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United States Patent O??ce 3,026,344 Patented Mar. 20, 1962 1 2 3,026,344 heat soaking the monomer at elevated temperatures, e.g. 50° to 210° C. for a period of several hours may be CYCLOPENTADIENYL CARBONYLS William J. Craven, Elizabeth, and Herbert K. Wiese, Cranford, N.J., assignors to Esso Research and En gineering Company, a corporation of Delaware No Drawing. Filed Oct. 29, 1958, Ser. No. 770,303 9 Claims. (Cl. 260-439) This invention relates to a novel process for the prep employed. As the cobalt containing reactant, there may be em ployed any cobalt compound such as oil soluble fatty acid ‘salts of cobalt, inorganic salts, metallic cobalt pref erably where the surface has been activated or, if desired, preformed cobalt carbonyl. Thus, for example, there can be employed the salts of cobalt and higher molecular weight fatty acids such as stearic, oleic, naphthenic, lin aration of cyclopentadienyl cobalt carbonyl including hy drocarbon-substituted cyclopentadienyl cobalt carbonyl compounds. More speci?cally, this invention relates to the preparation of the aforesaid cyclopentadienyl cobalt carbonyl compounds by a single step process. oleic and the like. Water soluble salts of organic acids may include cobalt acetate, cobalt formate and the like. As inorganic salts, there may be employed cobalt chlo are also useful as oil-soluble oxo catalysts. the term “cobalt carbonyl” it is intended to include such ride, cobalt bromide, cobalt iodide, cobalt sul?de and Oyclopentadienyl and substituted cyclopentadienyl co 15 oxides such as cobaltous and cobaltic oxides. When employing a cobalt halide or sul?de, it may be desirable balt carbonyls of this invention are known to have anti to use a halogen acceptor such as metallic copper. By knock qualities and are useful as gasoline additives. They For simpli ?cation, the term “a cyclopentadiene compound” will be employed to include a hydrocarbon-substituted cyclo pentadiene and dimers thereof. The term “cyclopenta diene cobalt carbony” is also intended to include the hydrocarbon-substituted cyclopentadiene cobalt carbonyl compounds, i.e. CpCo(CO)2, where Cp is any cyclo compounds as Co2(CO)8, H[Co(CO)4] and [Co(CO)3].,. To obtain an active metallic cobalt having a surface sub stantially free of oxides, sul?des and the like, cobalt salts such as cobalt oxalate may be decomposed to form cobalt oxide at temperatures of 125° to 250° C. and the cobalt oxide reduced with hydrogen at elevated temperatures of, for example, 300° C. to obtain the active metallic cobalt. 25 Another technique for obtaining metallic cobalt having In accordance with the prior art, the preparation of an active surface is to treat a cobalt-aluminum alloy with cyclopentadienyl cobalt carbonyl involved several steps. aqueous sodium hydroxide to dissolve away the alumi It was ?rst necessary to produce the sodium cyclopenta num leaving highly active metallic cobalt. It is evident, dienyl compound which was then reacted with a neutral cobalt salt to form the cyclopentadienyl cobalt salt, which 30 therefore, that cobalt in almost any form may be em ployed for the reaction of this invention since under re in turn was reacted with carbon monoxide to yield the action conditions, if cobalt carbonyl is not employed, it desired cyclopentadienyl cobalt carbonyl. While this will be formed in situ from any cobalt containing com process is satisfactory for the production of these cobalt pound. carbonyl compounds, the required three stages have ob As the carbon monoxide containing gas, it is preferred vious economic drawbacks with regard to commercial 35 to employ essentially pure carbon monoxide; however, application. impure gases may be utilized as long as the impurities do It has now been discovered that cyclopentadiene, hydro not interfere with the principal reactant. For example, carbon-substituted cyclopentadiene, or their dimers may a hydrogen'containing carbon monoxide gas may be em be reacted with cobalt comprising material at elevated temperatures under carbon monoxide pressures to effect 4:0 ployed if a hydrogen de?cient component is utilized in the reaction mixture to absorb the hydrogen and thereby the direct production of the desired cyclopentadienyl co avoid substantial hydrogenation of the cyclopentadiene balt carbonyl compounds. reactant. A hydrocarbon reactant is preferably employed The following general formula represents the class of to absorb any hydrogen formed in the reaction. This cyclopentadiene compounds suitable as reactants for the hydrocarbon may be the cyclopentadiene compound itself present process: 45 pentadiene compound. RTWR4 R I Y or some ole?n, such as hexene, pentene, octene, cyclo hexene and others. Although the use of a large excess or dimers thereof R5 of a cyclopentadiene compound to absorb any hydrogen formed in the reaction is not detrimental to the reaction, it is generally undesirable from a standpoint of vproduct work-up. Generally the cyclopentadiene cobalt carbonyl wherein each of the R’s represent the same or di?erent products boil close to the dimers or hydrogenated dimers radicals selected from the group consisting of hydrogen and hydrocarbon radicals. As examples of various com pounds coming within the scope of the above formula, ?cation ‘of the products di?icult. While the stoichiomet ric reaction requires one mole of the cyclopentadiene there are Z-methyl cyclopentadiene, 2-ethyl cyclopenta diene, 2-isopropyl cyclopentadiene, 1,4-dimethyl cyclopen tadiene, l-methyl-4-ethyl cyclopentadiene, l,2,3,4-tetra methyl cyclopentadiene, 2-tertiary butyl cyclopentadiene, 2-isopropenyl cyclopentadiene, 1-hexyl-2-(2-phenyl pro pyl) cyclopentadiene, 2-phenyl cyclopentadiene, 3,4-di cyclopropyl cyclopentadiene, 2-tolyl cyclopentadiene, phenyl-butyl cyclopentadiene, l-methyl cyclopentadiene of the cyclopentadiene compounds, thus making the puri dimer or two moles of the cyclopentadiene monomer for two moles of cobalt compound, it is preferred to employ a ratio of cobalt to cyclopentadiene monomer ranging from 1/3 to 3/1. If desired, a hydrocarbon solvent may be employed in a volume ratio of 1/10 to 10/1. The 60 solvent may comprise any ole?n, particularly an ole?n capable of reacting with any hydrogen formed in the re action, benzene, toluene, xylene, heptane and others. Temperatures for the reaction vary between 100-3000 and l-butyl cyclopentadiene and similar hydrocarbon substituted cyclopentadienes. The particular hydrocar 65 C. and even this range may be exceeded on either end to obtain the desired results. Carbon monoxide pressure bon substituent is not of critical importance with regard may be maintained between 500 and 10,000 p.s.i.g. ‘In to the operability of the present process since the hydro general, the higher carbon monoxide pressures permit a carbon substituents do not interfere with the principal faster reaction rate with higher conversions and yields reaction; however, preferred reactants are the C0—C8 for a given period of time. Good contact between the alkyl cyclopentadienes and/ or their dimers. To obtain the dimer of the cyclopentadiene compound 70 carbon monoxide gas and liquid reactants in accordance with known techniques is desirable for optimum results, from the monomer, any well-known technique such as 3,026,344: 3 4 although the process is operable by merely pressuring a Example 4 reactor, containing the cobalt and cyclopentadiene re actant, with carbon monoxide gas. The cyclopentadiene cobalt carbonyls are distillable under reduced pressure from the reaction mixture and may be stored for appreciable periods of time in an inert atmosphere. If some unconverted cyclopentadiene dimer distills over With the cyclopentadienyl cobalt carbonyl, A pressure reactor was charged with 38.5 grams (0.58 mole) of dicyclopentadiene, 221 grams of cobalt oleate (0.43 mole) and 650 ml. xylene. The mixture was heated to 180—190° C. for 8 hours with 3000 p.s.i.g. carbon monoxide. The mixture was then distilled and 60 grams of a dark red liquid boiling between 58° to 80° C. at 20 mm. was collected. The product contained 54 grams of other means such as extractive distillation, solvent extrac tion or fractional crystallization can be employed. If 10 desired, the solution of cyclopentadienyl cobalt carbonyl several microns to about 250 mm. To simplify the dis tillation and thus obtain a high purity product, it is gen erally important to select the ratio of cobalt/cyclopenta What is claimed is: , 1. A process for the preparation of a cyclopentadienyl cobalt carbonyl which comprises reacting a stoichiometric in hydrocarbons may be used as such as a fuel additive. The preferred technique of separation, however, in volves distillation under reducedpressure ranging from cyclopentadienyl cobalt carbonyl (65% yield). excess of a cyclopentadiene dimer compound selected from the group consisting of dimers of cyclopentadiene 15 and C0—C8 alkyl cyclopentadienes, and dimers thereof with a cobalt containing reactant selected from the group consisting of oil soluble cobalt salts of fatty acids and diene compound in the reactor in such a manner as to metallic cobalt under a carbon monoxide pressure of minimize the amount of unconverted cyclopentadiene from 500 to 10,000 p.s.i.g. and at a temperature from 20 100° to 300° C. and wherein said excess is employed compound. For a clearer understanding of the present invention, as a hydrogen acceptor to absorb hydrogen liberated reference may be had to the following examples which during the reaction. set forth various processes for the production of cyclo 2. A process in accordance with claim 1 wherein said pentadienyl cobalt carbonyl compounds. compound is di-cyclopentadiene. 3. A process in accordance with claim 1 wherein said Example 1 compound is di-methylcyclopentadiene. cobalt carbonyl which comprises reacting a stoichiometric mole) of Raney cobalt metal, 120 grams (0.7 mole) of methylcyclopentadiene dimer and 200 ml. of benzene sol vent. ' 4. A process for preparing methyl cyclopentadienyl A pressure reactor was charged with 24 grams (0.4 30 The mixture was then heated to 210° C. with a gauge reading of 1700 p.s.i.g. carbon monoxide pressure and a temperature was maintained in the closed reactor for a period of about 12 hours. The crude reaction mixture obtained was ?ltered free of unreacted metal powder and distilled. The fraction boiling at 55-65° C. at 5 mm. pressure was collected and found to contain methylcyclopentadienyl cobalt carbonyl excess of di-methylcyclopentadiene with metallic cobalt under a carbon monoxide pressure of from 500 to 10,000 p.s.i.g. and at a temperature of from 100° to 300° C. 5. A process in accordance with claim 1 wherein the cobalt-containing reactant is cobalt oleate. 6. A process in accordance with claim 1 wherein an ole?n is employed as the hydrogen acceptor. 7. A process in accordance with claim 1 wherein said compound is the dimer of 2~isobutyl cyclopentadiene. 8. A process for preparing cyclopentadienyl cobalt car bonyl which comprises reacting a stoichiometric excess (MCPD Co(CO)-2) 40 of dicyclopentadiene with cobalt oleate under a carbon monoxide pressure of from 500 to 10,000 p.s.i.g. and at as well as nnreacted methylcyclopentadiene dimer. In- ' a temperature of from 100° to 300° C. frared analysis of the distillate showed the characteristic 9. A process for preparing isobutyl cyclopentadienyl metal~carbonyl absorption peaks at 1960 cm.—1 and 2030 cmfl. The fraction weighed 33 grams and contained 45 cobalt carbonyl which comprises reacting a stoichiometric excess of 2-isobutyl cyclopentadiene dimer with metallic 3.62% cobalt. Example 2 The conditions of Example 1 are repeated employing 5000 p.s.i.g. to obtain larger yields of methylcyclopenta 50 dienyl cobalt carbonyl. Example 3 A reactor was charged with one mole of Raney cobalt and 1.5 moles of 2-isobutyl cyclopentadiene dimer with 55 350 mm. heptane solvent. The mixture was heated to 250° C. with a carbon monoxide pressure or" 650 p.s.i.g. for a period of 3 hours to obtain substantial yields of iso butyl cyclopentadienyl cobalt carbonyl. cobalt under a carbon monoxide pressure of from 500 to 10,000 p.s.i.g. and at a temperature of from 100° to 300° C. References Cited in the ?le of this patent UNITED STATES PATENTS 2,791,597 Anzilotti et al. _______ __ May 7, 1959 OTHER REFERENCES Piper et a1.: J. Inorganic and Nuclear Chemistry, vol. 7 I, pp. 165-174 (1955). Sidgwiclr: Chemical Elements and Their compounds, p. 1422 (1950).