Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2001-03-13
2004-03-16
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C560S204000, C560S232000, C562S517000, C562S522000
Reexamination Certificate
active
06706912
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to a process for the carbonylation of ethylenically unsaturated compounds having 3 or more carbon atoms, by reaction with carbon monoxide and a hydroxyl group containing compound in the presence of a catalyst system including a source of palladium cations; a bidentate diphosphine and a source of anions to prepare carboxylic acids and/or esters.
Such a process is known in the art and described in for example EP-A-0495547, EP-A-0495548 and WO-A-9842717.
Depending on the catalyst, reaction conditions and substrates, carbonylation of ethylenically unsaturated compounds having 3 or more carbon atoms can proceed with varying selectivities to the several possible isomeric products in varying yields. Generally only one isomeric product is preferred. The selectivity towards one of several possible isomeric products is called regioselectivity. For the carbonylation of ethylenically unsaturated compounds having 3 or more carbon atoms, regioselectivity towards a linear product, i.e. towards reaction at the primary carbon atom, is often desirable. For example, in the preparation of components of detergent compositions, efforts have been made to increase the selectivity with respect to linear carbonylation products.
Although good selectivities towards a linear product can be obtained by the processes described in EP-A-0495547, EP-A-0495548 and WO-A-9842717, there still exists a need for further improvement of the selectivity towards a linear product.
In WO-A-9619434 a process for the carbonylation of ethylene is described. The process is carried out in the presence of a catalyst system comprising palladium as a preferred Group VIII metal, and a bidentate diphosphine of formula I,
R
1
R
2
>P—R
3
—R—R
4
—P<R
5
R
6
(I)
wherein P represents a phosphorus atom; R
1
, R
2
, R
5
and R
6
can independently represent the same or different optionally substituted organic groups containing a tertiary carbon atom through which the group is linked to the phosphorus atom; R
3
and R
4
independently represent optionally substituted lower alkylene groups and R represents an optionally substituted aromatic group.
In WO-A-9619434 it is mentioned that propene was found to be difficult to carbonylate to the extent that the described catalyst system can be viewed as not being able to carbonylate propene.
SUMMARY OF THE INVENTION
A process for the carbonylation of ethylenically unsaturated compounds having 3 or more carbon atoms is provided, comprising reacting carbon monoxide and a hydroxyl group containing compound in the presence of a catalyst system comprising:
(a) a source of palladium cations;
(b) a bidentate diphosphine of formula I,
R
1
R
2
>P—R
3
—R—R
4
—P<R
5
R
6
(I)
wherein P represents a phosphorus atom; R
1
, R
2
, R
5
and R
6
independently represent the same or different optionally substituted organic groups containing a tertiary carbon atom through which the group is linked to the phosphorus atom; R
3
and R
4
independently represent optionally substituted alkylene groups and R represents an optionally substituted aromatic group;
(c) a source of anions derived from an acid having a pKa less than 3, as measured at 18° C. in an aqueous solution; in the presence of an aprotic solvent.
DETAILED DESCRIPTION OF THE INVENTION
It has now surprisingly been found that a catalyst system as described in WO-A-9619434 can be successful in the carbonylation of ethylenically unsaturated compounds having 3 or more carbon atoms, when the carbonylation process is carried out in the presence of an aprotic solvent. Moreover, carbonylation in the presence of this specific catalyst system and environment results in a high regioselectivity towards a linear product.
Accordingly, this invention provides a process for the carbonylation of ethylenically unsaturated compounds having 3 or more carbon atoms by reaction with carbon monoxide and a hydroxyl group containing compound in the presence of a catalyst system including:
(a) a source of palladium cations;
(b) a bidentate diphosphine of formula I,
R
1
R
2
>P—R
3
—R—R
4
—P<R
5
R
6
(I)
wherein P represents a phosphorus atom; R
1
, R
2
, R
5
and R
6
independently represent the same or different optionally substituted organic groups containing a tertiary carbon atom through which the group is linked to the phosphorus atom; R
3
and R
4
independently represent optionally substituted alkylene groups and R represents an optionally substituted aromatic group;
(c) a source of anions derived from an acid having a pKa less than 3, as measured at 18° C. in an aqueous solution; carried out in the presence of an aprotic solvent.
In the process according to the invention, suitable sources for palladium of component (a) include its salts, such as for example the salts of palladium and halide acids, nitric acid, sulphuric acid or sulphonic acids; palladium complexes, e.g. with carbon monoxide or acetylacetonate, or palladium combined with a solid material such as an ion exchanger. Preferably, a salt of palladium and a carboxylic acid is used, suitably a carboxylic acid with up to 12 carbon atoms, such as salts of acetic acid, propionic acid and butanoic acid, or salts of substituted carboxylic acids such as trichloroacetic acid and trifluoroacetic acid. A very suitable source is palladium(II) acetate.
In the diphosphine of formula I, R represents an optionally substituted aromatic group which is linked to the phosphorus atoms via the alkylene groups. The aromatic group can be a monocyclic group, such as for example a phenyl group or a polycyclic group, such as for example naphtyl, anthryl or indyl group. Preferably, the aromatic group R contains only carbon atoms, but R can also represent an aromatic group wherein a carbon chain is interrupted by one or more hetero atoms, such as nitrogen, sulphur or oxygen atom in for example a pyridine, pyrrole, furan, thiophene, oxazole or thiazole group. Most preferably the aromatic group R represents a phenyl group.
Optionally the aromatic group is substituted. Suitable substituents include groups containing hetero-atoms such as halides, sulphur, phosphorus, oxygen and nitrogen. Examples of such groups include chloride, bromide, iodide and groups of the general formula —O—H, —O—X
2
, —CO—X
2
, —CO—O—X
2
, —S—H, —S—X
2
, —CO—S—X
2
, —NH
2
, —NHX
2
, —NR
2
X
3
, —NO
2
, —CN , —CO—NH
2
, —CO—NHX
2
, —CO—NX
2
X
3
and —CI
3
in which X
2
and X
3
, independently, represent alkyl groups having from 1 to 4 carbon atoms like methyl, ethyl, propyl, isopropyl and n-butyl.
If the aromatic group is substituted it is preferably substituted with one or more aryl, alkyl or cycloalkyl groups, preferably having from 1 to 10 carbon atoms. Suitable groups include, methyl, ethyl, propyl, iso-propyl, butyl and iso-butyl, phenyl and cyclohexyl.
Most preferably, however, the aromatic group is non-substituted and only linked to the alkylene groups which connect it with the phosphorus atoms. Preferably the alkylene groups are connected at adjacent positions, for example the 1 and 2 positions, of the aromatic group.
Preferably the alkylene groups R
3
and R
4
are lower alkylene groups. By lower alkylene groups is understood alkylene groups comprising from 1 to 4 carbon atoms. The alkylene groups can be substituted, for example with alkyl groups, or non-substituted. Preferably the alkylene groups are non-substituted. More preferably the alkylene groups are unsubstituted methylene or ethylene groups, most preferably methylene groups.
R
1
, R
2
, R
5
and R
6
can independently represent organic groups containing a tertiary carbon atom through which the group is linked to the phosphorus atom. The groups R
1
, R
2
, R
5
and R
6
are only connected to each other via the phosphorus atom. The organic groups preferably have from 4 to 20 carbon atoms and more preferably from 4 to 8 carbon atoms. The tertiary carbon atom can be substituted with aliphatic, cyclo-aliphatic or aromatic substituents or can form part of a substituted saturated or non-saturated aliphatic ring str
Drent Eit
Jager Willem Wabe
Nazario-Gonzalez Porfirio
Shell Oil Company
Zucker Paul A.
LandOfFree
Process for the carbonylation of ethylenically unsaturated... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Process for the carbonylation of ethylenically unsaturated..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for the carbonylation of ethylenically unsaturated... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3280047