Catalyst for bisalkoxycarbonylation of olefins, and method...

Details Catalyst for bisalkoxycarbonylation of olefins, and method... Catalyst for bisalkoxycarbonylation of olefins, and method...

1999-09-27

2001-02-06

Vollano, Jean F (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C568S015000, C568S014000, C549S218000

Reexamination Certificate

active

06184390

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to catalysts used for the bisalkoxycarbonylation of olefins, to novel phosphine chalcogenides which are useful as ligands of the catalysts, to processes for the bisalkoxycarbonylation of olefins using the catalysts, and to methods for production of succinate derivatives.
2. Description of the Prior Art
Processes for the alkoxycarbonylation of olefins have been proposed in (1) J. Am. Chem. Soc., 98, 1806(1976); (2) J. Mol. Cat. A: Chemical 111, L3-L6(1996); (3) J. Chem. Soc. Perkin Trans., 1031(1993); (4) J. Org. Chem., 57, 4189(1992), and satisfactory results have been achieved by these processes.
For the bisalkoxycarbonylation of olefins, processes have been reported in documents (5) J. Org. Chem., 37, 2034(1972),; (6) J. Am. Chem. Soc., 98, 1806(1976); (7) Bull. Chem. Soc. Jpn., 64, 3600(1991); (8) Tetrahedron Lett., 28, 325(1987); (9) J. Am. Chem. Soc., 98, 1810(1976); (10) Angew. Chem. Int. Ed. Engl., 32, 1719(1993); and (11) Organometallics, 11, 1975(1992). These processes are, however, respectively disadvantageous: The processes in the documents (5) and (6) are low in yield, the process in the document (7) gives a mixture of a monoalkoxycarbonylated compound and a bisalkoxycarbonylated compound, the process in the document (8) requires the addition of tetramethylurea or propylene oxide and ethyl ortho-acetate, the process in the document (9) should be conducted under high pressure conditions (3 atm), processes in the documents (10) and (11) accompany oligomerization.
In a document (12) Bull. Chem. Soc. Jpn., 69, 735(1996) is disclosed the use of an optically active bisoxazoline as a ligand in the bisalkoxycarbonylation to obtain an optically active substance. This process requires a long time for the reaction and is low in reactivity.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a catalyst which can catalyze the bisalkoxycarbonylation of olefins with efficiency.
It is another object of the invention to provide a novel phosphine chalcogenide compound which is useful as a ligand in a catalyst for the asymmetric bisalkoxycarbonylation of olefins.
A further object of the invention is to provide an efficient process for the bisalkoxycarbonylation of olefins.
It is a yet another object of the invention to provide a process by which corresponding succinate derivatives can be obtained from olefins in high yields under moderate conditions.
The present inventors made intensive investigations to achieve the above objects, and found that the use of a noble metal compound catalyst including a phosphine chalcogenide as a ligand can catalyze the bisalkoxycarbonylation of olefins with efficiency. The invention has been accomplished based upon the finding.
To be more specific, the invention provides, in an aspect, a catalyst for the bisalkoxycarbonylation of olefins comprising a phosphine chalcogenide and a noble metal compound, the phosphine chalcogenide being of the following formula (1):
wherein R
1
, R
2
and R
3
are, independently, an alkyl group or an aryl group each of which may have a substituent, and A is a Group 16 element of the Periodic Table; R
1
, R
2
or R
3
may be combined, directly or through abridging group, with one another where the groups to be combined may be attached either to an identical phosphorus atom or to different phosphorus atoms.
The element A may include, for example, an oxygen atom, a sulfur atom and a selenium atom. As examples of the phosphine chalcogenide, there maybe mentioned triphenylphosphine oxide, triphenylphosphine sulfide, triphenylphosphine selenide, 2,2′-bis(diphenylthiophosphoryl)-1,1′-binaphthyl, 2,3-bis(diphenylthiophosphoryl)butane, and 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylthiophosphoryl)butane. The noble metal compound may include palladium compounds, for instance.
The catalyst for the bisalkoxycarbonylation of olefins may further include a co-catalyst such as a copper catalyst. By way of illustration, the catalyst can include a palladium(II) halide as a noble metal compound and a copper(I) halide as a co-catalyst.
The present invention provides, in another aspect, an optically active 2,2′-bis(diphenylchalcogenophosphoryl)-1,1′-binaphthyl of the following formula (1a):
wherein A
1
is a Group 16 element of the Periodic Table other than oxygen; an optically active 2,3-bis(diphenylchalcogenophosphoryl)butane of the following formula (1b):
wherein A
2
is a Group 16 element of the Periodic Table other than oxygen; and an optically active 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylchalcogenophosphoryl)butane of the following formula (1c):
wherein A
3
is a Group 16 element of the Periodic Table other than oxygen.
In a further aspect, the invention provides a process for the bisalkoxycarbonylation of olefins, which includes reacting an olefin with an alcohol, oxygen and carbon monoxide in the presence of the aforementioned catalyst for the bisalkoxycarbonylation of olefins.
In addition and advantageously, the invention provides a method of producing a succinate derivative, which comprises reacting an olefin with an alcohol, oxygen and carbon monoxide in the presence of the aforementioned catalyst to give a corresponding succinate derivative.
The method just mentioned above may preferably include a method composed of reacting an olefin of the following formula (2):
wherein each of R
4
, R
5
and R
6
is, independently, a hydrogen atom, an alkyl group or an aryl group each of which may have a substituent, or a substituted silyl group; at least two of R
4
, R
5
and R
6
may together form a ring with the adjacent carbon atom or carbon-carbon double bond, with an alcohol of the following formula (3):
 R
7
—OH  (3)
wherein R
7
is an alkyl group, cycloalkyl group or aryl group each of which may have a substituent, oxygen and carbon monoxide to give a succinate derivative of the following formula (4):
wherein R
4
, R
5
, R
6
and R
7
have the same meanings as defined above. As the olefin, use may be made of, for example, any olefin where R
4
is a hydrogen atom or an alkyl group which may have a substituent, either one of R
5
and R
6
is a hydrogen atom or an alkyl group which may have a substituent, and the other is an aryl group which may have a substituent or a substituted silyl group, and R
4
and R
6
may together form a ring with the adjacent carbon-carbon double bond.
The method of producing a succinate derivative may be a method which includes reacting an olefin capable of forming a chiral compound by reaction, with an alcohol, oxygen and carbon monoxide in the presence of a catalyst containing an optically active phosphine chalcogenide to give a corresponding optically active succinate derivative.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The catalyst for the bisalkoxycarbonylation of olefins according to the invention is composed of a phosphine chalcogenide of the formula (1) and a noble metal compound. In the formula (1), the alkyl groups in R
1
, R
2
and R
3
include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and other straight chain alkyl groups; and isopropyl, isobutyl, sec-butyl, t-butyl and other branched chain alkyl groups. The carbon number of the alkyl group ranges, but not limited to, for example from about 1 to about 20, preferably from about 1 to about 10, and more preferably from about 1 to about 4.
As the aryl group, there may be mentioned, for instance, phenyl group, naphthyl group (1-naphthyl group, 2-naphthyl group) and biphenyl group. The carbon number of the aryl group rages, but not limited to, from about 6 to about 18.
Each of the alkyl groups and aryl groups mentioned above may have a substituent. Examples of the substituent include, aryl groups (e.g., phenyl group, naphthyl group),alkyl groups (methyl, ethyl, propyl, isopropyl, butyl and other C
1
-C
4
alkyl groups), cycloalkyl groups, halogen atoms (e.g., chlorine, bromine, iodine atoms), hydroxyl groups which may be protected with a protective group,

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