the quaternary ammonium salt of
formula (2) or (3).
[0087] The used amount of tungstic acid compound is 1 to 3 molar
equivalents based on the quaternary ammonium salt of formula (2) or
(3).
[0088] The used amount of phosphoric acid is 0.1 to 1 molar
equivalent based on the quaternary ammonium salt of formula (2) or
(3).
[0089] The solvent used is not specifically limited so long as it
does not take part in the reaction, and includes aromatic
hydrocarbons such as benzene, toluene, xylene and the like,
aliphatic hydrocarbons such as hexane, heptane, dodecane, and the
like, halogen-containing solvents, such as chloroform,
dichloromethane, dichloroethane, and the like, ethers such as
tetrahydrofuran, dioxane, and the like, nitriles such as
acetonitrile, butyronitrile and the like, amides such as
N,N-dimethylformamide, N,N-dimethylacetamide, and the like, ureas
such as N,N'-dimethylimidazolidinone, and the like, water, and
mixtures of these solvents. Water, aromatic hydrocarbons, aliphatic
hydrocarbons, and mixtures of these solvents are preferable.
[0090] The temperature for warming is 40 to 80.degree. C.
[0091] Next, the olefin oxidation catalyst prepared from the
organic compound or polymer compound of formula (1), a tungsten
compound, and the quaternary ammonium salt of formula (2) or (3)
according to the present invention will be described.
[0092] The oxidation catalyst can be produced by dispersing the
organic compound or polymer compound of formula (1) in a solution
of the quaternary ammonium salt of formula (2) or (3) diluted with
a solvent, and adding dropwise an aqueous solution of the tungsten
compound therein, or by dispersing the organic compound or polymer
compound of formula (1) in an aqueous solution of the tungsten
compound, and adding dropwise a solution of the quaternary ammonium
salt of formula (2) or (3) diluted with a solvent.
[0093] The used amount of the organic compound or polymer compound
of formula (1) is 1 to 200 g per 1 mmol of the tungsten
compound.
[0094] The used amount of tungsten compound is 0.2 to 0.5 molar
equivalent based on the quaternary ammonium salt of formula (2) or
(3).
[0095] The solvent used is not specifically limited so long as it
does not take part in the reaction, and includes aromatic
hydrocarbons such as benzene, toluene, xylene and the like,
aliphatic hydrocarbons such as hexane, heptane, dodecane, and the
like, halogen-containing solvents, such as chloroform,
dichloromethane, dichloroethane, and the like, ethers such as
tetrahydrofuran, dioxane, and the like, nitriles such as
acetonitrile, butyronitrile and the like, amides such as
N,N-dimethylformamide, N,N-dimethylacetamide, and the like, ureas
such as N,N'-dimethylimidazolidinone, and the like, water, and
mixtures of these solvents. Water, aromatic hydrocarbons, aliphatic
hydrocarbons, and mixtures of these solvents are preferable.
[0096] In addition, the temperature in the reaction is 0 to
100.degree. C.
[0097] The olefin oxidation catalyst according to the present
invention prepared by the above-mentioned production process is
generally insoluble in the solvent. Therefore, the olefin oxidation
catalyst can be isolated by removing the solvent and aqueous phase
after reaction.
[0098] In the meanwhile, a solution prepared by dissolving the
olefin oxidation catalyst in a solvent can be used as such for the
production of oxirane compounds of formula (5).
[0099] In case where the used solvent is aromatic hydrocarbons such
as toluene, xylene or the like, or aliphatic hydrocarbon such as
hexane, heptane, dodecane or the like, the resulting olefin
oxidation catalyst is generally insoluble in the solvent, and
therefore the reaction solution forms three phases composed of an
aqueous phase, an organic phase and a catalyst phase.
[0100] In this case, after reaction, the removal of the aqueous and
organic phases enables the olefin oxidation catalyst to be
isolated.
[0101] Also in case where water is used as a solvent, the resulting
olefin oxidation catalyst is generally insoluble in the solvent,
and therefore the filtration or the removal of water enables the
olefin oxidation catalyst to be isolated.
[0102] As to the structure of the olefin oxidation catalyst
prepared from the organic compound or polymer compound of formula
(1), a tungstic acid compound, phosphoric acid, hydrogen peroxide
and the quaternary ammonium salt of formula (2) or (3), from the
indication of J. Org. Chem., Vol. 53, p. 1553-1557 (1988), it is
suggested that the compound having the following structure may be
adsorbed by or dissolved in the organic compound or polymer
compound of formula (1) and the resulting catalyst may be
heterogenized. ##STR13##
[0103] On the other hand, as to the structure of the olefin
oxidation catalyst prepared from the olefin oxidation catalyst
prepared from the organic compound or polymer compound of formula
(1), a tungsten compound and the quaternary ammonium salt of
formula (2) or (3), from the indication of J. Org. Chem., Vol. 53,
p. 3587-3593 (1988), it is suggested that the compound having the
following structure may be adsorbed by or dissolved in the organic
compound or polymer compound of formula (1) and the resulting
catalyst may be heterogenized. ##STR14##
[0104] Next, the process for producing the oxirane compound of
formula (5) with the olefin oxidation catalyst will be
described.
[0105] According to the present invention, the oxirane compound of
formula (5) can be produced by treating the olefins of formula (4)
in an organic solvent with hydrogen peroxide in the presence of the
olefin oxidation catalyst of the present invention.
[0106] The used amount of the olefin oxidation catalyst of the
present invention is 0.03 to 15 mol % based on the olefin of
formula (4) in term of the used amount of the quaternary ammonium
salt used in the production of the olefin oxidation catalyst of the
present invention.
[0107] The solvent used is not specifically limited so long as it
does not take part in the reaction, and includes aromatic
hydrocarbons such as benzene, toluene, xylene and the like,
aliphatic hydrocarbons such as hexane, heptane, dodecane, and the
like, ethers such as tetrahydrofuran, dioxane, and the like,
nitrites such as acetonitrile, butyronitrile and the like, amides
such as N,N-dimethylformamide, N,N-dimethylacetamide, and the like,
ureas such as N,N'-dimethylimidazolidinone, and the like, and
mixtures of these solvents. Aromatic hydrocarbons, aliphatic
hydrocarbons, and mixtures of these solvents are preferable.
[0108] The reaction temperature is 0 to 150.degree. C., but it is
preferable for the synthesis of oxirane compounds that the reaction
temperature is 90.degree. C. or less.
[0109] Although pH in the reaction system is not specifically
limited, it is preferably 0.5 to 7.
[0110] The control of pH in the reaction system can be carried out
by adding a proper amount of phosphoric acid aqueous solution or
sodium oxide aqueous solution while confirming pH with a pH
meter.
[0111] The reaction can be carried out under normal pressure or
pressure.
[0112] After the completion of the reaction, an organic phase
containing products and the catalyst used can be easily separated
by filtration process. Then, the reaction products can be purified
by distillation and column chromatography to obtain an aimed
product.
[0113] As the present reaction uses an aqueous solution of hydrogen
peroxide (hydrogen peroxide solution), in case where any solvent
insoluble in water is used, an organic phase and an aqueous phase
are separated. In this case, the olefin oxidation catalyst of the
present invention has generally a low solubility in organic
solvents and does not have a high solubility in water. Therefore,
in many cases, the reaction proceeds in a state which is separated
into three phases composed of an organic phase, a catalyst phase
and an aqueous phase.
[0114] As the catalyst is little dissolved in the organic phase,
the solution of the oxirane compound of formula (5) can be obtained
by only taking out the organic phase after the completion of the
reaction.
[0115] That is, the preparation of the olefin oxidation catalyst by
use of the organic compound or polymer compound of formula (1) can
make the separation of the olefin oxidation catalyst easy.
[0116] In addition, the oxirane compound of formula (5) can be
produced again by adding the olefin compound of formula (4) and
hydrogen peroxide to the oxidation catalyst recovered with
filtration after the completion of the reaction.
[0117] That is, the olefin oxidation catalyst can be re-used by
using the production process of the present invention.
[0118] Further, in case where any solvent dissoluble in water is
used, although the reaction is generally becomes homogeneous
reaction, the separation and re-use of the olefin oxidation
catalyst become possible as mentioned above by adding water and a
solvent indissoluble in water to cause separation into phases.
[0119] Next, without separately preparing the olefin oxidation
catalyst prepared from the organic compound or polymer compound of
formula (1), a tungstic acid compound, phosphoric acid, hydrogen
peroxide and the quaternary ammonium salt of formula (2) or (3),
the process for producing the oxirane compound of formula (5) will
be described.
[0120] The above-mentioned production process is shown in the
reaction scheme described below: ##STR15## wherein R.sub.1,
R.sup.2, R.sup.3 and R.sup.4 have the same meaning as the
above.
[0121] That is, the oxirane compound of formula (5) can be produced
by treating the olefin compound of formula (4) in an organic
solvent with the organic compound or polymer compound of formula
(1), tungstic acid, phosphoric acid, the quaternary ammonium salt
of formula (2) or (3) and hydrogen peroxide.
[0122] The adding order of the organic compound or polymer compound
of formula (1), tungstic acid, phosphoric acid, the quaternary
ammonium salt of formula (2) or (3) and hydrogen peroxide used is
not specifically limited.
[0123] The used amount of the organic compound or polymer compound
of formula (1) is 1 to 200 g per 1 mmol of phosphoric acid.
[0124] The used amount of the quaternary ammonium salt is 0.003 to
0.15 molar equivalent based on the olefins of formula (4).
[0125] The used amount of tungstic acid is 0.004 to 0.20 molar
equivalent based on the olefins of formula (4).
[0126] The used amount of phosphoric acid is 0.001 to 0.05 molar
equivalent based on the olefins of formula (4).
[0127] As the hydrogen peroxide used, commercially available
aqueous solution can be used as such or in a diluted state, and the
used amount thereof is 0.5 to 3 molar equivalents, preferably 0.8
to 1.5 molar equivalent based on the olefins of formula (4).
[0128] In the meanwhile, as to the reaction condition, the reaction
can be carried out similarly to those in the production process of
oxirane compounds of formula (5) by use of the oxidation catalyst
prepared from the organic compound or polymer compound of formula
(1), a tungstic acid compound, phosphoric acid, hydrogen peroxide
and the quaternary ammonium salt of formula (2) or (3).
[0129] In addition, the isolation and purification of the products,
and the separation and re-use of the olefin oxidation catalyst can
be also carried out similarly to those in the production process of
oxirane compounds of formula (5) by use of the olefin oxidation
catalyst according to the present invention.
[0130] The organic compounds of formula (1) used in the present
invention can be produced according to known methods, for example
the methods indicated in Nippon Kagaku Kaishi, Vol. 1999 (No. 2),
pp. 173-178 and Bull. Soc. Chim. Fr., p. 251 (1972).
[0131] The quaternary ammonium salts of formula (2) used in the
present invention can be produced according to the general
synthetic method of quaternary ammonium salts as follows: ##STR16##
That is, the quaternary ammonium salts of formula (2) can be
produced by reacting pyridines (6) with alkyl halides (7).
[0132] In addition, the salt of the quaternary ammonium salt can be
exchanged by using an ion exchange resin or the like.
[0133] As the quaternary ammonium salts of formula (3) used in the
present invention, commercially available ones can be used.
[0134] The polyimides composed of the repeating unit of formula (8)
among the polymer compounds used in the present invention can be
produced according to known methods, for example methods indicated
in U.S. Pat. No. 3,489,725 and JP 6-136120 A.
[0135] As polymer compounds such as other polyimides, acrylamides,
methacrylamides, polyamides, polyurethane and the like,
commercially available products can be used.
EXAMPLES
[0136] Hereinafter, the present invention is further described
according to examples to which the present invention is not
limited.
[0137] In the meantime, as ICP emission analyzer, SPS1200A
(manufactured by Seiko Instruments, Inc.) was used.
[0138] 5,6-dihydrodichloropentadiene and 3,4-epoxytricyclodecane
were analyzed according to the following condition: [0139]
Analyzer: GC (gas chromatography) [0140] Analytical condition:
column; HP-INNOWax (30.0 m.times.320 .mu.m.times.0.25 .mu.m), oven;
100.degree. C. (maintained for 2 minutes) 20.degree. C./min. (rise
in temperature 250.degree. C. (maintained for 5 minutes), pressure;
58.7 kPa, column flow rate; 1.4 mL/min., column average line speed;
27 cm/sec., sprit ratio; 40:1, temperature of inlet; 240.degree.
C., temperature of detector; 240.degree. C., internal standard
material; diethyl terephthalate
[0141] Polyimide composed of
3,4-dicarboxy-1,2,3,4-tetrahydronaphthalne-1-succinic acid and
4,4'-diaminodiphenylmethane was produced according to Example 2 of
JP 6-136120 A. In the meantime, the polyimide was analyzed
according to the following condition: [0142] Analyzer: SSC-7200 GPC
SYSTEM manufactured by Senshu Scientific Co., Ltd. [0143] Column:
KD-805, KD-803 (connected in series) [0144] Eluent: DMF [0145] Flow
rate: 1 mL/min. [0146] Detector: RI
[0147] In addition, ethoxytricyclodecene, allyloxytricyclodecene
and benzyloxytricyclodecene were produced by hydrolyzing
dicyclopentenol acetate produced according to the production
process described in Example 1 of JP 1-40446 A (the acetate was
reacted with sodium hydroxide in water-methanol), and then
etherizing (the hydrolyzed product was reacted with alkyl halide
(methyl iodide, allyl chloride, benzyl bromide) in the presence of
sodium hydroxide in DMF solvent).
Example 1
Preparation of Heterogeneous Catalyst with Cyanuric Acid
[0148] In a 200 mL-recovery flask equipped with a Dimroth condenser
and a stirrer, 1.250 g (5.00 mmol) of tungstic acid
(H.sub.2WO.sub.4) and 3.00 g (30.9 mmol) of 35% hydrogen peroxide
solution was added, and stirred at 60.degree. C. for 1 hour. After
cooling the resulting white suspension to room temperature, 0.144 g
(1.25 mmol) of 85% phosphoric acid (H.sub.3PO.sub.4) and 30 mL of
water were added. To this solution, 5 g of cyanuric acid was added
and fully dispersed, then 0.895 g (2.50 mmol) of cetyl pyridinium
chloride monohydrate aqueous solution was added dropwise over 30
minutes, and stirred at room temperature overnight. The reaction
solution was filtered and the resulting solid was collected. The
solid was washed further with water and toluene, then dried to
obtain 6.005 g of the entitled heterogeneous catalyst with cyanuric
acid as white solid.
[0149] ICP emission analysis: P; 0.18, W; 4.9
Example 2
Preparation of Heterogeneous Catalyst with N-methyl Cyanuric
Acid
[0150] Procedures were carried out similarly to those in Example 1,
except N-methyl cyanuric acid was used instead of cyanuric acid,
and 5.595 g of the entitled heterogeneous catalyst with N-methyl
cyanuric acid was obtained as white solid.
[0151] ICP emission analysis: P; 0.34, W; 10.1
Example 3
Preparation of Heterogeneous Catalyst with N-butyl Cyanuric
Acid
[0152] Procedures were carried out similarly to those in Example 1,
except N-butyl cyanuric acid was used instead of cyanuric acid, and
6.150 g of the entitled heterogeneous catalyst with N-butyl
cyanuric acid was obtained as white solid.
[0153] ICP emission analysis: P; 0.29, W; 11.7
Example 4
Preparation of Heterogeneous Catalyst with Polyimide
[0154] Procedures were carried out similarly to those in Example 1,
except polyimide composed of
3,4-dicarboxy-1,2,3,4-tetrahydronaphthalne-1-succinic acid and
4,4'-diaminodiphenylmethane was used instead of cyanuric acid, and
6.471 g of the entitled heterogeneous catalyst with polyimide was
obtained as white solid.
[0155] Number average molecular weight (Mn)=1.0.times.10.sup.4 ICP
emission analysis: P; 0.37, W; 15.6
Example 5
Synthesis of 3,4-epoxytricyclodecane (Re-use of Heterogeneous
Catalyst with Cyanuric Acid)
[0156] In a 50 mL-four-necked flask equipped with a thermometer, a
Dimroth condenser and a stirrer, 1.49 g (0.10 mmol) of
heterogeneous catalyst with cyanuric acid prepared in Example 1 and
2.68 g (20.0 mmol) of 5,6-dihydrodicyclopentadiene
(C.sub.10H.sub.14) and 3.49 g of toluene as a solvent were weighed
out, and heated to 80.degree. C. under stirring. Then, 2.14 g (22.0
mmol) of 35% hydrogen peroxide solution were added dropwise at the
same temperature over 30 minutes, and stirred further for 1 hour.
Thereafter, stirring was stopped and cooled to ordinary
temperature. The reaction mixture was filtered, the catalyst
filtered off was washed with toluene (100 mL). The washing and
filtrate was extracted with toluene (100 mL) to obtain the entitled
3,4-epoxytricyclodecane (C.sub.10H.sub.14O) in yield 93.6%
(quantitative analysis based on GC internal standard method).
(First Time Re-use of Catalyst)
[0157] The catalyst filtered off and recovered in the
above-mentioned procedures was placed again in a 50 mL-four-necked
flask equipped with a thermometer, a Dimroth condenser and a
stirrer, 2.68 g (20.0 mmol) of 5,6-dihydrodicyclopentadiene
(C.sub.10H.sub.14) and 3.49 g of toluene were weighed out therein,
and then heated to 80.degree. C. under stirring similarly to the
above. Then, 2.14 g (22.0 mmol) of 35% hydrogen peroxide solution
was added dropwise at the same temperature over 30 minutes, and
stirred further for 2 hours. Thereafter, stirring was stopped and
cooled to ordinary temperature. The reaction mixture was filtered,
the catalyst filtered off was washed with toluene (100 mL). The
washing and filtrate was extracted with toluene (100 mL) to obtain
the entitled 3,4-epoxytricyclodecane (C.sub.10H.sub.14O) in yield
95.9% (quantitative analysis based on GC internal standard
method).
(Second Time Re-use of Catalyst)
[0158] By using the catalyst recovered in the first time re-use,
second time re-use was carried out similarly to the above (reaction
time 6 hours) to obtain the entitled 3,4-epoxytricyclodecane in
yield 93.3%.
(Third Time Re-use of Catalyst)
[0159] By using the catalyst recovered in the second time re-use,
third time re-use was carried out similarly to the above (reaction
time 6 hours) to obtain the entitled 3,4-epoxytricyclodecane in
yield 94.0%.
Example 6
Synthesis of 3,4-epoxytricyclodecane (Re-use of Heterogeneous
Catalyst with N-methyl Cyanuric Acid)
[0160] Procedures were carried out similarly to those in Example 5,
except 0.909 g (0.10 mmol) of heterogeneous catalyst with N-methyl
cyanuric acid prepared in Example 2 was used instead of the
heterogeneous catalyst with cyanuric acid (reaction time 1 hour) to
recover the catalyst and obtain the entitled
3,4-epoxytricyclodecane in yield 97.6%.
(First Time Re-use of Catalyst)
[0161] By using the catalyst recovered in the above, first time
re-use was carried out similarly to Example 5 (reaction time 1
hour) to obtain the entitled 3,4-epoxytricyclodecane in yield
95.5%.
Example 7
Synthesis of 3,4-epoxytricyclodecane (Re-use of Heterogeneous
Catalyst with N-butyl Cyanuric Acid)
[0162] Procedures were carried out similarly to those in Example 5,
except 1.06 g (0.10 mmol) of heterogeneous catalyst with N-butyl
cyanuric acid prepared in Example 3 was used instead of the
heterogeneous catalyst with cyanuric acid (reaction time 1 hour) to
recover the catalyst and obtain the entitled
3,4-epoxytricyclodecane in yield 95.8%.
(First Time Re-use of Catalyst)
[0163] By using the catalyst recovered in the above, first time
re-use was carried out similarly to Example 5 (reaction time 2
hours) to obtain the entitled 3,4-epoxytricyclodecane in yield
92.3%.
(Second Time Re-use of Catalyst)
[0164] By using the catalyst recovered in the above, second time
re-use was carried out similarly (reaction time 2 hours) to obtain
the entitled 3,4-epoxytricyclodecane in yield 96.4%.
Example 8
Synthesis of 3,4-epoxytricyclodecane (Re-use of Heterogeneous
Catalyst with Polyimide)
[0165] In a 50 mL-four-necked flask equipped with a thermometer, a
Dimroth condenser and a stirrer, 0.836 g (0.10 mmol) of
heterogeneous catalyst with polyimide prepared in Example 4 and
2.68 g (20.0 mmol) of 5,6-dihydrodicyclopentadiene
(C.sub.10H.sub.14) and 3.81 g of toluene as a solvent were weighed
out, and heated to 80.degree. C. under stirring. Then, 2.14 g (22.0
mmol) of 35% hydrogen peroxide solution was added dropwise at the
same temperature over 30 minutes, and stirred further for 1 hour.
Thereafter, stirring was stopped and cooled to ordinary
temperature. The reaction mixture was filtered, the catalyst
filtered off was washed with toluene (100 mL). The washing and
filtrate was extracted with toluene (100 mL) to obtain the entitled
3,4-epoxytricyclodecane (C.sub.10H.sub.14O) in yield 99.2%
(quantitative analysis based on GC internal standard method).
(First Time Re-use of Catalyst)
[0166] The catalyst filtered off and recovered in the
above-mentioned procedures was placed again in a 50 mL-four-necked
flask equipped with a thermometer, a Dimroth condenser and a
stirrer, 2.68 g (20.0 mmol) of 5,6-dihydrodicyclopentadiene
(C.sub.10H.sub.14) and 3.81 g of toluene were weighed out therein,
and then heated to 80.degree. C. under stirring similarly to the
above. Then, 2.14 g (22.0 mmol) of 35% hydrogen peroxide solution
was added dropwise at the same temperature over 30 minutes, and
stirred further for 30 minutes. Thereafter, stirring was stopped
and cooled to ordinary temperature. The reaction mixture was
filtered, the catalyst filtered off was washed with toluene (100
mL). The washing and filtrate was extracted with toluene (100 mL)
to obtain the entitled 3,4-epoxytricyclodecane (C.sub.10H.sub.14O)
in yield 99.8% (quantitative analysis based on GC internal standard
method).
(Second Time Re-use of Catalyst)
[0167] By using the catalyst recovered in the first time re-use,
second time re-use was carried out similarly to the above (reaction
time 30 minutes) to obtain the entitled 3,4-epoxytricyclodecane in
yield 99.8%.
(Third Time Re-use of Catalyst)
[0168] By using the catalyst recovered in the second time re-use,
third time re-use was carried out similarly to the above (reaction
time 5 hours) to obtain the entitled 3,4-epoxytricyclodecane in
yield 96.0%.
(Fourth Time Re-use of Catalyst)
[0169] By using the catalyst recovered in the third time re-use,
fourth time re-use was carried out similarly to the above (reaction
time 8 hours) to obtain the entitled 3,4-epoxytricyclodecane in
yield 94.3%.
Example 9
Synthesis of 3,4-epoxytricyclodecane (Re-use of Heterogeneous
Catalyst with Polyimide)
[0170] In a 50 mL-four-necked flask equipped with a thermometer, a
Dimroth condenser and a stirrer, 0.836 g (0.10 mmol) of
heterogeneous catalyst with polyimide prepared in Example 4 and
2.68 g (20.0 mmol) of 5,6-dihydrodicyclopentadiene
(C.sub.10H.sub.14) and 3.81 g of toluene as a solvent were weighed
out, and heated to 80.degree. C. under stirring. Then, 2.14 g (22.0
mmol) of 35% hydrogen peroxide solution was added dropwise at the
same temperature over 30 minutes, and stirred further for 30
minutes. Thereafter, stirring was stopped and cooled to ordinary
temperature. The reaction mixture was filtered, the catalyst
filtered off was washed with toluene (100 mL). The washing and
filtrate was extracted with toluene (100 mL) to obtain the entitled
3,4-epoxytricyclodecane (C.sub.10H.sub.14O) in yield 96.9%
(quantitative analysis based on GC internal standard method).
(First Time Re-use of Catalyst)
[0171] The catalyst filtered off and recovered in the
above-mentioned procedures was placed again in a 50 mL-four-necked
flask equipped with a thermometer, a Dimroth condenser and a
stirrer, 2.68 g (20.0 mmol) of 5,6-dihydrodicyclopentadiene
(C.sub.10H.sub.14), 20.0 mg (0.08 mmol) of tungstic acid
(H.sub.2WO.sub.4),2.35 mg (0.02 mmol) of phosphoric acid
(H.sub.3PO.sub.4) and 3.81 g of toluene were weighed out therein,
and then heated to 80.degree. C. under stirring similarly to the
above. Then, 2.14 g (22.0 mmol) of 35% hydrogen peroxide solution
was added dropwise at the same temperature over 30 minutes, and
stirred further for 30 minutes. Thereafter, stirring was stopped
and cooled to ordinary temperature. The reaction mixture was
filtered, the catalyst filtered off was washed with toluene (100
mL). The washing and filtrate was extracted with toluene (100 mL)
to obtain the entitled 3,4-epoxytricyclodecane (C.sub.10H.sub.14O)
in yield 95.9% (quantitative analysis based on GC internal standard
method).
(Second Time Re-use of Catalyst)
[0172] By using the catalyst recovered in the first time re-use,
second time re-use was carried out similarly to the above (reaction
time 30 minutes) to obtain the entitled 3,4-epoxytricyclodecane in
yield 93.2%.
(Third Time Re-use of Catalyst)
[0173] By using the catalyst recovered in the second time re-use,
third time re-use was carried out similarly to the above (reaction
time 30 minutes) to obtain the entitled 3,4-epoxytricyclodecane in
yield 93.8%.
(Fourth Time Re-use of Catalyst)
[0174] By using the catalyst recovered in the third time re-use,
fourth time re-use was carried out similarly to the above (reaction
time 1 hour) to obtain the entitled 3,4-epoxytricyclodecane in
yield 92.1%.
(Fifth Time Re-use of Catalyst)
[0175] By using the catalyst recovered in the fourth time re-use,
fifth time re-use was carried out similarly to the above (reaction
time 2 hours) to obtain the entitled 3,4-epoxytricyclodecane in
yield 92.1%.
(Sixth Time Re-use of Catalyst)
[0176] By using the catalyst recovered in the fifth time re-use,
sixth time re-use was carried out similarly to the above (reaction
time 2 hours) to obtain the entitled 3,4-epoxytricyclodecane in
yield 93.1%.
Example 10
Synthesis of 3,4-epoxytricyclodecane (Re-use of Heterogeneous
Catalyst with Polyimide)
[0177] In a 20 L-large scaled reactor equipped with a thermometer,
a Dimroth condenser and a stirrer, 298 g (29.8 mmol) of
heterogeneous catalyst with polyimide prepared in Example 4 and 800
g (5.96 mmol) of 5,6-dihydrodicyclopentadiene (C.sub.10H.sub.14)
and 1.04 kg of toluene as a solvent were weighed out, and heated to
60.degree. C. under stirring. Then, 637 g (6.56 mmol) of 35%
hydrogen peroxide solution were added dropwise at the same
temperature over 5 hours, and stirred further for 1 hour.
Thereafter, stirring was stopped and cooled to 0.degree. C. The
reaction mixture was filtered (by sucking off through glass
filter), the catalyst filtered off was washed with toluene (1.49
L). From the washing and filtrate, the entitled
3,4-epoxytricyclodecane (C.sub.10H.sub.14O) was obtained.
(First Time Re-use of Catalyst)
[0178] In the 20 L-large scaled reactor in which the catalyst
filtered off and recovered in the above-mentioned procedures was
placed, 800 g (5.96 mol) of 5,6-dihydrodicyclopentadiene
(C.sub.10H.sub.14) and 1.04 kg of toluene were weighed out, and
then heated to 60.degree. C. under stirring similarly to the above.
Then, 637 g (6.56 mol) of 35% hydrogen peroxide solution was added
dropwise at the same temperature over 5.3 hours, and stirred
further for 2 hours. Thereafter, stirring was stopped and cooled to
ordinary temperature. The reaction mixture was filtered (by sucking
off through glass filter), the catalyst filtered off was washed
with toluene (1.49 L). From the washing and filtrate, the entitled
3,4-epoxytricyclodecane (C.sub.10H.sub.14O) was obtained.
(Second Time Re-use of Catalyst)
[0179] By using the catalyst recovered in the first time re-use,
second time re-use was carried out similarly to the above (reaction
time 8 hours in total) to obtain the entitled
3,4-epoxytricyclodecane.
[0180] The average yield in the above-mentioned 3 batches was 93%
(quantitative analysis based on GC internal standard method).
Example 11
Synthesis of ethoxy-3,4-epoxytricyclodecane
[0181] ##STR17##
[0182] In a 50 mL-four-necked flask equipped with a thermometer, a
Dimroth condenser and a stirrer, 1.29 g (0.10 mmol) of
heterogeneous catalyst with cyanuric acid prepared in Example 1 and
3.57 g (20.0 mmol) of ethoxy-tricyclodecene (C.sub.12H.sub.18O) and
5.06 g of toluene as a solvent were weighed out, and heated to
80.degree. C. under stirring. Then, 2.14 g (22.0 mmol) of 35%
hydrogen peroxide solution was added dropwise at the same
temperature over 30 minutes, and stirred further for 30 minutes.
Thereafter, stirring was stopped and cooled with ice. The reaction
mixture was filtered, the catalyst filtered off was washed with
toluene (100 mL). The washing and filtrate was extracted with
toluene (100 mL) to obtain the entitled
ethoxy-3,4-epoxytricyclodecane (C.sub.12H.sub.18O.sub.2) in yield
85.6% (quantitative analysis based on GC internal standard
method).
Example 12
Synthesis of allyloxy 3,4-epoxytricyclodecane
[0183] ##STR18##
[0184] In a 50 mL-four-necked flask equipped with a thermometer, a
Dimroth condenser and a stirrer, 1.29 g (0.10 mmol) of
heterogeneous catalyst with cyanuric acid prepared in Example 1 and
3.81 g (20.0 mmol) of allyloxy-tricyclodecene (C.sub.13H.sub.18O)
and 5.40 g of toluene as a solvent were weighed out, and heated to
40.degree. C. under stirring. Then, 2.14 g (22.0 mmol) of 35%
hydrogen peroxide solution was added dropwise at the same
temperature over 30 minutes, and stirred further for 3 hours.
Thereafter, stirring was stopped and cooled with ice. The reaction
mixture was filtered, the catalyst filtered off was washed with
toluene (100 mL). The washing and filtrate was extracted with
toluene (100 mL) to obtain the entitled allyloxy
3,4-epoxytricyclodecane (C.sub.13H.sub.18O.sub.2) in yield 66.6%
(quantitative analysis based on GC internal standard method).
Example 13
Synthesis of benzyloxy 3,4-epoxytricyclodecane
[0185] ##STR19##
[0186] In a 50 mL-four-necked flask equipped with a thermometer, a
Dimroth condenser and a stirrer, 1.29 g (0.10 mmol) of
heterogeneous catalyst with cyanuric acid prepared in Example 1 and
3.57 g (20.0 mmol) of benzyloxy-tricyclodecene (C.sub.17H.sub.20O)
and 6.83 g of toluene as a solvent were weighed out, and heated to
80.degree. C. under stirring. Then, 2.14 g (22.0 mmol) of 35%
hydrogen peroxide solution was added dropwise at the same
temperature over 30 minutes, and stirred further for 30 minutes.
Thereafter, stirring was stopped and cooled with ice. The reaction
mixture was filtered, the catalyst filtered off was washed with
toluene (100 mL). The washing and filtrate was extracted with
toluene (100 mL) to obtain the entitled benzyloxy
3,4-epoxytricyclodecane (C.sub.17H.sub.20O.sub.2) in yield 78.5%
(quantitative analysis based on GC internal standard method).
Example 14
Synthesis of 3,4-epoxypentane nitrile
[0187] In a 50 mL-four-necked flask equipped with a thermometer, a
Dimroth condenser and a stirrer, 1.29 g (0.10 mmol) of
heterogeneous catalyst with cyanuric acid prepared in Example 1 and
1.71 g (20.0 mmol) of 3-pentene nitrile (C.sub.5H.sub.7N) and 2.43
g of toluene as a solvent were weighed out, and heated to
80.degree. C. under stirring. Then, 2.14 g (22.0 mmol) of 35%
hydrogen peroxide solution were added dropwise at the same
temperature over 30 minutes, and stirred further for 30 minutes.
Thereafter, stirring was stopped and cooled with ice. The reaction
mixture was filtered, the catalyst filtered off was washed with
toluene (100 mL). The washing and filtrate was extracted with
toluene (100 mL) to obtain the entitled 3,4-epoxypentane nitrile
(C.sub.5H.sub.7NO) in yield 44.0% (quantitative analysis based on
GC intemal standard method).
INDUSTRIAL APPLICABILITY
[0188] According to the process of the present invention, aimed
oxirane compounds can be obtained by use of hydrogen peroxide that
is economic and an clean oxidizing agent, and the catalysts used
can be easily separated and re-used.
* * * * *