Polymeric homogeneous catalysts

Details Polymeric homogeneous catalysts Polymeric homogeneous catalysts

2000-04-21

2002-06-11

Bell, Mark L. (Department: 1755)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C502S152000, C502S156000, C502S169000

Reexamination Certificate

active

06403522

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a polymeric homogeneous catalyst containing an unsaturated polymer backbone. The polymeric backbone is generated by a ring opening metathesis polymerization reaction (ROMP).
2. Description of the Background
Polymeric catalysts are considered to be quite promising for the production of chemical compounds on an industrial scale due to their possible reuse, which, of course, is expected to provide a substantial reduction in production cost.
Recently, emphasis has been placed on the production of homogeneous forms of catalysts, in particular, because the omission of phase transitions during such catalysis leads to an increase in predictability of the reaction behavior of such catalysts. One of the principal reasons for evaluating increasingly sophisticated catalysts lies in the generation of products in enhanced yields and shorter time periods, i.e., in a more economical way.
The desirability of a catalytic system is predicated upon whether the synthesis of the polymeric portion of such catalysts is facile. DE 19910691.6 and DE 19647892.8 offer different solutions for this problem. Nevertheless, a need still exists for the production of new and different polymeric backbones for such compounds with superior properties.
Conventional polymerically—enlarged homogeneous catalysts exhibit more or less randomly distributed catalytically active sites along their polymeric backbone and contain an irregular polymer chain, which can deleteriously affect catalytic behavior.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide a polymerically-enlarged homogeneous catalyst exhibiting a polymeric backbone which is more rigid than conventional ones, and which is, nevertheless, easy to synthesize.
It is also an object of the present invention to provide a method of making the polymerically-enlarged homogeneous catalyst.
It is, moreover, yet another object of the present invention to provide a method of using the present polymerically-enlarged homogeneous catalyst.
The above objects and others are provided by a homogeneous catalyst obtained by reacting a compound of the formula (I), as shown hereinbelow in the specification, in a non-reactive organic solvent or solvent mixture with a bicyclic olefin of the formula (II), as shown hereinbelow in the specification.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The prevention invention provides catalysts, methods of using the same and a method of making the catalysts, the latter of which entails reacting a compound of the formula (I)
wherein:
D and Q each independently are Cl, Br, I, or OR;
G and Z each independently are PR′
3
, NR′ or D;
R′ is (C
6
-C
18
)-aryl, (C
3
-C
18
)-heteroaryl, (C
3
-C
8
)-cycloalkyl, (C
1
-C
8
)-alkyl, (C
6
-C
18
)-aryl-(C
1
-C
8
)-alkyl, (C
3
-C
18
)-heteroaryl-(C
1
-C
8
)-alkyl, (C
7
-C
19
)-aralkyl, or (C
4
-C
19
)-heteroaralkyl;
M is Ru or Mo;
R is (C
6
-C
18
)-aryl, (C
3
-C
18
)-heteroaryl, (C
3
-C
8
)-cycloalkyl, (C
3
-C
8
)-cycloalkenyl, H, (C
1
-C
8
)-alkyl, or (C
2
-C
8
)-alkenyl;
in a non-reactive organic solvent or solvent mixture with a bicyclic olefin of the formula (II):
wherein
X is O, NR
1
, C(R
1
)
2
, S, POR
6
, or PR
6
;
R
1
and R
2
are each independently H, (C
1
-C
8
)-alkyl, (C
2
-C
8
)-alkenyl, (C
2
-C
8
)-alkynyl, (C
6
-C
18
)-aryl, (C
7
-C
19
)-aralkyl, (C
3
-C
18
)-heteroaryl, (C
4
-C
19
)-heteroaralkyl, (C
3
-C
8
)-cycloalkyl, (C
3
-C
8
)-cycloalkenyl, (C
6
-C
18
)-aryl, (C
1
-C
8
)-alkyl, (C
3
-C
18
)-heteroaryl-(C
1
-C
8
)-alkyl, (C
3
-C
8
)-cycloalkyl-(C
1
-C
8
)-alkyl, (C
1
-C
8
)-alkyl-(C
3
-C
8
)-cycloalkyl, or together form an ═O group;
R
3
and R
4
, independently of each other, are OR
1
, SR
1
, NR
2
1
, OR
7
, SR
7
, or NR
5
R
7
provided that at least one residue of R
3
and R
4
bears a group R
7
;
R
6
is R
1
, with the proviso that R
6
is not H; and
R
7
is a catalytically active group;
and optionally with a further olefinic compound (III), which is preferably a cycloolefinic compound.
Polymerically enlarged homogeneous catalysts with a rigid unsaturated polymer backbone can be obtained advantageously in a highly modular way, and thus allow a flexible process optimization by combining independently selected bicyclic framework and catalytically active subunits.
In the formula (I), the dashed lines denote the possibility that groups G and Z can be connected to the central atom via a double bond or normal bond. For NR′ as a ligand, for example, and Mo as a central atom, this is the case. Nevertheless, in the case of PR
3
′ as a ligand and Ru as a central atom a normal bond exists in between.
Compounds of the formula (I) and (II) can be mixed in any proportion. Compound (III) can optionally be added to this mixture, preferably in a range from 0-100 times by weight of the sum of I and II, most preferably between 0-10 times by weight.
In accordance with the present invention, the catalytically activwe subunits embrace the subunit itself optionally combined with a linker between active site and polymer backbone. Such linking molecules are known to those skilled in the art, and may be introduced into the molecule in question by processes known in the art according to the demands of space and electronic behavior of the reaction, as shown below.
Linkers, which are feasible, are alkylenic, arylenic or silylenic linkers, for example. In DE 19910691.6 further linkers are disclosed, which are noted hereinbelow.
In general, any linker or spacer structure may be used which is able to couple the preactive center to the polymer. For example, structures, such as the following may be used.
Preferred, however, are spacers such as 1,4′-biphenyl, 1,2-ethylene, 1,3-propylene, PEG-(2-10), &agr;, &ohgr;-siloxanylene or 1,4-phenylene as well as &agr;, &ohgr;-1,4-bisethylenebenzene. Especially preferred are spacers which can be obtained starting from siloxanes of the formula (II):
These can be easily linked to the double bonds in the polymers and suitable functional groups of the preactive centers under hydrosilylization conditions (the hydrosilylization reaction is reviewed by Ojima in
The Chemistry of Organic Silicon Compounds,
1989, John Wiley & Sons Ltd., 1480-1526).
Any low molecular weight catalyst familiar to the person skilled in the art of organic synthesis is suitable as the active center in the polymer-enlarged catalysts. A review of this subject is presented by Noyori in
Asymmetric Catalysis in Organic Synthesis,
Wiley-Interscience Publication 1994, Chapter 2, 4, 5, by Ojima in
Catalytic Asymmetric Synthesis,
Wiley-VCH, 1993, and by Bolm and Beller in
Transition Metals for Organic Synthesis,
Vol. II, Chap. 1 and 2, VCH, 1998.
Preferred catalysts, however, are those from the group of catalysts for transfer hydrogenation and hydrogenation with elemental hydrogen, as are catalysts for the aldol reaction and Mukaijama aldol reaction, dialkyl addition to carbonyl groups, Jacobsen epoxidation, Sharpless dihydroxylation, the Diels-Alder and hetero Diels-Alder reaction, enantioselective anhydride opening, the reduction of ketones with hydrides and the Heck reaction.
The further olefinic compound (III) may be any organic molecule, which contains at least one double bond and which is known to those skilled in the art to be suitable for reacting in a ring opening metathesis reaction. This olefinic compound serves as a means for copolymerization and dilutes the number of active sites per unit of length within the polymeric backbone. Therefore, this is another manner of adapting the catalysts of the present invention to the most suitable demands of space necessary for the reaction in question.
Preferred compounds are ethylene, propene, butene, pentene, isobutene, isopropene and cyclic olefines like cyclopropene, cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, and cycloheptene, for example. Bicyclic olefinic compounds, such as norbornene or azulene, for example, may also be used.
Preferred are catalysts wherein R is Ph, X is

Affiliated with

Also associated with

Rating

Polymeric homogeneous catalysts does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Polymeric homogeneous catalysts, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Polymeric homogeneous catalysts will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2913490