Organic compounds -- part of the class 532-570 series – Organic compounds – Phosphorus containing
Patent
1999-04-22
2000-12-12
Vollano, Jean F
Organic compounds -- part of the class 532-570 series
Organic compounds
Phosphorus containing
568 13, 568 15, 568 17, 526274, 526275, C07F 950, C07F 928, C08F 3002
Patent
active
061601802
DESCRIPTION:
BRIEF SUMMARY
The present invention is in the field of organic phosphorus chemistry.
The invention relates to novel tertiary phosphines carrying alkylene glycol groups and to their preparation by nucleophilic substitution.
Complex compounds which contain, as central atom, a metal from subgroup 8 of the Periodic Table of the Elements and, as ligands, P(III) compounds, e.g. phosphines or phosphites, and optionally further groups able to form complexes, have been used increasingly in recent years as catalysts for syntheses in organic chemistry. For example, the reaction of olefins with synthesis gas to give aldehydes (hydroformylation), which is carried out industrially on a large scale, is carried out in the presence of catalyst systems consisting of cobalt and, in particular, rhodium and triphenylphosphine. Also, for the reaction of methanol with synthesis gas to give higher alcohols (homologization), catalysts based on complex compounds containing phosphine have proven successful. In most of the above cases, the ligands are present in excess, so that the catalyst system consists of complex compound and free ligand. Depending on the solubility of the catalysts in organic media, the reactions take place in homogeneous phase.
Instead of in homogeneous phase, it is also possible to carry out the reaction in heterogeneous, multiphase reaction systems. An advantage of this process variant is the simple and gentle separation of the catalyst dissolved in water from the water-insoluble reaction product. This principle is used, for example, in the process described in DE-C2-27 00 904 for the preparation of nitriles by the addition reaction of hydrogen cyanide to unsaturated organic compounds containing at least one ethylenic double bond. In the preparation of aldehydes by reaction of olefins with carbon monoxide and hydrogen according to the process described in DE-C2-26 27 354, rhodium in metallic form or in the form of its compounds together with a water-soluble phosphine, e.g. the alkali metal salt of tri(m-sulfonatophenyl)phosphine ("TPPTS") is used as catalyst. Other examples of reactions with a heterogeneous catalyst phase can be found in Agnew. Chem. 1993, 105, 1588 ff.
J. Chem. Soc., Perkin Trans. 1 1996, 1467, discloses chiral phosphine ligands which are used for the asymmetric Grignard cross-coupling. Chem. Abstracts, Vol. 125, no. 33125x, describes phosphine compounds which contain three polyether radicals per phosphorus atom. J. Organ. Chem. 1980, 1156 and Chem. Abstracts. Vol. 105, no. 60677x refer to biphosphine compounds bridged via a polyether chain.
Two-phase processes have also proven highly successful on an industrial scale. Recent work has further improved the processes. For example, attempts are being made to increase the activity of the catalysts by modifying the complex ligands and to extend their effectiveness in order to further reduce the specific catalyst requirement, both metal and ligand, and thus the product costs. Economic reasons are also a decisive factor in working toward a significant reduction in the phosphine/metal ratio. Finally, there are efforts to solve the product-specific problems associated with known processes. Moreover, the search is on for novel fields of application for these versatile catalyst systems.
The object of the present invention was to provide novel phosphines which are suitable, in particular, for use in catalyst systems for organic syntheses.
The present invention provides tertiary phosphines of the formula (I) ##STR2## in which m is a number from 2 to 300, preferably from 2 to 100; at least one of the numbers a, b, c, d and e being greater than 0; and are hydrogen, C.sub.1 -C.sub.5 -alkyl or a group of the formula ##STR3## R.sup.1 and R.sup.2 are identical or different and are a straight-chain, branched or cyclic C.sub.1 -C.sub.30 -alkyl radical or C.sub.6 -C.sub.10 -aryl radical, which is unsubstituted or substituted by from one to five C.sub.1 -C.sub.3 -alkyl radicals, or R.sup.1 and R.sup.2, together with the trivalent P atom, form a dibenzophospholyl of the formula
REFERENCES:
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CA:126:199246 abs of Mol Catal A :Chem by Jin 116 (1-2) pp. 55-58, 1997.
CA:130:95347 abs of J Organomet Chem by Chen 571 (2) pp. 201-204, 1998.
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Bahrmann Helmut
Bogdanovic Sandra
Frohning Carl-Dieter
Haber Steffen
Kleiner Hans-Jerg
Celanese Chemicals Europe GmbH
Vollano Jean F
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