Method of manufacturing phosphine compound

Details Method of manufacturing phosphine compound Method of manufacturing phosphine compound

2000-04-13

2002-01-01

Vollano, Jean F. (Department: 1621)

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

Organic compounds

Phosphorus containing

C568S008000

Reexamination Certificate

active

06335471

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 ligand 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 phosphorous atom to the group X and X is a bridging group comprising an optionally substituted aryl moiety to which the phosphorous atoms are linked on available adjacent carbon atoms; and a Group VIII metal or compound thereof. One example of such a bidentate phosphine ligand is bis(di-
t
butyl phosphino)-o-xylene.
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.
Zvezdina et al (VINITI 3581-80, Chemical Abstracts Vol 96 (1992) 52409) describe a method of forming 1,2-ethynediylbis[bis(1-methylethyl)phosphine] by reaction of dibromoethynyidimagnesium with di-isopropyl chlorophosphine to produce ligands for hydroformylation catalysts.
A paper by M. F. Lappert & T. R. Martin (J. Chem. Soc., Dalton Trans., 1982 p1952) describes the preparation of various metallocyclic compounds via a di-Grignard synthesis route.
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 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
(I), 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 phosphorous atom to the group X and X is a bridging group comprising an optionally substituted aryl moiety to which the phosphorous atoms are linked on available adjacent carbon atoms comprises the steps of i) reacting together a compound of formula A—L
1
—X—L
2
—A (II), in which A is a halogen atom, with a metal M in a suitable solvent to form an intermediate compound of formula A—M—L
1
—X—L
2
—M—A (III), ii) reacting said intermediate compound (III) with a compound of formula (R
3
—C)
2
P—A
1
(IV), where A
1
is a halogen atom which may be the same as or different from A, to form said compound (I).
The compound (I) 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 VII 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. Each R group may be the same as or different from each other R group. It is preferred that (R
3
—C)
2
P—L
1
—X—L
2
—P—(C—R
3
)
2
is symmetrical in that both (C—R
3
)
2
groupings are the same.
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.
The linking groups, L
1
and L
2
, are independently selected from an optionally substituted, particularly lower alkyl, 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 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 (I) which may advantageously be made by the method according to the invention are described in WO 96/19434, which is incorporated herein by reference, and include 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.
M may be any suitable metal which forms a polar organometallic group on reaction with an alkyl halide. Suitable metals include those of Group II and Group IIB, e.g. magnesium, calcium, zinc, cadmium, mercury, aluminium, gallium, indium, tin and lead. The preferred metal is magnesium. When magnesium is used, the compound (III) is known as a di-Grignard compound. The magnesium may be in any convenient form such as turnings, chips, granules, ribbon etc, but it is preferred to use magnesium powder.
The nature of the compound (II) is dependent upon the nature of the product compound (I) which is required. When the L
1
and L
2
are both methylene groups and X is an unsubstituted phenyl group, the preferred starting material is &agr;,&agr;′ dichloro-o-xylene. A is a halogen atom. The preferred halogen is chlorine although other halogens, e.g. bromine may be effective.
We have found that the compound (II) is beneficially added to the metal gradually, e.g. dropwise or by use of another means for achieving a slow addition, e.g. a controllable pump.
The formation of di-Grignard compounds, e.g. o-C
6
H
4
(CH
2
MgCl)
2
, is described by M. F. Lappert et al in J. Chem Soc. Dalton Trans. (1982) p.1959. This paper describes the preparation of metallocyclic compounds via a di-Grignard reaction, but the practical preparation of di-Grignard compounds is well described and may be useful in the preparation of compound (III) of this invention. Thus, following the teaching of this document, which is incorporated herein as a reference, the yield of a di-Grignard compound may be increased if THF is used as a solvent and when the concentration of the compound (II) and thus of a resulting di-Grignard compound (III) in the solvent is relatively low, e.g. less than about 0.1 mole/l, preferably of the order of about 0.075 mole/l.
The nature of the phosphine compound (IV) is dependent upon the product compound to be prepared. 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. Each R group may be the same as or different from each other R group. It is preferred that (R
3
—C)
2
P—L
1
—X—L
2
—P—(C—R
3
)
2
is symmetrical in that both (C—R

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