Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2001-10-19
2004-11-30
Desai, Rita (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C560S129000, C560S179000
Reexamination Certificate
active
06825377
ABSTRACT:
The present invention relates to a process for preparing 1,2-diols from olefins using catalysts based on transition metal compounds.
1,2-Diols, in particular cis-1,2-diols, are of industrial importance as fine chemicals, solvents, starting materials for polyesters and other polymers, and also as intermediates for agrochemicals. Propylene glycol and ethylene glycol in particular are of extraordinary importance as bulk chemicals. Numerous 1,2-diols are also of commercial interest for the preparation of pharmaceuticals, cosmetics, cleaners and are employed in the textiles and plastics industries. In many cases, the carboxylic esters display a constant viscosity over, a wide temperature range, combined with a high boiling point. They are good synthetic lubricants and plasticizers.
A frequently employed method of synthesizing 1,2-diols in the university sector are “dihydroxylation reactions” such as the Sharpless dihydroxylation reaction in which olefins are reacted in the presence of osmium tetroxide and an oxidant. Review articles which describe this methodology may be found, for example, in “
Asymmetric Dihydroxylation Reactions
” M. Beller, K. B. Sharpless, in B. Comils, W. A. Herrmann (Eds.), VCH, 1996, Weinheim, and H. C. Kolb, M. S. Van Nieuwenhze, K. B. Sharpless,
Chem. Rev.
1994, 94, 2483.
From an industrial point of view, olefins are available in virtually unlimited quantities as a source for the synthesis of diols, so that metal-catalyzed dihydroxylation reactions could in principle be used for the preparation of commercially interesting products such as propylene glycol and also fine chemicals such as 1,2-pentanediol and pinacol. Although catalytic oxidation processes are frequently superior in ecological terms to stoichiometric oxidation processes, the abovementioned products are at present produced predominantly via noncatalytic multistate processes. e.g. stoichiometric reactions with peracids or hydrogen peroxide and subsequent hydrolysis of the epoxide formed as an intermediate. This is due to the known reoxidants for manganese, ruthenium and osmium oxides being too expensive for an industrial preparation of fine and bulk chemicals and only allowing the economical preparation of extremely high-priced pharmaceutical intermediates.
The dialcohols can be synthesized stoichiometrically from olefins by reaction with KMnO
4
(A. J. Fatiadi,
Syntiesis
1984, 85-127; W. P. Weber, J. P. Shepard,
Tetrahedron Lett.
1972; 48, 4907-4908; E. Salamci, H. Segan, Y. Sübeyaz, M. Balci;
J. Org. Chem.
1997, 62, 2453-2557; B. G. Hazra, T. P. Kumar, P. L. Joshi,
Liebigs Ann. Chem.
1997, 1029-1034). RuO
4
gives dialcohols by stoichiometric reaction of olefins (L. Albarella, V. Piccialli, D. Smaldone, D. Sica,
J. Chem. Res.
1996, 9, 400-401) and by means of catalytic reaction using NaIO
4
as reoxidant (T. K. M. Shing, E. K. W. Tam, V. W. F. Tai, I. H. F. Chung, Q. Jiang,
Chem. Eur. J.
1996, 2, 50-57; T. Sugai, H. Okazaki, A. Kuboki, H. Ohta,
Bull. chem. Soc. Jpn.
1997, 70, 2535-2540; J. Angermann, K. Homann, H. U. Reissig, R. Zimmer
Synlett
1995, 1014-1016; M. Desjardins, L. Brammer Jr., T. Hudlicky,
Carbohydrate Res.
1997, 504, 39-42; M. J. Mulvihill, M. J. Miller,
Tetrahedron
1998, 54, 6625-6626). Initial work on dihydroxylation by means of osmium oxide involved stoichiometric reactions (O. Makowka,
Chem. Ber.
1908, 45, 943; R. Criegee,
Liebigs Ann. Chem.
1936, 522, 75; R. Criegee,
Angew. Chem.
1937, 50, 153). Reactions using catalytic amounts of osmium tetroxide and chlorates as reoxidants (K. A. Hoffmann,
Chem.
1912, 45, 3329) or H
2
O
2
in tert-butanol (N. A. Milas, J. H. Trepagnier, J. T. Nolan, M. Ji. Iliopolus,
J. Am. Chem. Soc.
1959, 81, 4730) as reoxidant lead to overoxidation of the diols formed. Use of H
2
O
2
results in formation of peroxoosmic acid H
2
O
2
O
6
which cleaves the diol formed as an intermediate and leads to carbonyl compounds. To reduce the overoxidation, tert-butyl hydroperoxide in the presence of Et
4
NOH (K. B. Sharpless, K. Akashi,
J. Am. Chem. Soc.
1976, 98, 1986; P. H. J. Carlsen, T. Katsuki, V. S. Martin, K. B. Sharpless,
J. Org. Chem.
1981, 46, 3936; F. X. Webster, J. Rivas-Enterrios, R. M. Silverstein,
J. Org. Chem.
1987, 52, 689; V. S. Martin, M. T. Nunez, C. E. Tonn,
Tetrahedron Lett.
1988, 29, 2701; M. Caron, P. R. Carlier, K. B. Sharpless.
J. Org. Chem.
1988. 53. 5185). tertiary amine oxides and in most cases N-methylmorpholine N-oxide (NMO: Upjohn Process) (W. P. Schneider. A. V. McIntosh, U.S. Pat. No. 2,769,824 (1956); V. Van Rheenen, R. C. Kelly, D. Y. Cha,
Tetrahedron Lett.
1976, 17, 1973) are used as reoxidants. Trimethylamine oxide is superior to NMO for trisubstituted and sometimes also tetrasubstituted alkenes (R. Ray, D. S. Matteson,
Tetrahedron Lett.
1980, 21, 449). Despite the selective and catalytic dihydroxylation which is possible using N-oxides, the price of these reoxidants is prohibitive for relatively large-scale industrial applications.
In recent years, Na
3
[Fe(CN)
6
] in the presence of sodium carbonate in a 2-phase system has been used very successfully as reoxidant for OsO
4
(M. Minato, K. Yamamoto, J. Tsuji,
J. Org. Chem.
1990, 55, 766; M. P. Singh, H. S. Singh, B. S. Arya, A. K. Singh, A. K. Sisodia,
Indian J. Chem.
1975, 13, 112), particularly also in enantioselective dihydroxylation (Y. Ogino, H. Chem, H. L. Kwong, K. B. Sharpless,
Tetrahedron Lett.
1991, 32, 3965). Significant disadvantages for the synthesis of the diols on a relatively large scale are again the price and the superstoichiometric amount of iron complex to be used (3 mol=990 g per 1 mol of substrate) with addition of potassium carbonate (3 mol=420 g). In the case of processes for the electrochemical oxidation of the Na
4
[Fe(CN)
6
] formed in the reaction to give Na
3
[Fe(CN)
6
] (Sepracor Inc. (Y. Gao, C. M. Zepp), PCT Int. Appl. WO 9 317 150, 1994; Anon.,
Chem. Eng. News.
1994, 72 (24), 41), too, industrial implementation is difficult since electrochemical processes are generally too expensive because of the apparatus required.
To circumvent the disadvantages of the abovementioned reoxidants, attempts have been made in the past to use air or oxygen for the reoxidation of Os
VI
to Os
VIII
. Such a process is the most attractive method from economic and ecological points of view. However, Cairns et al. have shown that no 1,2-dialcohol is observed in the reaction of allyl alcohol, ethylene, cyclohexene and styrene in the presence of OsO
4
and oxygen, but in all cases overoxidation results in formation of industrially unusable amounts of the corresponding carboxylic acids, e.g. benzoic acid (styrene as substrate) and CO
2
(J. F. Cairns. H. L. Roberts.
J Chem. Soc.
(C) 1968. 6-401. In a process of Celanese Corporation (GB-B 1.028.940). too, only formic acid and heptanoic acid are obtained from 1-octene. Even in the reaction of the less oxidation-sensitive ethylene, the 1,2-diol is obtained only in traces (2% of glycol after 4 hours at an O
2
-pressure of 7 MPa). Employees of Exxon utilize bimetallic systems comprising OsO
4
and Cu(II) salts (U.S. Pat. No. 4,496,779, EP-B 0 077 201, R. G. Austin, R. C. Michaelson, R. S. Myers in
Catalysis in Organic Ractions
(Ed: R. L. Augustine), Marcel Dekker, New York 1985, p. 269). In a manner analogous to the Wacker process, Os
VI
is reoxidized by the Cu salt which is then oxidized again by means of O
2
. In this process, maximum conversions of propylene are 3-5% after a reaction time of 2 hours and a pressure of 28 bar.
In summary, it can be seen that the known methods for reoxidizing osmium, ruthenium and manganese by means of molecular oxygen are not usable in dihydroxylation reactions for synthesizing dialcohols.
To avoid the abovementioned disadvantages of the known catalytic processes, it is an object of the invention to develop a novel process for metal-catalyzed dihydroxylation which is simple to carry out and gives 1,2-diols in high yield and purity, with molecular oxygen being used as reoxidant, and i
Beller Matthias
Döbler Christian
Mehltretter Gerald
Sundermeier Uta
Akorli Godfried R.
Bayer Aktiengesellschaft
Desai Rita
Eyl Diderico van
Reyes Hector M.
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