Chemistry of hydrocarbon compounds – Unsaturated compound synthesis – By alkyl transfer – e.g. – disproportionation – etc.
Reexamination Certificate
1998-12-23
2001-01-16
Wood, Elizabeth D. (Department: 1755)
Chemistry of hydrocarbon compounds
Unsaturated compound synthesis
By alkyl transfer, e.g., disproportionation, etc.
C585S643000, C585S644000, C502S150000, C502S152000, C502S155000, C502S162000
Reexamination Certificate
active
06175047
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel ruthenium metathesis catalyst and to a method for producing an olefin by using the ruthenium metathesis catalyst, and, more particularly, to a ruthenium metathesis catalyst used as a catalyst for a carbon-carbon bond formation reaction using various organic synthetic reactions, especially, a metathesis reaction and to a method for producing cyclic olefins, internal olefins or polyolefins.
2. Prior Art
Many transition metal complexes have been used as catalysts for organic synthetic reactions. Among these reactions, a metathesis reaction of an olefin by using a transition metal complex as the catalyst has been variously studied (R. H. Grubbs, W. Tumas, Science, 1989, 243, pp 907-915).
This reaction is conventionally used for synthesizing bioactive natural substances such as civetone, D
9,12
-capnellane or 9-tricosene by using a tungsten type catalyst (WCl
6
/EtAlCl
2
or WCl
6
/Cp
2
TiMe
2
, wherein Et represents an ethyl group, Me a methyl group and Cp a cyclopentadienyl group) or a titanium type catalyst (Cp
2
Ti(Cl)CH
2
AlMe
2
) (Grubbs et al. Acc. Chem. Res. 1995, 28, pp446-452). The metathesis reaction is generally inferior in selectivity of type of reaction, yield, and stability to a variety of functional groups.
Recently, there has been a report that ring closing metathesis of nonconjugated diene and enone proceed using a molybdenum carbon complex catalyst in a highly selective and efficient manner (R. H. Grubbs et al. Acc. Chem. Res. 1995, 28, pp 446-452). This catalyst is, however, very unstable to many functional groups, oxygen and moisture.
For this, a ruthenium carbene complex which is relatively stable to air and moisture has been developed (WO 93/20111, WO 96/04289, WO 97/06185, F. Ozawa et al. 44th Symposium on Organometallic Chemistry, Japan. Abstracts, 1997, pp 74-75). This catalyst is effective for a ring closing metathesis reaction of nonconjugated dienes, ring opening metathesis polymerization of cyclic olefins, and the like. However, many steps are required to prepare this catalyst.
In order for the catalyst to be prepared in short steps, the catalyst is used in situ to carry out the ring opening metathesis polymerization of norbornene and cyclooctenes (A. F. Noels et al., J. Chem. Soc., Chem. Commun., 1995, pp 1127-1128; Macromolecules, 1997, 30, pp3127-3136). However, because these methods use unstable compounds (for example, diazo compounds), the production of a large amount of the catalyst is made with difficulty in actual industrialization. Hence the metathesis reaction using such a catalyst cannot be utilized on an industrial scale.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a ruthenium metathesis catalyst which can be produced in a large amount safely and simply by using a stable precursor and compounding this precursor in the system and also to provide a method for producing cyclic olefins, internal olefins or polyolefins efficiently in a short period of time by using this catalyst to carry out the metathesis reaction and ring opening metathesis polymerization of olefins.
The object of the present invention can be attained by the provision of a metathesis catalyst comprising:
a ruthenium compound represented by the formula (1);
RuX
1
2
(arene) (PR
1
R
2
R
3
) (1)
and a compound selected from the group consisting of;
a dihalogeno compound represented by the formula (2);
R
4
CHX
2
2
(2)
or
a terminal alkyne represented by the formula (3);
R
5
C≡CH (3)
wherein X
1
and X
2
respectively represent a halogen atom; arene represents a hydrocarbon having a benzene ring; R
1
, R
2
and R
3
, which may be the same or different, respectively represent an alkyl group having 1-8 carbon atoms, a cycloalkyl group having 3-8 carbon atoms or an optionally substituted aryl group (wherein the substituent group is an alkyl group having 1-8 carbon atoms, an alkoxy group having 1-8 carbon atoms, an alkylamino group having 1-8 carbon atoms or a halogen atom); R
4
represents an alkyl group which has 1-8 carbon atoms and may have an ether bond or an ester bond or an aryl group which may have a substituent group (wherein the substituent group is a halogen atom or a hydroxyl group or a cycloalkyl group having 3-8 carbon atoms); and R
5
represents an alkyl group which has 1-8 carbon atoms and may have a substituent group and an ether bond or an ester bond (wherein the substituent group is a halogen atom or a hydroxyl group), an aryl group or a cycloalkyl group having 3-8 carbon atoms.
According to another aspect of the present invention, there is provided a metathesis catalyst comprising:
a ruthenium compound represented by the formula (4);
[RuX
1
2
(arene)]
2
(4)
a phosphine represented by the formula (5);
PR
1
R
2
R
3
(5)
and
a terminal alkyne represented by the formula (3);
R
5
C≡CH (3)
wherein X
1
represents a halogen atom; arene represents a hydrocarbon having a benzene ring; R
1
, R
2
and R
3
, which may be the same or different, respectively represent an alkyl group having 1-8 carbon atoms, a cycloalkyl group having 3-8 carbon atoms or an optionally substituted aryl group (wherein the substituent group is an alkyl group having 1-8 carbon atoms, an alkoxy group having 1-8 carbon atoms, an alkylamino group having 1-8 carbon atoms or a halogen atom); and R
5
represents an alkyl group which has 1-8 carbon atoms and may have a substituent group and an ether bond or an ester bond (wherein the substituent group is a halogen atom or a hydroxyl group), an aryl group or a cycloalkyl group having 3-8 carbon atoms.
In a preferred embodiment, the metathesis catalyst may comprise a dihalogeno compound represented by the formula (2) and a reducing agent instead of the terminal alkyne;
R
4
CHX
2
2
(2).
According to a further aspect of the present invention, there is provided a method for producing a cyclic olefin, an internal olefin or a polyolefin by using the metathesis catalyst.
DESCRIPTION OF THE PREFERRED INVENTION
A first ruthenium metathesis catalyst according to the present invention comprises a ruthenium compound represented by the formula (1):
RuX
1
2
(arene) (PR
1
R
2
R
3
) (1)
and a dihalogeno compound represented by the formula (2);
R
4
CHX
2
2
(2)
or comprises a ruthenium compound represented by the formula (1):
RuX
1
2
(arene) (PR
1
R
2
R
3
) (1)
and a terminal alkyne represented by the formula (3):
R
5
C≡CH (3)
Specific examples of X
1
in the formula RuX
1
2
(arene) (PR
1
R
2
R
3
) which is a first component constituting the catalyst include chlorine, bromine and iodine. Preferred examples of “arene” include benzene and benzene having a substituent group. Preferable examples of the substituent group include alkyl groups or alkoxy groups having 1-4 carbon atoms. Specifically, preferable arenes are benzene, p-cymene, methoxybenzene, and hexamethylbenzene.
Examples of the groups represented by R
1
, R
2
and R
3
in the formula (PR
1
R
2
R
3
) include, as the alkyl group having 1-8 carbon atoms, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, 1-methylpropyl group, pentyl group, 2-ethylpropyl group, 1-methylbutyl group, hexyl group, 1-methylpentyl group, 1-methylhexyl group and 1-methylheptyl group; as the cycloalkyl group having 3-8 carbon atoms, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and, as the aryl group which may have a substituent group, a phenyl group, 2-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 4-biphenyl group, 4-methoxyphenyl group, 4-dimethylaminophenyl group, 4-chlorophenyl group, 1-naphthyl group and 2-naphthyl group.
Specific examples of the phosphine include triisopropylphosphine, tri(butane-2-yl)phosphine, tri(pentane-3-yl)phosphine, tri(hexane-2-yl)phosphine, tri(heptane-2-yl)phosphine, tri(octane-2-yl)phosphine,
Hagiwara Toshimitsu
Hashimoto Tsutomu
Hori Yoji
Iwaya Yukiharu
Kubovcik & Kubovcik
Takasago International Corporation
Wood Elizabeth D.
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