Патент USA US3042703код для вставки
United States Patent O?lice 3,042,693 Patented July 3, 1962 7. 2 matic compoundshaving from 6 to 18 carbon atoms are 3,042,693 No Drawing. Filed Oct. 18, 1957, Ser. No. 690,90 generally preferred in compounds of this invention. Ben zene itself, mesitylene, toluene, biphenyl, tetralin, m hexylbiphenyl, and the like are examples of applicable aromatic compounds. Typical examples of other compounds which are also 4 Claims. (Cl. 260-429) suitable and which do not have an isolated benzene nucleus ORGANDMETALLHC CGR/EQUNDS Thomas H. (In?eld, Farmington, and Rex D. Closson, Northville, Mich, assignors to Ethyl Corporation, New York, N.Y., a corporation of Delaware ' - are styrene cyanomanganese dicarbonyl, methylstyrene This invention relates to novel organometallic com cyanomanganese dicarbonyl, naphthalene cyanomanga» pounds and more particularly to aromatic compounds of 10 nese dicarbonyl, and the like. manganese. In addition, the present invention relates to The compounds of this invention can be prepared by a manufacture and use of the above compounds. number of techniques. One typical method is to form It is an object of this invention to provide a new class of organometallic compounds. More particularly, it is an object to provide new compounds of manganese which are 15 the desired compound by decarbonylating the correspond ing aromatic metal tricarbonyl cyanide by pyrolysis in ac cordance with the following equation relatively stable and which are soluble in organic media, particularly hydrocarbons. Another object is to provide compounds of the above type which are useful as anti knocks in gasoline used for internal combustion engines. wherein'A is an aromatic molecule as de?ned above. Still another object is to provide a novel process for manu 20 This pyrolysis can be conducted at a temperature of be facture of such compounds and fuel compositions con tween about 20" and 300° C., but is usually carried out taining the same. Other objects and advantages of this between about 50° and 200° C. Likewise, while not invention will be more apparent from the following de essential, the reaction is best conducted in an inert liquid scription and appended claims. The above and other objects of this invention are ac medium and preferably in a solvent for‘the tricarbonyl 25 reactant but which is not a solvent for the product. For complished by the provision of a novel class of compounds this reason, polar solvents are frequently preferred. The pyrolysis to form the aromatic cyanomanganese dicarbonyl can be accomplished simultaneously with the formation of the aromatic manganese tricarbonyl cyanide reactant. For example, a typical method for producing the aromatic manganese tricarbonyl cyanide involves the having an aromatic molecule coordinated with a manga nese atom, the compound being stabilized by additional coordination with two carbonyl groups and a cyano group, the aromatic molecule contributing six electrons, the car bonyl groups each contributing two electrons and the cyano group contributing one electron to the manganese, reaction of an aromatic manganese tricarbonyl halide thereby giving the manganese a total of eleven additional with an active cyanide compound. This reaction can be electrons and resulting in the manganese atom having the conducted at temperatures de?ned above for pyrolysis, con?guration of krypton. More speci?cally, the aro 35 i.e., 20~300° C., to simultaneously produce the com matic cyano manganese dicarbonyl compounds of this in pounds of this invention. Likewise, the aromatic man vention have the general formula ganese tricarbonyl halide does not require isolation prior to conversion to the compounds of the present invention. A typical series of reactions which can be conducted to wherein A is an aromatic molecule. 40 form the aromatic manganese tricarbonyl cyanide reac tant is as follows: The compounds of this invention are unexpectedly stable to light, heat and other in?uences. As such, these compounds are very useful in many applications wherein stability is an important factor. The compounds are also 45 coordination complexes and thus are soluble in organic media, particularly of the hydrocarbon type. These com pounds are also antiknocks and, in use, are preferably injected into internal combustion engines as a component of the vfuel mixture. .50 Typical examples of compounds of this invention are benzene cyanomanganese dicarbonyl, toluene cyanoman wherein X is a halogen, M is a metal and m is the valence of the metal M. Thus, the above reactions can be con ducted separately and, in each instance, the desired inter mediate separated and isolated. Alternatively, the reac tions can be conducted simultaneously or sequentially without separation of products. . ganese dicarbonyl, o-xylene cyanomanganese dicarbonyl, p-xylene cyanomanganese dicarbonyl, mesitylene cyano The halogenation of the manganese pentacarbonyl (2) manganese dicarbonyl, diphenyl cyanomanganese dicar 55 can be conducted over a wide temperature range such, bonyl, tetralin cyanomanganese dicarbonyl, ethylbenzene cyanomanganese dicarbonyl, n-octyl benzene cyanoman ganese dicarbonyl, and the like. The aromatic compounds coordinated to the metal in the compounds of this invention which are represented by A in the above formula are‘in general compounds prefer ably containing an isolated benzene nucleus. That is, aro matic compounds which are free of aliphatic unsaturation on a carbon atom adjacent the benzene ring and which for example, as —70° to 100° C. although the reaction is preferably conducted at a temperature of 0° to 50° C. The reaction is preferably conducted in an inert liquid, preferably one which is a solvent for the manganese pentacarbonyl, for example, chlorinated hydrocarbons such as ethyl chloride and carbon tetrachloride, and the like; aliphatic hydrocarbons such as pentane and hexane; aromatic solvents such as benzene, toluene and xylene; solvents such as carbon disul?de and organic acids such do not contain unsaturation on a carbon atom of a fused as an acetic acid. ring which is adjacent the benzene nucleus. That is, the aromatic compounds which are preferred for this invention have no aliphatic double bond in conjugated relationship to the ring. Thus, aryl and alkyl substituted aromatic critical as long as there is enough to provide solubility for The concentration of solvent is not manganese carbonyl. Any of the halides are suitable in this reaction such as, for example, the chlorides, bromides, iodides or ?uorides. compounds are also preferred as are fused ring compounds 70 The reaction of the aromatic compound with the halo having isolated benzene nuclei, that is, having no unsatura gen manganese pentacarbonyl (3) is generally catalyzed tion on a carbon atom adjacent to a benzene ring. .Aro by a Friedel-Crafts catalyst and is normally conducted 3,042,693 4 . . sis of the product was as follows: preferred temperature range is in the order of 50° to 200° C. e manganese dicarbonyl was 170—172° C. Chemical analy I at a. temperature of from about 20° to 300° C. ‘A more " Bya Friedel-Crafts catalyst is meant a. salt having elec-' Found Calculated trophilic characteristics. . These are. usually" halides of metals of groups IIA, IIB, HIA, IVBLVB, VI-B, VIIB and VIII of the periodic table. The preferred halides Carbon ______________________________ _- ' 55. 8 Hydrogen Nitrogen _____________________________ __ 56. 0 . 4. 79 4. 65 5. 45 5. 45 are halides of groups lIIA, IVB and VVIH. Illustrative examples of preferred metal halides'are boron tn'?uoride, boron trichloride, boron tribromide, boron triiodide, alu minum trichloride, aluminum tri?uoride, titanium tetra An infrared spectrum con?rmed the structure of this prod 10 uct. The product obtained in this example is an effec tive antiknock when used in fuels for internal combustion chloride, titanium tetrabromide, ferric chloride, and the like. Also in many instances,it is desirable to employ the corresponding hydrohalide along with the metal hal ide, e.g. Val-boron trichloride-hydrogen chloride catalyst engines. ’ ' ' . " ‘ Example II , Mesitylene manganese tricarbonyl iodide (3.86 parts) 15 7 was reacted with 2 parts of potassium cyanide, but in this system. Other examples of suitable Friedel-Crafts cat alysts of generally lesser activity are .zinc, gallium, indium, example the iodide compound Was‘dissolved'in 150 parts of ice-cold water. A white precipitate was ‘formed im mediately which was thereafter, ?ltered and washed with .chromium, manganese and cobalthalides. The Friedel-Crafts reaction’ (3) is preferably carried 20 ethyl ether; This White preceipitate, mesitylene man thallium, beryllium, magnesium, zirconium, vanadium, ganese tricarbonyl cyanide, (2.45 parts) was analyzed by out in a liquid medium consisting primarily of the aro chemical analysis and .by infraredv analysis. F This product was thereafter re?uxed under nitrogen, resulting in the matic compound Which is reacted with the halogenman ganese pentacarbonyl. Thus, if it is ‘desired to make the evolution of carbon monoxide. ‘ benzene manganese .tricarbonyl, the react-ion is conducted Upon‘ cooling, yellow in .a benzenem'edium- The reaction can. also be con 25 crystals separated which were thereafter recrystallized from water. These yellow crystals were mesitylene cyano ' ducted in a halogenated benzene such as'chlorobenzene rnanganese dicarbonyl havinga melting point of 171 or bromoben'zene, inwhich event the chloroaromatic or ' bromoaromatic manganese .tricarbonyl-halide .is formed. ' 172° C. Thisrproduct Other substituted aromatic compounds can be‘produced acteristic infrared spectrum. in like manner. . . a . 30 a also analyzed and'gave char . . Example _III In addition to the aromatic compound,.other solvents or x Twenty¢?ve parts of bromomanganese pentacarbonyl, diluents can be employed. , Typical examples of such diluents are nitrobenzene; straight chain hydrocarbons 410 parts of aluminum chloride and 108 parts of mesity ‘such .as pentane, hexane, decane, and the like. These diluents can be used in concentrations of from 0.01 to 100 parts per part of the aromatic compound. 7 Reaction of the aromatic manganese tricarbonyl halide lene ‘were re?uxedunder nitrogen until the gas evolution P had terminated. After cooling the reaction mixture, the mesitylene manganese tricarbonyl bromide was hydro lyzed 'with 100 parts of water. The water vlayer was thereafter ‘separated . and treated with excess'potassium cyanide; A'green precipitatejwas formed. _ Thereafter with an active cyanide compound (4) is best conducted attemper'atures of from‘—30° to 250° C. Most pre ferredoperation employs temperatures of- above 50° C. 40 suf?cient sodium hydroxide (5 percent solution) was added to the reaction product to raise the pH to 8.5, un der which conditions the color of the solution changed to yellow. The product'was then extracted with water and below about200° -.C. At the more elevated temper-a tur'es', the aromatic manganese tricarbonylcyanide de composes immediately to therdesired aromatic manganese dicarbonyl cyanide. ' In this process, any active’ cyanide’ ’ and the extract was concentrated whereupon yellow crys compound can be used but the cyanides of metals‘of 45 tals of mesitylene cyanomanganese dicarbonyl were ob groups I to III of the periodic‘ table are preferred. Best results are obtained with the alkali metal compounds, such tained. This product was ‘thereafter recrystallized from as sodium‘ cyanide, potassium cyanide and lithium cya nide. Other typical examples of suitable metal cyanide ' carbonyl. The productwas identi?ed by infrared analy compounds are calcium cyanide, magnesium cyanide aluminum cyanide. _ ' l l' water giving’6.1‘2 parts of mesitylene'cyanomanganese di and V SIS. I Any of a wide variety of solvents can-be employed in Step 4, particularly polar solvents.’ Water, lower aliphatic Example IV ' 55. atoms ‘give excellent results. . The concentration of soil vent isnot critical. Quantities of from about 0.I part to ' about 100 parts per part of reactant can be used, although ' from about 1 ‘to 10 parts are preferred. . ' "The following are typical examples which illustrate the 60 present invention and in whichla-ll parts are give'u'by v > weight. . Mesiltylene manganese 'tricarbonyl iodide, (3.86" parts) 65 3 parts of potassium cyanide‘were added.‘ Mesitylene' cyanomanganese' dicarbonyl, a yellow precipitate, was formed’directly,'carbon monoxide being evolved’ in about one mole equivalent quantities. The reaction mixture 70 uct was recrystallized in water three, times, washed with a. 7 Example I is repeated using xylene manganese tricar bonyl chloride in ethylene glycol solvent to produce . Example I was dissolved in 100 parts of hot water and, while boiling, Example I is repeated except that benzene manganese tricarbonyl bromide is reacted with sodium cyanide in 1570 parts of ethyl alcohol. The solution isre?uxed until gas evolution ceases. Similar results are obtained except that the product is benzene cyanomanganese dicarbonyl. Example V ll ' ' was cooled and ?ltered and 2.26 parts‘of mesitylene cyano manganese dicarbonyl product was obtained. This prod , . tained. alcohols .and others ‘such as acetone are preferred. The alcohols havingalkyl groups containing} to 6 carbon r 'When the aboveexample is carried out in using other Friedel-Crafts catalyst such ‘as boron tri?uoride, boron trichloride-HCI and ferric'chloride' similar results‘are ob xylene cyanomanganese dicarbonyl. The pyrolysisreac tion is conducted at: 100°C. until‘all of the freed carbon monoxide has been evolved. - ' ‘ ‘ Example VI _ Tetralin manganese ltricarbonyl‘ iodide (4.4 parts) is dissolved in 120 parts of water, This solution is heated to a temperature of50° C. and 3.2’ parts of calcium cya nide is added over a period ‘of 10 minutes. The heating is continued withstirring until there is no evidence of fur smallramount of diethyl ether andrdried under reduced pressurei The meltingv point of the mesitylene cyano- 75 ther gas evolution. .The product reaction mass is then 3,042,698 5 . 6 cooled to room temperature and the tetralin cyanoman I words, a theory of halogen represents two atoms of halo ganese dicarbonyl puri?ed as in Example 1. Example VII gen for every atom of lead and/or manganese present. In like manner, a theory of phosphorus is the amount of phosphorus required to convert the lead present to lead Ethylbenzene manganese tricarbonyl cyanide is heated orthophosphate, Pb3(PO4)2, that is, a theory of phos in dioxane to a temperature of 100° C. The solution is maintained at this temperature until the gas evolution ceased. The reaction mixture is then cooled to room phorus based on lead represents an atom ratio of two atoms of phosphorus to three atoms of lead. When based on manganese, a theory of phosphorus likewise represents two atoms of phosphorus for every three atoms temperature and the product ethylbenzene cyanomanga nese dicarbonyl is recovered in accordance with the pre ceding examples. 10 of manganese, that is, su?icient phosphorus to convert manganese to manganese orthophosphate, Mn3(PO4)2. When employing the compounds of this invention to gether with scavengers, an antiknock ?uid for addition to hydrocarbon fuels is prepared comprising aromatic Example VIII Triethylbenzene manganese tricarbonyl chloride (8.3 parts) is dissolved in 250 parts of acetone. The solu tion is heated to a rolling boil and 5 parts of lithium 15 cyanomanganese dicarbonyl compounds together with various halogen-containing organic compounds having cyanide is added to the solution. Carbon monoxide gas from 2 to about 20 carbon atoms in such relative pro is evolved and the solution is maintained at re?ux until portions that the atom ratio of manganese-to-halogen is no additional gas evolution is apparent. The triethyl from about 50:1 to about 1:12. The scavenger com benzene cyanomanganese dicarbonyl is recrystallized from triethanol amine and subsequently recrystallized 20 pounds can be halohydrocarbons both aliphatic and aro matic in nature, .or a combination of the two, with line twice in water. The crystals are washed with a small gens being attached to carbons either in the aliphatic or amount of dimethyl ether and dried at reduced pressure. the aromatic portions of the molecule. The scavenger Example IX compounds may also be carbon, hydrogen, and oxygen Fifty parts of bromomanganese pentacarbonyl, 18 25 containing compounds, such as haloalkyl others, halo~ hydrins, halo esters, halonitro compounds, and the like. parts of aluminum bromide and 200 parts of n-cctyl Still other examples of scavengers that may be used in benzene are re?uxed in an inert atmosphere until gas conjunction with our manganese compounds either with evolution has ceased. After cooling the reaction mix ture, the product is hydrolyzed with 150 parts of water. 30 or without hydrocarbolead compounds are illustrated in The water layer is separated and 4 parts of sodium U.S. Patents 2,398,281, 2,479,900, 2,479,901, 2,479,902, cyanide is added to this solution. Su?icient potassium and 2,479,903, and the like. Mixtures of different scavengers may also be used. These fluids'can contain hydroxide (10 percent solution) is added to the reaction product to raise the pH of the solution to 8.0. The other components as stated hereinabove. In like man product, n-octylbenzene cyanornanganese dicarbonyl, is 35 ner, manganese-containing ?uids are prepared contain ing from 0.01 to 1.5 theories of phosphorus in the form thereafter recovered in accordance with the procedure of phosphorus compounds. of Example III. The compounds of this invention can be employed with hydrocarbon fuels and lubricating oils for improv ing operating characteristics of spark ignition internal combustion engines. The compounds can be used in fuels and lubricating oils by themselves or together with other additive components, such as scavengers, deposit To make up the ?nished fuels, the concentrated ?uids are added to the hydro carbon fuel in the desired amounts and the homogeneous 40 ?uid obtained by mixing, agitation, etc. The ratio of the weight of manganese to lead in ?uids and fuels containing the two components can vary from about 1:880 to about 50:1. When no lead is present, modifying agents containing phosphorus and/or boron, the latter ?gure becomes 1:0. A preferred range of ratios, however, when both the manganese compounds of and also other antiknock agents, such as tetraethyl this invention and hydrocarbolead compounds are em lead, etc. When an aromatic cyanomanganese dicar ployed, is from about 1:63 to about 30:1. . bonyl compound is added to gasoline, a substantial in The following examples are illustrative of ?uids and crease in the octane value of the fuel results. fuels containing our new compounds. The compounds can be added directly to the hydro carbon fuels or lubricating oils and the mixture'sub 50 Example X jected to stirring, mixing, or other means of agitation To 1000 gallons of a commercial fuel having an initial until a homogeneous ?uid results. Alternatively, the boiling point of 90° F. and a ?nal boiling point of compounds of our invention may be ?rst made up into 406° F. is added 55 grams of benzene cyanomanganese concentrated ?uids containing solvents, such as kerosene, toluene, hexane, and the like, as well as other additives 55 dicarbonyl, and the mixture subjected to agitation until the additive is distributed‘evenly throughout the fuel, in such as scavengers, antioxidants and other antiknock an amount equivalent to 0.013 gram‘ of manganese per agents, e.g., tetraethyllead. The concentrated ?uids can gallon of fuel. then be added to the fuels. Similar results are obtained with other aromatic cyano As the organo lead antiknock agent which is an in rnanganese dicarbonyls such as xylene cyanomanganese gredient of certain of the compositions of this invention, organolead compounds in general may be used. Prefer dicarbonyl, mesitylene cyauomanganese dicarbonyl, and able, however, are hydrocarbon lead compounds such as the like. tetraphenyllead, tetratolyllead, and particularly tetraalkyl lead compounds such as tetramethyllead, tetrapropyllead and the like. In general the amount of organolead anti knock agent is selected so that its content in the ?nished gasoline is equivalent to at least about 1 gram of lead per gallon. , Where halohydrocarbon compounds are employed as scavenging agents, the amounts of halogen used are given in terms of theories of halogen. A theory of halogen is de?ned as the amount of halogen which is necessary to react completely with the metal present in the antiknock mixture to convert it to the metal dihalide as, for ex . . Fuels containing mixtures of two or more aromatic cyanornanganese dicarbonyls, such as the mixture of benzene cyanomauganese dicarbonyl and xylene cyano manganese dicarbonyl are prepared in a manner similar to that employed in the above example. Example X] To 10 parts of benzene cyanomanganese dicarbonyl is added 5 parts of ethylene dichloride and the mixture agi tated until a homogeneous ?uid results. The manganese to chloride atom ratio in this ?uid is 1:12 and represents 6 theories of halogen based on the manganese. This ?uid ample, lead dihalide and manganese dihalide. In other 75 is added to hydrocarbon fuels in amounts so as to pro 3,042,693 ‘from 0.01 to'0.05 percent of manganese as a compound vide improved‘fuels containing 0.015 gram, 0.03 grain, 16 grams and 10“ grams of manganese per gallon. of this invention is bene?cially employed as a dryer in such Example XII a composition. a ' » ' For example, to a typical varnish composition contain . To 13.2 parts of ‘lead in the form of tetraethyllead ‘ of ing .100‘ parts ester gum, 173 parts, of tung oil, ‘23 parts of linseed oil and 275 parts of white ‘petroleum naphtha in an antiknock ?uid containing 0.5 theory of bromine is added 3.0 parts of mesitylene cyanomanganese dicar as ethylene dibromide and 1.0 theory of chlorine as bonyl. The resulting varnish composition is found to ethylene dichloride, wherein the theories of halogen are have excellent drying characteristics. Equallygood re based upon the amount of lead present, is added 0.015 apart of manganese in the form of mesitylene cyano-man 10 sults are obtained when other drying oil compositions and other aromatic cyanornanganese dicarbonyl com ganese dicarbonyl. _ pounds of this invention are employed. This fluid is then added to a commercial hydrocarbon Other important usesof the aromatic cyanoman-ganese fuel having an initial boiling point of 82° F. and a ?nal dicarbonyl compounds of'the present invention include boiling point of 420° F. in an amount so as to provide 13.2 ‘grams of lead and 0.015 gram of manganese per 15 the use thereof as chemical intermediates, particularly in gallon. . V ' V ' . the preparation of 'metal and metalloid containing poly 7 meric materials. In addition, some of the aromatic de rivatives of this invention can be used in the manufacture Example XIII To a fuel containing 0.02 gram of lead per gallon as . of medicinals and other therapeutic materials, as 'well as 7 diphenyldiethyllead, 1.0 theory of bromine as ethylene di agricultural chemicals such as, for example, fungicides, bromide, ‘and 0.2 theory of phosphorus in the form of tri cresyl phosphate, is added mesitylene cyanomanganese defoliants, growth regulants, and so on. Having fully described the'novel compounds of the present invention, the need therefor, and the bestjmethods 'dicarbonyl in an amount equivalent to v0.03 gram of man ganese per gallon. This small’ amount of manganese in devised for their preparation, We do not intend that our the, form of the compounds of this invention provides invention be limited except within the spirit and scope of 25 aconsiderable increase in the'antiknock quality of the the appened claims, ' .fuel as shown upon testing in a single-cylinder engine. Other‘fuels and ?uids areprepared in thersame man 'her as illustrated hereinabove which contain other deposit ,rnodifying agents, such as boric acid, borate esters, boronic ‘We claim: a 1. A compound having an aromatic hydrocarbon mole cule coordinated with manganese, the compound being by additional coordination with two carbonyl esters, etc. Likewise, lubricating oils containingrfrom 30 stabilized groups and a cyano group, the aromatic hydrocarbon about 0.1 to about 5 weight percent manganese in the molecule contributing six electrons, thecarbonyl groups form of the aromatic cyanomanganese dicarbonyl com each contributing two electrons and the cyano group con pounds of this invenion are prepared, and these lubricat ing oils, when used in reciprocating engines, are found to have a bene?cial effect on engine cleanliness and in the reduction of combustion chamber deposits. ~ tributing one electron to the manganese, thereby giving “ the manganese a total of eleven additional electrons and resulting in the manganese atom having the electron con 7 The fuels to which the antiknock compositions of this invention are-added may have a wide variation of com positions. These fuels generally are petroleum ‘hydro carbons and are usually blends of two'or more compo ?guration of krypton. 2.. The process for producing compounds having an aromatic hydrocarbon molecule coordinated with man 40 ganese, the compound being stabilized by additional co ordination with two carbonyl groups and a cyano group, nents. These fuels can'contain all types of hydrocar the aromatic hydrocarbon molecule contributing six elec trons, the carbonyl groups each contributing two electrons bons, including para?ins, both straight and branched chain; ole?ns; cycloaliphatics containing para?in or. ole ?n side chains; and aromatics containing aliphaticrside and the cyano group contributing one electron to the man ganese, thereby giving the manganese a total of eleven additional electrons and resulting in the manganese atom chains. The fueltype depends on the base stock'from which it is obtained and on the method of re?ning. For having the’ electron con?guration of krypton, comprising decarbonylating an aromatic hydrocarbon manganese tri carbonyl cyanide by heating to a temperature of 20 example, it can be a straight run or processed hydrocar bons, including thermally cracked, catalytically cracked, reformed fractions, etc. When used for spark-?red en- '50 gines, the boiling range of the components of gasoline can vary’ from zero to about 430‘* F.,,althoughr the boiling 300° C. range of the fuel blend is often found to be between an initial boiling point'of from about 80° F. to 100° F. r and a ?nal boiling point of about 430° F. While'the 55 t (1) the compound produced is'mesitylene'zcyanoman i rlganese dicarbonyl; and V (2) ,Thearomatic hydrocarbon manganese tricarbonyl above is true for ordinary gasoline, the boiling range is cyanide reactant is mesitylene manganese tricarbonyl a little more-restricted in the case of aviation gasoline. cyanide. Speci?cations forvthe latter often call for a boiling range of from about 82° F, to about 338° F., with certain frac tions of the fuel boiling away atrlparticular intermediate 60 The'amount of manganese that can be employed in the 7 ' temperatures. a 3. Mesitylene cyanomanganese dicarbonyl. 4. The process of claim 2 wherein: ' i 7 *References Cited in the ?le of this patent UNITED STATES PATENTS ~ 2,818,416 7 form of aromatic cyanomanganese dicarbonyl compounds Brown et al _________ __‘.._ Dec. 31, 1958 of this invention in hydrocarbon fuels of the gasoline OTHER REFERENCES boiling range can vary from. about 0.015 to about 1.0 :grams of manganese per gallon, preferably 0.03 to v6 grams of manganese per gallon. In addition, the fuel can also contain organolead antiknock agents such as tetra vol. 1, pp.‘ 165-174 '(pp. 167-168 relied on). Brook: I.A.C.S. 77, 4827-4829 (1955). Fischer: “Chemistry and Industry,” pp. 153-154, Mar. ethyllead in amount equivalent to from about‘ 0.02 to 3, 1956. about 13.2 grams of lead per gallon; , 7 _ V _ I The aromatic cyanomanganese dicar-bonyl compounds 70 Piper et al.: .1. Inorganic and Nuclear Chem, 1955, Fischer et al.: “Berichte” 89, 2397-2400, Oct. 3, 1956. Nicholls et al.: “Proceedings of The Chemical Society of this invention may be incorporated in paints, varnish, printing inks, synthetic‘ resins of the drying oil type, oil (London), p. 152, May 1958. enamels and the like, to impart excellent drying char 104-124 (1956). acteristics to such compositions. Generally speaking, ' ' Piper et al.: “J. Inorg. Nuclear Chem.,” vol. 3, pp. ' .