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United States Patent Office Patented Apr 3,381,023 United States Patent Office Patented Apr. 30, 1968 1. 2 Furthermore, the isolation procedures for separating the 3,381,023 resulting compounds are simplified by the process of this PREPARATION OF AROMATIC GROUP VI-B METAL TRICARBONYS invention, as a minimum of unreacted starting materials Mark Crosby Whiting, Oxford, England, assignor to and side products are present in the final composition. In Ethyl Corporation, New York, N.Y., a corpora addition, Superior yields are obtained. For example, tion of Virginia O-cresyl methylether chromium tricarbonyl was prepared No Drawing. Filed Mar. 10, 1958, Ser. No. 720,083 in 99 percent yield by the process of this invention. Yields 31 Claims. (Ci. 260-429) of this order of magnitude have not heretofore been pos sible. This invention relates to a process for the preparation The temperatures employed in the process of this inven of organometallic compounds and more particularly the O tion may vary over a wide range. In general, tempera preparation of aromatic Group VI-B transition metal tures of from about 100° C. to 300° C. are employed. carbonyl compounds. However, a preferred range of temperature is from Recently a method for the preparation of aromatic 150 C. to 225 C. as the reaction in this temperature chromium tricarbonyl compounds has been proposed, 5 range leads to a high yield of products with a minimum which method comprises the equilibration, in an aromatic of undesirable side reactions. Solvent of a di-aromatic chromium compound with chro The aromatic compound which is a reactant in the mium hexacarbonyl and which employs a reaction time process of this invention can be selected from a wide of 12 hours under pressure at temperature in excess of range of aromatic organic compounds including mono 200 C. In order to accomplish this preparation, it is 20 nuclear hydrocarbons, poly-nuclear hydrocarbons, mono first necessary to prepare di-benzene chromium itself, and poly-nuclear aromatic amines, aromatic esters, aro which is a complex and inefficient process. matic ethers and phenolic compounds. The applicable aro It is, therefore, an object of this invention to provide matic compounds should be free of oxidizing substituents a novel method for the preparation of aromatic Group and be less acidic than benzoic acid. Examples, therefore, VI-B transition metal carbonyl compounds. A further 25 of the applicable aromatic compounds include phenol, object is the preparation of aromatic chromium tricar amylbenzoate, propylbenzoate, butylphenyl ether, para bonyi compounds which does not first require the prepara methyl anisole, n-hexylaniline, 2-amino-4-isopropylnaph tion of a di-aromatic chromium compound. Other objects thalene, N,N-di-methyl-o-methylaniline, 1 - methyl - bi will be apparent from the following description. phenyl, tetrahydronaphthalene, 6-methylnaphthalene, an The above and other objects are accomplished by a 30 thracene, phenanthracene, mesitylene, meta-di-methylben process for preparing an aromatic Group VI-B transi Zene, m, m'-di-tert-butyl-diphenyl and the like. Those aro tion metal carbonyl coordination complex which com matic compounds having up to about 20 carbon atoms are prises reacting a Group VI-B transition metal carbonyl preferred since they lead to more easily recoverable with an aromatic compound. It has now been found that products and are, of course, the principal available aro this preparation may be accomplished in a system where matic compounds. A preferred embodiment of this inven the only reactants are the Group VI-B transition metal tion employs an aromatic compound in which the sub carbonyl and the aromatic compound. When desired, the stituents on the benzene nucleus, if any, are not para reaction can be conducted in a high-boiling solvent. oriented. Thus preferred aromatic compounds employed The process of this invention can be summarized by the have substituents in the meta or ortho relationship, as it following chemical equation in which Ar represents an 40 has been found that higher yields of aromatic Group aromatic compound and M represents a Group VI-B VI-B transition metal carbonyl compounds can be pre transition metal: pared from these reactants. Whereas the process of the present invention can be Ar--M(CO)6) ArM(CO)3--3CO conducted at atmospheric pressure at the reflux tempera Thus, carbon monoxide is given off as a product of the 45 ture of the system, higher or lower temperatures and reaction. higher pressures may also be conveniently employed. Thus The Group VI-B transition metal carbonyl compounds benzene chromium tricarbonyl has been prepared by reac which are reactants in the process of this invention in tion of benzene with chromium hexacarbony in a sealed clude chromium hexacarbonyl, molybdenum hexacar vessel at 225 C. at the prevailing pressure. In this em bonyl and tungsten hexacarbonyi. A preferred embodi 50 bodiment of the invention, temperatures of from 150 C. ment of this invention comprises the reaction of chro to 250 C. are preferred although temperatures outside mium hexacarbonyl with an aromatic compound to pro this range may also be employed. Since carbon monoxide duce an aromatic chromium tricarbonyl. This embodi is given off as a product of this reaction, and an excess of ment is preferred as the compounds prepared are highly carbon monoxide pressure may inhibit further formation useful chemical entities. of the desired aromatic Group VI-B transition metal tri As an example of the preferred embodiment of the carbonyl compound, it is advantageous to vent excess car process of this invention, a suspension of chromium hexa bon monoxide through a condenser when the process of carbonyl in an excess of anisole was heated under reflux this invention is conducted at elevated pressures. in a nitrogen atmosphere until sublimation of the chro A particularly preferred embodiment of this invention mium hexacarbonyl had ceased, resulting in a deep yel 80 comprises reacting under reflux conditions at atmospheric low-colored solution. This solution was evaporated to pressure, an aromatic organic compound, as defined dryness under reduced pressure leaving a yellow crystal above, which contains at least seven carbon atoms with a line residue which comprised a 94 percent yield of anisole Group VI-B transition metal carbonyl. It has been found chromium tricarbonyl. This compound has a melting point that when the aromatic compound employed has a mo of 86-87 C. lecular weight of above 90 it is unnecessary to employ The process of this invention has numerous advantages. elevated pressures to obtain an excellent yield of an aro It is a simple and straight forward reaction to obtain the matic Group VI-B transition metal tricarbonyl com desired products. In distinction to previously known meth pound. When the aromatic compound employed has a mo ods for making the compounds, it is conducted in a single lecular weight of below about 90, it is preferred to con step beginning with the metal carbonyl. As pointed out 70 duct the process at slightly elevated pressures as described above, the previous method involved the initial prepara above, as it has been found that superior yields of the tion of a di-aromatic metal compound as an intermediate. lower molecular weight aromatic Group VI-B transition 3,381,023 3 4. metal tricarbonyl compounds are formed in this manner. for six hours while the reactants were protected by a No solvent is required in conducting the process of stream of nitrogen. The reaction was conducted in a glass this invention, the aromatic compound being employed in reaction vessel fitted with a reflux condenser and heating excess to serve as a carrier for the Group VI-B transition means. The resulting deep yellow solution was cooled and metal carbonyl. However, it is often convenient to em diluted with 713 parts of ethylether and then filtered. The ploy an inert diluent in the process. High-boiling satu resulting solution was evaporated to dryness under re rated hydrocarbons are the preferred solvents. Other sol duced pressure. One hundred thirty-five parts of yellow vents which can be employed include higher boiling crystalline solid were obtained which had a melting point ethers, high-boiling aliphatic esters, silicone oils, aliphatic of 86-87 C. after recrystallization from isopropylether. polyesters, and other liquids inert to the primary re This represents a 94 percent yield of anisole chromium actants. Examples of the compounds useable as solvents 0 tricarbonyl. Elemental analysis of the compound showed in the process of this invention include n-octane, n-no it to contain 49.5 percent carbon and 3.5 percent hydro nane, n-decane and the various iso-decanes and other gen as compared to a calculated content of 49.2 percent parafinic hydrocarbons having up to about 20 carbon carbon and 3.3 percent hydrogen. atoms such as eicosane, octadecane, pentadecane and the 5 Examples II-VIII like. Ether solvents which may be employed include ethyl octylether, amyl ethyl ether, ethyl heptylether, and ethyl Following the basic procedure outlined in Example I hexylether. Ester solvents which may be employed in above, aromatic chromium tricarbonyl compounds of clude pentyl 2-methylpropanoate, pentyl butanoate, butyl mesitylene, o-xylene, m-xylene, para-xylene, tetralin, o butanoate, y-methylbutyl butanoate, ethyl decanoate, cresyl methylether, and para-cresyl methylether were ob methyl decanoate, pentylhexanoate, ethylhexanoate, and 20 tained. The details of these preparations are given in the like. Applicable silicone oils include copolymers and Table I. The reactions were all conducted at the reflux homopolymers of the various organosiloxanes and or temperature of the system. In each instance where the ganosilanes having the appropriate boiling range. Exam product was analyzed for its elemental constituents, re ples of these are the dimethyl polysiloxanes, methylphen 25 sults exceptionally close to the theoretical content were yl polysiloxanes, diphenyl polysiloxanes, di(chlorophen obtained.
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