Process for the preparation of bisphosphines

Details Process for the preparation of bisphosphines Process for the preparation of bisphosphines

2000-12-01

2002-04-23

Vollano, Jean F. (Department: 1621)

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

Organic compounds

Phosphorus containing

Reexamination Certificate

active

06376715

ABSTRACT:

The present invention relates to a phosphine compound which is useful as a component of a catalyst system which may be used in the carbonylation of olefins, and in particular to a method of manufacturing such phosphine compounds.
WO 96/19434 discloses a process for the carbonylation of ethylene and a catalyst system for use therein. The catalyst system described in that document comprises a bidentate phosphine of general formula (R
3
—C)
2
P—L
1
—X—L
2
—P—(C—R
3
)
2
, in which each R is independently a pendant, optionally substituted, organic group through which the group is linked to tertiary carbon atom C; L
1
, L
2
are independently a linking group selected from an optionally substituted lower alkylene chain connecting the respective phosphorus atom to the group X and X is a bridging group comprising an optionally substituted aryl moiety to which the phosphorus atoms are linked on available adjacent carbon atoms. One example of such a bidentate phosphine is bis(di-
t
butyl phosphino)-o-xylene (also known as 1,2,bis(di-t-butylphosphinomethyl)benzene).
Such catalysts may be made by mixing the phosphine ligand with a suitable source of palladium such as palladium acetate. WO 96/19434 describes the preparation of one form of the ligand via the phosphonium salt produced from the reaction of the appropriate secondary phosphine with the corresponding aromatic dihalide. In the preferred form of the phosphine ligand in WO 96/19434, R is a lower alkyl group, in particular methyl. A problem with manufacturing this ligand by the route described is that the secondary phosphine which is used (e.g. di-
t
butyl phosphine) is toxic, highly reactive, smelly and flammable. We have also found that the reaction is low yielding and converts some of the di-
t
butyl phosphine to a non-reclaimable waste product which must be disposed of.
Al-Salem et al in Journal of the Chemical Society (Dalton) 1979 page 1980 describes making 1,5 bis(di-t-butylphosphino)pentane by reacting lithium metal with 1,5-dibromopentane and then phosphorylating the resulting lithiated intermediate with t-butylchlorophosphine. This method, for forming a phosphine of an alkyl compound, starts from the halogenated alkyl compound. Alkyl halides typically require considerable care during storage and use and may be very unpleasant to use. Therefore using this method of making the phosphine using the non-halogenated alkyl compound as a starting material would require an extra step of converting first to the alkyl halide.
We have now found that phosphine ligands of the type described in WO 96/19434 may be prepared by a high yielding route using more benign materials which produce less waste phosphorus product than the route described in WO 96/19434.
According to the invention, a method of manufacturing a compound of general formula (R
3
—C)
2
P—L
1
—X—L
2
—P—(C—R
3
)
2
in which each R is independently a pendant, optionally substituted, organic group through which the group is linked to tertiary carbon atom C; L
1
, L
2
are independently a linking group selected from an optionally substituted lower alkylene chain connecting the respective phosphorus atom to the group X and X is a bridging group comprising an optionally substituted aryl moiety to which the phosphorus atoms are linked on available adjacent carbon atoms comprises the steps of
i) reacting together a compound of formula H—L
1
—X—L
2
—H with an organometallic compound to form an intermediate compound of formula M—L
1
—X—L
2
—M, where M is an alkali metal atom,
ii) reacting said intermediate compound with a compound of formula (R
3
—C)
2
P—A, where A is a halogen atom, to form said compound of general formula (R
3
—C)
2
P—L
1
—X—L
2
P—(C—R
3
)
2
.
The compound of general formula (R
3
—C)
2
P—L
1
—X—L
2
—P—(C—R
3
)
2
may be useful as a component of a catalyst compound. In particular WO 96/19434 describes the use of such compounds as bidentate ligands which, when used together with a Group VIII metal such as palladium are effective catalysts for the carbonylation of olefins.
The pendant, optionally substituted organic groups, R may be independently selected from a wide range of components. Preferably, the pendant groups are optionally substituted lower alkyl, e.g. C
1-8
, and may be branched or linear.
Particularly preferred is when the organic groups, R, when associated with their respective carbon atom, form composite groups which are at least as sterically hindering as tert-butyl. Steric hindrance in this context is as discussed at page 14 et seq of “Homogeneous Transition Metal Catalysis—A Gentle Art”, by C Masters, published by Chapman and Hall, 1981. In one preferred embodiment, the organic groups R are all methyl groups, i.e. a preferred form of R
3
—C group is a tertiary butyl group.
The linking groups, L
1
and L
2
, are independently selected from an optionally substituted, particularly lower alkylene, e.g. C
1
to C
4
, substituted, lower alkylene, e.g. C
1
to C
4
chain. Especially preferred is when both L
1
and L
2
are methylene.
The bridging group X is, preferably, an aryl moiety, e.g. a phenyl group, which may be optionally substituted, provided that the two phosphorus atoms are linked to adjacent carbon atoms, e.g. at the 1 and 2 positions on the phenyl group. Optional substitution of the aryl moiety may be by other organic groups, e.g. alkyl, particularly C
1-8
, aryl, alkoxy, carbalkoxy, halo, nitro, trihalomethyl and cyano. Furthermore, the aryl moiety may be a fused polycyclic group, e.g. naphthalene, biphenylene or indene.
Examples of compounds which may advantageously be made by the method according to the invention are bis(di-tert-butyl phosphino)-o-xylene (also known as 1,2 bis(di-tert-butylphosphinomethyl)benzene), bis(di-t-neopentyl phosphino)-o-xylene and bis 1,2 (di-tert-butyl phosphino)naphthalene.
The reaction of a compound of formal H—L
1
—X—L
2
—H with a basic organometallic compound of formula R
m
M to form an intermediate compound of formula M—L
1
—X—L
2
—M, where M is an alkali metal atom, may be carried out by various means which are known in the art of organometallic chemistry. For example, such metallation methods are described by Wilkinson et al. in “Comprehensive Organometallic Chemistry” at page 54; and by Lambert et al. in “Preparative Polar Organometallic Chemistry”.
The organometallic compound may comprise a compound of formula R
m
—M, where R
m
is an organic group which tends to withdrawn electrons from the metal atom M. Suitable organic groups include aromatic or aliphatic groups, especially alkyl groups, which may be substituted. Lower alkyl groups have been found to be particularly suitable, for example preferred R
m
compounds include n-butyl, t-butyl, sec-butyl, methyl or pentyl. M may be any suitable alkali metal which forms a polar organometallic group with R
m
. Suitable metals include those of Group IA, e.g. sodium, potassium or lithium. When M comprises K or NA the R
m
—M metallating agent is preferably generated in situ by an exchange mechanism, e.g. by the reaction between R
m
—Li and potassium or sodium t-butoxide as described by Lochman et al. in Tetrahedron Letter No. 2 pages 257-262 (1966). Preferred metallating compounds are butyl lithium, butyl sodium and butyl potassium, the latter compounds preferably being formed in situ by the reaction of butyl lithium with potassium or sodium t-butoixde.
Alternative organometallic compounds are also known in the art and may comprise Me
3
SiCH
2
K, alkali amides MNH
2
preferably used in liquid ammonia, lithium dialkylamides e.g. lithium diisopropylamide (LDA), lithium, sodium or potassium metals, metal hydrides e.g. KH in the presence of coordinating compounds.
The reaction between R
m
M and H—L
1
—X—L
2
—H may be carried out in the presence of a solvent. Any solvent used must not contain any component which reacts with the intermediate compound, and suitable such solvents will be well known to the skilled chemist. Favoured solvents include dry alkyl ethers e.g. diethyl ether, methyl t-butyl ether, di(n-propyl)ether; tetrahydrofuran(THF), and hydrocarbons such as hex

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