United States Patent (19) 11 Patent Number: 4,496,778 Myers Et Al

United States Patent (19) 11 Patent Number: 4,496,778 Myers et al. (45) Date of Patent: Jan. 29, 1985 (54) PROCESS FOR THE HYDROXYLATION OF 56 References Cited OLEFINS USING MOLECULAR OXYGEN, U.S. PATENT DOCUMENTS ANOSMIUM CONTAINING CATALYST, A COPPER CO-CATALYST, AND AN 2,773, 101 12/1956 Smith et al. ......................... 568/860 AROMATIC AMINE BASED PROMOTER 3,317,592 5/1967 Maclean et al. ... 568/860 3,337,635 8/1967 Norton et al. ....... 568/860 75 Inventors: Richard S. Myers, Fairlawn; Robert 4,390,739 6/1983 Michaelson et al. .... ..., 568/860 C. Michaelson, Waldwick; Richard FOREIGN PATENT DOCUMENTS G. Austin, Ridgewood, all of N.J. 32522 8/1974 Japan ................................... 568/860 73) Assignee: Exxon Research & Engineering Co., Primary Examiner-J. E. Evans Florham Park, N.J. Attorney, Agent, or Firm-Robert A. Maggio 21 Appl. No.: 538,190 57 ABSTRACT A process directed to the hydroxylation of olefins by 22 Filed: Oct. 3, 1983 reacting said olefins in the presence of oxygen, water, and a catalyst composition comprising (i) a catalytically 51 Int. Cl. ...................... C07C 29/04; CO7C 31/18; active osmium containing compound, (ii) a Co-catalyst C07C 31/22; CO7C 31/42 I comprising a copper containing compound such as 52 U.S.C. ................................. 568/860; 260/.397.2; CuBr2, and (iii) a Co-catalyst II capable of increasing 560/186; 562/587; 568/811; 568/821; 568/833; the rate and/or selectivity of the hydroxylation reac 568/838; 568/847 tion, such as pyridine is disclosed. 58 Field of Search ............... 568/860, 833, 811, 821, 568/838, 847; 562/587; 560/186; 260/.397.2 31 Claims, No Drawings 4,496,778 1. 2 that the reaction is highly pH dependent (see Schroder, PROCESS FOR THE HYDROXYLATION OF page 210, Col. 1). OLEFINS USING MOLECULAR OXYGEN, AN The poor performance of oxygen based osmium cata OSMIUM CONTAINING CATALYST, A COPPER lyzed olefin hydroxylation systems is unfortunate, since CO-CATALYST, AND AN AROMATIC AMINE 5 such systems have inherent advantages over organic BASED PROMOTER hydroperoxide based systems. For example, hydroxyl ation systems employing organohydroperoxide oxi BACKGROUND OF THE INVENTION dants result in the conversion of the organohydroperox ide to its corresponding alcohol during the formation of The present invention relates to a process for con 10 the desired olefin derived diol. Thus, for example, t verting olefinically unsaturated compounds directly to butylhydroperoxide is converted to t-butylalcohol. The their corresponding diols or polyols in the presence of a commercial attractiveness of such processes is depen specifically defined oxidation catalyst composition, wa dent on the ability to use or sell the organic alcohol ter, and an oxygen containing gas. co-product in addition to the diol. Given the fluctuation It is well known from the technical literature, that 15 in economic conditions, however, it may be difficult to olefins can be oxidized to their corresponding diols, dispose of large quantities of these organic alcohol co stoichiometrically or catalytically with osmium oxide products in an economically attractive manner. In any compounds, particularly osmium tetroxide. event, it can be troublesome, when the quantity of one The non-catalytic, i.e. stoichiometric, cis-hydroxyla product, selected on the basis of marketing possibilities tion of alkenes with OsO4 has been conventionally char 20 for a given period, necessarily determines the quantity acterized as taking place via the formation, with the of some other product which may be smaller or larger alkene, of an osmium (VI) intermediate ester complex. than desirable in view of changing marketing require (For a recent review, see, "Osmium Tetroxide Cis Hy ments within that same period. It can, therefore, under droxylation of Unsaturated Substrates', by M. certain circumstances be considered as a disadvantage Schroder, Chem. Rev. Vol 80, pp. 187-213 (1980) here 25 of the aforenoted organohydroperoxide based processes inafter Schroder). that such large quantities of organic alcohols are formed To convert the non-catalytically prepared osmium as co-products, even though under other circumstances (VI) ester complex intermediate to the diol, the interme the formation of two products may well be found ac diate can be hydrolyzed reductively. Reductive hydro ceptable. lysis is conventionally carried out by using alkali metal 30 In contrast, oxygen based hydroxylation systems do sulfites, bisulfites, lithium aluminum hydride, or hydro not produce an oxidant derived alcohol co-product that gen sulfide to yield the corresponding cis-diols together must be disposed of, which can be a significant advan with lower valence forms of osmium which are re tage. moved by filtration. The search has, therefore, continued for ways of It has been observed by Criegee (see Schroder, page 35 improving the rate and/or selectivity of osmium cata 191, Col. 1 11-12) that for non-catalytic cis hydroxyl lyzed oxygen based processes for hydroxylating olefins. ation of alkenes, the rate of formation of the Osmium One step in this direction, is disclosed in commonly (VI) ester complex is greatly increased in the presence assigned U.S. Pat. No. 4,390,739 by R. Austin and R. of tertiary amines such as pyridine. This rate enhance Michaelson. This patent describes a process for the ment is believed to occur via the formation of some type 40 hydroxylation of olefins using oxygen as an oxidant, a of amine Osmium (VI) ester complex (see Schroder catalytically active metal oxide catalyst such as OsO4, page 191, Col. 2). However, enhancement of the rate of and at least one transition metal salt co-catalyst such as the Osmium (VI) ester complex does not necessarily copper bromide. This process can also be conducted in result in an enhancement of the overall hydroxylation the optional presence of a second co-catalyst such as 45 alkali metal halides. Pyridine is disclosed as a suitable rate, since the rate of hydrolysis of the ester complex solvent for this process but no mention is made of any must also be considered. In this regard, it has been noted promoting effect being associated with this solvent that whereas certain osmium ester complexes and amine medium. While the use of the transition metal co ester complexes (e.g. with pyridine) can be hydrolyzed catalyst substantially improves the reaction rate and/or reductively, amine ester complexes are more resistant to 50 selectivity of the hydroxylation reaction, a further im such hydrolysis. (See Schroder page 191, Col. 2, last provement in this process is still being sought. paragraph; and page 193, Col. 1, first paragraph). U.S. patent application Ser. No. 310,217, filed Oct. 9, In contrast to the stoichiometric non-catalytic mode 1981, now abandoned, of common assignee herein by R. of cis hydroxylation with OsO4, the catalytic mode Michaelson and R. Austin discloses the use of various employs a secondary oxidant to oxidatively hydrolyze 55 osmium halide and oxyhalide catalysts in the presence the intermediate Osmium (VI) ester and regenerate the or absence of a wide variety of co-catalysts and an OsO4 which can undergo further reduction by the sub oxidant selected from hydrogen peroxide, organohy strate olefin. A variety of oxidants have been employed droperoxides, or oxygen. Pyridine is disclosed as a suit in conjunction with OsO4 such as H2O2, t-butylhy able buffer for pH control in this application, which pH droperoxide and oxygen. 60 control is required when employing hydrogen peroxide. The use of oxygen as an oxidant has encountered Commonly assigned U.S. Pat. No. 4,314,088 and a considerable difficulty due to the appreciable overoxi continuation-in-part thereof, namely, U.S. Pat. No. dation of the products, particularly at elevated tempera 4,393,253 by R. Austin and R. Michaelson collectively, tures (e.g. 70-80 C.), leading to the formation of keto disclose the use of various halide containing co or acid products. However, if the reaction temperature 65 catalysts in conjunction with osmium tetroxide catalyst is lowered to reduce overoxidation, the reaction rate is and organohydroperoxide oxidants to hydroxylate ole so low that yields of cis-diol are drastically reduced. An fins. The halide containing co-catalysts include alkali additional disadvantage of the use of oxygen oxidant is and alkaline earth metal halides, hydrogenhalides, qua 4,496,778 3 4. ternary hydrocarbyl phosphonium halides, halogens, This yield is extremely low, i.e. 22%, and includes both and transition metal halides. half-acetate and diol. When an equivalent of Example 2 U.S. patent application Ser. No. 399,270 filed July 19, of this patent was conducted, the conversion of hydro 1982, by R. Austin and R. Michaelson is directed to a gen peroxide was found to be 10%, the selectivity to process for hydroxylating olefins in the presence of an diol was 10%, the selectivity to diacetate was 20% and organohydroperoxide oxidant, an osmium containing the diol yield was 1%. Thus, among the major disad catalyst and an organic halogenated hydrocarbon co vantages of the process described in this patent are the catalyst. low selectivities to diol and the corrosiveness of metal Commonly assigned U.S. patent application Ser. No. halides in the presence of glacial acids such as acetic 394,414, filed July 1, 1982 by R. Michaelson and R. O acid. Austin, is directed to the use of carboxylate salts as Japanese Patent Application No. Sho 54-145604, pub co-catalysts for use in conjunction with osmium oxides lished Nov. 14, 1979, is directed to a process for hydrox as a catalyst and organohydroperoxide as oxidant to ylating olefins in the presence of OsO4, a quaternary hydroxylate olefins. ammonium salt such as tetraethylammonium bromide, Commonly assigned allowed U.S. patent application 5 and a peroxide including organoperoxides and H2O2 as Ser.

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