Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Patent
1999-06-25
2000-11-21
Marschel, Ardin H.
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
502156, 568840, B01J 3100
Patent
active
061502987
DESCRIPTION:
BRIEF SUMMARY
DESCRIPTION
Process for the telomerization of dienes
The present invention relates to a process for the telomerization of dienes. In particular, the present invention relates to a process, according to which the diene is reacted in the presence of a bidentate phosphine ligand and a palladium compound to give the corresponding dimer. The process according to the invention gives the desired dimer in large yield and high selectivity.
PRIOR ART
The telomerization of ethylenically unsaturated compounds, such as, for example, dienes, can be used to obtain low molecular weight oligomers of these compounds, which are useful starting materials for the synthesis.
For example, the telomerization of dienes such as butadiene can be used to prepare the corresponding dimers. Butadiene in particular has attracted a lot of attention since it is readily obtainable at low cost and can be used for many purposes.
For example, it is known that butadiene can be reacted with alcohols (Takahashi, S. Shibano, T. Hagihara, N.; Bull. Chem. Soc. Japan. 1968, 41, 454 (b) Tetrahedron Letter. 1967, 2451), phenol (Smutny, E. J.; J. Am. Chem. Soc. 1967, 89, 6793), carboxylic acids (Manyik, R. M. Walker, W. E. Atkins, K. E.; Chemical Communication, 1971, 330), water (Tsuji, J. Takahashi, M.; J. Molec. Catalysis. 1981, 10, 107), ammonia (Tsuji, J. Mori, Y.; Tetrahedron. 1972, 28, 3721) and carbon monoxide (Kohle, J. F. Slaugh, L. H. Nakamaye, K. L.; J. Am. Chem. Soc. 1969, 91, 5904) to give the corresponding octadienyl ethers, esters, alcohols, amines and carboxylic acids.
These reactions, referred as to as telomerization, usually take place in the presence of a catalyst system comprising a transition metal compound and a complex ligand. Known transition metal compounds are palladium compounds, and known complex ligands are monodentate phosphine ligands.
For example, the reaction of butadiene with water in the presence of a palladium catalyst is an elegant method for the preparation of 2,7-octadienol. 2,7-Octadienol is an important intermediate for the synthesis of di-n-octyl phthalate, which is a plasticizer of industrial importance. The synthesis proceeds via the hydrogenation of 2,7-octadienol to give 1-octanol, which is reacted with phthalic anhydride to give di-n-octyl phthalate (see FIG. 1). ##STR2##
For example, U.S. Pat. No. 4,356,333 describes a process for the telomerization of butadiene with water (hydrodimerization), the reaction of the butadiene with water taking place in an aqueous sulfolane solution in the presence of palladium or a palladium compound, a water-soluble monodentate phosphine ligand and an amine compound having a base constant pKa=7 or higher.
In view of its low cost and good solubility properties, triethylamine is a particularly preferred amine compound. In addition, it has been found that merely replacing triethylamine with tri-n-propylamine results in a reduction in the octadienyl yield.
In addition, in the case of the process described here, the reaction rate drops considerably when the content of sulfolane is less than 30% by mass. If, on the other hand, the sulfolane content exceeds 80% by mass, then the extraction efficiency of 2,7-octadienol from the reaction mixture is impaired. The above process has the disadvantage that as well as requiring an amine compound, it additionally requires an organic solvent, namely sulfolane, which complicates the process, in particular product isolation.
U.S. Pat. No. 5,043,487 describes a process for the preparation of octadienols by reaction of 1,3-butadiene with water in the presence of a palladium compound and an optionally water-soluble, monodentate phosphine ligand, the addition of a triorganophosphine oxide and CO.sub.2 being essential. In addition, the reaction requires an organic solvent.
Solvent-free reactions of butadiene and water in the presence of a palladium compound and a monodentate, water-soluble phosphine ligand, such as, for example, sodium trisulfnatophosphine (TPPTS) are described in U.S. Pat. Nos. 5,345,007 and 4,142,060.
The reaction in U.S. Pat
REFERENCES:
patent: 4142060 (1979-02-01), Kuntz
patent: 4356333 (1982-10-01), Yoshimura et al.
patent: 5118885 (1992-06-01), Tokitoh et al.
patent: 5345007 (1994-09-01), Monflier et al.
patent: 5565398 (1996-10-01), Herrmann et al.
patent: 5736480 (1998-04-01), Davis et al.
P. N. Rylander: "Organic Syntheses with Noble Metal Catalysts Oligomerizats, Telomerizations & Condensat.", 1973.
Derwent Publication, Week 9401, Dec. 15, 1992.
Beller Matthias
Krause Jochen
Tafesh Ahmed
Celanese GmbH
Kafafi Sherif
Marschel Ardin H.
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