Guanidinium phosphanes, their production and their use

Details Guanidinium phosphanes, their production and their use Guanidinium phosphanes, their production and their use

1999-11-17

2001-02-13

Vollano, Jean F (Department: 1621)

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

Organic compounds

Amino nitrogen containing

C564S230000, C568S017000

Reexamination Certificate

active

06187953

ABSTRACT:

The invention relates to guanidinium phosphines, a process for preparing them and their use.
For many reactions in the chemical industry, water is of great interest as solvent. However, organic reactions frequently have the disadvantage that they do not proceed or proceed to only an unsatisfactory extent in aqueous systems. However, complexes such as the trisodium salt of tris(m-sulfophenyl)phosphine make it possible to prepare catalyst systems which are employed in the hydroformylation of olefins (DE-A-38 40 600).
Compared to other known catalysts which are used for the abovementioned reaction, they have the advantage of being soluble in water. The hydroformylation can therefore by carried out in a heterogeneous reaction medium consisting of an aqueous phase and an organic phase (two-phase system), as is described in DE-A-38 40 600.
The advantage of such a process is that the final product can be separated from the water-soluble catalyst by simple phase separation. Furthermore, the noble metal catalyst can be recovered virtually without losses in this way or can be recirculated to the synthesis step (DE-A-26 27 354).
To prepare water-soluble catalyst systems, phosphorus-containing compounds are of particular interest. Examples are catalysts comprising palladium complexes containing anionic phosphines as ligands.
Cationic phosphine-containing ligands have been little studied in the past, although they should likewise have a favorable effect on the abovementioned reactions.
This object is achieved by guanidinium phosphines of the formula I,
where
n is an integer from 1 to 3,
X is Cl, Br, I or PF
6
,
R
1
and R
2
are hydrogen and R
3
and R
4
are methyl or R
1
and
R
2
are methyl and R
3
and R
4
are hydrogen and R
5
is a phenyl group
and the guanidinium substituent is located in the meta or para position relative to the P atom.
The object is likewise achieved by guanidinium phosphines of the general formula II
where
n is 1 or 2,
X is Cl, Br, I or PF
6
,
R
1
, R
2
, R
3
, R
4
are identical or different and are each a C
1
-C
6
-alkyl group or hydrogen, with the exception of R
1
and R
2
being hydrogen and R
3
and R
4
being methyl or R
1
and R
2
being methyl and R
3
and R
4
being hydrogen, and R
5
is a phenyl group
and the guanidinium substituent is located in the meta or para position relative to the P atom.
The invention likewise provides a process for preparing guanidinium phosphines of the general formula I, which comprises reacting N-aminophenylphosphines of the formula III,
where n and R
5
are as defined in formula I, with dimethylcyanamide to give guanidinium phosphines of the formula I. The preparation of N-aminophenylphosphines is known, for example, from J. Organomet. Chem. 1996, 522, 69, Phosphorus 1997, 1, 187 or from Chem. Ber. 1971, 104, 1722.
Preferably, the N-aminophenylphosphines of the formula III are first reacted with equimolar amounts of a solution of HCl in ether or water to form the HCl adducts of the formula IV,
where n and R
5
are as defined in formula I, and the reaction step with the dimethylcyandiamide is then carried out.
The invention likewise provides a process for preparing guanidinium phosphines of the formula I, with the exception of n=3, or II, which comprises reacting primary and secondary phosphines R
5
3-n
PH
n
(n=1 or 2) with meta- or para-iodophenylguanidines of the formula V,
where
R
1
, R
2
, R
3
, R
4
are as defined in formula I or II and the iodine atom is located in the meta or para position relative to the guanidine group. C. Ferri, Reaktionen der organischen Synthese, Georg Thieme Verlag, Stuttgart, 1978, Synthesis 1988, 460 and Y. Yamomoto, S. Kojima, The Chemistry of Amidines and Imidates, vol. 2, edited by S. Patai, Z. Rappoport, John Wiley & Sons, New York 1991, page 491, disclose that alkyl-substituted cyanamides can be reacted with amines or substituted anilines to give substituted guanidines.
Preference is given to using acetonitrile, dimethylacetamide, ether and/or hydrocarbons as solvents.
As catalysts for this reaction, preference is given to using palladium(II) acetate, palladium(II) halidephosphine complexes, palladium(0)-olefin complexes, palladium(0)-phosphine complexes and finely divided metallic palladium.
The invention likewise provides for the use of the compounds of the formula I or II for preparing catalyst ligands for carbon-carbon linkage reactions.


REFERENCES:
patent: 5057618 (1991-10-01), Herrmann et al.
patent: 5155274 (1992-10-01), Herrmann et al.
patent: 3840600 (1990-06-01), None
1997 American Chemical Society, Hessler et al p. 2362-2369 Tetrahedron, vol. 51, No. 8, pp. 2325-2330, 1995 Dibowski et al.

Affiliated with

Also associated with

Rating

Guanidinium phosphanes, their production and their use does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Guanidinium phosphanes, their production and their use, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Guanidinium phosphanes, their production and their use will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2600865