CN101010275B

CN101010275B - Method for the telomerization of non-cyclic olefins

Info

Publication number: CN101010275B
Application number: CN200580029241.8A
Authority: CN
Inventors: C·博格曼; D·罗特格; D·奥尔特曼; R·布科尔; S·豪布雷克茨; F·尼尔利克
Original assignee: Oxeno Olefinchemie GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2004-08-28
Filing date: 2005-08-23
Publication date: 2013-05-08
Anticipated expiration: 2025-08-23
Also published as: ES2360865T3; CN101014559B; CN101018754B; CN101014559A; CN101018754A; CN101010275A

Abstract

Disclosed is a method for telomerizing non-cyclic olefins comprising at least two conjugated double bonds with at least one electron donor by using a catalyst that contains a metal from group 8, 9, or 10 of the periodic table of elements. The inventive method is characterized in that the entire telomerization process includes a catalyst recirculation step in which hydrogen is added to the mixture provided in said step via a hydrogen source.

Description

The telomerization method of non-ring olefin

The present invention relates to have the telomerization method of the non-ring olefin of at least two conjugated double bonds, especially by making the hydrocarbon mixture that contains 1,3-butadiene, cracking C particularly ₄react to prepare 1-suffering-2 with nucleophilic reagent, the method for 7-dialkylene derivative.

By the nucleophilic reagent of the 1,3-butadienes of two moles and a mole, formed to telomerize product (unsaturated amine, unsaturated alcohol and ester thereof and ether) be the raw material of organic synthesis.Containing oxygen derivative is to prepare chain C ₈-ol and C ₈the precursor of-alkene, especially 1-octanol and 1-octene.After the 1-octanol again for, for example, obtain softening agent.The 1-octene is the valuable common monomer for polyethylene and polypropylene modification.

Divinyl reacts the telomerization method that obtains the octadienyl derivative with nucleophilic reagent be by metal complexes, and particularly palladium compound carrys out catalysis.

The example of telomerization especially referring to, E.J.Smutny, J.Am.Chem.Soc., 1967,89,6793; S.Takahashi, T.Shibano, N.Hagihara, Tetrahedron Lett., 1967,2451; EP-A-0561779, US3499042, US3530187, GB1178812, NL6816008, GB1248593, US3670029, US3670032, US3769352, US3887627, GB1354507, DE2040708, US4142060, US4146738, US4196135, GB1535718, US4104471, DE2161750 and EP-A-0218100.

Raw material for the preparation of the octadienyl derivative can be pure 1,3-butadiene or the hydrocarbon mixture that contains 1,3-butadiene, as cracking C ₄.

Because the subtractive process cost is higher and inconvenient, therefore, 1,3-butadiene is relatively costly raw material.Thereby, as a rule more economical feasible be to select hydrocarbon mixture containing 1,3-butadiene as telomerizing raw material.The material coexisted due to major part, as stable hydrocarbon, such as normal butane or Trimethylmethane, or monoolefine, such as iso-butylene and linear butenes, to telomerization, be inertia, therefore, above-mentioned selection is possible.Only have inhibitor, that is, the material that can reduce space-time yield or selectivity or increase catalyst consumption should remove in advance.

According to DE19523335, suggestion is when using the C that comes from the naphtha cracking device ₄cut as containing the raw material of 1,3-butadiene the time, limit the concentration of acetylenic compound and diolefine in the telomerization thing.The summation of acetylene series and diolefinic unsaturated compound should be no more than take the 1 quality % that 1,3-butadiene is basis.In order to remove these interfering components, can not need to mention or quote special technique with reference to known technique.

With reference to this patent (DE19523335), DE10149348, DE10229290 and DE10329042, show, to remove acetylene series and diolefinic compound before telomerizing be favourable but specifically do not indicate concentration limit.

WO 91/09822 shows, when having acetylenically unsaturated compound, by the C by obtaining in petroleum naphtha, diesel oil or LPG cracking process ₄it is suitable that this acetylenically unsaturated compound is removed in the mixture selective hydrogenation.But unexposed hydrogenation process.In an embodiment, use is the acetylene total amount lower than 60ppm and not containing the raw material of the diolefine of any appointment content.

Acetylenic compound can pass through extraction or the hydrogenation and removing of these compounds.In passing through the process of hydrogenation and removing acetylenic compound (methylacetylene (propine), ethylacetylene (butine), vinylacetylene (butenyne)), the method of using is, wherein acetylenic compound highly selective hydrogenation is not made basically to the method for 1,3-butadiene and monoolefin hydrogenation.The catalyzer used is to comprise the combination of copper, copper and alkali-metal combination, copper and precious metal or the metal catalyst of periodic table of elements transition VIII family metal, as the hydrogenation catalyst of palladium catalyst.Corresponding process is especially referring to following patent: US 6576588, and US 6417419, and US 6225515, and US 6015933, US6194626, US 6040489, and US 4493906, US 4440956, and US 4101451, US3912789, US 3751508, and US 3541178, and US 3327013, US 3218268, EP1217060, and EP 1151790, EP 1070695, and EP 0273900, and NL 6613942.

By the hydrogenation and removing diolefine, 1，2-butadiene especially, it is more difficult in fact with the selectively removing acetylenic compound, to compare.In hydrogenation process, the reactive behavior of 1，2-butadiene is only slightly higher than 1,3-butadiene.Therefore, remove 1，2-butadiene by hydrogenation from contain the hydrocarbon mixture of 1,3-butadiene and will inevitably will lose 1,3-butadiene.

For example, describe a kind of method of acetylenic compound and 1，2-butadiene that simultaneously removes in WO 98/12160 in detail in reactive distillation column, on palladium catalyst, by hydrogenation from contain the hydrocarbon stream of 1,3-butadiene.Although reported in embodiment 1: in overhead product, the content of acetylenic compound has only reduced approximately 60%, and the content of 1，2-butadiene has only reduced by 32%,, 3% 1,3-butadiene is arranged nearly because hydrogenation has been lost.

At Angew.Chem., 2005,117, in 2062-2065, the people such as Jeroen W.Sprengers report, there is the N-heterocyclic bond and be suitable as hydrogenation catalyst as the Pd composition catalyst of part, especially be suitable for 1-phenyl-1-propine is hydrogenated to 1-phenyl-1-propylene and 1-phenyl-1-propane.

According to prior art, by telomerizing by cracking C ₄in the process of preparation 2,7-octadienyl derivative, need to use complicated technique (especially aspect equipment complexity) to remove the inhibitor in raw mix, as alkynes.The disadvantage of these techniques is, a part of 1,3-butadiene, and particularly, when attempt makes alkynes content in raw mix lower than detection limit, a part of 1,3-butadiene can be lost in removing the process of inhibitor.When by saving when basically removing inhibitor fully and avoiding the loss of 1,3-butadiene, have to be received in space time yield lower in the process of telomerizing or selectivity or higher catalyst consumption.

Therefore, the object of the present invention is to provide a kind of alternative telomerization method, it preferably avoids some or all disadvantage of above-mentioned prior art.

Surprisingly, have been found that now hydrogen joined at least one step of whole telomerization method and can prevent telomerizing the inhibition of catalyzer through hydrogen source, or in the situation that catalyzer be suppressed can be by its reactivate.

Therefore, the invention provides a kind of catalyzer with containing element periodictable 8-10 family metal, telomerize the method for the non-ring olefin (VI) with at least two conjugated double bonds with at least one nucleophilic reagent (VII), it is characterized in that, whole telomerization method comprises the step that at least one adds hydrogen, wherein, through the hydrogen source that is selected from hydrogen-containing gas, hydrogen is joined in the process mixture existed in this step.

Equally, the invention provides a kind of prepare by method of the present invention, mixture of comprising 2,7-octadienyl derivative, and described mixture is for the preparation of the purposes of 1-octene.

The advantage of the inventive method is, can save and remove all inhibitor from raw mix, the very expensive and inconvenient process of especially all alkynes.Except reducing equipment complexity, the method also has an advantage to be, also can avoid using expensive hydrogenation catalyst.

Method of the present invention also has additional advantage, that is, can save and telomerize catalyzer, because it is obviously slower to telomerize the inactivation of catalyzer, if its inactivation.

The inventive method additional advantage is, form diolefine and the cumulene hydrocarbon of organic synthesis important source material, that is, there is the compound of cumulative double bond, as 1, the 2-divinyl, basically be not damaged, but be retained in hydrocarbon stream, and can be in telomerizing the last handling process of product, at the second processing step, after telomerizing step, remove.

Below will describe method of the present invention by example, but do not want to be confined to this, protection scope of the present invention can Accessory Right requires and specification sheets obtains.Claim itself also belongs to open scope of the present invention.When following while mentioning scope, general formula or classes of compounds, they not only are intended to comprise scope or the classes of compounds of clearly mentioning accordingly, and comprise all inferior scopes or the compound subgroup that can obtain by omitting indivedual numerical value (scope) or compound.

In the present invention with the catalyzer of containing element periodictable the 8th, 9 or 10 family's metals, telomerize the method for the non-ring olefin (VI) with at least two conjugated double bonds with at least one nucleophilic reagent (VII), it is characterized in that, whole telomerization method comprises the step that at least one adds hydrogen, wherein, through the hydrogen source that is selected from hydrogen-containing gas, hydrogen is joined in the process mixture of this step.Described hydrogen-containing gas can original position obtain, and for example by the hydrazine original position, is obtained.

The hydrogen source used can be especially the gas that comprises hydrogen, preferably hydrogen itself or hydrogen and for telomerizing the gas for inertia, such as the mixture of nitrogen, methane or rare gas element.

Preferably, just add hydrogen source when starting appropriate step.Hydrogen source preferably is fed in step through the equipment that is suitable for described hydrogen source is distributed into superfine form.When hydrogen source is gas, described equipment can be mixing tank nozzle for example.In order to make gas reach particularly preferred homogenizing in mixture, when processing step pressure is 2Mpa at least, preferably 4Mpa is favourable.When hydrogen source exists with liquid form, for example, by using static mixer just can reach superfine distribution.

The raw material used can be the mixture of the pure non-ring olefin with conjugated double bond, different this alkene or the mixture of one or more described alkene and other hydrocarbon.The raw material used preferably includes the hydrocarbon mixture of one or more non-ring olefins, and preferably, a kind of have the non-ring olefin of at least two conjugated double bonds and a mixture of other alkene.

As the non-ring olefin with conjugated double bond, particularly preferred raw material comprises 1,3-butadiene and/or isoprene, in each situation all as the form of the mixture of the mixture of pure substance, pure substance or one or both alkene and other hydrocarbon.The raw material used is more preferably and comprises the above C of 90 quality % ₄hydrocarbon, the preferably mixture of 1,3-butadiene.

Suitable raw material for the inventive method is more preferably the hydrocarbon stream that is rich in 1,3-butadiene.The hydrocarbon stream used can be especially C ₄hydrocarbon-fraction.Described hydrocarbon stream can be preferably for example 1,3-butadiene and other C ₄and C ₃or C ₅the mixture of hydrocarbon.This mixture for example can derive from for the preparation of the cracking process of ethene and propylene, and wherein refinery gas, petroleum naphtha, gas and oil, LPG (liquefied petroleum gas (LPG)), NGL (natural gas liquids) etc. are converted.The C obtained as by product in described process ₄cut, except 1, outside the 3-divinyl, can also comprise monoolefine (1-butylene, cis-but-2-ene, trans-but-2-ene, iso-butylene), stable hydrocarbon (normal butane, Trimethylmethane), acetylenically unsaturated compound (ethylacetylene (butine), vinylacetylene (butenyne), methylacetylene (propine) and diolefine ethylenically unsaturated compounds (being mainly 1，2-butadiene)).In addition, these cuts can comprise a small amount of C ₃and C ₅hydrocarbon.C ₄the composition of cut depends on cracking process, operating parameters and raw material separately.For the concentration of the various components of steam crackers usually in following scope:

In the method for the invention, preferably use the content of 1,3-butadiene to be greater than the hydrocarbon mixture of 35 quality %.

What raw material hydrocarbon can comprise trace usually can be interfering oxygen compound, nitrogen compound, sulphur compound, halogen compounds, especially chlorine compound and heavy metal compound in the method for the invention.Therefore, suitable is at first to remove these materials.Interfering compound can be for example carbonic acid gas or carbonyl compound, as acetone and acetaldehyde.

These impurity can for example pass through washing, especially water or solution washing, or pass through adsorbing and removing.

Washing can partially or completely remove hydrophilic component from hydrocarbon mixture, as the nitrogen component.The example of nitrogen component is acetonitrile or N-Methyl pyrrolidone (NMP).Oxygen compound also can part remove by water elution.Washing directly water is carried out, or also with comprising for example salt, such as NaHSO ₃the aqueous solution carry out (US3682779, US3308201, US4125568, US3336414 or US5122236).

Can advantageously, after washing, make hydrocarbon mixture pass through drying step.Dry can being undertaken by method known in prior art.In the situation that there is dissolved water, drying can for example be carried out as siccative or by component distillation with molecular sieve.Free-water can, by being separated, for example use coalescent filter (Koaleszer) to remove.

Adsorber can be for removing trace impurity.Therefore this is particularly advantageous, because use noble metal catalyst in telomerizing step, and it even can react with the impurity of trace and obviously reduces its activity.Usually, remove denitrification or sulphur compound by the upstream adsorber.The example of operable sorbent material is the clay (as US 4571445 or WO 02/53685) of aluminum oxide, molecular sieve, zeolite, activated carbon or metal impregnation.Sorbent material is on sale in many companies, and the name of selling as UOP or Axens company is called Selexsorb alcoa, for example product line SAS, MS, AA, TG, TGS or CMG.

Use method of the present invention, especially can use raw mix, wherein especially also contain diolefinic unsaturated compound and/or content and be more than or equal to 50 quality (wppm), preferably greater than or equal to the acetylenically unsaturated compound of 100 quality ppm.In the method for the invention, the raw material of use can be preferably to comprise non-ring olefin with conjugated double bond, comprise the highest 5 quality %, preferably the highest 3 quality %, the more preferably mixture of the highest 1 quality % alkynes or acetylenically unsaturated compound.Owing to can using the raw mix that still comprises a small amount of acetylenically unsaturated compound, therefore, can use a large amount of hydrocarbon mixture obtained, especially C in industry ₄or C ₅hydrocarbon mixture, directly as the raw material for telomerizing in the inventive method.Will there is obviously relatively large acetylenically unsaturated compound in possible raw mix, can be advantageously, for before telomerizing, for example by selective hydrogenation or extraction, remove the acetylenically unsaturated compound (alkynes) that at least a portion exists from this mixture, thereby making raw mix used can be to comprise the 0-5 % by weight, preferred 50wppm-3 quality %, the more preferably mixture of the acetylenically unsaturated compound of 100wppm-1 quality %.The method of extraction or selective hydrogenation can be with reference to prior art.

Remove acetylenic compound by extraction for some time known, and, as post-processing step, be from cracking C ₄the integral part of the integral body of most of devices of middle acquisition 1,3-butadiene.From cracking C ₄the method that middle extraction removes acetylenically unsaturated compound referring to, for example, Erd

lund Kohle-Erdgas-Petrochemie vereinigt mit Brennstoffchemie, the 34th volume, the 8th phase, in August, 1981,343-346 page.In the method, in the first stage, by carry out extractive distillation with moisture NMP, remove many unsaturated hydrocarbons and acetylenically unsaturated compound from monoolefine and stable hydrocarbon.From the NMP extract, distillation removes unsaturated hydrocarbons.From the hydrocarbon distillment, carry out extractive distillation for the second time with moisture NMP, remove the acetylenically unsaturated compound with 4 carbon atoms.At cracking C ₄aftertreatment in, remove pure 1,3-butadiene by twice other distillation, the by product obtained is methylacetylene and 1，2-butadiene.In the method for the invention, multistep method described here can be used as the pre-treatment of raw mix to carry out, and in this case, can save the step that distillation removes 1，2-butadiene.

Optionally, can use one or more ionic liquids, such as extraction agent, from contain the logistics of 1,3-butadiene, removing acetylenic compound.

By extraction, obtain, preferably comprise lower than the hydrocarbon stream of 5 quality % acetylenic compounds more preferably can be directly as raw material for method of the present invention.

In the situation that have diolefine and monoolefine, by partly being removed to acetylenically unsaturated compound from the hydrocarbon stream that will use, the acetylenically unsaturated compound selective hydrogenation can or carry out at mixed catalyst at for example cupric or palladium-containing catalyst.

If there is acetylenically unsaturated compound,, for the raw material of the inventive method, especially works as and use the C that contains 1,3-butadiene ₄during hydrocarbon mixture, will comprise the acetylenically unsaturated compound that is preferably selected from vinylacetylene and/or ethyl acetylene.

While in raw mix, having alkynes, preferably by hydrogen source, in whole technique, add enough hydrogen, so that the mol ratio of hydrogen and acetylenically unsaturated compound (alkynes) is at least 1: 1, preferably 1: 1-2: 1, more preferably 1: 1-1.5: 1, most preferably 1: 1-1.1: 1.Obviously surpass the non-ring olefin that these numerical value can cause having conjugated double bond, as the 1,3-butadiene loss.In raw mix the concentration of alkynes can be for example by gas-chromatography constantly or with regular time interval measure.

In the method for the invention, can use all catalyzer that are suitable for telomerizing.The catalyzer that is preferred for telomerizing is the metal complexes of palladium metal (Pd), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni) or platinum (Pt).The part used can be phosphorus part for example, such as phosphine, inferior phosphine (Phosphinine), phosphinates (Phosphinite), phosphonate (Phosphonite) or phosphite as triphenylphosphine or carbenes, are used different parts also favourable simultaneously.Particularly preferably use the metal carbene title complex as catalyzer.

Particularly preferably use palladium compound, especially palladium-arbine complex is as the catalyzer that telomerizes step.Part in the metal complexes used as catalyzer is trivalent phosphorous compound or Cabbeen more preferably.

Particularly preferably use and there is the metal complexes of at least one stable carbenes by heteroatoms as catalyzer.The example of this part is especially referring to file DE10128144, DE10149348, DE10148722, DE10062577, EP1308157 and WO 01/66248.These files, the part of particularly wherein describing all is included in the application's disclosure.In addition, labile coordination compound can comprise other part.Carbenes can be open part or ring-type part.

Palladium-the arbine complex that catalyzer preferably has the described carbenes of general formula (VIII) that telomerizes for the inventive method:

Wherein, R ², R ", R ' and R ³can be identical or different, can be hydrogen or alkyl separately, wherein alkyl can be identical or different, be straight chain, side chain or cyclic group, be selected from the alkyl with 1 to 50 carbon atom, there is the thiazolinyl of 2 to 50 carbon atoms, alkynyl with 2 to 50 carbon atoms, and the aryl with 6 to 30 carbon atoms, wherein at least one hydrogen atom can be substituted by the functional group

And/or R ²and R " and/or R ' and R ³each is the part of ring bodies system naturally, and it can be identical or different, and its carbon skeleton has 2 to 20 carbon atom and nitrogen-atoms, wherein R according to formula VIII ²and R " and/or R ' and R ³carbon atom do not count, and wherein in the ring-type system at least one hydrogen atom can be substituted by functional group and/or the ring-type system at least one carbon atom heteroatoms that can be selected from S, P, O and N substitute.

And/or R ²and/or R " and/or R ' and R ³by being connected with ligand L by 1 to 20 bridge that carbon atom forms, radicals R wherein ², R ", R ' and R ³carbon atom do not count,

With L be other part, it is two neutral electron donor(ED)s, a part and/or the anion ligand of ring-type system, wherein said functional group can for example be selected from following group :-CN,-COOH ,-COO-alkyl ,-COO-aryl,-OCO-alkyl ,-OCO-aryl ,-OCOO-alkyl,-OCOO-aryl ,-CHO ,-CO-alkyl,-CO-aryl,-O-alkyl ,-O-aryl ,-NH ₂,-NH (alkyl) ,-N (alkyl) ₂,-NH (aryl) ,-N (aryl) ₂,-F ,-Cl ,-Br ,-I ,-OH ,-CF ₃,-NO ₂, ferrocenyl ,-SO ₃h and-PO ₃h ₂, wherein alkyl can comprise for example 1 to 24 carbon atom, and aryl 5 to 24 carbon atoms for example.The preparation of this class part can reference example as DE10148722.

The method according to this invention, the telomerization catalyzer of use is preferably palladium-arbine complex, and it has the carbenes as general formula VIII,

Wherein:

R ²; R ³: identical or different separately, for thering is the straight chain of 1 to 24 carbon atom, side chain, replacement or unsubstituted ring-type or alicyclic ring shape alkyl, or there is replacement or unsubstituted, list or the polyaromatic of 6 to 24 carbon atoms, or

There is 4 to 24 carbon atoms and at least one and be selected from N, O, heteroatomic single or many rings, the replacement of S or unsubstituted heterocycle,

R ', R ": identical or different separately, be 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 ,-NH ₂,-NH (alkyl) ,-N (alkyl) ₂,-NH (aryl) ,-N (alkyl) ₂,-F ,-Cl ,-Br ,-I ,-OH ,-CF ₃,-NO ₂, ferrocenyl ,-SO ₃h and-PO ₃h ₂, wherein alkyl comprises 1 to 24 carbon atom, and aryl and heteroaryl comprise 5 to 24 carbon atoms, and R ' and R " and group can also be the part of bridge aliphatic series or aromatic ring.

Very particularly preferably use and there is pentacyclic carbenes.Having five-ring and being preferred for part in the inventive method is following formula I X for example, X, those parts of XI and XII

R wherein ²; R ³: identical or different separately, for

Straight chain, side chain, replacement or unsubstituted, ring-type or alicyclic ring shape alkyl with 1 to 24 carbon atom, or

Replacement or unsubstituted, list or polyaromatic with 6 to 24 carbon atoms, or

There is 4 to 24 carbon atoms and at least one heteroatoms and be selected from N, O, the list of S or many rings, replacement or unsubstituted heterocycle,

R ⁴, R ⁵, R ⁶, R ⁷: identical or different separately, for

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 ,-NH ₂,-NH (alkyl) ,-N (alkyl) ₂,-NH (aryl) ,-N (alkyl) ₂,-F ,-Cl ,-Br ,-I ,-OH ,-CF ₃,-NO ₂, ferrocenyl ,-SO ₃h ,-PO ₃h ₂, wherein alkyl contains 1 to 24 carbon atom, and aryl and heteroaryl contain 5 to 24 carbon atoms, and radicals R ⁴, R ⁵, R ⁶and R ⁷it can also be the part of bridge aliphatic series or aromatic ring.

According to the carbenes of general formula I X or X, and the example of the title complex that contains this part has been described in (W.A.Herrmann, C.K in technical literature

cher, Angew, Chem.1997,109,2257; Angew.Chem.Int.Ed.Engl.1997,36,2162; V.P.W.B

hm, C.W.K.Gst

ttmayr, T.Weskamp, W.A.Herrmann, J.Organomet.Chem.2000,595,186; DE 44 47 066).

Especially, R ²and R ³group can be to contain heteroatomic single or many ring that at least one is selected from elemental nitrogen, oxygen and sulphur, and optionally also has the substituting group that is selected from following group :-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 ,-NH ₂,-NH (alkyl) ,-N (alkyl) ₂,-NH (aryl) ,-N (alkyl) ₂,-F ,-Cl ,-Br ,-I ,-OH ,-CF ₃,-NO ₂, ferrocenyl ,-SO ₃h ,-PO ₃h ₂.Alkyl contains 1 to 24 carbon atom, and aryl contains 5 to 24 carbon atoms.In the situation that use the metal of Pd as 8-10 family in the periodic table of elements, preferably R ²and R ³in part one or both meet above-mentioned definition.

Radicals R ², R ³, R ⁴, R ⁵, R ⁶and/or R ⁷separately can be identical or different, and there is at least one and be selected from following substituting group :-H ,-CN ,-COOH,-COO-alkyl ,-COO-aryl ,-OCO-alkyl ,-OCO-aryl,-OCOO-alkyl ,-OCOO-aryl ,-CHO,-CO-alkyl ,-CO-aryl ,-aryl,-alkyl ,-thiazolinyl ,-allyl group,-O-alkyl ,-O-aryl ,-NH ₂,-NH (alkyl) ,-N (alkyl) ₂,-NH (aryl) ,-N (alkyl) ₂,-F ,-Cl ,-Br ,-I ,-OH ,-CF ₃,-NO ₂, ferrocenyl ,-SO ₃h ,-PO ₃h ₂, wherein alkyl contains 1 to 24, preferred 1-20 carbon atom, and thiazolinyl contains 2 to 24 carbon atoms, and allyl group contains 3 to 24 carbon atoms, and list or polyaromatic contain 5 to 24 carbon atoms.R ₄-R ₆group can for example pass through (CH ₂)-or (CH)-group covalently be connected with each other.

In the situation that substituting group has acid hydrogen atom, proton can be substituted by metal or ammonium ion.

R ²and R ³group can be more preferably such group, and it is derived from five and hexa-atomic assorted alkyl, assorted thiazolinyl and heteroaryl, as Isosorbide-5-Nitrae-dioxane, morpholine, γ-pyrans, pyridine, pyrimidine, pyrazine, the pyrroles, furans, thiophene, pyrazoles, imidazoles, thiazole and

azoles.Following table 1 shows such R ²and R ³the specific examples of group.In this table ,～all expression and five-membered ring or the position that is connected with formula VIII compound in all cases.

Table 1:R ²and/or R ³the example of group

In content of the present invention, carbenes is appreciated that as both referring to can, as the free Cabbeen of part, refer to again be coordinated to the Cabbeen on metal.

Form the catalyst metal of active catalyst under reaction conditions, can be incorporated into by different modes in described technique in particular as the palladium of catalyst metal.

Metal (palladium) can be incorporated in technique in the following manner:

A) with the form of metal-arbine complex (palladium-arbine complex), in this case, metal (palladium) preferably is (II) or (0) valency oxidation state, or

B) with the form of metal precursor (palladium precursor), by this precursor original position, form catalyzer.For a)

Example is palladium (0)-Cabbeen-olefin(e)complex, palladium (0)-bis-arbine complex, and palladium (II)-bis-arbine complex, palladium (0)-Cabbeen-1,6-diene complexes.1,6-diene can be for example 1,1 '-divinyl tetramethyl disiloxane, 2,7-octadienyl ether or 2,7-octadienyl amine.Other example is shown in following formula I-a to I-e.

Can prepare in several ways by the arbine complex of palladium.A kind of simple mode is for example to add carbenes or the ligand exchange on palladium complex is become to carbenes.For example, the title complex of I-f to I-i can obtain (T.Weskamp, W.A.Herrmann, J.Organomet.Chem., 2000,595,186) by the phosphorus part of two (tri-o-tolyl phosphine) palladium (0) title complexs of exchange.

I-f R ²=R ³=

base

I-g R ²=R ³=cyclohexyl

I-h R ²=R ³=the tertiary butyl

I-i R ²=R ³=sec.-propyl

For b)

The palladium precursor used can be acid chloride (II) for example, Palladous chloride (II), palladium bromide (II), the tetrachloro-palladium acid lithium, acetopyruvic acid palladium (II), palladium (0)-dibenzalacetone title complex, propionic acid palladium (II), two acetonitrile-palladiums (II) muriate, bi triphenyl phosphine palladium (II) dichloride, two cyanophenyl-palladiums (II) muriate, two (tri-o-tolyl phosphine) palladiums (0) and other palladium (0) and palladium (II) title complex.

The Cabbeen of general formula I X and X can be to dissociate Cabbeen or use with the form of metal complexes, or they can be obtained by the carbene precursor original position.

Suitable carbene precursor is the salt of the Cabbeen of general formula X III and XIV for example:

Wherein: R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷all, suc as formula defining in IX and X, Y is the monovalent anion group, or, according to stoichiometry, is the part of multivalent anions group.

The example of Y is halogen ion, hydrosulphuric acid root, sulfate radical, alkyl sulfate, aromatic sulfuric acid root, borate, bicarbonate radical, carbonate, alkyl carboxylic acid root, aryl carboxylic acid root.

Corresponding Cabbeen can be by the salt of Cabbeen, for example, by discharging with alkali reaction.

In the method for the invention, the concentration of catalyzer (ppm with catalytic metal in formal situation means (quality)), particularly the metallic palladium based on the total mass meter, be preferably 0.01ppm-1000ppm, more preferably 0.5-100ppm, also 1-50ppm more preferably.Part in reaction mixture, preferably Cabbeen and ratio (mol/mol), particularly Cabbeen of metal and the ratio of palladium are preferably 0.01: 1-250: 1, more preferably 1: 1-100: 1, also more preferably 1: 1-50: 1.Except carbenes, can also there is other part in reaction mixture, as the phosphorus part, such as triphenylphosphine.

The nucleophilic reagent (VII) used is preferably the compound of following general formula:

R ^1a-O-H (VIIa) or (R ^1a) (R ^1b) N-H (VIIb) or R ^1a-COOH (VIIc)

Wherein, R ^1aand R ^1bindependently selected from hydrogen, straight chain, side chain or ring-type C ₁-C ₂₂alkyl, thiazolinyl, alkynyl, C ₅-C ₁₈aryl, or-CO-alkyl-(C ₁-C ₈) group or-CO-aryl-(C ₅-C ₁₀) group, wherein these groups can comprise be selected from-CN ,-COOH ,-COO-alkyl-(C ₁-C ₈) ,-CO-alkyl-(C ₁-C ₈) ,-aryl-(C ₅-C ₁₀) ,-COO-aryl-(C ₆-C ₁₀) ,-CO-aryl-(C ₆-C ₁₀) ,-O-alkyl～(C ₁-C ₈) ,-O-CO-alkyl-(C ₁-C ₈) ,-the N-alkyl ₂-(C ₁-C ₈) ,-CHO ,-SO ₃h ,-NH ₂,-F ,-Cl ,-OH ,-CF ₃with-NO ₂substituting group, and R wherein ^1aand R ^1bgroup can be connected to each other by covalent linkage.The nucleophilic reagent used is R wherein preferably ^1awith optional R ^1bgroup is hydrogen, methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, normal-butyl, sec-butyl, amyl group, hexyl, heptyl, octyl group, octenyl, octadienyl, different nonyl, 2-ethylhexyl, n-nonyl, phenyl, m-, o-or p-methylphenyl, naphthyl, 2,4-di-tert-butyl-phenyl, 2, the compound of 6-di-t-butyl aminomethyl phenyl, hydrogen carbonyl, methyl carbonyl, ethyl carbonyl, propyl group carbonyl or phenylcarbonyl group.

The nucleophilic reagent (VII) used is water more preferably, alcohol, phenol, polyvalent alcohol, carboxylic acid, ammonia and/or uncle or secondary amine.These are especially:

-water, ammonia;

-monohydroxy-alcohol and phenol, as methyl alcohol, ethanol, n-propyl alcohol, Virahol, vinyl carbinol, propyl carbinol, isopropylcarbinol, octanol, 2-Ethylhexyl Alcohol, isononyl alcohol, benzylalcohol, hexalin, suberyl alcohol or 1,7-octadiene-1-alcohol, phenol;

-glycol, as ethylene glycol, 1,2-PD, 1,3-PD, BDO, 1,2-butyleneglycol, 2,3-butanediol, and 1,3 butylene glycol;

-oxy-compound, as the Alpha-hydroxy acetic ester,

-primary amine, as methylamine, ethamine, propylamine, butylamine, octylame, 1,7-octadienyl amine, amino dodecane, quadrol or hexanediamine;

-secondary amine, as dimethylamine, diethylamine, methylphenylamine, two (2,7-octadienyl) amine, dicyclohexyl amine, methyl cyclohexylamine, tetramethyleneimine, piperidines, morpholine, piperazine or hexamethylene imine, or

-carboxylic acid, as formic acid, acetic acid, propionic acid, butyric acid, methylacrylic acid, phenylformic acid, 1,2-benzenedicarboxylic acid (phthalic acid).

For the nucleophilic reagent (VII) that telomerizes step, be very preferably methyl alcohol, ethanol, 2-Ethylhexyl Alcohol, octanol, octenol, octadienyl alcohol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, isononyl alcohol, formic acid, acetic acid, propionic acid, butanic acid, isopropylformic acid, phenylformic acid, phthalic acid, phenol, dimethylamine, methylamine, ammonia and/or water.Advantageously, the nucleophilic reagent of use is methyl alcohol.

The nucleophilic reagent that itself can obtain by telomerization can directly be used, or also can original position form.For example, 2,7-octadiene-1-alcohol can original position under the existence that telomerizes catalyzer be formed by water and divinyl, and 2,7-octadienyl amine can be formed by ammonia and 1,3-butadiene original position, etc.

For nucleophilic reagent in telomerization with there is the ratio of the raw material olefin of at least two conjugated double bonds, must consider the active hydrogen atom number in telogen.For example, methyl alcohol has an active hydrogen atom, and ethylene glycol has two active hydrogen atoms, and methylamine has two active hydrogen atoms etc.

In telomerization, with respect to the active hydrogen atom of every mole of nucleophilic reagent that can react with raw material olefin, preferably use the raw material olefin of 0.001 mole-10 moles.In liquid phase reaction, preferred every mole of active hydrogen atom raw material olefin of 0.1-2 mole.

Favourable while carrying out under the existence of method of the present invention at solvent.When the nucleophilic reagent used is liquid form under reaction conditions, for the solvent of telomerization, can be the nucleophilic reagent itself used, and/or inert organic solvents.When the nucleophilic reagent used is solid form or, when the product that will obtain is solid form under reaction conditions, preferably adds solvent under reaction conditions.Suitable solvent for example, particularly including aliphatic series, cyclic aliphatic and aromatic hydrocarbon, C ₃-C ₂₀alkane, lower paraffin hydrocarbons (C ₃-C ₂₀) mixture, hexanaphthene, cyclooctane, ethylcyclohexane, alkene and polyene hydrocarbon, vinyl cyclohexene, 1,3,7-sarohornene, carry out autothermic cracking C ₄the C of cut ₄hydrocarbon, benzene, toluene and dimethylbenzene; Polar solvent, as uncle and secondary alcohol; Acid amides, as ethanamide, N,N-DIMETHYLACETAMIDE and dimethyl formamide; Nitrile, as acetonitrile and cyanophenyl; Ketone, as acetone, mibk and diethyl ketone; Carboxylicesters, as ethyl acetate; Ether, as dipropyl ether, ether, dme, Methyl Octyl Ether, methyl tertiary butyl ether, Ethyl Tertisry Butyl Ether, 3-methoxyl group octane, two

alkane, tetrahydrofuran (THF), methyl-phenoxide, the alkyl of ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, polyoxyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycol and aryl ethers, and other polar solvents, as tetramethylene sulfone, dimethyl sulfoxide (DMSO), ethylene carbonate, propylene carbonate and water.Also can use ionic liquid, as imidazoles salt or pyridine

salt is as solvent.Described solvent can be used separately or use with the form of the mixture of different solvents.

Carry out the temperature of telomerization preferably 10-180 ℃ of scope, preferably 30-120 ℃, more preferably 40-100 ℃.Reaction pressure is preferably the 1-300 bar, preferably 1-120 bar, more preferably 1-60 bar, most preferably 1-20 bar.

Usually advantageously under the existence of alkali, carry out telomerization.Preferably use pK _bbasic component lower than 7, particularly be selected from the compound of amine, alkoxide, phenol oxide compound, an alkali metal salt or alkaline earth salt.

Suitable basic component is amine for example, and as trialkylamine, it can be alicyclic or/and open chain; Amide; Aliphatic series or/and aromatic carboxylic acid's basic metal or/and alkaline earth salt, as acetate, propionic salt, benzoate or corresponding carbonate, supercarbonate, the alkoxide of alkali metal or alkali earth metal, phosphoric acid salt, hydrophosphate be or/and oxyhydroxide, preferred lithium, sodium, potassium, calcium, magnesium, caesium, ammonium and phosphorus

compound.Preferably add the oxyhydroxide of alkali and alkaline earth metal ions element, and add the metal-salt according to the nucleophilic reagent of general formula III, IV or V.

Preferably use the basic component (based on raw material olefin) of 0.01-10 % by mole, preferably 0.1-5 % by mole, most preferably 0.2-1 % by mole.

Telomerizing can be continuously or periodical operation, and is not limited to use the reactor of particular type.The reactor example that can be reacted is stirred-tank reactor, chain of stirred tanks, tubular reactor and annular-pipe reactor flow.Also can use the combination of different reactor, for example the combination of the mobile tubular reactor of stirred-tank reactor and downstream formula.

In order to obtain high space time yield, telomerize preferably and can not proceed to and make raw material olefin transform fully.Especially particularly like this when raw material olefin is 1,3-butadiene.In this case, preferably transformation efficiency is limited to maximum 95%, more preferably to 88%.

Of the present invention hydrogen is joined in the process mixture existed in a step and can carry out in one or more steps by hydrogen source.When telomerization method of the present invention only has a step, i.e., during telomerization itself, hydrogen will join in this step by hydrogen source certainly.Method of the present invention also preferably includes one or more other steps.This step can be the step of for example Removal of catalyst and optionally catalyst recirculation be got back to the step in reactor.Hydrogen source preferably is added in whole telomerization method in reactions steps.In reactions steps, by hydrogen source, add the favourable part of hydrogen to be, can prevent that the acetylenically unsaturated compound directly existed in reaction mixture from suppressing to telomerize.But, in reactions steps, add the disadvantage of hydrogen to be, reactant or product can be added the unwanted by product of hydrogen evolution, and this can cause yield to reduce.When the acetylenically unsaturated compound adopted and exist is compared excessive hydrogen and telomerized, particularly like this.

When whole telomerization method has the catalyst recirculation step, hydrogen source preferably joins in whole telomerization method in the catalyst recirculation step.The favourable part that hydrogen source is joined in the catalyst recirculation step is, product and reactant have basically been removed in step before from catalyzer, therefore, the hydrogen added by hydrogen source can not be hydrogenated into unwanted by product by valuable reactant or product, thereby can not reduce yield.Hydrogen source had both been joined in reactions steps, joined again in the catalyst recirculation step favourable.

Method of the present invention especially can prepare for the hydrocarbon stream by containing 1,3-butadiene the compound of Formula Il:

Wherein, X is OR ^1aor NR ^1ar ^1bgroup, wherein, R ^1aand R ^1ball independently selected from hydrogen, straight chain, side chain or ring-type C ₁-C ₂₂alkyl, thiazolinyl, alkynyl, C ₅-C ₁₈aryl, or-CO-alkyl-(C ₁-C ₈) group, or-CO-aryl-(C ₅-C ₁₀) group, wherein these groups can comprise be selected from-CN ,-COOH ,-COO-alkyl-(C ₁-C ₈) ,-CO-alkyl-(C ₁-C ₈) ,-aryl-(C ₅-C ₁₀) ,-COO-aryl-(C ₆-C ₁₀) ,-CO-aryl-(C ₆-C ₁₀) ,-O-alkyl-(C ₁-C ₈) ,-O-CO-alkyl-(C ₁-C ₈) ,-the N-alkyl ₂-(C ₁-C ₈) ,-CHO ,-SO ₃h ,-NH ₂,-F ,-Cl ,-OH ,-CF ₃with-NO ₂substituting group, and R wherein ^1aand R ^1bgroup can be connected to each other by covalent linkage.

Use technique of the present invention, especially can react with the nucleophilic reagent (VII) of following formula VIIa, VIIb or VIIc the compound for preparing Formula Il Ia or IIIb by making 1,3-butadiene:

R ^1a-O-H VIIa (R ^1a)(R ^1b)N-H VIIb R ^1a-COOH VIIc

Wherein, R ^1aand R ^1ball as above definition.

Particularly preferably by method of the present invention, preparing wherein X is OR ^1aor NR ^1ar ^1bthe formula II compound of group, wherein:

R ^1ah, methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, normal-butyl, sec-butyl, amyl group, hexyl, heptyl, octyl group, octenyl, octadienyl, different nonyl, 2-ethylhexyl, n-nonyl, phenyl, m-, o-or p-methylphenyl, naphthyl, 2,4-di-tert-butyl-phenyl, 2,6-di-t-butyl aminomethyl phenyl, hydrogen carbonyl, methyl carbonyl, ethyl carbonyl, propyl group carbonyl or phenylcarbonyl group, and/or

R ^1bh, methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, normal-butyl, sec-butyl, amyl group, hexyl, heptyl, octyl group, octenyl, octadienyl, different nonyl, 2-ethylhexyl, n-nonyl, phenyl, m-, o-or p-methylphenyl, naphthyl, 2,4-di-tert-butyl-phenyl, 2,6-di-t-butyl aminomethyl phenyl, hydrogen carbonyl, methyl carbonyl, ethyl carbonyl, propyl group carbonyl or phenylcarbonyl group.Particularly preferably by method of the present invention, prepare wherein R ^1athe formula III a compound of=hydrogen, methyl, ethyl, phenyl or methyl carbonyl.The compound of formula III a and IIIb can be with cis or trans the existence.

The effluent of telomerization step can be such as the nucleophilic reagent that mainly comprises the raw material olefin that telomerizes product, by product, " unreactive hydrocarbons ", residual volume, residual volume and catalyst system (catalyst metal, part and optional alkali etc.) or its solvent that continues and produce thing and optionally add, or its composition.The effluent of telomerization step can extremely normally pass through known commercial run, especially thermal separation process, as the distillation or the extraction and separated.For example, can carry out fractionation by distillation, be separated into following cut:

-C ₄cut, comprise normal butane, Trimethylmethane, 1-butylene, 2-butylene, iso-butylene, 1,3-butadiene, 1，2-butadiene and optionally, all or some nucleophilic reagent;

-comprise the cut of target product (2,7-octadienyl derivative);

-comprise the cut of by product; And/or

-comprise the cut of catalyzer; With

-optionally, comprise the cut of nucleophilic reagent, and/or

-optionally, solvent cut.

The cut, the cut that comprises solvent and the cut that comprises catalyzer that comprises nucleophilic reagent be can be separately all or part of, together with or be recycled in reactions steps respectively, or also can be fed in post-processing step.Preferably these cuts are looped back in reactions steps.

But, separate and also can carry out to such an extent that have to two kinds of components.In this case, a kind of cut comprises most target product, and the second cut comprises most used catalyst.Containing all or part of recirculation after the cut of catalyzer, get back in reactions steps.

The precursor of other materials is used or be used as to the target product former state.For example, can be by by two double-bond hydrogenations, then eliminate methyl alcohol and, by 1-methoxyl group suffering two-2,7-alkene target product prepares the 1-octene.Therefore contain 1-methoxyl group suffering two-2, the mixture of 7-alkene by utilizing method of the present invention, can preparing.These mixtures then can be for the preparation of the 1-octene.

When the nucleophilic reagent for telomerizing is methyl alcohol or ethanol, use C ₄hydrocarbon stream is as raw material (1, the 3-divinyl is as raw material olefin) can provide a kind of selection,, select not remove nucleophilic reagent from reaction product, but can be by target product (as 1-methoxyl group suffering two-2,7-alkene) hydrogenation effluent is directly delivered to etherification step, wherein is used as alcohol and the C of nucleophilic reagent ₄the isobutene reaction existed in logistics, generate methyl tertiary butyl ether or Ethyl Tertisry Butyl Ether.This reaction is also to carry out according to industrial known method, usually under the catalysis of ion-exchanger, carries out.For iso-butylene is transformed fully, must add in addition alcohol in some cases.

Below with reference to Fig. 1, the present invention is carried out to detailed illustrating, but do not want to limit the invention to the embodiment shown in Fig. 1.Fig. 1 schematically shows a kind of possible embodiment of the inventive method.The whole telomerization method here comprises three steps: a telomerization step (Telo), one removes step (A), and a catalyst recirculation step (KR).In reactions steps (Telo), transmission together with reactant stream and catalyst recirculation logistics (KR) and optional sources of hydrogen (WQ1).The reaction mixture as reaction product (P1) obtained is transferred in next step (A), and there, catalyzer and optional solvent are removed out from all the other components of reaction mixture.The product mixtures (P2) containing catalyzer can not be sent in another post-processing step.The catalyzer that removes out is sent back in reactant stream by catalyst recirculation (KR).In the catalyst recirculation process, also sources of hydrogen (WQ2) can be joined in catalyst stream.When carrying out method of the present invention, can be sources of hydrogen by WQ1 or WQ2 or be fed in one or more steps of whole telomerization method by WQ1 and WQ2 simultaneously.Self evident, when carrying out described technique, can exist or must have other equipment, such as pump or valve etc., or, the device of for example for discharging a part, discarding catalyzer and/or adding live catalyst, but these equipment are also not shown in Fig. 1.

The following examples are for illustrating in detail the present invention, rather than restriction protection scope of the present invention, and scope of the present invention is apparent by specification sheets and claims.

Embodiment

Embodiment 1: do not have telomerizing in the alkynes situation

In 100ml Schlenk pipe, by 55.9mg (0.18mmol) acetopyruvic acid palladium and 0.390g (0.75mmol) 1, two (2,4, the 6-trimethylphenyl) imidazoles of 3-

during-o-cresylol compound-ortho-cresol is dissolved in 51.2g (1.59mol) methyl alcohol under protection gas.In the autoclave of 3 liters of B ü chi companies, the ortho-cresol and 3.47g (0.06mol) sodium methylate that 6.72g (0.06mol) are heated in water-bath to 40 ℃ are dissolved in 115g (3.59mol) methyl alcohol and 100g (0.52mol) tripropylene glycol.Subsequently, by the pressurization gas tank, by 536g C ₄hydrocarbon mixture is injected in autoclave and (passes through C ₄in the feed bottle, the minimizing of quality is measured).Autoclave under agitation is heated under temperature of reaction (80 ℃), disposable being incorporated in the content of autoclave containing palladium solution, and by online gas-chromatography monitoring reaction.Reaction times is 14 hours.The hydrocarbon mixture obtained is not contain the C of alkynes ₄hydrocarbon mixture, wherein contain 1 of 42.61 quality %, the 3-divinyl, the iso-butylene of 1.77% quality, the normal butane of 7.05% quality %, the trans-2-butene of 5.14 quality %, the 1-butylene of 15.05 quality %, 24.80 the iso-butylene of quality %, the cis-butene of 3.8 quality % (alkynes not detected).

GC analyzes:

GC (first post: DB-WAX/Al ₂o ₃, second post: DB-WAX/HP-5MS; Starting temperature: 50 ℃, top temperature: 200 ℃, time of origin: 1 minute, starting time: 3 minutes; Temperature program(me): since 50 ℃, be raised to 200 ℃ with the speed of 15 ℃/minute, working time: 11 minutes; Inject: 220 ℃, constant flow rate).Retention time [tR] (C ₄hydrocarbon)=2762 minutes, tR (methyl alcohol)=3152 minute, tR (1, the 7-octadiene)=3866 minute, tR (trans-1, the 6-octadiene)=3958 minute, tR (cis-1, the 6-octadiene)=4030 minute, tR (cis-1, 3, the 7-sarohornene)=4291 minute, tR (trans-1, 3, the 7-sarohornene)=4292 minute, tR (vinyl cyclohexene)=4448 minute, tR (Trimethylmethane)=4552 minute, tR (normal butane)=4822 minute, tR (3-MODE)=5523 minute, tR (trans-butylene)=6116 minutes, tR (1-butylene)=6240 minute, tR (iso-butylene)=6412 minute, tR (cis-butylene)=6616 minutes, tR (1-MODE)=6650 minute, tR (1, the 2-divinyl)=6900 minute, tR (1, the 3-divinyl)=7526 minute.

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

1,7-octadiene-3-methyl ether (=3-MODE)

Embodiment 2: telomerizing under 2273 quality ppm acetylene exist (contrast experiment)

In 100ml Schlenk pipe, by 56.2mg (0.18mmol) acetopyruvic acid palladium and 0.395g (0.76mmol) 1, two (2,4, the 6-trimethylphenyl) imidazoles of 3-

during-o-cresylol compound-ortho-cresol is dissolved in 51.2g (1.59mol) methyl alcohol under protection gas.In the autoclave of 3 liters of B ü chi companies, the ortho-cresol and 3.80g (0.07mol) sodium methylate that 6.80g (0.062mol) are heated in water-bath to 40 ℃ are dissolved in 115.1g (3.59mol) methyl alcohol and 101.1g (0.52mol) tripropylene glycol.Subsequently, by the pressurization gas tank, by 573g C ₄hydrocarbon mixture is injected in autoclave and (passes through C ₄in the feed bottle, the minimizing of quality is measured).Autoclave under agitation is heated under temperature of reaction (80 ℃), will be incorporated in the content of autoclave containing palladium solution, and by online gas-chromatography monitoring reaction.Reaction times is 14 hours.

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

1,7-octadiene-3-methyl ether (=3-MODE)

At embodiments of the invention, the C of use ₄hydrocarbon mixture has 1 of 45.39 quality %, the 3-divinyl, 1.46 the Trimethylmethane of quality %, 4.61 the normal butane of quality %, 5.20 the cis-butylene of quality %, 15.22 the 1-butylene of quality %, the cis-butylene of 23.85 quality %, the ethyl acetylene of the vinylacetylene of 0.1866 quality % and 0.0407 quality %.

Embodiment 3: add water to be telomerized (according to the present invention)

In 100ml Schlenk pipe, by 55mg (0.181mmol) acetopyruvic acid palladium and 0.384g (0.96mmol) 1, two (2,4, the 6-trimethylphenyl) imidazoles of 3-

during-o-cresylol compound-ortho-cresol is dissolved in 50.2g (1.57mol) methyl alcohol under protection gas.In the autoclave of 3 liters of B ü chi companies, the ortho-cresol and 3.95g (0.070mol) sodium methylate that 6.98g (0.064mol) are heated in water-bath to 40 ℃ are dissolved in 115.2g (3.59mol) methyl alcohol and 100.7g (0.52mol) tripropylene glycol.Subsequently, by the pressurization gas tank, by 526g C ₄hydrocarbon mixture is injected in autoclave and (passes through C ₄in the feed bottle, the minimizing of quality is measured).

The reacting by heating mixture in each situation, did not inject 0.1Mpa hydrogen after 1 minute, 3 hours 2 minutes, 22 hours 35 minutes, 25 hours 10 minutes, 27 hours 11 minutes, 29 hours 50 minutes and 49 hours 10 minutes, and by gas chromatographic detection gaseous state C ₄the concentration of alkynes in sample.After 52 hours 45 minutes, autoclave under agitation is heated under temperature of reaction (80 ℃), the reaction times under 80 ℃ is 8.5 hours.

GC (first post: DB-WAX/Al ₂o ₃, second post: DB-WAX/HP-5MS; Starting temperature: 50 ℃, top temperature: 200 ℃, time of origin: 1 minute, starting time: 3 minutes; Temperature program(me): since 50 ℃, be raised to 200 ℃ with the speed of 15 ℃/minute, working time: 11 minutes; Inject: 220 ℃, constant flow rate).Retention time [tR] (C4 hydrocarbon)=2762 minutes, tR (methyl alcohol)=3152 minute, tR (1, the 7-octadiene)=3866 minute, tR (trans-1, the 6-octadiene)=3958 minute, tR (cis-1, the 6-octadiene)=4030 minute, tR (cis-1, 3, the 7-sarohornene)=4291 minute, tR (trans-1, 3, the 7-sarohornene)=4292 minute, tR (vinyl cyclohexene)=4448 minute, tR (Trimethylmethane)=4552 minute, tR (normal butane)=4822 minute, tR (3-MODE)=5523 minute, tR (trans-butylene)=6116 minutes, tR (1-butylene)=6240 minute, tR (iso-butylene)=6412 minute, tR (cis-butylene)=6616 minutes, tR (1-MODE)=6650 minute, tR (1, the 2-divinyl)=6900 minute, tR (1, the 3-divinyl)=7526 minute.

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

1,7-octadiene-3-methyl ether (=3-MODE)

At embodiments of the invention, the C of use ₄hydrocarbon mixture has 1 of 43.48 quality %, the 3-divinyl, 3.58 the Trimethylmethane of quality %, 5.69 the normal butane of quality %, the cis-butylene of 4.00 quality %, the 1-butylene of 14.78 quality %, 24.9 the iso-butylene of quality %, 2.56 the cis-butylene of quality %, the propine of 0.005 quality %, the ethyl acetylene of the vinylacetylene of 0.6299 quality % and 0.1058 quality % (alkynes of 7407 quality ppm).

Embodiment 4: add water to be telomerized (according to the present invention)

In 100ml Schlenk pipe, by 57.6mg (0.189mmol) acetopyruvic acid palladium and 0.399g (0.76mmol) 1, two (2,4, the 6-trimethylphenyl) imidazoles of 3- during-o-cresylol compound-ortho-cresol is dissolved in 51.3g (1.60mol) methyl alcohol under protection gas.In the autoclave of 3 liters of B ü chi companies, the ortho-cresol and 3.80g (0.070mol) sodium methylate that 6.90g (0.064mol) are heated in water-bath to 40 ℃ are dissolved in 115.1g (3.59mol) methyl alcohol and 102g (0.53mol) tripropylene glycol.Subsequently, by the pressurization gas tank, by 495g C ₄hydrocarbon mixture is injected in autoclave and (passes through C ₄in the feed bottle, the minimizing of quality is measured).Autoclave under agitation is heated under temperature of reaction (80 ℃), and will be incorporated in the content of autoclave containing palladium solution.Then, inject the hydrogen of 1.4Mpa.By online gas-chromatography monitoring reaction.Reaction times is 14 hours.

GC (first post: DB-WAX/Al ₂o ₃, second post: DB-WAX/HP5MS; Starting temperature: 50 ℃, top temperature: 200 ℃, time of origin: 1 minute, starting time: 3 minutes; Temperature program(me): since 50 ℃, be raised to 200 ℃ with the speed of 15 ℃/minute, working time: 11 minutes; Inject: 220 ℃, constant flow rate).Retention time [tR] (C ₄hydrocarbon)=2762 minutes, tR (methyl alcohol)=3152 minute, tR (1, the 7-octadiene)=3866 minute, tR (trans-1, the 6-octadiene)=3958 minute, tR (cis-1, the 6-octadiene)=4030 minute, tR (cis-1, 3, the 7-sarohornene)=4291 minute, tR (trans-1, 3, the 7-sarohornene)=4292 minute, tR (vinyl cyclohexene)=4448 minute, tR (Trimethylmethane)=4552 minute, tR (normal butane)=4822 minute, tR (3-MODE)=5523 minute, tR (trans-butylene)=6116 minutes, tR (1-butylene)=6240 minute, tR (iso-butylene)=6412 minute, tR (cis-butylene)=6616 minutes, tR (1-MODE)=6650 minute, tR (1, the 2-divinyl)=6900 minute, tR (1, the 3-divinyl)=7526 minute.

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

1,7-octadiene-3-methyl ether (=3-MODE)

At embodiments of the invention, the C of use ₄hydrocarbon mixture has 1 of 44.69 quality %, the 3-divinyl, 2.56 the Trimethylmethane of quality %, 4.82 the normal butane of quality %, the cis-butylene of 3.96 quality %, the 1-butylene of 15.50 quality %, 24.68 the iso-butylene of quality %, 2.76 the cis-butylene of quality %, the propine of 0.0415 quality %, the ethyl acetylene of the vinylacetylene of 0.4609 quality % and 0.2328 quality % (alkynes of 7350 quality ppm).

Can be easy to find out the C used by comparing embodiment 1 and 2 ₄in hydrocarbon mixture, exist alkynes can cause catalyzer to be suppressed, thereby make otherwise can not telomerize under identical condition.In embodiment 3, raw material is to have the even more C of vast scale alkynes ₄hydrocarbon mixture.Regularly hydrogen is joined in reaction mixture.Approximately after 37 hours, also can observe even at low temperatures and slowly start reaction.After temperature increases subsequently, although raw material C ₄there is alkynes in hydrocarbon mixture, but still can observe the carrying out telomerized.The present invention adds hydrogen source can make downtrod reactivation of catalyst in reaction mixture.

Embodiment 4 also shows, while in telomerization, having hydrogen can in and the restraining effect of alkynes.In embodiment 4, hydrogen is metered into before reaction soon starting, and mixture is heated to 80 ℃ immediately.Although compare relatively large alkynes is arranged with embodiment 2, in the situation that existing, hydrogen can observe a large amount of product formation, even can not return to the speed of reaction of embodiment 1 fully.The side reaction of observing is that butadiene hydrogenation generates butylene.

We guess, with embodiment 1, with 4, compare, in embodiment 3, reaction has extra high transformation efficiency to start under the existence that telomerizes catalyzer owing to the alkynes that makes catalyst deactivation to be removed fully by hydrogenation before real reaction while starting, and the catalyzer of optional inactivation has obtained reactivate.We guess, with embodiment 4, compare, in embodiment 3, MODE has the reason of higher yields to be, according to embodiment 4, in reaction mixture under the greatly excessive existence of this hydrogen, simple hydrogenation has occurred, made butadiene hydrogenation become butylene, and this hydrogenation has carried out larger degree when the hydrogenation reaction of alkynes completes.In embodiment 3, the amount of MODE larger Another reason with respect to the comparable residence time/reaction times may be, do not regenerated soon, but hydrogenation with telomerize parallel carrying out, therefore, obtained a small amount of active catalyst.In embodiment 4, the advantage of the embodiment of the inventive method is, can save that pre-hydrogenation or pre-regeneration step as carried out in embodiment 3 consuming time.

Claims

1. use catalyzer, telomerize the method for the non-ring olefin (VI) with at least two conjugated double bonds with at least one nucleophilic reagent (VII), wherein, whole telomerization method comprises the step that at least one adds hydrogen, wherein, by the hydrogen source that is selected from hydrogen-containing gas, hydrogen is joined in the process mixture existed in this step;

Use therein raw material is to comprise non-ring olefin with at least two conjugated double bonds and the hydrocarbon mixture of other hydrocarbon; The alkynes that wherein said mixture comprises the highest 5 quality %;

Neutralized the restraining effect of the alkynes that makes catalyst deactivation while wherein in telomerization, having hydrogen;

Wherein, the used catalyzer that telomerizes is palladium-arbine complex, the carbenes that it comprises general formula I X, X, XI or XII:

Wherein:

R ²; R ³: identical or different separately, and be

A) there is straight chain, side chain, replacement or unsubstituted, the cyclic alkyl of 1 to 24 carbon atom, or

B) there is replacement or unsubstituted, list or the polyaromatic of 6 to 24 carbon atoms, or

C) there are 4 to 24 carbon atoms and at least one is selected from N, O, heteroatomic single or many rings, the replacement of S or unsubstituted heterocycle, and

R ⁴, R ⁵, R ⁶, R ⁷: identical or different separately, and be

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 ,-NH ₂,-NH (alkyl) ,-N (alkyl) ₂,-NH (aryl) ,-N (alkyl) ₂,-F ,-Cl ,-Br ,-I ,-OH ,-CF ₃,-NO ₂, ferrocenyl ,-SO ₃h ,-PO ₃h ₂, wherein alkyl contains 1 to 24 carbon atom, and aryl and heteroaryl contain 5 to 24 carbon atoms, or R ⁴, R ⁵, R ⁶and R ⁷group is the part of bridge aliphatic series or aromatic ring.

2. method as desired as claim 1, wherein, described mixture comprises the alkynes that is selected from vinylacetylene and ethyl acetylene.

3. method as desired as claim 1 or 2, wherein, the part alkynes of existence for before telomerizing by the selectivity hydrogenation.

4. method as desired as claim 1 or 2, wherein, hydrogen source in whole technique, makes the mol ratio of hydrogen and alkynes be at least 1: 1 sufficient hydrogen feed.

5. method as desired as claim 1 or 2, wherein, described mixture comprises the above C of 90 quality % ₄hydrocarbon.

6. method as desired as claim 1 or 2, wherein, the described non-ring olefin of use is 1,3-butadiene or isoprene.

7. method as desired as claim 1 or 2, wherein, used the precursor systems of catalyzer to be: two (2,4, the 6-trimethylphenyl) imidazoles of acetopyruvic acid palladium and 1,3- -o-cresylol compound-ortho-cresol system.

8. method as desired as claim 1, wherein R ², R ³identical or different separately, and straight chain, side chain, replacement or unsubstituted alicyclic ring shape alkyl for thering is 1 to 24 carbon atom.

9. method as desired as claim 1, wherein, in reaction mixture, the ratio of part and metal [mol/mol] is 0.01: 1-250: 1.

10. method as desired as claim 1 or 2, wherein, using nucleophilic reagent VII is the compound of general formula VIIa, VIIb or VIIc:

R ^1a-O-H (R ^1a)(R ^1b)N-H R ^1a-COOH

VIIa VIIb VIIc

Wherein, R ^1aand R ^1bindependently selected from hydrogen, straight chain, side chain or ring-type C ₁-C ₂₂alkyl, alkenyl or alkynyl, C ₅-C ₁₈aryl, or-CO-alkyl-(C ₁-C ₈) group, or-CO-aryl-(C ₅-C ₁₀) group, wherein these groups optionally comprise be selected from-CN ,-COOH ,-COO-alkyl-(C ₁-C ₈) ,-CO-alkyl-(C ₁-C ₈) ,-aryl-(C ₅-C ₁₀) ,-COO-aryl-(C ₆-C ₁₀) ,-CO-aryl-(C ₆-C ₁₀) ,-O-alkyl-(C ₁-C ₈) ,-O-CO-alkyl-(C ₁-C ₈) ,-the N-alkyl ₂-(C ₁-C ₈) ,-CHO ,-SO ₃h ,-NH ₂,-F ,-Cl ,-OH ,-CF ₃with-NO ₂substituting group, and R wherein ^1aand R ^1bgroup is optionally connected to each other by covalent linkage.

11. method as desired as claim 10, wherein, the nucleophilic reagent of use (VII) is water, alcohol, phenol, carboxylic acid, ammonia and/or uncle or secondary amine.

12. method as desired as claim 10, wherein, the nucleophilic reagent of use (VII) is water, phenol, polyvalent alcohol, carboxylic acid, ammonia and/or uncle or secondary amine.

13. method as desired as claim 1 or 2, wherein, telomerize under the existence of solvent and carry out.

14. method as desired as claim 1 or 2, wherein, telomerize under the existence of solvent and carry out, and the solvent used is nucleophilic reagent (VII) and/or inert organic solvents.

15. method as desired as claim 1 or 2, wherein, hydrogen source is added in whole telomerization method in reactions steps.

16. method as desired as claim 1 or 2, wherein, whole telomerization method has the catalyst recirculation step, and hydrogen source is added in whole telomerization method in the catalyst recirculation step.