KR20010103800A - Method for producing alkapolyenyl compounds using certain cocatalysts - Google Patents

Abstract

The process for preparing an alcapolyenyl compound by homogeneous catalytic reaction of 1-substituted alka-2,7-diene of formula (I) and / or 3-substituted alka-1,7-diene of formula (II) in the presence of a rhodium compound As cocatalyst, it is carried out using at least one mineral acid and / or at least one inorganic halide dissolved in the reaction mixture. The product of this method can be used as an intermediate in the preparation of surfactant materials.

Description

METHODS FOR PRODUCING ALKAPOLYENYL COMPOUNDS USING CERTAIN COCATALYSTS}

Long chain alcohols are the basic constituent of many surfactants. Suitable alcohols can be obtained industrially by various methods such as hydroformylation of long chain olefins, Ziegler alcohol synthesis or extraction from natural sources. A particularly inexpensive method is to prepare surfactant alcohols using butadiene or derivatives thereof as building blocks. For example, side chain or linear dodecanol can be obtained by appropriate reaction of dodecatrienyl ether or ester.

Synthesis of suitable polyenyl compounds is known. For example, GB-A-1316725 is a 1-substituted 2,7-octadiene (eg 1-acetoxy-2,7-octadiene, 1-methoxy-2,7-octadiene and 1-phenoxy Ci-2,7-octadiene) and 1,3-conjugated dienes (e.g., 1,3-butadiene and isoprene) are prepared by ethanol, acetic acid, acetone, benzene, methylene chloride, tetrahydrofuran, acetonitrile, dimethylformamide or In solvents such as dimethylacetamide, various rhodium compounds (eg, rhodium trichloride, rhodium tribromide, rhodium trinitrate, dirhodium tetraacetate, tetrakis (ethylene) dichlorodirhodium and bis (cycloocta-1,5-) Dienes) dichlorodirhodium) to various polymerization inhibitors (e.g. t-butylcatechol, phenothiazine, tetrabutoxytitanium and titanium tetrachloride) and also phosphorus-containing compounds (e.g. tri-n-butylphosphine, tricyclo Hexylphosphine, triphenylphosphine and triphenoxyphosphine) It discloses solidifying amount every ball.

Methods developed on the basis of these catalyst systems are known and offer suggestions for increasing catalyst activity.

According to Japanese Patent No. 77-38533, the catalytic activity can be increased, for example, by carrying out the reaction in the presence of hydrogen.

GB-A-2107700 proposes adding chromium halides to the reaction mixture. Addition of CrCl ₃ × 6H ₂ O initiates co-dimerization of 1-acetoxy-2,7-octadiene or 1-phenoxy-2,7-octadiene with 1,3-butadiene and rhodium catalyst. Apart from rhodium trichloride, bis (π-crotyl) tetrachloro (butadiene) dirhodium is used.

GB-A-2107701 is characterized by the addition of chromium compounds and also organic halides such as crotyl chloride or cinnamil chloride to 1-hydroxyalkoxy-2,7-octadiene or derivatives thereof (e.g. 1- (2'-hydride). Oxyethoxy) -2,7-octadiene, 1- (2'-acetoxyethoxy) -2,7-octadiene, 1- (2'-methoxyethoxy) -2,7-octadiene, 1- (3'-hydroxypropoxy) -2,7-octadiene or 1- (4'-hydroxybutoxy) -2,7-octadiene) and 1,3-butadiene It starts. GB-A-2108104 discloses 1-acyloxy-2,7-octadiene (eg 1-acetoxy-2,7-octadiene, 1-propionoxy-2,7-octadiene or 1-pivaloxy- Similar statements are made regarding the reaction of 2,7-octadiene) with 1,3-butadiene.

Most of the above are confirmed by Bochmann et al. In Journal of Molecular Catalysis, 22 (1984) 363-365 and Journal of Molecular Catalysis, 26 (1984) 79-88. It is reported that organic chlorides containing activated C-Cl bonds, in particular allyl chloride and hydrated chromium (III) chloride, accelerate the reaction of 1-acetoxy-2,7-octadiene with 1,3-butadiene. On the other hand, phosphines, amines, molecular nitrogen, water, ethanol and ionic chlorides (eg NMe ₄ ⁺ Cl ⁻ ) slow the reaction, which is why the efficacy of hydrated chromium trichloride is not understood. Moreover, the use of chromium compounds leads to heterogeneous systems in which the chromium compounds form a solid phase and the catalyst is dissolved in the liquid phase. This is important in process engineering.

However, organic halides which are generally soluble in the reaction medium and which are advantageous in this respect do not sufficiently increase the activity. In particular, when the alcapolyenyl ethers are reacted in view of economically important synthesis of dodecatrienyl ethers such as, for example, methoxydodecatenyl compounds.

The present invention relates to alcapoli by homogeneously catalyzed reaction of 1-substituted alka-2,7-dienes and / or 3-substituted alka-1,7-dienes with 1,3-conjugated dienes in the presence of a rhodium compound. A process for preparing a neyl compound, the use of mineral acids and organic halides as cocatalysts in this reaction, and the use of the products of the process in the preparation of surfactant materials.

The purpose of providing an advantageous method for the production of alcapolyenyl compounds by homogeneous catalytic reaction of substituted alkadienes with 1,3-conjugated dienes in the presence of rhodium compounds is surprisingly mineral acids and inorganic halides which can be dissolved in the reaction mixture. By using it is made according to the invention.

Accordingly, the present invention relates to the 1-substituted alkane-2,7-dienes of formula (I) and / or the 3-substituted alka-1,7-dienes of formula (II) in the presence of rhodium compounds. And a homogeneous catalytic reaction with an alcapolyenyl compound, wherein at least one mineral acid and / or at least one inorganic halide is dissolved in the reaction mixture.

Wherein R ¹ is hydrogen or C ₁ -C ₆ -alkyl, C ₅ -C ₈ -cycloalkyl, C ₁ -C ₆ -alkanoyl, C ₆ -C ₁₂ -aryl, C ₆ -C _12- Aryloil or C ₇ -C ₁₈ -aralkyl, which are unsubstituted or monosubstituted, disubstituted or substituted with hydroxy, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkanoyloxy and / or halogen, respectively May be substituted, and R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ -alkyl.

Wherein R ⁶ and R ⁷ are independently hydrogen or C ₁ -C ₆ -alkyl, and R ⁸ is hydrogen, C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl.

For the purposes of the present invention, homogeneous catalysis refers to the fact that catalyst components such as catalysts and cocatalysts do not form heterogeneous phases, in particular do not form solid phases under reaction conditions. They are generally present in the phase in which the reaction of the reactants in the reaction mixture takes place. The reaction mixture itself may consist of one or more phases. If the reaction mixture consists of a plurality of phases, the catalyst components and / or reactants may also be distributed in two, three or possibly more phases. In such a case, the reaction may occur in only one phase, two phases or possibly two or more phases.

In one embodiment of the invention, the reaction mixture consists of a single phase and this phase is a liquid. In an embodiment, the reaction mixture consists of a plurality of phases, which phases are liquid and / or gaseous. In a two-phase mixture, it is common for one phase to be liquid and the other to gas. In three phase mixtures, it is common for two phases to be liquid and one to gas, for example gaseous reactants (e.g. gas under reaction conditions) together with liquid / liquid mixtures such as reaction mixtures of organic liquids and aqueous liquids. A gaseous phase comprising a diene of formula III, eg butadiene) and / or a cocatalyst. Some of the components present in the gas phase are generally also present in solution in the liquid phase (s).

Mineral acids suitable for use in the process of the invention include, for example, hydrogen chloride, sulfuric acid, nitric acid, phosphoric acid, HBF ₄ , HPF ₆ and HSbF ₆ . Hydrogen chloride is preferred. The mineral acid can be dissolved in the reaction mixture by mixing the mineral acid itself or the mineral acid solution with the other components of the reaction mixture. If a mineral acid solution is used, an aqueous solution, in particular hydrochloric acid, is preferred.

Suitable inorganic halides include, for example, alkali metals, alkaline earth metals and transition metal chlorides and bromide, and also chlorides and bromide of group III, IV, V and VI elements. Halides found to be beneficial are halides that are sensitive to hydrolysis. That is, they react with water to form the corresponding hydrohalic acid. In this way, hydrohalic acid can be formed in situ. Chloride is generally preferred. Examples of suitable chlorides are ZrCl ₄ , SnCl ₄ , TiCl ₄ and in particular GeCl ₄ and WCl ₆ . Inorganic halides are generally solid or liquid. If they are solid, a suitable halide such as WCl ₆ is dissolved in the reaction mixture in sufficient amount. The halides can be mixed as such or in dissolved form with other components of the reaction mixture. If a solution is used, an aqueous solution is preferred.

Suitable amounts of dissolved mineral acids and / or dissolved inorganic halides range from 1 to 10 ⁵ moles, preferably 5 to 10 ³ moles per gram of rhodium. Based on the amount of alkadiene reacted, molar ratios of from 0.5 to 10 ⁻³ are generally preferred, except for dissolved mineral acids and / or dissolved inorganic halides. Thus, the cocatalyst used in accordance with the present invention should have a solubility of at least about 10 mg / l in the reaction mixture. A solubility of at least 50 mg / l is preferred, in particular at least 100 mg / l.

In certain embodiments of the invention, the reaction is carried out in the presence of further compounds known to have a beneficial effect on the type of reaction carried out according to the invention, in particular on the reaction rate and selectivity. Examples that may be mentioned in the present invention are hydrogen gases which are generally added at moderate pressures, preferably 5 to 20 bar. The addition of organic halides may also be beneficial. In the present invention, attention is paid to the organic halides disclosed in GB-A-2107701 and GB-A-2108104. Particularly suitable organic halides for the purposes of the present invention are benzotrichloride, allyl chloride, crotyl chloride, benzylidene chloride and cinnamil chloride. The amount of dissolved organic halide is generally the amount of the amount selected according to the invention relative to the amount of dissolved mineral acid and / or inorganic halide.

The reaction of the 1-substituted alka-2,7-dienes of formula I with 1,3-conjugated dienes of formula III is generally a mixture of linear and branched alcapolyenyl compounds, specifically compounds of formulas IVa, IVb and IVc. Create

Wherein R ¹ to R ⁸ are as defined above, and isomerization of the double bond can take place while the reaction is catalyzed according to the invention.

The ratio of Formula IVa compound to Formula IVb and / or IVc compound is referred to as the n / iso ratio. Mixtures obtainable by the process of the invention generally have an n / iso ratio of 0.2 to 2.5.

Reaction of the 3-substituted alka-1,7-dienes of formula II with 1,3-conjugated dienes of formula III generally also results in a complex mixture of linear and branched alcapolyenyl compounds.

C ₁ -C ₆ -alkyl is a linear or branched hydrocarbon radical having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, i-propyl n-butyl, sec-butyl, i-butyl, t- Butyl, n-pentyl, i-pentyl, neopentyl and n-hexyl. Preferred are C ₁ -C ₄ -alkyl groups, in particular methyl and ethyl.

C ₁ -C ₆ -alkoxy means C ₁ -C ₆ -alkyl-O—, wherein C ₁ -C ₆ -alkyl is as defined above.

Alkanoyl means C ₁ -C ₆ -alkyl-C (O) —, wherein C ₁ -C ₆ -alkyl is as defined above.

Alkanoyloxy means C ₁ -C ₆ -alkyl-C (O) O—, wherein C ₁ -C ₆ -alkyl is as defined above.

Halogen refers to, for example, fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.

C ₃ -C ₈ -cycloalkyl refers to cyclic hydrocarbon radicals having 3 to 8 carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

C ₆ -C ₁₂ -aryl refers to aromatic radicals having 6 to 12 carbon atoms, for example phenyl, naphthyl and biphenyl, with phenyl being preferred.

C ₆ -C ₁₂ -aryloil refers to C ₆ -C ₁₂ -aryl-C (O)-, wherein C ₆ -C ₁₂ -aryl is as defined above.

C ₇ -C ₁₈ -aralkyl refers to C ₆ -C ₁₂ -aryl-C ₁ -C ₆ -alkylene, wherein C ₆ -C ₁₂ -aryl is as defined above and C ₁ -C ₆ -alkyl The lene is derived from the aforementioned C ₁ -C ₆ -alkyl groups and is, for example, methylene, 1,1- or 1,2-ethylene, 1,1-, 1,2-, 1,3- or 2,2- Propylene. Benzyl is preferred.

Examples of hydroxy-substituted C ₁ -C ₆ -alkyl groups are hydroxymethyl, 2-hydroxyeth-1-yl, 3-hydroxyprop-1-yl, 4-hydroxybut-1-yl . Preference is given to 2-hydroxyeth-1-yl.

Examples of C ₁ -C ₆ -alkoxy-substituted C ₁ -C ₆ -alkyl groups are methoxymethyl, 2-methoxyeth-1-yl, 3-methoxyprop-1-yl, 4-methoxybut -1-yl.

C ₁ -C ₆ - alkanoyloxy-substituted C ₁ -C ₆ - Examples of alkyl groups include, but are acetoxymethyl, 2-acetoxy-eth- 1-yl, 3-acetoxy-prop-1-yl, 4-acetoxy Oxybut-1-yl.

Examples of halogen-substituted C ₁ -C ₆ -alkyl groups are trifluoromethyl and trichloromethyl.

C ₂ -C ₆ -alkenyl has 2 to 6 carbon atoms and the C ₂ -C ₆ -alkyl radicals defined above, such as prop-2-en-1-yl and but-3-en-1-yl Monounsaturated hydrocarbon radicals derived from

In certain embodiments of the invention, the reaction is for example an alkadienyl ether, such as 1-substituted alka-2,7-dienes of Formula I and / or 3-substituted alka-1,7-dienes of Formula II. Wherein R ¹ in the formula is C ₁ -C ₆ -alkyl, specifically methyl or ethyl, C ₃ -C ₈ -cycloalkyl, C ₆ -C ₁₂ -aryl, specifically phenyl, Or C ₇ -C ₁₈ -aralkyl, specifically benzyl, each of which is unsubstituted, hydroxy, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkanoyloxy, specifically acetoxy, and And / or mono-, di-, or tri-substituted by halogen.

In a particularly preferred embodiment, the reaction is 1-alkoxyalka-2,7-diene, in particular 1-methoxyalka-2,7-diene and / or 3-alkoxyalka-1,7-diene, specifically 3- It is carried out using methoxyalka-1,7-diene.

As an alternative, 1-hydroxyalkoxyalka-2,7-diene, specifically 1- (2'-hydroxyethoxy) alka-2,7-diene and / or 3-hydroxyalkoxyalka-1,7 Dienes, specifically 3- (2'-hydroxyethoxy) alka-1,7-dienes, may be reacted.

In further specific embodiments, the reaction is a compound of Formula I or II wherein 1-substituted octa-2,7-diene and / or 3-substituted octa-1,7-diene, ie, R ² to R ⁵ are hydrogen Is performed using

In certain preferred embodiments, 1-methoxyocta-2,7-diene and / or 3-methoxyocta-1,7-diene are reacted.

As an alternative, 1- (2'-hydroxyethoxy) octa-2,7-diene and / or 3- (2'-hydroxyethoxy) octa-1,7-diene can be reacted.

The aforementioned starting materials can be prepared by known methods ("Aspects of Homogeneous Catalysis", vol. 5, pp. 3-73, 1984, A. Behr and references cited therein). In principle, 1,3-conjugated dienes, for example compounds of formula III, are reacted with a suitable carboxylic acid or alcohol. If carboxylic acid is used, it produces an alka-2,7-diene-1-oleate ester and / or an alka-1,7-diene-3-oleate ester. If alcohol is used, alka-2,7-diene-1-oleate ether and / or alka-1,7-diene-3-oleate ether are obtained. Thus, a carboxylic acid such as acetic acid, propionic acid, butyric acid or benzoic acid is reacted with 1,3-butadiene to produce 1-acyloxyocta-2,7-diene and / or 3-acyloxyocta-1,7-diene Or by reacting an alcohol such as alkanol, phenol or benzyl alcohol, such as methanol, ethanol or ethylene glycol, with 1,3-butadiene to the corresponding 1-alkoxyocta-2,7-diene and / or 3-alkoxyocta-1 , 7-diene, 1-hydroxyalkoxyocta-2,7-diene and / or 3-hydroxyalkoxyocta-1,7-diene, 1-aryloxyocta-2,7-diene and / or 3-aryl It is possible to produce oxyocta-1,7-dienes or 1-aralkoxyocta-2,7-dienes and / or 3-arkoxyocta-1,7-dienes. Suitable catalysts for this type of reaction are, for example, catalysts based on palladium such as palladium acetate and phosphorus compounds such as triarylphosphine or triaryl phosphite (e.g. triphenylphosphine or tris (O-tolyl) phosphite). to be.

In certain embodiments of the invention, the reaction is carried out using a 1,3-conjugated diene of formula III wherein R ⁶ and R ⁷ are independently hydrogen or C ₁ -C ₆ -alkyl and R ⁸ is hydrogen . If R ⁶ and / or R ⁷ is C ₁ -C ₆ -alkyl, methyl is preferred.

In a preferred embodiment, R ⁶ and R ⁷ are hydrogen, R ⁸ is hydrogen, C ₁ -C ₆ -alkyl, specifically methyl, or C ₂ -C ₈ -alkenyl, specifically but-3-ene-1 -It's work.

1,3-conjugated diene isoprene, 2,3-dimethylbutadiene, piperylene, octa-1,3,7-triene, 2,6-dimethylocta-1,3,7-triene, 2,7-dimethyl Particular preference is given to the reaction of octa-1,3,7-triene and especially 1,3-butadiene.

The 1,3-conjugated diene reacted according to the present invention can be prepared or purchased by known methods.

The molar ratio of alkadiene to 1,3-conjugated diene used in the reaction of the present invention is generally in the range of about 1:10 to 10: 1, preferably 2: 1 to 1: 5, and 1: 1 to 1: 3 is particularly preferred. The alkadiene component may be a pure compound or may be a mixture of two or more compounds, in particular a mixture of 1-substituted alka-2,7-dienes and 3-substituted alka-2,7-dienes. Such mixtures are frequently obtained as reaction products in the preparation of these compounds. If a mixture is used, a mixture rich in 1-substituted alka-1,7-dienes is preferred. Mixtures containing at least 80%, preferably at least 95% of 1-substituted alka-2,7-dienes are advantageous. The 1,3-conjugated diene may also be a mixture of two or more compounds. However, essentially pure compounds are preferred, for example having a purity of at least 99% is preferred for synthetic purposes.

Suitable rhodium compounds include, for example, inorganic or organic rhodium salts and organic rhodium complexes. Inorganic salts are generally rhodium (III) salts containing conventional anions such as chlorine, bromine or nitrates. Organic salts are generally rhodium (III) salts containing conventional carboxylate anions such as acetate or acetylacetonate. Suitable complexes are in particular π-allyl complexes in which rhodium is in oxidation state III, for example tetrakis (π-allyl) dichlorodirhodium, tetrakis (ethylene) dichlorodirhodium and bis (cycloocta-1,5-diene Dichlorodirhodium. Particularly preferred is bis (π-crotyl) tetrachloro (butadiene) dirhodium of the formula

Chemical formula

The reaction of the present invention may be carried out in the presence of one or more rhodium compounds. The rhodium compound preferably uses rhodium in an amount of 10 ^-6 to 10 ^-1 gram atoms, preferably 10 ^-5 to 10 ^-3 gram atoms, and especially 2x10 ^-5 to 5x10 ^-4 gram atoms per mole of alkadiene. .

The process of the invention is generally carried out at 0 ° C to 250 ° C, preferably 60 ° C to 130 ° C in a suitable reactor such as an autoclave. In view of catalyst stability, it may be advantageous to work at relatively low temperatures, such as in the 60 ° C region. The reaction can also be carried out under superatmospheric pressure such as 5 to 20 bar, especially when gaseous components such as hydrogen are added to the reaction mixture.

Further embodiments may be derived by appropriate combination of the foregoing details and / or preferred embodiments.

The invention further provides for the use of mixtures of alcapolyenyl compounds obtainable by the process of the invention in the preparation of surface active substances such as surfactants and detergents. The product of the process obtained according to the invention acts as an intermediate, especially in the preparation of long chain fatty alcohols having 12 to 20 carbon atoms. In particular, these products are suitable for preparing side chain and / or linear dodecanols such as lauryl alcohol. For use as intermediates, these products can be used in the form in which they can be obtained by the process of the invention or in a form in which their capacity is improved by increasing the n / iso ratio. Water and / or low boiling by-products (eg, octatriene) present can be removed by distillation of the reaction product. If necessary, the catalyst can be returned to the reaction with the rest of the bottom.

The present invention further provides 1-substituted alka-2,7-dienes of formula I and / or 3-substituted alka-1,7-dienes of formula II and 1,3 of formula III, which are carried out in the presence of a rhodium compound. -The use of at least one mineral acid and / or at least one inorganic halide as a cocatalyst dissolved in the reaction mixture of a homogeneous catalytic reaction of conjugated diene, wherein R ¹ is hydrogen, or C ₁ -C ₆ -Alkyl, C ₅ -C ₈ -cycloalkyl, C ₁ -C ₆ -alkanoyl, C ₆ -C ₁₂ -aryl, C ₆ -C ₁₂ -aryloil or C ₇ -C ₁₈ -aralkyl, each of which is Unsubstituted or monosubstituted, disubstituted or trisubstituted by hydroxy, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkanoyloxy and / or halogen; R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ -alkyl, R ⁶ and R ⁷ are independently hydrogen or C ₁ -C ₆ -alkyl, R ⁸ is hydrogen, C _1- C ₆ -alkyl or C ₂ -C ₆ -alkenyl.

Formula I

Formula II

Formula III

In the present invention, the cocatalyst is a compound that has a beneficial effect on the catalytic activity of the rhodium catalyst in the homogeneous catalysis described above, for example increasing the reaction rate and / or selectivity. Preferred embodiments of this use according to the invention may be derived from the embodiments of the method of the invention described above.

The following examples illustrate the invention without limiting its scope.

A tempered glass autoclave (Comparative Examples and 1,2,5: 50 mL; Examples 3,4,6-8: 250 mL) was prepared with bis (π-crotyl) tetrachloro (butadiene) dirhodium (Rh complex). ), 1-methoxy-2,7-octadiene (MOOD), and, if appropriate, mineral acids, inorganic halides and / or organic halides (Example 4: 0.50 g of benzotrichloride). Butadiene was condensed at 0 ° C. The mixture was heated at 120 ° C. for 2 hours. The reaction mixture was then cooled and analyzed by gas chromatography using FID (column: OV-1-DF-0.25, 50 m x 0.32 mm). Dodecane was used as internal standard either by addition to the reaction mixture (Comparative Examples and Examples 1,2,5: about 0.80 g) or by addition in gas chromatography analysis. Reaction rate expressed in terms of amount of starting material used, conversion of 1-methoxyocta-2,7-diene, number of 1-methoxy-octa-2,7-diene molecules reacted per hour of rhodium atom and meth The selectivity based on the oxydodecarytrienyl compound is shown in Table 1 below.

Example Rh Complex (mg) MOOD (g) Butadiene (g) Addition % Conversion Reaction rate (mol / mol · h) Selectivity (%) type (g) Comparative example 6.5 3.50 3.2 - - 35.5 174 97.0 One 6.5 3.50 4.0 GeCl ₄ 1.10 83.9 411 87.0 2 6.8 3.50 3.2 WCl ₆ 0.20 56.1 263 93.0 3 6.5 35 40.6 GeCl ₄ 1.05 52.1 2554 100.0 4 3.25 35 42.5 GeCl ₄ 0.50 33.4 3227 99.7 5 6.6 3.50 3.2 HCl; 10% aqueous solution 0.05 91.6 442 62.0 6 6.6 35 28.7 HCl; 32% aqueous solution 0.58 62.9 3039 97.9 7 6.7 35 35.5 HCl; 32% aqueous solution 1.86 75.9 3610 96.6 8 3.25 35 32.5 HCl; 32% aqueous solution 0.93 43.5 4262 96.6

Claims (12)

In the presence of a rhodium compound, homogeneously catalyzed reaction of 1-substituted alka-2,7-dienes of formula (I) and / or 3-substituted alka-1,7-dienes of formula (II) with 1,3-conjugated dienes of formula (III) A process for preparing an alcapolyenyl compound, wherein at least one mineral acid and / or at least one inorganic halide is dissolved in the reaction mixture. Formula I Formula II Formula III Wherein R ¹ is hydrogen or C ₁ -C ₆ -alkyl, C ₅ -C ₈ -cycloalkyl, C ₁ -C ₆ -alkanoyl, C ₆ -C ₁₂ -aryl, C ₆ -C ₁₂ -aryl Oil or C ₇ -C ₁₈ -aralkyl, which are unsubstituted or monosubstituted, disubstituted or trisubstituted, respectively, by hydroxy, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkanoyloxy and / or halogen R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ -alkyl, R ⁶ and R ⁷ are independently hydrogen or C ₁ -C ₆ -alkyl, R ⁸ Is hydrogen, C ₁ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl. The method of claim 1, wherein the reaction mixture consists of two phases, where one phase is a liquid and the other phase is a gas. The process of claim 1, wherein the reaction mixture consists of three phases, wherein the two phases are liquid and one phase is a gas. 4. Process according to any of the preceding claims, wherein hydrogen chloride, preferably hydrochloric acid, is used. 5. The process according to claim 1, wherein chlorides, in particular GeCl ₄ and / or WCl _6, are used. ₆ . The process according to claim 1, wherein hydrogen is added and / or at least one organic halide is dissolved in the reaction medium. 7. The process according to claim 1, wherein R ¹ is C ₁ -C ₆ -alkyl, preferably methyl or phenyl. 8. The compound of claim 1, wherein R is 9.², R³, R⁴, R⁵, R⁶, R⁷And R⁸This is hydrogen. The π-allyl complex of rhodium (III) salt, in particular rhodium trichloride, and / or rhodium, in particular bis (π-crotyl) tetrachloro (butadiene) How rhodium is used. Homogeneity of 1-substituted alka-2,7-dienes of formula I and / or 3-substituted alka-1,7-dienes of formula II and 1,3-conjugated dienes of formula III carried out in the presence of a rhodium compound Use of at least one mineral acid and / or at least one inorganic halide as a cocatalyst dissolved in the reaction mixture of the catalytic reaction. Formula I Formula II Formula III R ¹ in the formula is hydrogen, or C ₁ -C ₆ -alkyl, C ₅ -C ₈ -cycloalkyl, C ₁ -C ₆ -alkanoyl, C ₆ -C ₁₂ -aryloil or C ₇ -C _18- Aralkyl, which may be unsubstituted, or mono-, di-, or tri-substituted, respectively, by hydroxy, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkanoyloxy and / or halogen, R ² , R ³ , R ⁴ and R ⁵ are independently hydrogen or C ₁ -C ₆ -alkyl, R ⁶ and R ⁷ are independently hydrogen or C ₁ -C ₆ -alkyl, R ⁸ is hydrogen, C _1- C ₆ -alkyl or C ₂ -C ₆ -alkenyl. Use according to claim 10 in the method of claim 1. Use of a mixture obtained by the method of any one of claims 1 to 9 in the preparation of surfactants and detergents.