DE1263735B - Process for the production of araliphatic hydrocarbons with a saturated aliphatic radical - Google Patents

Description

Process for the production of araliphatic hydrocarbons with saturated aliphatic residue According to the procedure of the older German patents 1196 186 and 1 201 328 result in mixed oligomers of 1,3-dienes and vinylaromatic ones Compounds by reacting these substances in the presence of compounds of metals of the VIII group of the Periodic Table of the Elements, in which these metals are in zero-valent Form.

It is known to use compounds with olefinic double bonds in Presence of catalysts containing metals of Group VIII of the Periodic Table of the Elements contain to hydrogenate.

It has now been found. that one araliphatic in an advantageous manner Hydrocarbons with a saturated aliphatic radical from the hydrogenation of araliphatic ones Hydrocarbons with an unsaturated aliphatic radical in the presence of catalysts which contain metals from Group VIII of the Periodic Table of the Elements, when using mixed oligomers consisting of 1,3-dienes and vinyl aromatic hydrocarbons according to the processes of German patents 1196 186 and 1 201 328 are without separation of the catalyst used for the mixed oligomerization treated with hydrogen at temperatures from 0 to 250 "C and pressures from 1 to 300Atm.

Suitable 1,3-dienes are, for example, conjugated unsaturated open-chain ones Hydrocarbons with 4 to 7 carbon atoms, such as butadiene, isoprene, 2,3-dimethylbutadiene - (1,3), pentadiene - (1,3) and hexadiene (2,4). Of the vinyl aromatic hydrocarbons those having a benzene nucleus containing 8 to 15 carbon atoms are preferred contain. Such compounds are, for example, styrene, <i-methylstyrene, 2-methylstyrene, 4-ethylstyrene and propenylbenzene.

The starting materials mentioned are advantageous in such amounts uses 1 to 2 vinyl aromatic hydrocarbons and 1 to 3 1,3-dienes come together to form a mixed oligomer.

Of the compounds of the metals of the Vl l l. Group of the periodic table of the elements in which the metal is zero-valued are classified according to the German U.S. Patent 1,201,328, those of the iron group and in particular those of nickel preferred. Suitable compounds are, for example, metal carbonyl, such as iron pentacarbonyl, Nickel tetracarbonyl and dicobalt octacarbonyl. Also metal carbonyl compounds, which additionally contain hydrogen can be used for the process. Such Substances are z. B. K obaltearbonylwasserstoff and Eisenearbonylwasserstoff Furthermore Carbonyl compounds are suitable in which the carbon monoxide in whole or in part way is replaced by isonitriles or amines. Such connections include: Nickel (0) -tetraphenylisonitrile, nickel (0) -tetra-p-bromophenyl-isonitrile, nickel (0) - monocarbonyl - tri - methylisonitrile, nickel (0) - dicarbonyl - 2,2 - dipyridyl, Nickel (0) - dicarbonyl - 0 - phenanthroline, Di - nickel (0) - tricarbonyldipyridine, Di - nickel (0) - tetracarbonyl - tri - pyridine and compounds of the general Formula [Ni (B) "] [Ni4 (Cob] in which B stands for pyridine, morpholine or piperidine and in which n is an integer from 2 to 6.

Nickel (0) compounds, the unsaturated ones, are particularly suitable Contain hydrocarbons as ligands, such as nickel (0) - bis - cyclooctadiene - (1,5), nickel (0) -cyclododecatriene- (1,5,9) and nickel (0) -diallyl.

Catalysts for the production of the mixed oligomers are also used the known compounds of zero-valent nickel with compounds that activated one Contain double bond, into consideration. Of these nickel (0) compounds, let nickel (0) - bis - acrolein, nickel (0) - bis - acrylonitrile, nickel (0) - bis - acrylonitrile - dipyridyl, bis - triphenyl phosphite - nickel (0) - acrylonitrile, nickel (0) - bisfumaronitrile and nickel (0) -bis-cinnamonitrile mentioned.

Also compounds of transition metals of the full. Group of the periodic table, which have aromatic ligands. can be used. Such connections have z. B. the formula Ni Ar2 (AlCl) "in which Ar is an aromatic hydrocarbon means and n can assume values between 3 and 5.

(Suitable compounds of cobalt and iron as well as the other metals of Group VIII are among others: Co2-Ar4 7 7 AICI3 Ar2 Rh (AICI3) Ar2 Fe (AICI3) Rh2 (CO) B and Ru (CO) 5. In the formulas, Ar means an aromatic hydrocarbon as above.

Others suitable according to the method of German patent 1196 186 Catalysts have the formula (R3 P) XNi (CO) 4-X in which R is optionally above an organic radical bonded to an oxygen atom, in particular an alkyl, alkoxy, Denotes aryl or aryloxy radical, while x stands for 1, 2, 3 or 4. Such Connections are e.g. B. bis-triphenylphosphite nickel dicarbonyl, bis-triäthylphosphit-nickel dicarbonyl, Bistriphenylphosphine nickel dicarbonyl and tris triphenylphosphite nickel carbogyl. Such compounds are obtained by reacting nickel carbonyl with phosphines or esters of phosphorous acid.

Other suitable starting catalysts are carbonyl-free and have the general Formula [Ni.t P (ORb}) Zy1] where R denotes an alkyl, aryl or haloaryl radical, Z denotes the remainder of an a, fl-ethylenically unsaturated aldehyde or nitrile, x can be 2 or 3 and y 1 or 2, where the sum of x and y - 1 2 or 3 is. Such connections are made by converting connections of the zero-valued Nickel with u, ii-unsaturated aldehydes or nitriles with esters of phosphorous Acid obtained.

In some cases, following the procedure of the German patent 1 201 328 the catalysts by a pretreatment with organometallic Compounds, especially with organoaluminum compounds, such as aluminum triethyl or diethyl aluminum chloride.

The organometallic activator is advantageously used in amounts of 10 to 1000 percent by weight, based on the catalyst. A sharing of substances that form complexes with these organometallic activators acts often have a beneficial effect on the performance of the catalyst. Such substances are z. B. ethers, amines, alkali metal halides and sulfoxides. May be mentioned in detail Diethyl ether. Tetrahydrofuran, triethylamine, - phenyl-, 8-napthylamine, sodium chloride, Sodium hydride, potassium chloride, dimethyl sulfoxide. These complexing agents are used advantageously in 0.1 to times the amount, based on the organometallic activator, at. Another way of activating the catalysts is pretreatment with olefins, polyolefins or acetylene derivatives, for example at 50 to 120 "C can be made. Suitable Substances of this type are styrene, cyclooctadiene, Cyclododecatriene (1,5,9), butadiene, acetylene, phenylacetylene and tolane. It is also possible the catalyst both by adding an organometallic compound as well as in the way described last. You can also do the pre-treatment connect with the mixed oligomerization, by already during the action of the metal alkyl or the olefin, polyolefin or the acetylene compound on the The catalyst feeds the monomers to be converted or the activators at the beginning of the Mixed oligomerization admits.

According to the method of the German patent 1196 186 one does not need of the mentioned catalytically active compounds of the metals of Group VIII to go out with zero-valent metal itself, but can use it in an appropriate manner, z. B. by reducing compounds of the metals mentioned, in which these in their usual valence level (i.e. usually bivalent or trivalent are), and without separation from the reaction mixture as a catalyst use. An iron or cobalt compound is advantageously used in this procedure and in particular from nickel compounds in which the metals mentioned are two-or are trivalent. It is preferred to use inorganic or organic salts or Chelate complexes in which the metals are bound to organic residues. Suitable Connections of this type are e.g. B.

Nickel chloride, nickel cyanide, nickel bromide, nickel iodide, nickel carbonate, Nickel formate, nickel acetate, nickel oxalate, nickel benzoate, nickel sulfate, nickel nitrate, Nickel acetylacetonate, nickel acetoacetate, nickel benzoylacetonate, nickel dimethylglyoxime, Iron (II) chloride, iron (III) chloride, iron (III) bromide, iron (111) nitrate, iron (II) sulfate, Iron (III) sulfate, iron (II) acetate, iron (III) acetylacetonate, iron (III) benzoylacetonate, Cobalt (II) chloride, cobalt (II) bromide, cobalt (II) iodide, cobalt (II) carbonate, cobalt (II) sulfate, Cobalt (II) phosphate, neutral and basic cobalt (II) acetate, cobalt (II) propionate, Cobalt (II) naphthenate, cobalt (II) stearate, cobalt (II) phthalate, cobalt (II) benzoate, Cobalt (II) xanthate, cobalt (lI) dithiocarbamate, cobalt (II) citrate, cobalt (III) acetylacetonate, Cobalt (II) acetylacetonate, cobalt (III) acetoacetic ester. Other suitable metal compounds are z. B. Nickel (II) oxide, nickel (II) hydroxide, nickel (III) hydroxide, nickel sulfide, FeCl2 (CH2 = CHCN) 6.

FeCl3 (C6H ^) 2S, FeCl3 (pyridine) 4, ClCl2 (pyridine) 2, CoCl2 (dioxane, Oxalato-chloro-tetrammine-cobalt (III), triethylenediamine-cobalt (III) chloride, cobalt dinitrosyl chloride. But also non-salty iron or cobalt compounds, such as iron (III) oxide, Iron (III) hydroxide, iron (II) sulfide, cobalt (II) sulfide and cobalt (III) sulfide ("Aged cobalt sulfide") can be used.

The metal compounds mentioned must now be used to produce the catalysts be reduced. Compounds of are primarily suitable as reducing agents Elements of the Ia-, IIa-, IIb-. Mlb and IVb groups of the Periodic Table of the Elements, the at least one hydrogen atom bonded to the element and / or one contain organic radical bonded via a carbon atom. Others well suited Reducing agents are metals of the 1 IIa, IIIa, IIb and Ilib groups of the periodic table of the elements. The name of the groups in the periodic table refers to that so-called long-period system of elements (cf. H o 11 e -m a n W i b e r g, "Textbook of Inorganic Chemistry", 28th and 29th edition, p. 428).

Of the organometallic compounds or hydrides mentioned - if only for reasons of accessibility - those of lithium, sodium, potassium, Magnesium, calcium, zinc, boron and aluminum are preferred. Suitable connections include: lithium hydride, sodium hydride, calcium hydride, aluminum hydride, Phenyl sodium, phenyllithium, tert-butyllithium, benzyl potassium, phenyl magnesium bromide, Ethyl magnesium chloride, diethyl magnesium, diethyl zinc, diethyl cadmium, triethyl aluminum, Triphenyl aluminum. Triisobutyl aluminum. Diisobutylaluminum hydride, diethylaluminumhe drid, diethyl aluminum chloride, ethyl aluminum sesquichloride, phenyl aluminum sesquichloride, Ethyl aluminum dibromide, ethyl aluminum dichloride, diethyl ethoxy aluminum, beryllium diethyl, Diborane, Vriäthylbor and Tetraäthyldiboran. It is also possible to use complex compounds to use that contain several of the metals mentioned, e.g. B. one of the 1 and one of the III b group. Such compounds are for example: lithium alanate, Sodium ethyl ethoxyalanate and lithium boranate. You get the best results with those compounds which allow the catalyst to be prepared in a homogeneous phase. It is Z. B. more advantageous to use aluminum triethyl than lithium hydride.

The preferred metals used as reducing agents are lithium, sodium, potassium, magnesium, calcium, zinc, aluminum and cerium. The metals are expediently used in a form that is not too compact, e.g. Am Form of metal powder or grits with a grain size knife between about 0.01 and 2 mm. The compound of a metal of Group VIII to be reduced is used of the periodic table and the reducing agent expediently in amounts corresponding to a ratio Oxidation equivalents of the metal compound to reducing equivalents of the reducing agent from 1: 0.1 to 1:10.

The reduction of the metal compound is carried out in the presence of electron donors performed.

These are substances that have lone pairs of electrons. By choosing the additives, the competitive reaction of mixed oligomerization, namely the homooligomerization of 1,3-diene. be strongly pushed back. Suitable Additives with lone pairs of electrons are e.g. B. tertiary amines, phosphines, Phosphine oxides, phosphorous acid esters, thiophosphorous acid esters, substituted Phosphorous acid triamides, ethers, arsines, stibines. Of the appropriate additives are for example: triphenylamine, triethylamine, triethylphosphine, tributylphosphine, Triphenylphosphine, tri- (o-tolyl) -phosphine, diethoxyphenylphosphine, diphenylphosphine, Tri-a-naphthylphosphine, tris-trimethylphenylphosphine, triphenylphosphite, tri- (o-tolyl) -phosphite, Triethyl phosphite, tri-a-naphthyl phosphite, phosphorous acid trimorpholide, triphenyl thiophosphite, Tritolylthiophosphite, tri-o-methoxyphenylphosphine, tri-o-methoxyphenylphosphite, Triphenylphosphine oxide, phosphorous acid tri-N-methylanilide, tri-p-nitrophenyl phosphite, Triethylarsine, tribenzylarsine, tributylarsine, triphenylarsine, tri- (o-tolyl) -arsine, Phenyl diethoxyarsine, phenyldimethoxyarsine, tripropylstibine, tri- (o-tolyl) - stibine, Tribenzylstibine, triphenylstibine, bismuth triethyl, bismuth triphenyl, bismuth tri-o-tolyl. If necessary, one uses the electron donor in the 0.01 to 4 times molar Amount, preferably in 0.1 to 2 times the amount, based on the nickel compound.

Particularly effective catalysts for the first and also for the second stage of the process are those that can be achieved by reducing the mentioned Metal compounds in the presence of olefins, especially polyenes, and or or acetylene compounds. For example, one can be in the presence of the person 1,3-diene or in the presence of that vinyl-substituted aromatic hydrocarbon work that is to be mixed oligomerized. It is also possible to use the Make reduction in the presence of both starting materials. Other suitable olefins and acetylene compounds are e.g. B. cyclododecatriene (1,5,9), cyclooctadiene (1,5), 3,3-dimethylpentadiene- (1,4), isobutene, methylacetylene. Dimethylacetylene, phenylacetylene and - diphenylacetylene. The olefin or the acetylene compound is advantageously used in double or a larger molar amount, based on the amount to be reduced Compound of a metal of group VIII of the periodic table.

The aforementioned preparation of the catalyst by reducing a compound of a metal of Group VIII of the Periodic Table is preferably in a solvent carried out. For example, one can use the vinyl substituted aromatic compound or use the aforementioned olefin or the acetylene compound as a solvent. However, other solvents which are inert under the reaction conditions can also be used be e.g. B. hexane, heptane, cyclohexane, cyclohexene, benzene, ethylbenzene, octane, Chlorobenzene, cyclooctane, between 50 and 200-C boiling hydrocarbons from petroleum.

In some cases ethers such as diethyl ether, diisopropyl ether, Tetrahydrofuran, tetrahydropyran and dioxane. suitable solvents. Of course Mixtures of the solvents mentioned can also be used. One uses the solvent expediently in 10 to 100 times the amount, based on the compound a metal of group VIII of the periodic table. For the manufacture of the catalyst one gives the compound of a metal of the VI II group of the periodic table, the Reducing agent, expediently a compound with lone pairs of electrons Olefin or an acetylene compound and optionally a solvent together. The temperature at which the reduction is carried out is advantageously between 0 and 250 C, especially between 40 and 150 C.

If the reducing agent is a metal or not in the reaction mixture Is readily soluble, like lithium hydride, it is recommended for thorough mixing to ensure, for example, by stirring in a stirred vessel with an effective stirrer or works in a ball mill. One can also separate from undissolved parts and so wins a solution that the.

Contains catalyst. The electron donor can be used if desired add to the finished catalyst solution. But it is also possible to use the electron donor to be added before or during the reduction.

The catalysts are made according to the method of the German patent 1,201,328 expediently in quantities from 0.01 to 10 percent by weight, based on the monomers to be reacted, applied. The reaction can be Stir successfully with other amounts of catalyst. One works well at temperatures between 0 and 2500 C, in particular between 40 and 1500 C. The The process is generally carried out under atmospheric pressure, but one can also apply increased or decreased pressure. Increased pressure comes especially in question when volatile starting materials are to be converted. It it is advisable to use oxygen and atmospheric humidity during the reaction an inert gas such as nitrogen, carbon monoxide or argon.

You can start the first step of the present process after German Patent 1 201 328 perform in the absence of solvents. It is but also possible to use inert solvents. Suitable inert solvents are e.g.

Ethers, alcohols, aromatic and aliphatic chlorinated hydrocarbons and especially aliphatic, cycloaliphatic and aromatic hydrocarbons. Of the suitable solvents, the following may be mentioned in detail: hexane, heptane, cyclooctane, Benzene, ethylbenzene, toluene, chlorobenzene. Hydrocarbons boiling between 50 and 3000 ° C from petroleum, diethyl ether, tetrahydrofuran, dioxane, 2-sithylhexanol and ethanol.

One can take the first step of the procedure according to the German patent specification 1 201 328 carry out discontinuously so that you get the mixture of the starting materials and the catalyst for some time, for example 5 minutes to a few hours, heated to the reaction temperature. One can also work continuously by the mixture of starting materials and the catalyst are continuously passed through heated pipe leads.

Claims (1)

This according to the method of German patents 1196 186 and 1 201 328 reaction mixture obtained is then treated in a second process step, optionally after removing unreacted vinyl aromatic compounds and of oligomers of 1,3-dienes, without separation of the catalyst with hydrogen. Expediently, temperatures between 0 and 250 ° C., preferably between 0, are used and 100 ° C, and works advantageously at pressures between 1 and 300 atmospheres, especially between 1 and 50 atmospheres. The hydrogenation increases, depending on the temperature and the amount of the catalyst, generally from 30 to 300 minutes. the end The araliphatic which are saturated in the aliphatic part are then obtained from the hydrogenation mixture Hydrocarbons by distillation. It is known that nickel (0) compounds of the type such as they can be used as catalysts in the first step of the process, decompose when exposed to hydrogen with the deposition of metallic nickel (G. W j I k e, E. M ü I I e r and M. K r ö n e r, »Angewandte Chemie«, 73rd year, 1961, No. 1, p. 33). Finely divided metals of the iron group of the periodic table are Again, as is known, suitable catalysts stir the hydrogenation of olefinic Double bonds. It is noteworthy, however, that the method according to the I found higher bulges in araliphatic hydrocarbons with saddled aliphatic The remainder is obtained than with the yields of araliphatic hydrocarbons unsaturated aliphatic radical that can be obtained without the action of hydrogen on the The first stage conversion mixture received should be expected. Maybe that is due to the fact that higher molecular weight under the hydrogenation conditions after working up the mixtures without hydrogenation, secondary products can no longer be distilled cleaved again into the mixed oligomers and these are then hydrogenated. The araliphatic hydrocarbons obtainable by the process with saturated aliphatic radicals are valuable intermediates for further reactions. For example, 1-phenyl-n-decane can be used as a high-boiling solvent and as a starting material use for the manufacture of detergents. For example, the alkali salts of the sulfonic acid are l-phenyl-n-decane low-foaming detergents that can be biodegraded. The parts mentioned in the following examples are parts by weight. Example 1 A stirred vessel is made under an inert gas atmosphere with 270 parts Styrene, 10 parts of butadiene, 2.6 parts of nickel acetylacetonate and 3.86 parts of triethylaluminum loaded. Butadiene is passed in and the mixture is heated to 95.degree. Within 200 parts of butadiene are taken up for 2 hours. Of this, 108 parts will not converted styrene and 25 parts of butadiene oligomers are distilled off from the reaction mixture. (Kp.lo 32 ° C to Kp ,, 100 ° C.) The residue is passed as much at 900C Hydrogen to how is absorbed. This is obtained in the subsequent distillation 320 parts of 1-phenyl-n-decane with a boiling point of "115" C, a hydrogenation iodine number (Pt) of 350 and a molecular weight 216. In addition, 15 parts become high-boiling products and 17 parts cannot be distilled Obtain residue. The yield of 1-phenyl-n-decane, based on butadiene, is 79% the theory. If the reaction mixture is distilled without treatment with hydrogen, 1-phenyl-n-decatriene is only obtained in a yield of 70% of theory, based on butadiene. Example 2 The procedure is as described in Example I, but leads Immediately after the butadiene feed has ended, hydrogen is introduced into the reaction mixture. at the work-up gives 480 parts of liquid distillable products and 10 parts solid undistillable residue. The liquid part consists according to gas chromatography Analysis from 1.2 percent by weight cyclooctane, 20.8 percent by weight ethylbenzene, 5.6 Percent by weight cyclododecane, 68.5 percent by weight l-phenyl-n-decane and 4.9 percent by weight of unknown substances. Claim: Process for the production of aromatic hydrocarbons with a saturated aliphatic radical by hydrogenation of araliphatic hydrocarbons with unsaturated aliphatic radical in the presence of catalysts, the Mctallc the VIII. Group of the Periodic Table of the Elements, marked thereby e t that one mixed oligomers produced according to the method of German patents 1196 186 and 1,201,328 made from 1,3-dienes and vinyl aromatic hydrocarbons without separation of the catalyst used for the mixed oligomerization with hydrogen Temperatures from 0 to 250 "C and pressures from 1 to 300 atmospheres treated. Publications considered: Angewandte Chemie, 73rd year, 1961, p. 33. Older Patents Considered: German Patents No. 1196 186, 1 201 328.