ES2360865T3 - PROCEDURE FOR TELOMERIZATION OF NON-CYCLIC OLEFINS. - Google Patents

Abstract

Procedure for telomerization of non-cyclic olefins with at least two conjugated double bonds (VI) with at least one nucleophile (VII) using a catalyst containing a metal of Groups 8, 9 or 10 of the Periodic System of the Elements, characterized in that in the global process of telomerization at least a partial stage is present in which, through a source of hydrogen, chosen from a gas having hydrogen, hydrogen is added to the process mixture present in this partial stage.

Description

The invention relates to a process for the telomerization of non-cyclic olefins with at least two conjugated double bonds, in particular to the preparation of 1-octa-2,7-dienyl derivatives, by reacting a mixture of hydrocarbons containing 1,3-butadiene, in particular C4 cracking, with nucleophiles.

The telomerization products (unsaturated amines, unsaturated alcohols and their esters and ethers) resulting in this case from two moles of 1,3-butadiene and one mole of nucleophile are the starting substances for organic syntheses. Derivatives containing oxygen are precursors for the preparation of linear C8 alcohols and C8 olefins, in particular 1-octanol and 1-octene. Again, 1-octanol is used, for example, for the production of plasticizers. 1-octene is a coveted comonomer for the modification of polyethylene and polypropylene.

Telomerization of butadiene with a nucleophile to give octadienyl derivatives is catalyzed by metal complexes, in particular palladium compounds.

Examples of telomerization reactions are described, among others, in E. J. Smutny, J. Am. Chem. Soc. 1967, 89, 6793; S. Takahashi, T. Shibano, N. Hagihara, Tetrahedron Lett. 1967, 2451; EP-A-0 561 779, US 3 499 042, US 3 530 187, GB 1 178 812, NL 6 816 008, GB 1 248 593, US 3 670 029, US 3 670 032, US 3 769 352, US 3 887 627, GB 1 354 507, DE 20 40 708, US 4 142 060, US 4 146 738, US 4 196 135, GB 1 535 718, US 4 104 471, DE 21 61 750 and EP-A-0 218 100 .

As raw materials for the preparation of octadienyl derivatives, pure 1,3-butadiene or mixtures of hydrocarbons containing 1,3-butadiene can be used such as, for example, C4 cracking.

1-3-Butadiene is, due to the complex preparation process a relatively expensive raw material. Therefore, most of the times it is more profitable to choose mixtures of hydrocarbons containing 1,3-butadiene as raw material for telomerization. This is possible, since most of the accompanying substances such as saturated hydrocarbons such as, for example, n-butane or iso-butane, or mono-olefins such as, for example, isobutene and linear butenes, behave inertly in the telomerization reaction. Only inhibitors, ie substances that reduce space-time efficiency or selectivity or increase catalyst consumption, should be previously separated.

According to DE 195 23 335, it is advisable, in the case of using the C4 fraction of naphtha crackers as a raw material with 1,3-butadiene content, to limit the concentration of acetylenic compounds and alloys in the educt for telomerization The sum of acetylenic and allenically unsaturated compounds must not exceed 1% by mass based on 1,3butadiene. For the elimination of these disturbing components, reference is made to known procedures, without specific procedures being indicated or cited.

With reference to this patent specification (DE 195 23 335), documents DE 101 49 348, DE 102 29 290 and DE 103 29 042 indicate, without indicating the concentration limits, that it is favorable to separate acetylenic and allenic compounds before of telomerization.

In WO 91-09822 it is described that it is convenient to separate from the mixture of C4 obtained in the cracking process of naphtha, diesel or LPG, by selective hydrogenation, acetylenically unsaturated compounds before telomerization whenever these compounds are present. The hydrogenation process used in this case is not disclosed. In the examples a raw material with less than 60 ppm of total acetylenes content is used, which does not contain any indicated proportion of alenes.

The separation of the acetylenic compounds can take place by extraction or hydrogenation of these compounds. In the case of the separation of the acetylenic compounds (methylacetylene (propino), ethylacetylene (butyne), vinylacetylene (butenin)) by hydrogenation processes are used in which the acetylenic compounds are hydrogenated with a high selectivity, essentially without hydrogenation of , 3-butadiene and mono-olefins. As catalysts, hydrogenation contacts having copper, copper in combination with non-noble metals, copper in combination with noble metals or metal catalysts of Secondary Group VIII of the Periodic System of the Elements, for example palladium contacts, are used. Corresponding procedures are described, among others, in the following patent reports: US 6 576 588, US 6 417 419, US 6 225 515, US 6 015 933, US 6 194 626, US 6 040 489, US 4 493 906, US 4 440 956, US 4 101 451, US 3 912 789, US 3 751 508, US 3 541 178, US 3 327 013, US 3 218 268, EP 1 217 060, EP 1 151 790, EP 1 070 695, EP 0 273 900, NL 6 613 942.

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The separation of alenes, in particular 1,2-butadiene, by hydrogenation is essentially more complicated than the selective separation of acetylenic compounds. The reactivity of 1,2-butadiene in hydrogenation is only slightly greater than that of 1,3-butadiene. Therefore, in the case of the separation of 1,2-butadiene from mixtures of hydrocarbons containing 1,3butadiene by hydrogenation, losses of 1,3-butadiene are inevitable.

For example, in WO 98/12160 a procedure for the simultaneous separation of acetylenic compounds and 1,2-butadiene from a stream of 1,3-butadiene-containing hydrocarbons by hydrogenation in a palladium contact in a reactive distillation column. Although in Example 1 indicated herein, the content of acetylenic compounds was only reduced by approximately 60% in the head product and the 1,2-butadiene content by only around 32%, since 3% of 1,3-butadiene had been lost by hydrogenation.

Jeroen W. Sprengers et al. They report in Angew. Che. 2005, 117, 2062-2065 that complex catalysts of Pd, which as ligands have N-heterocyclic ligands, are suitable as catalysts for hydrogenation, in particular for the hydrogenation of 1-phenyl-1-propyne to give 1-phenyl-1 -propene and 1-phenyl-1-propane.

In the preparation of 2,7-octadienyl derivatives from C4 cracking by telomerization according to the known state of the art complex procedures are necessary, in particular in relation to the deployment of apparatus in order to separate inhibitors such as alkynes from of the mixture of raw materials. These procedures have the disadvantage that in the separation of the inhibitors a part of 1,3-butadiene is lost, in particular when it comes to obtaining the alkyne content in the mixture of raw materials below the detection limit. If, in order to avoid losses of 1,3butadiene, a completely complete inhibitor separation is waived, then a lower space-time efficiency or selectivity in telomerization or a higher catalyst consumption must be assumed.

DE 101 49 348 describes a process for the preparation of 1-olefins using palladium-carbine compounds. In this case, olefins are telomerized with double bonds conjugated to a telogen in the presence of a noble metal catalyst and then hydrogenated and separated to form 1-olefin.

It was the mission of the present invention to provide an alternative telomerization process that preferably avoided some or all of the aforementioned drawbacks of the known state of the art.

Surprisingly, it was now found that by inhibiting hydrogen through a source of hydrogen, an inhibition of the telomerization catalyst can be reduced, at least in a partial stage of the global process of telomerization, or, in the case of a catalyst inhibition, it can be reactivated again.

Object of the invention is, therefore, a process for the telomerization of non-cyclic olefins with at least two conjugated double bonds (VI) with at least one nucleophile (VII) using a catalyst containing a Group 8 a metal. 10 of the Periodic System of the Elements, which is characterized in that in the global process of telomerization there is at least a partial stage in which, through a source of hydrogen, chosen from a gas that presents hydrogen, hydrogen is added to the mixing of the process present in this partial stage.

The process according to the invention has the advantage that a very complex separation of all inhibitors, in particular of all alkynes, from the mixture of raw materials can be waived. Together with the reduced deployment of apparatus, the process also has the advantage that the use of an expensive hydrogenation catalyst can also be avoided.

The process according to the invention also has the advantage that telomerization catalyst can be saved, so that the telomerization catalyst is deactivated, in any case, in a clearly slower manner.

The process according to the invention also has the advantage that the alenos or cumulenes, that is, the compounds that have accumulated double bonds such as 1,2butadiene, which represent an important starting material for organic synthesis, are not widely destroyed, but are available in the hydrocarbon stream, and after the second stage of the process, telomerization can be separated during the treatment of the telomerization product.

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The procedure according to the invention is described by way of example, without the invention, whose scope of protection resulting from the claims and the specification, being limited thereto. The claims themselves also belong to the disclosure content of the present invention. If intervals, general formulas or classes of compounds are indicated in the following, they should not only include the corresponding intervals or groups of compounds that are explicitly mentioned, but also all the partial intervals and partial groups of compounds that can be obtained by suppressing individual values (intervals) or compounds.

The process according to the invention for the telomerization of non-cyclic olefins with at least two conjugated double bonds (VI) with at least one nucleophile (VII) using a catalyst containing a group 8, 9 or 10 metal of the System Periodic of the Elements is distinguished because in the global process of telomerization there is at least a partial stage in which, through a source of hydrogen, chosen from a gas that presents hydrogen, hydrogen is added to the mixture of the present process in this partial stage. The hydrogen-presenting gas can be obtained in situ, e.g. ex. from hydrazine.

As a source of hydrogen, in particular, a gas having hydrogen, preferably hydrogen gas alone or in admixture with inert gases for telomerization such as, for example, nitrogen, methane or noble gas or gases, can be used.

Preferably, the addition of the hydrogen source already takes place at the beginning of the corresponding partial stage. The hydrogen source is fed in the partial stage preferably through equipment that is suitable for dividing the hydrogen source as finely as possible. If the source of hydrogen is a gas, then the equipment can be, for example, a mixing nozzle. For the particularly good homogenization of the gas in the mixture it can be advantageous that the pressure in the process stage amounts to at least 2, preferably 4 MPa. If the source of hydrogen is presented in liquid form, then a division as thin as possible can be achieved, e.g. ex. by using static mixers

As raw materials, pure non-cyclic olefins with conjugated double bonds, mixtures of different olefins of this type or mixtures of one or more of the mentioned olefins with other hydrocarbons can be used. Preferably as a raw material a mixture of hydrocarbons having one or more olefins, preferably a non-cyclic olefin with at least two conjugated double bonds in admixture with other hydrocarbons, is used.

Particularly preferred raw materials have, as non-cyclic olefins with conjugated double bonds, 1,3-butadiene and / or isoprene, in each case in the form of a pure substance, a mixture of the pure substances or a mixture of one or two of the olefins with other hydrocarbons. Very particularly preferably, as raw materials mixtures containing more than 90% by mass C4 hydrocarbons and, preferably, 1,3-butadiene are used.

As raw materials for the process according to the invention, hydrocarbon streams rich in 1,3-butadiene are particularly preferred. As a hydrocarbon stream, in particular, a fraction of C4 hydrocarbons can be used. The hydrocarbon streams can be, e.g. eg, mixtures of 1,3-butadiene with other C4 and C3 or C5 hydrocarbons. Mixtures of this type result, for example, in cracking processes for the production of ethylene and propylene in which gases from the refinery, naphtha, diesel, LPG (liquefied petroleum gas), LGN (natural gas liquid) are reacted. , etc. The C4 fractions that result in the processes as a secondary product may contain, together with 1,3-butadiene, mono-olefins (1-butene, cis-but-2-ene, trans-but-2-ene, isobutene), saturated hydrocarbons (n-butane, isobutane), acetylenically unsaturated compounds (ethylacetylene (butyne), vinylacetylene (butenin), methylacetylene (propyne)) as well as allenically unsaturated compounds (mainly 1,2-butadiene). In addition, these fractions may contain small amounts of C3 and C5 hydrocarbons. The composition of the C4 fractions depends on the respective cracking procedures, the operating parameters and the raw material. The concentrations of the different components are, in the case of steam crackers, typically at the following intervals:

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Four. Five

fifty

Mass% component

1,3-butadiene 25-70

1-butene 9 - 25

2-butene 4 - 20

isobutene 10 - 35

n-butane 0.5 - 8

isobutane 0.5 - 6

Σ acetylenic compounds 0,05 - 4

1,2-butadiene 0,05 - 2

Mixtures of hydrocarbons with a 1,3-butadiene content greater than 35% by mass are preferably used in the process according to the invention.

The hydrocarbons used as raw material can often have traces of oxygenated, nitrogen, sulfur, halogenated compounds, in particular chlorinated compounds and heavy metals, which could be disruptive in the process according to the invention. Therefore, it is convenient to separate these substances first. Disturbing compounds may be, e.g. eg, carbon dioxide or carbonyl compounds such as, e.g. eg, acetone or acetaldehyde.

The separation of these impurities can take place, e.g. eg, by washing, in particular with water or aqueous solutions, or through adsorbers.

By washing with water, hydrophilic components such as, for example, nitrogen components can be separated from the hydrocarbon mixture, in whole or in part. Examples of nitrogen components are acetonitrile or N-methylpyrrolidone (NMP). Oxygenated compounds can also be separated in part by washing with water. Washing with water can be carried out directly with water or with aqueous solutions that may occur, e.g. eg, salts such as, e.g. e.g., NaHSO3 (US 3,682,779, US 3,308,201, US 4,125,568, US 3, 336,414 or US 5,122,236).

It may be advantageous for the hydrocarbon mixture to pass, after washing with water, a drying stage. Drying can be carried out according to the procedures known in the state of the art. In the case of the presence of dissolved water, drying can be carried out, e.g. eg, using a molecular sieve as a drying agent or by azeotroping distillation. Free water can be separated by phase separation, e.g. ex. With a coalescer.

Adsorbers can be used to separate impurities in the range of traces. This can be particularly advantageous, because in the telomerization stage, noble metal catalysts that react with a clear decrease in activity are used, already with traces of impurities. Often, nitrogen or sulfur compounds are separated through pre-adsorbed adsorbers. Examples of employable adsorption agents are aluminum oxides, molecular sieves, zeolites, activated carbon or clay soils impregnated with metals (eg, US 4,571,445 or WO 02/53685). The adsorption agents are marketed by different firms, for example by the firm Alcoa under the name Selexsorb®, of UOP or of Axens, p. eg, with the SAS, MS, AA, TG, TGS or CMG product series.

With the process according to the invention it is particularly possible to use mixtures of raw materials which, among others, also contain compounds that are genetically unsaturated and / or with a proportion greater than or equal to 50 ppm by mass

(wppm) preferably greater than or equal to 100 ppm by mass. In the process according to the invention, mixtures containing non-cyclic olefins containing conjugated double bonds, preferably having up to 5% by mass, preferably up to 3% by mass, particularly preferably up to 1% by mass of alkynes, may preferably be used. or acetylenically unsaturated compounds. Through the ability to use mixtures of raw materials that still have small residual amounts of acetylenically unsaturated compounds, it is possible to use directly in the process according to the invention for telomerization, as raw materials, numerous technically resulting hydrocarbon mixtures , in particular mixtures of C4 or C5 hydrocarbons. In the event that a clearly greater proportion of acetylenically unsaturated compounds were present in a possible mixture of raw materials, then it may be advantageous to separate from this mixture, at least a part of the acetylenically unsaturated compounds (alkynes) present before use in the telomerization, p. ex. by selective hydrogenation or extraction, so that a mixture can then be used as a mixture of raw materials having 0 to 5% by mass, preferably 50 wppm to 3% by mass, particularly preferably, from 100 wppm to 1% in mass of acetylenically unsaturated compounds. Procedures for selective extraction or hydrogenation can be taken from the known state of the art.

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The separation of acetylenic compounds by extraction has long been known and is, as a treatment step, an integral component of most installations that obtain 1,3-butadiene from C4 cracking. A procedure for extractive separation of acetylenically unsaturated compounds from C4 cracking is described, for example, in Erdöl und Kohle-Erdgas-Petrochemie vereinigt mit Brennstoffchemie Volume 34, notebook 8, August 1981, pages 343-346. In this process, in a first stage the mono-olefins and saturated hydrocarbons are separated by extractive distillation with water-containing NMP, several times unsaturated hydrocarbons as well as acetylenically unsaturated compounds. The unsaturated hydrocarbons are distilled from the NMP extract. From the hydrocarbon distillate, acetylenically unsaturated compounds with 4 C atoms are separated by a second extractive distillation with water-containing NMP. In the C4 cracking treatment, 1,3-butadiene is separated by two additional distillations. pure, resulting as a secondary product methylacetylene and 1,2-butadiene. Within the framework of the process according to the invention, the multi-stage process described herein can be carried out as a pretreatment for the mixing of raw materials, being able to give up the distillative separation of 1,2-butadiene.

Optionally, the separation of acetylenic compounds from a stream containing 1,3-butadiene can take place using one or more ionic liquids, e.g. ex. as extraction agents.

The hydrocarbon streams obtained by extraction, which preferably contain less than 5% by mass of acetylenic compounds, can be used particularly preferably directly as a raw material in the process according to the invention.

Partial separation of the acetylenically unsaturated compounds from the hydrocarbon stream to be used by selective hydrogenation of the acetylenically unsaturated compounds in the presence of dienes and mono-olefins can be carried out, e.g. eg, in catalysts with copper content, with palladium or mixed content.

In case acetylenically unsaturated compounds are present, the raw materials used in the process according to the invention, in particular in the case of using mixtures of C4 hydrocarbons having 1,3-butadiene, contain as alkylenically unsaturated compounds, alkynes which are preferably selected from vinylacetylene and / or 1-butyne.

In the case of the presence of alkynes in the mixture of raw materials, the general process, through the source of hydrogen, is preferably given such an amount of hydrogen that the molar ratio of hydrogen to alkyne is at least 1 to 1, preferably from 1 to 1 to 2 to 1, particularly preferably from 1 to 1 to 1.5 to 1 and, very particularly preferably, from 1 to 1 to 1.1 to

1. The fact of clearly exceeding these values leads to an increasing loss of non-cyclic olefins that have conjugated double bonds such as, e.g. eg, 1,3-butadiene. The concentration of the alkyne in the raw material mixture can be determined continuously or at regular intervals,

p. ex. by gas chromatography.

In the process according to the invention, all catalysts suitable for telomerization can be used. As a catalyst for telomerization, metal complexes of the palladium (Pd), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir) metals are preferably used. nickel (Ni) or platinum (Pt). As ligands they can be used, e.g. eg, phosphorus ligands such as, e.g. eg, phosphines, phosphines, phosphites, phosphonites or phosphites such as, e.g. eg, triphenylphosphines or carbine ligands, it may also be advantageous to use different ligands at the same time. Particularly preferably, metal-carbine complexes are used as catalysts.

Palladium compounds, in particular palladium-carbene complexes as catalysts in the telomerization stage, are used in a particularly preferred manner. The ligands in the metal complexes used as a catalyst are, particularly preferably,

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Trivalent phosphorus compounds or carbons.

Particularly preferably, metal complexes are used as a catalyst which, as a ligand, have at least one carbon stabilized by heteroatoms. Examples of such ligands are described, among others, in DE 101 28 144, DE 101 49 348, DE 101 48 722, DE 100 62 577, EP 1 308 157 and WO 01/66248. These documents and, in particular, the ligands described therein, belong to the dissemination content of the present application. In addition, the active complex may still have other ligands. The carbine ligands can be open ligands or cyclic ligands.

Preferably, in the process according to the invention a palladium-carbine complex having a carbine ligand of the general formula is used as a telomerization catalyst.

(VIII)

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with R2, R ", R 'and R3 the same or different hydrogen or hydrocarbon groups, wherein the hydrocarbon groups can be the same or different radicals, linear, branched or cyclic, selected from the group of alkyl radicals with 1 to 50 carbon atoms, alkenyl radicals with 2 to 50 carbon atoms, alkynyl radicals with 2 to 50 carbon atoms and aryl radicals with 6 to 30 carbon atoms, in which at least one hydrogen atom may be replaced by a functional group and / or R2 and R ”and / or R´ and R3 are part of a cyclic system, which is the same or different, that has a carbon network of 2 to 20 carbon atoms and a nitrogen atom according to formula VIII, not counting carbon atoms of R2 and R ”and / or R´y R3 and wherein at least one hydrogen atom in the cyclic system may be replaced by a functional group and / or at least one carbon atom in the cyclic system may be replaced by a heteroatom selection ado of the group consisting of S, P, O and N,

and / or R2 and / or R "and / or R" and / or R3 are linked with a ligand L through a bridge based on 1 to 20 carbon atoms, not counting the carbon atoms of the radicals R2, R ”, R´ and R3,

and L is another ligand representing a neutral two-electron donor, part of a cyclic system and / or an anionic ligand where the functional groups can be chosen, e.g. eg, of the groups: -CN, -COOH, COO-alkyl-, -COO-aryl-, -OCO-alkyl,

-OCO-aryl-, -OCOO-alkyl-, -OCOO-aryl-, -CHO, -CO-alkyl-, -CO-aryl-, -O-alkyl,

-O-aryl-, -NH2, -NH (alkyl) -, -N (alkyl) 2-, -NH (aryl) -, -N (alkyl) 2-, -F, -Cl, -Br-, - I,

-OH, -CF3, -NO2, -ferrocenyl, -SO3H and -PO3H2, where the alkyl groups may contain, e.g. eg, 1 to 24 and the aryl groups, p. eg, 5 to 24 carbon atoms. The preparation of ligands of this type can be deduced, e.g. eg, from document DE 101 48 722.

Preferably, in the process according to the invention a palladium-carbine complex is used as a telomerization catalyst, which has a carbine ligand of the general formula (VIII) with

R2; R3: alkyl groups with 1 to 24 carbon atoms, the same or different, linear, branched, substituted or unsubstituted, cyclic or alicyclic, or aryl groups with 6 to 24 substituted or unsubstituted carbon atoms, monocyclic or polycyclic, or

heterocycle with 4 to 24 monocyclic or polycyclic carbon atoms, substituted or unsubstituted, and at least one heteroatom of the group N, O, S,

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R ’, R”: same or different

hydrogen, alkyl, aryl, heteroaryl, -CN, -COOH, -COO-alkyl-, -COO-aryl-, -OCO-alkyl, OCO-aryl-, -OCOO-alkyl-, -OCOO-aryl-, -CHO , -CO-alkyl-, -CO-aryl-, -O-alkyl, -O-aryl-, NH2, -NH (alkyl) -, -N (alkyl) 2-, -NH (aryl) -,

-N (alkyl) 2-, -F, -Cl, -Br-, -I, -OH, -CF3, -NO2, -ferrocenyl, -SO3H, -PO3H2, where the alkyl groups contain 1-24 and the aryl and heteroaryl groups 5 to 24 carbon atoms, and the radicals R 'and R "may also be part of an aliphatic or aromatic bridge ring.

Very particularly preferably, carben ligands having a 5-membered ring are employed. Preferably, in the process according to the invention the ligands employed, which have a 5-member ring, are those, e.g. e.g., of formulas IX, X, XI and XII

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with R2; R3: same or different

alkyl groups with 1 to 24 carbon atoms, linear, branched, substituted, cyclic or alicyclic, or

replaced or no

aryl groups with 6 to 24 substituted or unsubstituted, monocyclic carbon atoms

or

polycyclic, or

heterocycle with 4 to 24 monocyclic or polycyclic carbon atoms, substituted or unsubstituted, and at least one heteroatom of the group N, O, S,

R4, R5, R6, R7: same or different

hydrogen, alkyl, aryl, heteroaryl, -CN, -COOH, -COO-alkyl-, -COO-aryl-, -OCO-alkyl, OCO-aryl-, -OCOO-alkyl-, -OCOO-aryl-, -CHO , -CO-alkyl-, -CO-aryl-, -O-alkyl, -O-aryl-, NH2, -NH (alkyl) -, -N (alkyl) 2-, -NH (aryl) -, -N (alkyl) 2-, -F, -Cl, -Br-, -I, -OH, -CF3, -NO2, ferrocenyl, -SO3H, -PO3H2, wherein the alkyl groups contain 1-24 and the aryl groups and heteroaryl 5 to 24 carbon atoms, and the radicals R4, R5, R6 and R7 can also be part of an aliphatic or aromatic bridge ring.

Examples of carbeno ligands corresponding to general formulas IX and X, and complexes containing ligands of this type have already been described in the scientific literature (WA Hermann, C. Köcher, Angew. Chem 1997, 109, 2257, Angew , Chem. Int. Ed. Engl. 1997, 36, 2162; VPW Böhm,

C.W.K. Gstöttmayr, T. Weskamp, W.A. Hermann, J. Organomet. Chem. 2000, 595, 186; document DE 44 47 066).

The radicals R2 and R3 may, in particular, represent a monocyclic or polycyclic ring containing at least one heteroatom chosen from the elements nitrogen, oxygen and sulfur and which optionally has other substituents chosen from the groups -CN, -COOH, -COO- alkyl-, -COO-aryl-, OCO-alkyl, -OCO-aryl-, -OCOO-alkyl-, -OCOO-aryl-, -CHO, -CO-alkyl-, -CO-aryl-, -aryl, alkyl , -O-alkyl, -O-aryl-, -NH2, -NH (alkyl) -, -N (alkyl) 2-, -NH (aryl) -, - N (alkyl) 2-, -F, -Cl , -Br-, -I, -OH, -CF3, -NO2, -ferrocenyl, -SO3H, -PO3H2 .. The alkyl groups have 1 to 24 and the aryl groups 5 to 24 carbon atoms. In the case where Pd is used as the metal of Groups 8 to 10 of the Periodic System, one or both of the ligands R2 and R3 preferably have these meanings.

The radicals R2, R3, R4, R5, R6 and / or R7 may in each case be the same or different and have at least one substituent of the group -H, -CN, -COOH, -COO-alkyl-, -COO-aryl -, -OCO-alkyl, OCO-aryl-, -OCOO-alkyl-, -OCOO-aryl-,

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-CHO, -CO-alkyl-, -CO-aryl-, -aryl, -alkyl, -aluqneyl, -alyl, -O-alkyl, -O-aryl-, -NH2, -NH (alkyl), N (alkyl ) 2, -NH (aryl), -N (alkyl) 2, -F, -Cl, -Br-, -I, -OH, -CF3, -NO2, -ferrocenyl, -SO3H, -PO3H2, where alkyl groups contain 1 to 24, preferably 1 to 20, alkenyl groups 2 to 24, groups

5 allyl 3 to 24 and the monocyclic or polycyclic aryl groups 5 to 24 carbon atoms.

The radicals R4a R6 may be covalently linked to each other, e.g. eg, through groups (CH2) or (CH).

In the case of substituents with hydrogen atoms of an acidic nature, the protons may be replaced by metal or ammonium ions.

The radicals R2 and R3 may be particularly preferably radicals that are derived from heteroalkanes, heteroalkenes and five- and six-membered heteroaromatic compounds such as 1,4-dioxane, morpholine, γ-pyran, pyridine, pyrimidine, pyrazine, pyrrole, furan, thiophene, pyrazole, imidazole, thiazole and oxazole. Specific examples for radicals R2 and R3 of this type are reproduced in the following Table 1. In them, the ~ in each case designates the point of attachment to the five-ring heterocycle or the compliant compound

15 to Formula VIII.

Table 1: Examples of radicals R2 and / or R3

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Within the framework of this invention, carbine ligands are understood to mean both free carbons that can function as ligands as well as coordinated carbons to metals.

The catalyst metal, in particular the palladium used as the catalyst metal, from which the active catalyst is formed under reaction conditions, can be incorporated into the process in different ways.

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Metal (palladium) can be incorporated into the process

a) in the form of a metal-carbenium complex (palladium-carbine complex), wherein the metal (palladium) is preferably present in the oxidation stages (II) or (0), or

5 b) in the form of metal precursors (palladium precursors), from which the catalysts are formed in situ.

With respect to a)

Complex examples of palladium (0) carbenolefin, palladium (0) dicarbeno complexes and palladium (II) dicarbeno complexes, palladium (0) carbeno-1,6-diene complexes are examples. As 1,6-diene 10, for example, diallylamine, 1,1′-divinyltetramethyldisiloxane, 2,7-octadienyl ethers or 2.7 can work

octadienylamines Other examples are represented by the following Formulas I-a through I-e.

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Palladium carbine complexes can be prepared in the most diverse ways. A simple route is, for example, the reaction of adding carbine ligands or exchanging ligands in palladium complexes for carbine ligands. Thus, for example, the I-f to I-i complexes can be obtained by exchanging the phosphorus ligands of the bis (tri-o-tolylphosphine) palladium (0) complex (T. Weskamp,

W.A. Hermann, J. Organomet. Chem. 2000, 595, 186).

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10 I-f R2 = R3 = mesityl

I-g R2 = R3 = c-hexyl

I-h R2 = R3 = t-butyl

I-i R2 = R3 = i-propyl

15 Regarding b)

As palladium precursors, for example: palladium (II) acetate, palladium (II) chloride, palladium (II) bromide, lithium tetrachloropalate, palladium (II) acetylacetonate, palladium (0) complexes can be used -dibenzylidenacetone, palladium (II) propionate, palladium (II) chloride bisacetonitrile, palladium (II) dichloride -bistriphenylphosphane, palladium (II) chloride -bisbenzonitrile, bis- (tri-o

20 tolylphosphine) palladium (0) and other complexes of palladium (0) and palladium (II).

The carbenes according to general formulas IX and X can be used in the form of free carbenes or in the form of metal complexes, or they can be generated in situ from carbine precursors.

As carbine precursors, for example, salts of the carbenos according to general formulas XIII and XIV are suitable,

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wherein R2, R3, R4, R5, R6, R7 have the same meaning as in formulas IX and X, and Y represents a once-charged anionic group or, correspondingly proportionate to stoichiometry, represents a several charged anionic group times.

Examples of Y are halides, hydrogen sulfate, sulfate, alkyl sulfates, arylsulfates, borates, hydrogen carbonate, carbonate, alkyl carboxylates, arylcarboxylates.

The corresponding carbennes can be released from the salts of the carbenes, for example by reaction with a base.

The concentration of the catalyst, formally indicated in ppm (mass) in the catalyst metal, in particular palladium metal, based on the total mass, preferably in the process according to the invention is preferably 0.01 ppm to 1000 ppm, preferably 0 , 5 to 100 ppm, particularly preferably at 1 to 50 ppm. The ratio [mol / mol] of ligand, preferably carbine to metal, in particular the ratio of carbine to Pd, in the reaction mixture is preferably 0.01: 1 to 250: 1, preferably 1: 1 to 100: 1, particularly preferably at 1: 1 to 50: 1. In addition to the carbine ligands, other ligands may also be present in the reaction mixture, for example phosphorus ligands such as, e.g. eg, triphenylphosphine.

As nucleophile (VII), compounds of the general formulas are preferably used

R1a-O-H (VIIa) or (R1a) (R1b) N-H (VIIb) or R1a-COOH (VIIc)

wherein R1a and R1b, independently of one another, are selected from hydrogen, a linear, branched or cyclic C1 to C22 alkyl group, an alkenyl group, an alkynyl group, a C5 to C18 aryl group or a CO-alkyl- group (C1-C8), or a group -CO-aryl- (C5-C10), where these groups may contain substituents chosen from the group -CN, -COOH, -COO-alkyl- (C1-C8), -CO- alkyl- (C1-C8), -aryl- (C5-C10), -COO-aryl (C6-C10), -CO-aryl- (C6-C10), -O-alkyl- (C1-C8), - O-CO-alkyl- (C1-C8), -N-alkyl2- (C1-C8), -CHO, -SO3H, -NH2, -F, -Cl, -OH, -CF3, -NO2, and where the radicals

R1a and R1b can be linked to each other through covalent bonds. Preferably, as nucleophiles, compounds are used in which the radicals R1a and, possibly R1b are hydrogen, methyl, ethyl, n-propyl, iso-propyl, tert-butyl, n-butyl, sec-butyl, pentyl, hexyl, heptyl, octyl, octenyl, octadienyl, isononyl, 2-ethylhexyl, n-nonyl, phenyl, m-, o- or p-methylphenyl, naphthyl, 2,4-di-tert-butylphenyl, 2,6di-tert-butylmethylphenyl, hydrogencarbonyl, methylcarbonyl, ethylcarbonyl, propylcarbonyl or phenylcarbonyl.

Particularly preferably, as nucleophiles (VII), water, alcohols, phenols, polyols, carboxylic acids, ammonia and / or primary or secondary amines are used. Especially, it is about:

- water, ammonia,

- monoalcohols and phenols such as, for example, methanol, ethanol, n-propanol, isopropanol, allyl alcohol, n-butanol, i-butanol, octanol, 2-ethylhexanol, isononanol, benzyl alcohol, cyclohexanol, cyclopentanol or 2,7- octadienti-1-ol, phenol,

- dialcohols such as, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 2,3-butanediol and 1,3-butanediol,

image12

- hydroxy compounds such as, for example, α-hydroxyacetic acid ester,

-

primary amines such as, for example, methylamine, ethylamine, propylamine, butylamine, octylamine, 2,7-octadienylamine, dodecylamine, ethylenediamine or hexamethylenediamine,

-

secondary amines such as dimethylamine, diethylamine, n-methylaniline, bis (2,7-octadienyl) amine, dicyclohexylamine, methylcyclohexylamine, pyrrolidine, piperidine, morpholine, piperazine or hexamethyleneimine or

- carboxylic acids such as formic acid, acetic acid, propanoic acid, butenoic acid, isobutenoic acid, benzoic acid, 1,2-benzenedicarboxylic acid (phthalic acid).

Very particularly preferably, as nucleophiles (VII), in the telomerization stage, methanol, ethanol, 2-ethylhexanol, octanol, octenol, octadienol, isopropanol, n-propanol, isobutanol, n-butanol, iso- are used Nonanol, formic acid, acetic acid, propionic acid, n-butanoic acid, iso-butanoic acid, benzoic acid, phthalic acid, phenol, dimethylamine, diethylamine, ammonia and / or water. Advantageously, methanol is used as nucleophiles.

Nucleophiles that can be obtained by themselves through a reaction

Telomerization can be used directly or formed in situ. Thus, for example, 2,7-octadien-ol is formed in situ from water and butadiene in the presence of the telomerization catalyst, 2,7-octadienylamino, from ammonia and 1,3-butadiene, etc.

For the ratio of nucleophile to the starting olefin with at least two conjugated double bonds in the telomerization reaction, the number of hydrogen atoms active in the telogen must be taken into account. Thus, for example, methanol has an active hydrogen atom, ethylene glycol has two, amine has two, etc.

For each mole of the active hydrogen atom of the nucleophile, which can react with the starting olefin, 0.001 mol to 10 mol of starting olefin are preferably used in the telomerization reaction. In the case of carrying out the reaction with a liquid phase, a ratio of 0.1 moles to 2 moles of starting olefin is particularly preferred for each mole of active hydrogen.

It may be advantageous to carry out the process according to the invention in the presence of a solvent. As solvents for the telomerization reaction, the nucleophile used can be used, if it is present as a liquid under the reaction conditions, and / or inert organic solvents. The addition of solvents is preferred in the case of using nucleophiles that are present as solids under the reaction conditions, or in the case of products that would precipitate as solids under the reaction conditions. Suitable solvents are, among others, aliphatic, cycloaliphatic and aromatic hydrocarbons, such as, for example, C3-C20 alkanes, mixtures of lower alkanes (C3-C20), cyclohexane, cyclo-octane, ethylcyclohexane, alkenes and polyenes, vinylcyclohexene, 1 , 3,7-octatriene, C4 hydrocarbons from C4 cracking, benzene, toluene and xylene fractions; polar solvents such as, for example, tertiary and secondary alcohols, amides such as, for example, acetamide, dimethylacetamide and dimethylformamide, nitriles such as, for example, acetonitrile and benzonitrile, ketones such as, for example, acetone, methyl isobutyl ketone and diethyl ketone; esters of carboxylic acids such as, for example, ethyl ester of acetic acid, ethers such as, for example, dipropyl ether, diethyl ether, dimethyl ether, methylctyl ether, methyl tertiary butyl ether, ethyl tertiary ethyl ether, 3-methoxyoctane, dioxane, tetrahydrofuran , anisole, alkyl- and aryl ethers of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycol, and other polar solvents such as, for example, sulfolane, ethyloxycarbonate, dimethylsulfate, carbonate Water. Ionic liquids can also be used as solvents, for example imidazolium or pyridinium salts. The solvents can be used alone or in the form of mixtures of different solvents.

The temperature at which the telomerization reaction is carried out is preferably in the range of 10 to 180 ° C, preferably in the range of 30 to 120 ° C and, particularly preferably, in the range of 40 to 100 ° C. The reaction pressure preferably amounts to 1 to 300 bar, preferably 1 to 120 bar, particularly preferably 1 to 64 bar and, most particularly preferably, 1 to 20 bar.

It is often advantageous to carry out the telomerization reaction in the presence of bases. Basic components with a pKb value of less than 7 are preferred, in particular compounds selected from the group of amines, alcoholates, phenolates, alkali metal salts or alkaline earth metal salts.

image13

As a basic component, for example, amines such as trialkylamines, which may be alicyclic and / or open chain, amides, alkali metal and / or alkaline earth metal salts of aliphatic and / or aromatic carboxylic acids such as acetates are suitable , propionates, benzoates or corresponding carbonates, hydrogen carbonates, alkali metal alcoholates and / or

5 alkaline earths, phosphates, hydrogen phosphates and / or hydroxides, preferably lithium, sodium, potassium, calcium, magnesium, cesium, ammonium and phosphonium compounds. Hydroxides of the alkaline and alkaline earth elements and salts of nucleophilic metals according to general formulas III, IV or V are preferred as additive.

Preferably, from the basic component, 0.01 mol% to 10 mol% (based on the starting olefin), preferably 0.1 mol% to 5 mol%, and very particularly preferably are used , from 0.2 mol% to 1 mol%.

Telomerization can be performed continuously or discontinuously and is not limited to the use of certain types of reactors. Examples of reactors in which the reaction can be carried out are boiler reactor with agitator, boiler cascade with agitator, flow tube and loop reactor. Combinations of different reactors are also possible, for example a boiler reactor with

15 agitator with a flow tube connected below.

The telomerization can be carried out, in order to obtain a high space-time yield, preferably not until the complete conversion of the olefin used. This is particularly valid when the olefin used is 1,3-butadiene. In this case, it is preferred to limit the conversion to a maximum 95%, particularly preferably 88%.

The addition according to the invention of hydrogen through a source of hydrogen to a mixture of the process that occurs in a partial stage can take place in one or several partial stages. If the telomerization process according to the invention has only a partial stage, namely the telomerization reaction itself, then the addition of hydrogen takes place naturally by adding the hydrogen source to this (partial) stage. Preferably, in the

One or more additional partial stages are still present according to the invention. Partial stages of this type can be, e.g. eg, a stage of catalyst separation and, possibly, a partial stage of catalyst recycling in the reactor. The hydrogen source is preferably added to the overall telomerization process in the reaction step. The addition of hydrogen through the source of hydrogen in the reaction stage has the advantage that telomerization inhibition by acetylenically unsaturated compounds directly in the reaction mixture can be avoided. A drawback of the addition of hydrogen in the reaction stage may, however, be that the educts or products can be hydrogenated to form unwanted by-products and, thus, yield losses can occur. This is particularly the case when telomerization is carried out with an excess of hydrogen in

Comparison with the acetylenically unsaturated compounds present.

If the global telomerization process has a catalyst recycling stage, then the hydrogen source is added to the global telomerization process preferably in the partial catalyst recycling stage. The addition of the hydrogen source in the catalyst recycling has the advantage that the product and also the educt were widely separated from the catalyst at a previous stage and, consequently, the hydrogen added through the non-hydrogen hydrogen educto source or valuable product to form unwanted byproducts and, therefore, the yield is not reduced. It may be advantageous for the hydrogen source to be added both to the partial stage of the reaction and also to the partial stage of catalyst recycling.

The process according to the invention can be used, in particular, for the preparation of a compound according to formula II

image6

wherein X is an OR1a or NR1aR1b radical, wherein R1a and R1b, independently of one another, are selected from hydrogen, a linear, branched or cyclic C1 to C22 alkyl group, an alkenyl group, an alkynyl group, an aryl group C5 to C18 or a group

-CO-alkyl- (C1-C8), or a group -CO-aryl- (C5-C10), where these groups may contain substituents chosen from the group -CN-, -COOH-, -COO-alkyl- (C1 -C8), -CO-alkyl- (C1-C8), -aryl- (C5-C10), -COO-aryl

image14

10

fifteen

twenty

25

30

35

40

Four. Five

(C6-C10), –CO-aryl- (C6-C10), –O-alkyl- (C1-C8), –O-CO-alkyl- (C1-C8), - N-alkyl2- (C1-C8 ), -CHO, -SO3H, NH2, -F, -Cl, -OH, -CF3, -NO2, and where the radicals R1a and R1b can be linked to each other through covalent bonds, from a current of hydrocarbons containing 1,3-butadiene.

Compounds of the formula IIIa or IIIb can be prepared in particular with the process according to the invention

image6

by reaction of 1,3-butadiene with a nucleophile (VII) according to formulas VIIa, VIIb or VIIc

R1a-O-H (VIIa) (R1a) (R1b) N-H (VIIb) R1a-COOH (VIIc)

where R1a and R1b have the meaning mentioned above.

Particularly preferably, with the process according to the invention compounds of the formula II are prepared, in which the X represents OR1a or NR1aR1b, with

R1a

equal to H, methyl, ethyl, n-propyl, iso-propyl, tert-butyl, n-butyl, sec-butyl, pentyl, hexyl, heptyl, octyl, octenyl, octadienyl, isononyl, 2-ethylhexyl, n-nonyl, phenyl, m-, o- or p-methylphenyl, naphthyl, 2,4-di-tert-butylphenyl, 2,6-di-tert-butylmethylphenyl, hydrogencarbonyl, methylcarbonyl, ethylcarbonyl, propylcarbonyl or phenylcarbonyl. and / or

R1b

equal to H, methyl, ethyl, n-propyl, iso-propyl, tert-butyl, n-butyl, sec-butyl, pentyl, hexyl, heptyl, octyl, octenyl, octadienyl, isononyl, 2-ethylhexyl, n-nonyl, phenyl, m-, o- or p-methylphenyl, naphthyl, 2,4-di-tert-butylphenyl, 2,6-di-tert-butylmethylphenyl, hydrogencarbonyl, methylcarbonyl, ethylcarbonyl, propylcarbonyl or phenylcarbonyl. Very particularly preferably, with the process according to the invention, a compound according to Formula IIIa is prepared with R 1a = hydrogen, methyl, ethyl, phenyl or methylcarbonyl. The compounds of formulas IIIa and IIIb can be presented both in the cis form and also in the trans form.

The material discharged from the telomerization reaction stage can be presented or composed, e.g. eg, mainly of the telomerization product, secondary products, "inert hydrocarbons", residual amounts of olefin used as raw material, residual amounts of nucleophile and catalyst system (catalyst metal, ligands and possibly bases, etc.) or their metabolites and , eventually, solvents added. The separation of the material discharged from the reaction stage of the telomerization can take place very generally according to known technical procedures, in particular by thermal separation processes such as, for example, distillation or extraction. For example, distillation separation can take place in the following fractions:

-

a C4 fraction containing n-butane, isobutane, 1-butene, 2-butene, isobutene, 1,3-butadiene, 1,2-butadiene and, eventually, in whole or in part to the nucleophile,

-

a fraction with the target product (2,7-octadienyl derivative),

-

a fraction with the secondary product and / or

-

a fraction with the catalyst and

- if any, a fraction with the nucleophile and / or

- possibly a fraction with solvent.

The fraction with the nucleophile, the fraction with the solvent as well as the fraction with the catalyst can be recycled in each case in whole or in part, together or separately, to the reaction step, or it can be contributed to a treatment. Preferably, these fractions are returned to the reaction step.

However, separation can also be carried out so that only two fractions are obtained. One of the fractions in this case contains the essential part of the target product, and the second fraction contains the essential part of the catalyst used. The catalyst-containing fraction is recycled, in whole or in part, to the reaction stage.

image15

The target product is used as such or serves as a precursor for other substances. For example, from the target product 1-methoxyoctadi-2,7-ene, 1-octene can be prepared by hydrogenation of the two double bonds and subsequent separation of methanol. By means of the process according to the invention, mixtures having 1-methoxyoctadi-2,7-ene can therefore be prepared. These mixtures can then be used for the preparation of 1-octene.

If methanol or ethanol is used as a nucleophile in telomerization, in the case of using C4 hydrocarbon streams as the starting stream (1,3-butadiene as the starting olefin), it is the option not to separate the nucleophile from the reaction product . Instead, the material discharged from the hydrogenation of the target product (eg 1-methoxyoctadi-2,7-ene) can be directly contributed to an etherification in which the alcohol used as a nucleophile is reacted with the isobutene with C4 current content to give methyl tert-butyl ether or ethyl tert-butyl ether. This reaction also takes place according to procedures known in the art, most often under catalysis of ion exchangers. For a complete conversion of isobutene, additional alcohol should eventually be added.

The invention is explained in more detail with the aid of Figure Fig. 1, without the invention having to be limited to the embodiment represented in Fig. 1. In Fig. 1 a possible embodiment of the process of according to the invention. The global telomerization process represented here presents three partial stages. A telomerization reaction stage (Telo), a separation stage (A) and a catalyst recycling stage (KR). In the reaction stage (Telo) an educt stream is conducted together with the catalyst recycle stream (KR) and, eventually, a hydrogen source (WQ1). The reaction mixture obtained as a reaction product (P1) is conducted in the next partial stage (A), separating the catalyst and, eventually, a solvent from the remaining components of the reaction mixture. The mixture of products (P2) released from catalyst can be brought to a further treatment. The separated catalyst is brought back into the educt stream through catalyst recycling (KR). In the catalyst recycling, a source of hydrogen (WQ2) can also be added to the catalyst stream. In carrying out the process according to the invention, a source of hydrogen in one or several partial stages of the global telomerization process can be provided through WQ1 or WQ2, or also through WQ1 and WQ2. It is understood that, in carrying out the procedure, other devices such as, e.g. e.g., pumps and valves, etc., or possibilities, e.g. ex. for the expulsion of a part of the catalyst consumed and / or for the addition of recently added catalyst, but which in the scheme according to Fig. 1 are not represented.

The following examples have to explain the invention in more detail, without limiting its scope of protection resulting from the specification and claims.

Examples

Example 1: Telomerization without the presence of alkynes

In a 100 ml Schlenk tube, 55.9 mg (0.18 mmol) of palladium acetylacetonate and 0.390 g (0.75 mmol) of 1,3-bis o-cresolate (2, 4,6-trimethylphenyl) imidazolium-ocresol in 51.2 g (1.59 mol) of methanol. 6.72 g (0.06 mol) of o-cresol - heated to 40 ° C in a water bath - and 3.47 g (0.06 mol) of methanolate were dissolved in a 3-liter autoclave. sodium in 115 g (3.59 mol) of methanol and in 100 g (0.52 mol) of tripropylene glycol. Then, with the help of a canister of pressurized gas, 536 g of a mixture of C4 hydrocarbons were introduced under pressure into the autoclave (quantitative determination by loss of mass in the C4 reserve bottle). The autoclave was heated under stirring to the reaction temperature (80 ° C), the palladium-containing solution was added at once to the autoclave content and the reaction was monitored with the help of an in-line gas chromatograph. The duration of the reaction was 14 h. As a mixture of hydrocarbons, a mixture of C4 hydrocarbons free of alkynes with 42.61% by mass of 1,3butadiene, 1.77% by mass of i-butane, 7.05% by mass of n-butane, 5, 14% by mass of trans-butene, 15.05% by mass of 1-butene, 24.80% by mass of i-butene, 3.58% by mass of cis-butene (no detectable alkyne).

GC Analytics:

CG (1st column: DB-WAX / AI2O3, 2nd column: DB-Wax / HP5MS; initial temperature: 50ºC, maximum temperature: 200ºC, start time: 1 min, equilibrium time: 3 min; temperature program: 50ºC at 15ºC min-1 to 200ºC, operating time: 11 min; injection: 220ºC, (constant flow) Retention time [tR] (C4 hydrocarbons) = 2762 min, tR (methanol) = 3152 min, tR (1 , 7-octadiene) = 3866 min, tR (trans-1,6-octadiene) = 3958 min, tR (cis-1,6-octadiene) = 4030 min, tR (cis-1,3,7-octatriene) = 4291 min, tR (trans-1,3,7-octatriene) = 4292 min, tR (vinylcyclohexene) = 4448 min, tR (i-butane) = 4552 min, tR (nbutane) = 4822 min, tR (3-MODE ) = 5523 min, tR (trans-butene) = 6116 min, tR (1-butene) = 6240 min, tR (i-butene) 6412 min, tR (cis-butene) = 6616 min, tR (1-MODE) = 6650 min, tR (1,2-butadiene) = 6900 min, tR (1,3-butadiene) = 7526 min.

image16

2,7-octadienyl-1-methyl ether (= 1-MODE)

1,7-octadien-3-methyl ether (= 3-MODE).

Example 2: Telomerization in the presence of 2273 ppm by mass of acetylenes

(Comparative Test)

In a 100 ml Schlenk tube, 56.2 mg (0.18 mmol) of palladium acetylacetonate and 0.395 g (0.76 mmol) of 1,3-bis o-cresolate (2, 4,6-trimethylphenyl) imidazolium-ocresol in 51.2 g (1.59 mol) of methanol. In a 3-liter autoclave from Büchi, 6.80 g (0.062 mol) of o-cresol - heated to 40 ° C in a water bath - and 3.80 g (0.07 mol) of sodium methanolate were dissolved in 115.1 g (3.59 mol) of methanol and in 101.1 g (0.52 mol) of tripropylene glycol. Then, with the help of a canister of pressurized gas, 573 g of a mixture of C4 hydrocarbons were introduced under pressure into the autoclave (quantitative determination by loss of mass in the C4 reserve bottle). The autoclave was heated under stirring to the reaction temperature (80 ° C), the palladium-containing solution was added at once to the autoclave content and the reaction was monitored with the help of an in-line gas chromatograph. The duration of the reaction was 14 h.

GC Analytics:

CG (1st column: DB-WAX / AI2O3, 2nd column: DB-Wax / HP5MS; initial temperature: 50ºC, maximum temperature: 200ºC, start time: 1 min, equilibrium time: 3 min; temperature program: 50ºC at 15ºC min-1 up to 200ºC, operating time: 11 min; injection: 220ºC, (constant flow), tR (C4 hydrocarbons) = 2762 min, tR (methanol) = 3152 min, tR (1,7-octadiene) = 3866 min, tR (trans-1,6octadiene) = 3958 min, tR (cis-1,6-octadiene) = 4030 min, tR (cis-1,3,7-octatriene) = 4291 min, tR (trans1, 3,7-octatriene) = 4292 min, tR (vinylcyclohexene) = 4448 min, tR (i-butane) = 4552 min, tR (n-butane) = 4822 min, tR (3-MODE) = 5523 min, tR ( trans-butene) = 6116 min, tR (1-butene) = 6240 min, tR (i-butene) = 6412 min, tR (cis-butene) = 6616 min, tR (1-MODE) = 6650 min, tR ( 1,2-butadiene) = 6900 min, t R (1,3butadiene) = 7526 min.

2,7-octadienyl-1-methyl ether (= 1-MODE)

1,7-octadien-3-methyl ether (= 3-MODE).

A mixture of C4 hydrocarbons with 45.39% by weight of 1,3-butadiene, 1.46% by mass of i-butane, 4.61% by mass of pressure was used in the example according to the invention n-butane, 5.20% by mass of trans-butene, 15.22% by mass of 1-butene, 23.85% by mass of cis-butene, 0.1866% by mass of vinylacetylene and 0.0407% 1-butyne mass.

Example 3: Telomerization under the addition of hydrogen (according to the invention):

In a 100 ml Schlenk tube, 55 mg (0.181 mmol) of palladium acetylacetonate and 0.384 g (0.96 mmol) of 1,3-bis o-cresolate (2,4,6-) were dissolved under protective gas trimethylphenyl) imidazolium-ocresol in 50.2 g (1.57 mol) of methanol. In a 3-liter autoclave from Büchi, 6.98 g (0.064 mol) of o-cresol - heated to 40 ° C in a water bath - and 3.95 g (0.070 mol) of sodium methanolate were dissolved in 115, 2 g (3.59 mol) of methanol and in 100.7 g (0.52 mol) of tripropylene glycol. Then, with the help of a canister of pressurized gas, 526 g of a mixture of C4 hydrocarbons were introduced under pressure into the autoclave (quantitative determination by loss of mass in the C4 reserve bottle).

Without heating the reaction mixture, it was compressed in each case to 0.1 MPa of hydrogen after 1 min, 3 h 2 min, 22 h 35 min, 25 h 10 min, 27 h 11 min, 29 h, 50 min and 49 h 10 min, and the concentration of the alkynes in the C4 gas sample was measured by means of a gas chromatograph (GC). The autoclave was heated to the reaction temperature (80 ° C) after 52 h 45 min under stirring. The reaction duration at 80 ° C was 8.5 h.

CG (1st column: DB-WAX / AI2O3, 2nd column: DB-Wax / HP5MS; initial temperature: 50ºC, maximum temperature: 200ºC, start time: 1 min, equilibrium time: 3 min; temperature program: 50ºC at 15ºC min-1 up to 200ºC, operating time: 11 min; injection: 220ºC, (constant flow), tR (C4 hydrocarbons) = 2762 min, tR (methanol) = 3152 min, tR (1,7-octadiene) = 3866 min, tR (trans-1,6octadiene) = 3958 min, tR (cis-1,6-octadiene) = 4030 min, tR (cis-1,3,7-octatriene) = 4291 min, tR (trans1, 3,7-octatriene) = 4292 min, tR (vinylcyclohexene) = 4448 min, tR (i-butane) = 4552 min, tR (n-butane) = 4822 min, tR (3-MODE) = 5523 min, tR ( trans-butene) = 6116 min, tR (1-butene) = 6240 min, tR (i-butene) = 6412 min, tR (cis-butene) = 6616 min, tR (1-MODE) = 6650 min, tR ( 1,2-butadiene) = 6900 min, t R (1,3butadiene) = 7526 min.

image17

2,7-octadienyl-1-methyl ether (= 1-MODE)

1,7-octadien-3-methyl ether (= 3-MODE).

In the example according to the invention a mixture of C4 hydrocarbons with 43.48% by weight of 1,3-butadiene, 3.58% by mass of i-butane, 5.69% by mass of n-butane was used , 4.00% by mass of trans-butene, 14.78% by mass of 1-butene, 24.9% by mass of i-butene, 2.56% by mass of cisbutene, and 0.005% by mass of tip 0.6299% by mass of vinyl acetylene and 0.1058% by mass of 1-butyne (7407 ppm by mass of alkynes).

Example 4: Telomerization under the addition of hydrogen (according to the invention):

In a 100 ml Schlenk tube, 57.6 mg (0.189 mmol) of palladium acetylacetonate and 0.399 g (0.76 mmol) of 1,3-bis o-cresolate (2,4, 6-trimethylphenyl) imidazolium-ocresol in 51.3 g (1.60 mol) of methanol. In a 3-liter autoclave from Büchi, 6.90 g (0.064 mol) of o-cresol - heated to 40 ° C in a water bath - and 3.80 g (0.070 mol) of sodium methanolate were dissolved in 115, 1 g (3.59 mol) of methanol and in 102 g (0.53 mol) of tripropylene glycol. Then, with the help of a canister of pressurized gas, 495 g of a mixture of C4 hydrocarbons were introduced under pressure into the autoclave (quantitative determination by loss of mass in the C4 reserve bottle). The autoclave was heated under stirring to the reaction temperature (80 ° C) and the palladium-containing solution was added once to the autoclave content. Then, it was pressed to 1.4 MPa of hydrogen and the reaction was monitored with the help of an in-line gas chromatograph. The duration of the reaction was 14 h.

CG (1st column: DB-WAX / AI2O3, 2nd column: DB-Wax / HP5MS; initial temperature: 50ºC, maximum temperature: 200ºC, start time: 1 min, equilibrium time: 3 min; temperature program: 50ºC at 15ºC min-1 up to 200ºC, operating time: 11 min; injection: 220ºC, (constant flow), tR (C4 hydrocarbons) = 2762 min, tR (methanol) = 3152 min, tR (1,7-octadiene) = 3866 min, tR (trans-1,6octadiene) = 3958 min, tR (cis-1,6-octadiene) = 4030 min, tR (cis-1,3,7-octatriene) = 4291 min, tR (trans1, 3,7-octatriene) = 4292 min, tR (vinylcyclohexene) = 4448 min, tR (i-butane) = 4552 min, tR (n-butane) = 4822 min, tR (3-MODE) = 5523 min, tR ( trans-butene) = 6116 min, tR (1-butene) = 6240 min, tR (i-butene) = 6412 min, tR (cis-butene) = 6616 min, tR (1-MODE) = 6650 min, tR ( 1,2-butadiene) = 6900 min, t R (1,3butadiene) = 7526 min.

2,7-octadienyl-1-methyl ether (= 1-MODE)

1,7-octadien-3-methyl ether (= 3-MODE).

In the example according to the invention a mixture of C4 hydrocarbons with 44.69% by mass of 1,3-butadiene, 2.56% by mass of i-butane, 4.82% by mass of n-butane was used , 3.96% by mass of trans-butene, 15.50% by mass of 1-butene, 24.68% by mass of iso-butene, 2.76% by mass of cis-butene, and 0.0415% by mass of gratuity, 0.4609% by mass of vinylacetylene and 0.2328% by mass of 1butyne (7350 ppm by mass of alkynes).

image18

Table 2: Summary of the results of Examples 1 to 4

image19

Example 1

Example 2 Example 3 Example 4

Min time

% Conversion Sel. MODE% * Yield MODE  Min time % Conversion Sel. MODE% * Yield MODE  Min time % Conversion Sel. MODE% * Yield MODE  Min time % Conversion Sel. MODE% * Yield MODE

0

0.67 100 0.5  0 2.6 100 2.6  0 3.62 100 3.2  0 2.57 96.8 2.6

140

65.22 96.53 62.0  140 1.53 90.48 1.4  140 84.07 96.59 75.3  140 37.45 96.42 26.0

350

97.71 96.37 93.3 380 1.75 82.18 1.4 330 98.0 96.27 88.3  350 96.22 96.83 74.8

710

99.33 95.89 94.4 800 2.18 72.13 1.6 510 98.64 95.82 89.1 770 99.06 95.76 76.1

* Sel MODE = Selectivity MODE between C8 products Yield % MODE = mol MODE (of CG) for each mole of butadiene in the educt * 2 * 100%

As can be easily recognized by the comparison of Examples 1 and 2, the presence of acetylenes in the C4 hydrocarbon mixture used leads to an inhibition of the catalyst, so that telomerization does not take place under otherwise identical conditions. In Example 3, one starts from a mixture of C4 hydrocarbons that still has a large proportion of alkynes. Hydrogen is regularly added to the reaction mixture. After approx. 37 hours a slow start of the reaction can be observed, also at low temperature. After a subsequent increase in temperature, telomerization can be observed, despite the presence of alkynes, in the starting C4 hydrocarbon mixture. By adding a hydrogen source to the reaction mixture according to the invention, the inhibited catalyst could be activated again.

Also by Example 4 it is confirmed that by the presence of hydrogen in the telomerization reaction, the alkyne inhibitory effect can be neutralized. In Example 4, hydrogen is supplied dosed shortly before the start of the reaction, and immediately the mixture is heated to 80 ° C. Despite the high amount of alkyne with respect to Example 2, in the presence of hydrogen a high degree of product formation can be observed, even though the reaction rate could not be fully recovered with respect to Example 1. As a secondary reaction hydrogenation of butadiene is observed to give butenes.

The particularly high conversion, as compared to Examples 1 and 4, at the beginning of the reaction in Example 3 is presumably attributed to the alkynes that deactivate the catalyst were already completely separated by hydrogenation before the start of the reaction itself in the presence of the telomerization catalyst and, eventually, the deactivated catalyst was activated again. The higher MODE yield in Example 3 compared to Example 4 is presumably justified because in the case of the one-time addition of hydrogen according to Example 4 such a large excess of hydrogen is present in the reaction mixture. that the hydrogenation of butadiene to give butenes occurs in an increased manner as a competitive reaction to the hydrogenation of the alkynes. Another reason that in Example 3 the amount of MODE is greater in the case of a time of permanence / duration of the comparable reaction, could be that the regeneration does not run very quickly, but in parallel yes the hydrogenation and telomerization, so that less active catalyst is available. The advantage of the embodiment of the process according to the invention according to Example 4 is that a prolonged stage of prior hydrogenation or prior regeneration can be waived, as is carried out in Example 3.

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Claims (17)

1.- Procedure for the telomerization of non-cyclic olefins with at least two conjugated double bonds (VI) with at least one nucleophile (VII) using a catalyst containing a metal of Groups 8, 9 or 10 of the Periodic System of the Elements, characterized in that in the global process of telomerization there is at least a partial stage in which, through a source of hydrogen, chosen from a gas that has hydrogen, hydrogen is added to the mixture of the process present in this partial stage 2. Method according to claim 1, characterized in that as a raw material a mixture of hydrocarbons is used which has non-cyclic olefins with at least two conjugated double bonds in admixture with other hydrocarbons. 3. Method according to claim 2, characterized in that the mixture contains up to 5% by mass of alkynes. 4. Process according to claim 3, characterized in that the mixture contains alkyls selected from vinyl acetate and 1-butyne. 5. Process according to claims 3 or 4, characterized in that a part of the alkynes present is selectively hydrogenated before being used in telomerization. 6. Method according to at least one of claims 3 to 5, characterized in that by means of the hydrogen source so much hydrogen is provided to the global process that the molar ratio of hydrogen to alkyne amounts to at least 1 to 1. 7. Method according to at least one of claims 2 to 6, characterized in that the mixture contains more than 90% by mass of C4 hydrocarbons. 8. Method according to at least one of claims 1 to 7, characterized in that 1,3-butadiene or isoprene is used as non-cyclic olefins. 9. Method according to at least one of claims 1 to 8, characterized in that a palladium-carbine complex having a carbine ligand of the general formula (VIII) is used as a telomerization catalyst: image 1 with R2; R3: same or different a) alkyl groups with 1 to 24 carbon atoms, linear, branched, substituted or unsubstituted, cyclic or alicyclic, or b) aryl groups with 6 to 24 substituted or unsubstituted, monocyclic or polycyclic carbon atoms, or c) heterocycle with 4 to 24 monocyclic or polycyclic carbon atoms, substituted or unsubstituted, and at least one heteroatom of the group N, O and S, R ’, R”: same or different hydrogen, alkyl, aryl, heteroaryl, -CN, -COOH, -COO-alkyl-, -COO-aryl-, -OCO-alkyl, OCO-aryl-, -OCOO-alkyl-, -OCOO-aryl-, -CHO , -CO-alkyl-, -CO-aryl-, -O-alkyl, -O-aryl-, image2 5 10 fifteen twenty 25 30 35 NH2, -NH (alkyl) -, -N (alkyl) 2-, -NH (aryl) -, -N (alkyl) 2-, -F, -Cl, -Br-, -I, -OH, -CF3, -NO2, -ferrocenyl, -SO3H, -PO3H2, where the alkyl groups contain 1-24 and the aryl and heteroaryl groups 5 to 24 carbon atoms, and the radicals R 'and R "may also be part of an aliphatic or aromatic bridge ring. 10. Method according to at least one of claims 1 to 8, characterized in that a palladium-carbine complex having a carbine ligand of the general formulas IX, X, XI and XII is used as a telomerization catalyst: image 1 with R2; R3: same or different a) alkyl groups with 1 to 24 carbon atoms, linear, branched, substituted or unsubstituted, cyclic or alicyclic, or b) aryl groups with 6 to 24 substituted or unsubstituted, monocyclic or polycyclic carbon atoms, or c) heterocycle with 4 to 24 monocyclic or polycyclic carbon atoms, substituted or unsubstituted, and at least one heteroatom of the group N, O and S, and R4, R5, R6, R7: same or different hydrogen, alkyl, aryl, heteroaryl, -CN, -COOH, -COO-alkyl-, -COO-aryl-, OCO-alkyl, -OCO-aryl-, -OCOO-alkyl-, -OCOO-aryl-, -CHO , -CO-alkyl-, -CO-aryl, -O-alkyl, -O-aryl-, -NH2, -NH (alkyl) -, -N (alkyl) 2-, -NH (aryl) -, -N (alkyl) 2-, -F, -Cl, -Br-, -I, -OH, -CF3, -NO2, -ferrocenyl, -SO3H, -PO3H2, wherein the alkyl groups contain 1-24 and the aryl groups and heteroaryl 5 to 24 carbon atoms, and the radicals R4, R5, R6 and R7 may also be part of an aliphatic or aromatic bridge ring. 11. Method according to one of claims 9 or 10, characterized in that the ratio of ligand to metal [mol / mol] in the reaction mixture amounts to 0.01 to 1 to 250 to 1. 12. Method according to one of claims 1 to 11, characterized in that as nucleophile VII compounds of the general formulas VIIa, VIIb or VIIc are used R1a-O-H (R1a) (R1b) N-H R1a-COOH VIIa VIIb VIIc wherein R1a and R1b, independently of one another, are selected from hydrogen, an alkyl group, an alkenyl group or a linear, branched or cyclic C1 to C22 alkynyl group, a C5 to C18 aryl group or a -CO-alkyl group (C1-C8), or a group -CO-aryl- (C5-C10), where these groups may contain substituents chosen from the group -CN, -COOH, -COO-alkyl- (C1-C8), -CO- alkyl- (C1-C8), -aryl- (C5-C10), -COO-aryl (C6-C10), -CO-aryl- (C6-C10), -O-alkyl- (C1-C8), - O-CO-alkyl- (C1-C8), -N-alkyl2- (C1-C8), -CHO, -SO3H, -NH2, -F, -Cl, -OH, -CF3 and -NO2, and where the radicals R1a and R1b can be linked to each other through covalent bonds. image3 13. Method according to claim 12, characterized in that water, alcohols, phenols, polyols, carboxylic acids, ammonia and / or primary or secondary amines are used as the nucleophile (VII). 14. Method according to one of claims 1 to 13, characterized in that the telomerization is carried out in the presence of a solvent. 15. Method according to one of claims 1 to 14, characterized in that the telomerization is carried out in the presence of a solvent, the nucleophile being used as solvent. (VII) and / or inert organic solvents. 16. Method according to one of claims 1 to 15, characterized in that the source of hydrogen is added to the overall process of telomerization in the reaction stage. 17. Method according to one of claims 1 to 16, characterized in that the global telomerization process has a catalyst recycling stage, and the hydrogen source is added to the global telomerization process in the catalyst recycling stage.