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United States Patent 0 3,009,766 United States Patent 0 " ice Patented Nov. 21, 1961 1 2 inates problems under a wide variety of storage condi 3,009,766 tions. This thermal stability is also tremendously im DIHALODIMANGANESE OCTACARBONYIS AND portant in that the dihalodimanganese octacarbony-ls de PROCESS FOR PRODUCING THE SAME compose at the correct point in the combustion cycle of Vernon R. Sandel, L’Anse, Mich., assignor to Ethyl Cor poration, New York, N.Y., a corporation of Delaware the spark ignition engines operated on fuels containing No Drawing. Filed Aug. 11, 1958, Ser. No. 754,152 these compounds. This means that the compounds can 10 Claims. (CI. 23-14) exert their profound antiknock effects under conditions where less thermally stable additives would have already This invention relates to and has as its chief object been decomposed. the provision of new halomanganese carbonyls and 10 The bene?cial thermal stability properties of the com processes for their preparation. pounds of this invention are also of great value when the Provided by this invention are dihalodimanganese octa compounds are used in conjunction with organolead anti carbonyls having the empirical formula knock agents. Because of their stability, the dihalodiman ganese octacarbonyls decompose relatively late in the X2Mn2 (Co) a 15 engine cycle and thereby liberate the halogen in a form where the X’s are halogen atoms. Typical of these com that reacts with the decomposition products of the organo pounds are bromochlorodimanganese octacarbonyl, di lead antiknock agent. Formed are relatively volatile ?uorodimanganese octacarbonyl, bromoiododimanganese lead halides which are removed from the engine via the octacarbonyl, etc. It is preferable that the two halogen exhaust gas stream. Hence, the compounds of this in atoms be the same and that the halogen have an atomic 20 vention are not only powerful antiknocks, but possess weight between 35 and 127. In other words, the pre— good scavenging characteristics. ferred compounds of this invention are dichlorodiman The thermal stability of the dihalodimanganese octa ganese octacarbonyl, dibromodimanganese octacarbonyl carbonyls is also exceedingly important insofar as their and diiododimanganese octacarbonyl. use as chemical intermediates is concerned. These com These novel compounds exist as dimers, and thus can 25 pounds can thus be heated to cause various chemical be represented by the formula reactions to take place without inopportune thermal de composition occurring. Therefore, the fact that dihalo dimanganese octacarbonyls have much greater thermal where X is halogen. They are characterized by being stability than other manganese carbonyl halides makes very stable, crystalline substances. They have no sharp 30 these compounds of extraordinary value in the chemical melting points and are not readily sublima-ble. They are and allied arts. The above distinguishing features of the soluble in various organic solvents and, therefore, have compounds of this invention set them apart from the solubility in hydrocarbons, including gasoline, jet fuel, compounds known heretofore. diesel fuel, burner fuel, lubricating oils, and the like. There exist a number of ways of preparing the com They are also characterized by being essentially insoluble 35 pounds of this invention. One elegant method-a pre in water. ferred embodiment of this invention—-involves the pyrol The di'halodimanganese octacarbonyls are powerful ysis of halomanganese pent-acarbonyls. In this thermal antiknock agents when dissolved in gasoline even at very reaction, the compounds of this invention are formed in low concentrations (e.g., 0.005-0.2 gram of manganese good yield and in high purity. Carbon monoxide is a per gallon). This antiknock potency is especially pro by-product. The heating can be carried out in the pres nounced when these compounds are used in conjunction ence or absence of an inert solvent. However, use of with organolead antiknock agents, such as tetraethyllead. a solvent is preferable because of better temperature con Thus, very small concentrations of dihalodimanganese trol. The pyrolysis temperature is generally that which octacarbonyls in gasolines containing from about 0.5 to is su?icient to cause the liberation of carbon monoxide about 10 grams of lead per gallon cause very substantial 45 from the reaction mixture. Thus, temperatures in the improvements in the octane quality of the fuel. range of 30 to 150° C. can be used, depending upon The water insolu-bility of the ‘dihalodimanganese octa whether or not a solvent is used; the type of solvent, if carbonyls is a vitally important factor in their utility as used; and the particular halomanganese pentacarbonyl antiknocks. Because they are so insoluble in water, their used as the starting material. Generally speaking, higher gasoline solutions are not deprived of the valuable manga 50 temperatures should be used when the halomanganese nese content by means of water extraction. Thus, gaso pentacarbonyl is the chloro or lbromo compound. Some lines containing these compounds can be processed, stored, what lower temperatures can 'be used when heating iodo and shipped in the customary manner. Contact with manganese pentacarbonyl. In most cases, temperatures water which is encountered in such customary opera ranging from about 75 to about 100° C. are preferred tions has no adverse leaching el‘I’ect upon these fuels. 55 as the pyrolysis reaction occurs very readily and smoothly Another tremendously important factor making the at these temperatures. Solvents which can be elfectively present compounds ideally suited as fuel antiknocks is used in this process are those which are inert liquids their very great thermal stability. This means that gaso having boiling points above the temperature used to line solutions of dihalodimanganese octacarbonyls can effect pyrolysis. Thus, these solvents include such halo be stored for long periods of time at elevated tempera .60 genated hydrocarbons as carbon tetrachlodide; chloro tures (e.g., desert storage) without fear of catastrophic form; methylene chloride; 1,1,1-trichloroethane; dichloro thermal deterioration. This is important because thermal benzene; bromobenzeue; bromoform; etc. Ethers, such deterioration would not only result in the formation of as tetrahydrofuran, etc., and hydrocarbons, such as iso sludge and loss of valuable antiknock properties, but octane, decane, xylene, decalin, petroleum ether, mineral would result in the liberation of halogen leading to very 65 oil, etc., can also be used. severe corrosive problems. This would be especially in Another way of making the compounds of this inven tolerable if such thermal decomposition occurred in gaso t-ion involves pyrolyzing aromatic manganese tricarbonyl lines stored over water. In such systems halogen decom halides, such as benzene manganese tricarbonyl bromide, position products are readily hydrolyzed. The resultant toluene manganese tricarbonyl chloride, mesitylene man halogen acids are known to be severely corrosive of stor 70 ganese tricarbonyl iodide, and the like. The reaction con age tanks, pipelines, and so on. Hence, the very great ditions for this reaction are generally similar to those thermal stability of the compounds of this invention elim described above, except that somewhat higher tempera 3,009,766 3 4 tures are desirable. Thus, the use of a solvent of the However, generally speaking, concentrations of dihalo type described above is optional, though preferable. The dimanganese octacarbonyls equivalent to from about temperatures which are su?icient to cause the liberation 0.005 to about 0.2 gram of manganese per gallon are of carbon monoxide range from about 80 to about 180D C. preferred. At these concentrations, signi?cant improve The following speci?c examples in which all parts and ments in octane quality are achieved because of the percents are by weight illustrate various aspects of this potency of the compounds of this invention in this invention. regard. Example I It is preferable to use the dihalodimanganese octa A mixture of 5.5 parts of bromomanganese pentacar carbonyls as antiknocks in conjunction with organolead bonyl (0.02 mole) in 96 parts of carbon tetrachloride 10 antiknock agents, such as tetramethyllead, tetraethyllead, was re?uxed for approximately 45 minutes. Carbon tetrabutyllead, methyl triethyllead, tetraoctyllead, di monoxide was evolved during this time and the mixture methyldiethrylleadl, tetratolyllead, and the like. Such became progressively darker. The reaction mixture was combinations of antiknock agents cause especially great then cooled to room temperature and a dark, coppery improvements in octane quality, particularly when the colored crystalline material precipitated from the solvent amount of the lead antiknock exceeds that of the dihalo in a 65 percent yield. Chemical analysis showed this dimanganese octacarbonyl. Thus, excellent results are product to ‘be dibromodimanganese octacarbonyl. Cal achieved in gasolines containing from about 0.5 to about culated for CsOsMnzBrz: carbon, 19.43 percent; manga 10 grams of lead per gallon as an organolead antiknock nese, 22.3 percent; bromine, 32.39 percent. Found: agent and from about 0.005 to about 0.2 gram of manga carbon, 19.7 percent; manganese, 22.7 percent; bromine, 20 nese per gallon as a dihalodimanganese octacarbonyl. 34.3 percent. For most purposes, lead concentrations ranging from Example II about 0.5 to ‘about 6.3 grams per gallon are preferable. In these leaded fuel compositions the dihalodimanga
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