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It Tates Patent ()??Ce * * 3,915,553 it tates Patent ()??ce Patented Jan. 2, 1962 1 2 The process may'be carried out at temperatures be 3,015,668 tween about 20 to about 200° C. Preferably tempera PROCESS FOR PRODUCING CYCLOMATIC MAN tures of about 25 to about 100° C. are used since, within GANESE TRICARBONY L COMPOUNDS the range, relatively higher yields are obtained with a John Kozikowski, Walled Lake, Mich., assignor to Ethyl minimum of undesirable side reactions. The pressure is Corporation, New York, N.Y., a corporation of Dela not critical, but preferably is atmospheric or slightly ware No Drawing. Filed Nov. 24, 1959, Ser. No. 855,016 higher. 4 Claims. (Cl. 260—429) The process is generally conducted under a blanket of inert gas such as nitrogen, helium, argon and the like. This invention relates to a novel process for forming 10 The process is conducted in the presence of a non organometallic compounds. More speci?cally, it relates reactive solvent. The nature of the solvent is not critical. to a process for forming cyclomatic manganese tricarbonyl Typical solvents are high boiling saturated hydrocar~ compounds wherein the cyclomatic radical donates ?ve bons such as n-octane, n-decane, and other paraf?nic electrons for pi-bonding with the manganese atom, and hydrocarbons having up to about 20 carbon atoms such the manganese atom by virtue of the ?ve electrons donated 15 as pentadecane, and the like. Typical ether solvents are to it from the cyclomatic radical and the six electrons ethyl octyl ether, diethylene 'glycol methyl ether, diethyl donated to it by the three carbonyl groups has an electron ene glycol dibutyl ether, ethylene glycol dimethyl ether, con?guration which is isoelectronic with that of krypton. ethylene glycol diethyl ether, tetrahydrofuran, ethylene It is an object of this invention to provide a novel glycol dibutyl ether and the like. Silicone oils such as process for forming cyclomatic manganese tricarbonyl 20 the dimethyl polysiloxanes, bis(chlorophenyl) polysilox compounds. Additional objects of this invention will be anes, hexapropyldisilane, and diethyldipropyldiphenyl come apparent from a reading of the speci?cation and disilane may also be used. Solvents which are preferred claims which follow. ' are the high boiling others such as tetrahydrofuran and The objects of this invention are accomplished by pro ethylene glycol dimethylether. All of the above solvents viding a process for forming cyclomatic manganese tri 25 will not be suitable for all of the speci?c embodiments of carbonyl compounds. These compounds have the gen the invention since certain of the reactants are relatively eral formula ' insoluble in some of the above solvents. Thus, care CyMn(CO)3 should be used in selecting the speci?c solvent for the Cy, in the above formula, represents a cyclomatic hydro speci?c reaction. carbon radical which is a hydrocarbon containing a The solvent should be one having the requisite boiling cyclopentadienyl radical. Typical of such hydrocarbon and/or freezing point, for control of reaction temperature radicals are those represented by the formulae: and ease of separation of the product. It is preferable to select a solvent whose normal boiling Ra R4 point varies by at least 25 ° C. from the normal boiling 4 | | 35 point of a liquid product, and the freezing point of the solvent be at least 25° C. less than the temperature at RI WE’ r? which separation of a solid product is effected through i crystallization. The process is preferably conducted with agitation of 40 the reaction mixture. where the R’s are selected from the group consisting of The time required for the process varies depending on hydrogen and un-ivalent organic hydrocarbon radicals. the other reaction variables. In general from about 30 A preferred class of cyclomatic radicals are those which minutes to about 24 hours is su?icient. contain from ?ve to about 13 carbon atoms. These are , In general, the metal carbonyl halide reactant employed exempli?ed by cyclopentadienyl, indenyl, methylcyclo 45 in the process is more expensive than the cyclomatic-alkali pentadienyl, propylcyclopentadienyl, diethylcyclopentadi metal reactant. In order to insure maximum conversion enyl, phenylcyclopentadienyl, tert-butyl cyclopentadienyl, of the metal carbonyl halide, it is, therefore, preferred to p-ethylphenyl cyclopentadienyl, 4-tert-butyl indenyl and use excess quantities of the alkali metal-cyclomatic react the like. These radicals are preferred since they are ant. Generally, from about one to about 1.5 moles of the derived from the more readily available cyclomatic com alkali metal cyclomatic compound are employed for each pounds. Further, cyclomatic manganese tricarbonyl com mole of manganese carbonyl halide reactant since, within pounds containing these groups have the more desirable this range, a good conversion of the metal carbonyl halide characteristics of volatility and solubility which are pre is obtained. In some cases, alkali metal cyclomatic react requisites for superior hydrocarbon additives. ant may be more expensive than the particular carbonyl In the compounds formed by my process the manganese 55 halide employed. In these instances, excess manganese atom has an electron con?guration which is isoelectronic carbonyl halide will be employed to insure complete con with that of krypton. In other words, the atomic number version of the alkali metal cyclomatic compound. of manganese plus the number of electrons donated to To further illustrate the compounds of the invention it—eleven—equals the atomic number of krypton. In and their mode of preparation, there are presented the each of the compounds formed by my process, six elec 60 following examples in which all parts and percentages are trons are donated to the manganese atom from the three by weight unless otherwise indicated. carbonyl groups, and ?ve electrons are donated to the manganese atom from the cyclomatic radical. Example I Although not bound by any theory, my process may be Cyclopentadienyl sodium (0.03 mole) was prepared by schematically represented by way of the following 65 reacting (under nitrogen) cyclopentadiene with sodium equation: dispersed in tetrahydrofuran. This solution was added Mn(CO)5X+CyZ—>CyMn(CO)3+ZX slowly (under nitrogen) to a tetrahydrofuran solution containing 8.25 parts (0.03 mole) of manganese penta where Cy represents a cyclomatic radical as hereinbefore carbonyl bromide. Very little heat was evolved, but a described; Z is an alkali metal, e.g. sodium, potassium, 70 ?nely-divided solid was formed, and carbon monoxide cesium or rubidium and X is a halogen, such as chlorine, was slowly evolved. The solvent was removed under re bromine, iodine or ?uorine. duced pressure and the residues sublimed at 70° C. and 3,015,668 3 4 a pressure of less than one mm. The product was found knock. When used as additives to a leaded gasoline, the to contain cyclopentadienyl manganese tricarbonyl and gasoline may also contain a scavenging amount of a halo dimanganese decacarbonyl. The presence of cyclopenta hydrocarbon such as ethylene dichloride or ethylene di dienyl manganese tricarbonyl was con?rmed by taking a brornide. The antiknock effectiveness of my products mixed melting point with an authentic sample of this and many formulations in which‘ they are used is described compound. The same procedure was used to charac in detail in US. Patent 2,818,417. terize and identify the dimanganese decacarbonyl. The The compounds produced by my process have many crystals of cyclopentadienyl manganese tricarbonyl and other utilities. For example, they may be utilized in the manganese carbonyl were separated mechanically to give gaseous plating of metals by decomposing the compound essentially pure cyclopentadienyl manganese tricarbonyl. 10 in an enclosed space so as to form a metal coating on an Example II object contained within the enclosed space. The plating operation is customarily carried out in the presence of an A solution comprising 1.1 mole of methylcyclopenta inert atmosphere to reduce oxidation of the object to be dienyl sodium and one mole of chloromanganese penta coated or the coating metal itself. carbonyl in te-trahydrofuran is agitated under nitrogen for 15 Another utility for the compounds produced by my 30 minutes after which it is heated at re?ux under nitrogen process is additives to home heater fuels, diesel fuels and until no further evolution of carbon monoxide is observed. fuels employed for jet engines. In this application, the The reaction product is then discharged and ?ltered and elfect of the additive is to reduce smoke and/or soot the ?ltrate is heated under reduced pressure to remove formation. Still another utility for the cyclomatic man the solvent. The residue is then distilled under reduced 20 ganese tricarbonyl compounds is as additives to lubricants. pressure to give a good yield of methylcyclopentadienyl In this application, the additive acts to increase the lubri manganese tricarbonyl. city of the lubricating medium and reduce wear of the Example III rubbing surfaces. Having fully de?ned my novel process, the compounds A solution comprising 1.5 moles of indenyl sodium, 25 produced by it and their manifold utilities, I desire to be and one mole of chloromanganese pentacarbonyl in tetra limited only within the lawful scope of the appended hydrofuran is heated at re?ux under a nitrogen atmos claims, which, as is evident from the above description, phere for 24 hours while agitating the reaction mixture. comprises the reaction of a cyclomatic-alkali metal com The reaction product is then discharged, ?ltered and the pound with a manganese pentacarbonyl halide in the ?ltrate is heated under reduced pressure to remove the 30 presence of an inert solvent and under a blanketing atmos solvent. The residue is then distilled under reduced pres phere of an inert gas to yield a cyclomatic manganese sure to give a good yield of indenyl manganese tricarbonyl.
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