United States Patent Office Patented Apr

3,377,397 United States Patent Office Patented Apr. 9, 968 2 3,377,397 Syliron halides are considered to be monomeric having DMERIZATION OF DOLEFENS but one atom of iron per molecule. Perry L. Maxfield, Bartlesville, Okla., assignor to Phillips For example, iron dicarbonyl dinitrosyl can be reacted Petroleum Company, a corporation of Delaware with a halogen to form the dinitrosyliron halide as dis No Drawing. Filed Oct. 22, 1965, Ser. No. 502,481 cussed in Chemical Abstracts, volume 27, 2646, (1933). 15 Claims. (Cl. 260-666) The iron dicarbonyl dinitrosyl can be formed by reacting iron pentacarbonyl with nitric oxide as disclosed in Chemistry of Organic Compounds by Carl R. Noller, ABSTRACT OF THE DISCLOSURE second edition, p. 905, W. B. Saunders Company, (1957). Diolefin such as butadiene is dimerized using a dini 10 The reducing agents of this invention are conventional trosile halide, an organometallic reducing agent, such as and well known materials which are available commer a Grignard reagent, and organo non-metal. cially and therefore will not be described in detail. Some examples of reducing agents that can be em ployed in the catalyst system include This invention relates to dimerization methods and catalysts for effecting dimerization. methylmagnesium chloride, Heretofore, conjugated dienes have been dimerized by ethylmagnesium bromide, thermal, non-catalytic techniques. However, these tech n-butylmagnesium iodide, niques have yielded besides the desired dimer a wide allylmagnesium bromide, variety of by-products and other polymers which sub 20 phenylmagnesium chloride, stantially reduce the ultimate yields of the desired dimer. p-tolylmagnesium iodide, Quite surprisingly, it has now been found that butadi cyclohexylmagnesium bromide, ene, isoprene, and mixtures of these dienes can be dimer n-dodecylmagnesium iodide, ized in substantial quantities under mild dimerization con o-naphthylmagnesium chloride, ditions by contacting same with a catalyst formed on cyclooctylmagnesium chloride, mixing a dinitrosyliron halide, a reducing agent as here cyclooctylmagnesium bromide, inafter defined, and a third component as hereinafter de 4-phenylcyclohexylmagnesium iodide, fined. ethyllithium, The catalyst of this invention is that formed upon mix n-butyllithium, ing dinitrosyliron halide with a reducing agent and said 30 n-amyllithium, third material. n-dodecyllithium, Accordingly, it is an object of this invention to provide phenylpotassium, a new and improved method for dimerizing conjugated cyclohexyllithium, dienes. It is another object of this invention to provide a n-octylcesium, new and improved catalyst useful for dimerization of n-dodecylrubidium, conjugated dienes. benzylsodium, According to this invention, butadiene, isoprene and allylsodium, mixtures thereof are dimerized with a catalyst formed on diethylzinc, admixing a dinitrosyliron halide wherein the halogen is dialyzinc, preferably one of chlorine, bromine, and iodine, with a 40 dicycloheptylzinc, reducing agent selected from the group consisting of diphenylzinc, Grignard reagents having the formula RMgX, organo di-n-butylcadmium, alkali metals having the formula RM, zinc and cadmium diallylcadmium, organometals of the type (R)Zn and (R):Cd, and or dicyclooctylcadmium, ganoaluminum compounds having the formulas (R)2AlOR dibenzylcadmium, and R3Al, preferred are RMgX and RM, in the presence dimethylmethoxyaluminum, of a third component selected from the group consisting diethylethoxyaluminum, of acyclic and cyclic ethers having from 2 to 8 carbon diallylpropoxyaluminum, atoms per molecule, stibines of the formula (R) Sb, diphenylphenoxyaluminum, arsines of the formula (R)8As, phosphines of the formu diethylcyclohexoxyaluminum, la (R)3P, phosphine oxides of the formula (R)3P=O, di-n-dodecylethoxyaluminum, sulfides of the formula (R)2S, heterocyclic nitrogen com dicyclohexylphenoxyaluminum, pounds having from 4 to 10 carbon atoms per molecule triethylaluminum, and heterocyclic sulfide compounds having 3 to 8 carbon tricyclopentylaluminum, atoms per molecule, preferably the ethers, stibines, triphenylaluminum, arsines, sulfides, heterocyclic nitrogen compounds, and triallylaluminum, and the like. heterocyclic sulfide compounds, wherein each R contains The ethers according to this invention can be either from 1 to 12, preferably 1 to 7, carbon atoms and is at cyclic or acyclic ethers and include such materials as least one radical selected from the group consisting of methyl ether, ethyl ether, methyl ethyl ether, n-butyl alkyl, alkenyl, aryl, cycloalkyl, and combinations there 60 ether, isopentyl ether, propyl hexyl ether, cyclohexyl of, preferably alkyl, alkenyl, and aryl, and wherein X is ether, cyclohexyl ethyl ether, allylether, phenylether, selected from the group consisting of chlorine, bromine, tetrahydrofuran, p-dioxane, and the like. and iodine, and wherein the alkali metal (M) is one Representative stibines include trimethylstibine, tri selected from the group consisting of lithium, sodium, ethylstibine, trihexylstibine, tri-n-dodecylstibine, triphen potassium, rubidium, and cesium, preferably lithium. ylstibine, diphenylethylstibine, tricyclohexylstibine, tri The dinitrosyliron halides of this invention have the allylstibine, triphenylstibine, and the like. formula Fe(NO)2X wherein X is the halide and can be Representative arsines include trimethylarsine, tri formed in any conventional manner. Some dinitrosyiron pentylarsine, tri-n-dodecylarsine, tri(p-tolyl)arsine, tri halides are believed to exist in dimeric and possibly other phenylarsine, tri-o-naphthylarsine, diphenylbutylarsine, polymeric forms. However, for purpose of this invention, 70 tricyclohexylarsine, tri(2-hexenyl)arsine, triallylarsine, particularly in regard to molar calculations, the dinitro and the like. 3,377,397 3 4. Representative phosphines include triethylphosphine, low as about 0.1:1 third component to reducing agent tri-n-butylphosphine, tridecylphosphine, triphenylphos ratio. Other compounds such as tetrahydrofuran and the phine, tri-6-naphthylphosphine, diphenylisopentylphos lower alkyl ethers can be used in much greater propor phine, triallylphosphine, tricyclohexylphosphine, and tions such that they may also serve as convenient diluents the like. 5 for the reactants. Representative phosphine oxides include triethylphos After the active catalyst is formed the conjugated diene phine oxide, tri-n-butylphosphine oxide, tri-n-decylphos can be dimerized in the presence of this catalyst at rela phosphine oxide, diphenylisopentylphosphine oxide, tri tively mild temperatures for dimerization purposes. Gen allylphosphine oxide, tricyclohexylphosphine oxide, and erally, the temperature for dimerization will be from the like. O about 0 to about 100 C. Higher temperatures can lead Representative sulfides include dimethyl sulfide, di-n- to the formation of Substantial amounts of higher molec butyl sulfide, di-n-dodecyl sulfide, dicyclohexyl sulfide, di ular weight polymers. The reaction time for the dimeriza phenyl sulfide, di-3-naphthyl sulfide, cyclohexyl ethyl sul tion process can vary widely but will generally be from fide, diallylsulfide, and the like. a few minutes, e.g. 3 minutes, to 24 hours or more. The Representative heterocyclic nitrogen compounds in- 3 conversion can be carried out in either the presence or clude pyridine, quinoline, quinaldine, and the like. The absence of an inert diluent, and cyclic and acyclic par heterocyclic nitrogen compounds employed can also con- affinic materials having up to about 20 carbon atoms per tain alkyl substituents. For example, 2-methyl-5-ethyl- molecule can be used for this purpose. Generally, the pyridine, and the like. reaction time is quite low since the catalysts of this inven Representative heterocyclic sulfide compounds include 20 tion are very active even at low temperatures. The dimer thiophene, benzothiophene, and the like. The heterocyclic ization can be carried out in a batch process or continuous sulfide compounds can also contain alkyl substituents. For process or even a Semi-continuous process wherein buta example, 2-methyl-5-butylthiophene, 2-isopropyl-3,4-di- diene is intermittently charged as needed to replace that methylthiophene, and the like. already dimerized. In forming he active catalyst the dinitrosyliron halide 25 At the end of the dimerization reaction, the dimer can is contacted with at least one of the above reducing agents be recovered by conventional methods well known in the in the presence of at least one of the above-described art such as fractional distillation, solvent extraction, ad third materials, the third material preferably being present Sorption techniques, and the like. before addition of the reducing agent. Other than this, It is important to note that this invention, unlike other any order of addition can be used. The catalyst compo- 30 catalytic butadiene oligomerization reactions, converts nents can also be combined, if desired, in the presence of butadiene substantially quantitatively to 4-vinylcyclohex the diene monomer. About 0.01 to about 10, preferably ene without the production of substantially any other about 1 to about 4, moles of reducing agent per mole products. In addition to the feature of very substantial of dinitrosyliron halide can be employed. Formation of ultimate yields of the dimer, high conversion and high the catalyst can be carried out in a reaction vessel under 35 productivity in pounds of product per pound of catalyst autogenous or higher pressures if desired and

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