Helmut Bahrmann

Water-soluble metal complexes and catalysts Part 6. A new, efficient water-soluble catalyst for two-phase hydroformylation of olefins

Abstract The diphosphane 2,2′-bis(diphenylphosphinomethyl)-1,1′-biphenyl (1, BISBI) was sulfonated by means of oleum containing 65% SO3. The sulfonation product, 2 (BISBIS), was purified by extraction-reextraction techniques. The sodium salts, 3, of BISBIS (2) are accessible as a mixture of several sulfonated derivatives. In the heterogeneous (biphasic) hydroformylation of propene, this sulfonated ligand 3 yields exceptionally high n/iso ratios of the resulting butyric aldehyde (rhodium catalysis). High activity and productivity at low phosphane/rhodium ratios are additional advantages of using 3. Hydroformylation of higher olefins, e.g., 1-hexene, is also within the scope of the new catalytic Rh(I)/BISBIS system.

Water-soluble metal complexes and catalysts. Part 71. New efficient water-soluble catalysts for two-phase olefin hydroformylation: BINAS-Na, a superlative in propene hydroformylation

The monophosphine 3,4-dimethyl-2,5,6-triphenyl-1-phosphanorborna-2,5-diene (1, DMTPPNOR) and the diphosphine 2,2′-bis (diphenylphosphinomethyl)-1,1′-binaphthalene (7) were sulfonated by means of oleum. The sulfonation products 8 (BINAS) and 2 (NORBOS) were purified by extraction-reextraction and by gel permeation chromatography. While the sodium salt 9 (BINAS-Na) of BINAS (8) was accessible as a mixture of different degrees of sulfonation, the sodium salt of NORBOS (2) was available as an analytically clean, completely characterized, triply sulfonated compound, NORBOS-Na (3). For the synthesis of 2,2′-bis (diphenylphosphinomethyl)-1,1′-binaphthalene (7), a new method has been used: Commercially available 1-bromo-2-methylnaphthalene (4) was first dimerized by means of magnesium, and then the resulting 2,2′-dimethyl-1,1′-binaphthalene (5) was treated with n-BuLiTMEDA and chlorodiphenylphosphine. In the ‘heterogeneous’ (bi-phasic) hydroformylation of propene, the sulfonated ligands 3 and 9 exhibited very high activities and productivities at low phosphine/rhodium ratios. Furthermore, phosphine 9 was advantageous in n/iso ratios of the resulting butyric aldehyde (rhodium catalysis). The new catalyst system RhI/BINAS-Na has an apparent activation energy of 10.8 kcal/mol explaining the outstanding performance of this system in continuous hydroformylation, with the activity data being: 16 (TPPTS), 90 (BISBIS-Na), 118 (NORBOS-Na), and 178 (BINAS-Na).

The hydroformylation of conjugated dienes, v aliphatic tertiary phosphines and p-substituted phospholanes as cocatalysts of the rhodium-catalysed hydroformylation of 1,3-dienes

Abstract The hydroformylation of conjugated dienes to dialdehydes by rhodium carbonyl/tert. phosphine catalyst systems is determined by the nature of the tertiary phosphine cocatalyst. The influence of some typical aliphatic phosphines and of P-substituted phospholanes on the bishydroformylation of butadiene-1,3 is reported.

BINAS - synthesis and use of a new ligand for propylene hydroformylation

Abstract BINAS is a new, very efficient ligand for propylene hydroformylation. BINAS is made by the sulfonation of NAPHOS. Different synthetic routes to NAPHOS are discussed. A new two step synthesis starting from 2,2′-bis(bromomethyl)-1,1′-binaphthyl is described.

n-Valeric acid: Expansion of the two phase hydroformylation to butenes

Abstract n -valeric acid ( n -pentanoic acid) is the basis of new ester-type lubricants for CFC-substitutes in refrigeration systems which are made from the carboxylic acid with trimethylolpropane, pentaerythritol or dipentaerythritol. Together with UCC, Hoechst is one of the largest producers of n -valeric acid for this field of application. Valeric acid is prepared from butene cuts through hydroformylation to valeraldehyde with subsequent oxidation. The RCH-RP process of low-pressure hydroformylation [1] used at the Ruhrchemie side of Hoechst, involving an aqueous rhodium-TPPTS catalyst system (TPPTS = triphenylphosphane trisulfonate, sodium salt), has been used since 1984 to produce roughly 300,000 ton of n -butyraldehyde from propylene per year. A further development of this successful technology has been achieved using the available feedstock base of isomeric butenes (raffinate II) for the preparation of n -C 5 products ( n -valeraldehyde, n/iso -amyl alcohol and n -valeric acid) [2]. The process developed permits high selectivity of the n/iso ratio to the desired n -aldehyde and it is environmentally benign as waste water contamination has been substantially reduced. In December 1995 production of n -valeraldehyde was started up in a new plant. Oxidation to produce the acid using the Hoechst/Ruhrchemie process is carried out with proven technology.

Quaternary ammonium salts of phosphines as ligands and their recycling by membrane techniques or phase separation. Part I: monophasic systems

Abstract Quaternary ammonium salts of functionalized tertiary amines may serve as ligands for transition metal catalysts in hydroformylation reactions. Besides these properties they offer special advantages for the catalyst separation using phase separation or membrane techniques.