WO2013079820A1 - Method for metathesizing linear alpha olefins using a ruthenium complex comprising an asymmetrical n-heterocyclic carbene - Google Patents

Method for metathesizing linear alpha olefins using a ruthenium complex comprising an asymmetrical n-heterocyclic carbene Download PDF

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WO2013079820A1
WO2013079820A1 PCT/FR2012/000458 FR2012000458W WO2013079820A1 WO 2013079820 A1 WO2013079820 A1 WO 2013079820A1 FR 2012000458 W FR2012000458 W FR 2012000458W WO 2013079820 A1 WO2013079820 A1 WO 2013079820A1
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Prior art keywords
carbon atoms
groups
selected
alkyl
preceding
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PCT/FR2012/000458
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French (fr)
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Mikael Berthod
Hélène Olivier-Bourbigou
Etienne Borre
Marc Mauduit
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IFP Energies Nouvelles
Ecole Nationale Superieure De Chimie De Rennes
Centre National De La Recherche Scientifique
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0046Ruthenium compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24Phosphines

Abstract

The invention relates to a method for metathesizing identical or different linear alpha olefins into linear internal olefins having excellent selectivity, using a ruthenium complex comprising an asymmetrical N-heterocyclic carbine as a catalyst, wherein one of the nitrogen atoms has a cycloalkyl grouping having a carbon number greater than 3 and the other nitrogen atom has an aryl grouping.

Description

PROCESS ÉTATHÈSE DOLEFINES LINEAR ALPHA USING

RUTHENIUM COMPLEX WITH A CARBENE

N-HETEROCYCLIC ASYMMETRIC

Field of the Invention

The present invention relates to the metathesis of alpha olefins, which is a catalytic reaction of olefins processing of exchanging alkylidene groups of the starting olefins.

5 More particularly, the invention relates to a process for metathesis of linear alpha olefins (same or different) linear internal olefins using a specific catalyst according to the reaction: Cross metathesis if R 'different from R "homometathesis or if R' = R ".

Figure imgf000002_0001

prior art Study

The metathesis reaction has become an important tool for the formation of carbon-carbon bonds. It is carried out in the areas of the L 5 petrochemicals, polymers, oleo-chemistry and fine chemistry. The carbene complexes isolated ruthenium have been described to catalyze this reaction (Chem Rev, 2010, 1˝ 10, 1746-1787).

WO 01/46096 discloses a process for converting C4-C10 olefins from a Fisher-Tropsch process, C6-C18 olefins using a homogeneous catalyst 10 based Grubbs type ruthenium (1st generation) of the formula RuCl 2 (PCy 3) 2 (CHPh) with improved selectivity with respect to heterogeneous catalysts known to those skilled in the art.

Complexes of Ru having a heterocyclic carbene ligand to 5 unsymmetrical NHC type members have been described by Bléchert

> 5 (Organometallics, 2006, 25, 25-28). complex is understood to mean "NHC" complex N-heterocyclic carbene according to English terminology "N-heterocyclic carbenes". The complexes described in Bléchert were used to catalyze the cross-metathesis of olefins, but they do not show an advantage over the complex bearing symmetrical NHC carbenes previously described by

30 Grubbs. Patent WO2011 / 056874 describes a catalyst composition based on a Ru complex comprising a carbene NHC asymmetrical for the production of alpha olefins by metathesis or triglycerides of fatty acids, for example for the production of 1-decene by reacting methyl oleate with ethylene. Patent WO2007 / 075427 discloses a ruthenium complex bearing a 5-membered NHC carbene wherein one of the nitrogen atoms is substituted by a phenyl group which contains a hydrogen in ortho-position and which is substituted in the ortho position premium. These complexes are used to catalyze olefin metathesis ring-closing (RCM). A wide variety of ruthenium catalysts is described, but each of these catalysts is designed to be applied to a very specific metathesis reaction. Their transposition to another metathesis reaction is not obvious.

Moreover, the parasitic isomerization of the double bond olefins of the load or product metathesis very often leads to the formation of by products undesirable and appears as a limitation to the economic development of these catalytic systems. The isomerization of the double bond results in a decrease in selectivity of linear internal olefins sought.

li has now been found that, surprisingly, the use of a carbene complex N heterocyclic (NHC) asymmetrical 5-membered ruthenium having specific substituents on both nitrogen atoms of the carbene in a process of linear alpha olefin metathesis it possible to obtain linear internal olefins with excellent selectivity. Indeed, when the two nitrogen atoms of the heterocyclic carbene 5-membered NHC are respectively substituted by i) a cycloalkyl group whose carbon number is greater than 3 and ii) an aryl group, then the selectivity of the reaction metathesis of linear alpha olefins is significantly improved. An advantage of the invention is in particular to improve the selectivity of the réacti'on metathesis of linear alpha olefin in order to optimize the yield of desired olefin, which has the effect of simplifying the separation of the products and improve the overall process economics. Another advantage of the invention is that the method according to the invention allows to obtain a good conversion of the olefin to be transformed and that with very low ruthenium concentrations.

Object of the invention

An object of the invention is to provide a metathesis process using a catalyst system for producing linear internal olefins from linear alpha olefins, with both good conversions, low ruthenium content and with excellent selectivity to olefin, including limiting the production of other olefins by isomerizing the double bond.

Detailed Description of the Invention

The present invention discloses a linear alpha olefin metathesis process in internal linear olefins using as a catalyst a ruthenium complex having the formula (I) below, having at least one N-heterocyclic carbene asymmetrical to which one of the atoms nitrogen carries a cycloalkyie R 7 group having a carbon number of greater than 3 and the nitrogen atom further bears an aryl group R 8,

Figure imgf000004_0001

Formula I wherein:

- X are identical or different and are anionic ligands,

- L is a donor ligand with 2 electrons,

- Y represents an alkylidene moiety, vinylidene, allenylidene or indenylidene, substituted or unsubstituted, Y can optionally form a ring with L,

- R 3, R 4, R 5 and R 6, identical or different, are hydrogen, halogen, alkyl, cycloalkyl, aryl or arylalkyl, each of which may be substituted by alkyl, halide, alkoxy or by phenyl optionally substituted by halide groups, alkyl or alkoxy.

The catalyst (formula I)

The catalyst used in the process according to the invention is an N-heterocyclic carbene complex (NHC) asymmetric ruthenium. The term complex NHC unsymmetrical a complex in which a nitrogen atom has a different group of the group from the other nitrogen atom. In the case of formula I, R 7 is different ligand of the ligand R 8.

Within the meaning of the present invention, R 7 is a cycloalkyl group having a carbon number greater than 3.

By "cycloalkyl having a carbon number greater than 3" means a monocyclic hydrocarbon group having a carbon number greater than 3, preferably between 4 and 24, more preferably between 6 and 12, preferably cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl, or polycyclic (bi- or tricyclic) having a carbon number greater than 3, preferably between 4 and 18, such as for example adamantyl or norbornyl groups.

R 8 is an aryl group. "Aryl" means a mono- or polycyclic aromatic group, preferably mono- or bicyclic, having a carbon number between 6 and 20. Preferred aryl groups are advantageously selected from phenyl, naphthyl and mesityl. When the group is polycyclic, that is to say it comprises more than one cyclic ring, cyclic rings may advantageously be fused in pairs or attached in pairs by σ bonds.

Within the meaning of the present invention, the substituents R 3, R 4, R 5 and R 6, identical or different, are alkyl, cycloalkyl, aryl or arylalkyl, each of which may be substituted by alkyl, halide, alkoxy or a phenyl group optionally substituted with halide groups, alkyl or alkoxy. Substituent is defined as a "alkyl" means a straight or branched hydrocarbon chain having from 1 to 15 carbon atoms, preferably having from 1 to 10 carbon atoms, and still more preferably having from 1 to 4 carbon atoms. Examples of preferred alkyl substituents include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl. Shall mean a substituent "alkoxy" an alkyl-O- in which the term alkyl has the meaning given above. Preferred examples of alkoxy substituents are methoxy or ethoxy groups.

By "alkyl" is meant to R 3, R 4, R 5 and R 6 a straight or branched hydrocarbon chain having from 1 to 15 carbon atoms, preferably 1 to 10 and even more preferably from 1 to 4. preferred alkyl groups are preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.

"Cycloalkyl" refers to R 3, R 4, R 5 and R 6 is a cyclic hydrocarbon group having monocyclic 3 to 10 carbon atoms preferably, such as a cyclopentyl or cyclohexyl group, or polycyclic (bi- or tricyclic ) having from 4 to 18 carbon atoms, in particular adamantyl or norbornyl. "Aryl" refers to R 3, R 4, R 5 and R 6 is a mono- or polycyclic aromatic group, preferably mono- or bicyclic group containing 6 to 20 carbon atoms, preferably phenyl or naphthyl. When the group is polycyclic that is to say it comprises more than one cyclic ring, cyclic rings may be fused in pairs or attached in pairs by σ bonds.

"Arylalkyl" or "aralkyl" refers to R 3, R 4, R 5 and R 6 is a hydrocarbon group, linear or branched bearer of a monocyclic aromatic ring having 7 to 12 carbon atoms, the aliphatic chain comprising 1 or 2 carbon atoms. Arylalkyl or preferred aralkyl group is benzyl.

The ligands X

X is an anionic ligand preferably selected from halides, sulfates, alkyl sulfates, aryl sulfates, alkylsulfonates, arylsulfonates, the alkylsulfinates, the arylsulfinate, acyl, carbonates, carboxylates, alkoxides, phenoxides, amides and the pyrolures. Said anionic ligands may preferably be unsubstituted or substituted, preferably by one or more substituent groups selected from alkyl groups having 1 to 12 carbon atoms, alkoxide groups having 1 to 12 carbon atoms, aryl groups having 5 to 24 carbon atoms, and halides. Said substituent groups, except halides, may advantageously be themselves unsubstituted or substituted by one or more groups selected from halides, alkyl groups having 1 to 6 carbon atoms, alkoxide groups having 1 to 6 carbon atoms, and aryl groups.

Preferably, the ligands X are anionic ligands, which are identical or different, selected from halide ligands, benzoates, tosylates, mesylates, trifluoromethane sulfonates, pyrolures, trifluoroacetates CF3CO2, the CH3CO2 acetates, alcoholates groups such as CH 3 0, CH 3 CH 2 0, (CH 3) 3 CO, (CF 3) 2 (CH 3) CO, (CF 3) (CH 3) 2 CO, phenates such as C 6 F 5 0, C 6 H 5 0. preferably, the anionic ligands X are ligands chosen from the halides and more preferably in the two ligands X are identical and are chlorides or bromides.

5 The ligand L

L is a donor ligand with 2 electrons. Preferably L is a phosphorus ligand of the formula PR '3 wherein P is a phosphorus atom and R' is selected from R and (OR) wherein the groups R are identical or different and are selected from hydrogen, halogen, halides, alkyls,

Three cycloalkyl, aryl and arylalkykes, substituted or unsubstituted groups each having up to 20 carbon atoms. The substituents of said groups may advantageously be selected from halides, alkyl groups and aryl groups having up to 20 carbon atoms. In the case where R 'is OR, R' and R are not a hydrogen or a halide. In the case where R '

5 is R, at least one R is not hydrogen or halogen.

The group (PR '3) is preferably selected from phosphines and phosphites of the formula PR 3, P (OR) 3, PH 2 R, PHRR 1, PRR 1 R 2 and P (OR) (OR 1) (OR 2) wherein the groups R, R 1 and R 2 are identical or different and are selected from alkyl, cycloalkyl, aryl and arylalkyl having

D in each case 1 to 20 carbon atoms and preferably from 1 to 12 carbon atoms.

Each of said groups R, R 1 and R 2 may preferably be substituted or unsubstituted. Substituents may advantageously be selected from halogen, preferably fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), alkyl groups and aryl groups having up to 20 carbon atoms,

5 preferably up to 12 carbon atoms and even more preferably up to 8 carbon atoms.

The phosphorus ligand (PR '3) of the ruthenium compound (I) is preferably a phosphine, most preferably a tri-alkyl or tri-cycloalkyl phosphine selected from tricyclohexylphosphine, triisopropylphosphine and D tricyclopentylphosphine, a dialkyl or di-cycloalkyl phosphine selected from the dicyclohexylphosphine, dicyclohexylphenylphosphine, di-tert-butylphosphine and the di-tert-butylchlorophosphine or tri-aryl phosphine selected from triphenylphosphine, tri (methylphenyl) phosphine, trimesitylphosphine, tri (dimethylphenyl) phosphine, tri [(trifluoromethyl) phenyl] phosphine.

Particularly preferably, the catalyst used in this invention satisfies the following formulas:

Figure imgf000009_0001

wherein X is selected from chloride and bromide ligands and R 3, R 4, R 5, R 6, R 7 and R 8 are as defined for formula I.

R 9 can be hydrogen or a substituted aryl group or not. Preferably R 9 is a phenyl group substituted or not.

Very preferably, the ligands X are identical and are chosen from the chlorides or bromides ligands, L is a tricyclohexylphoshine and Y is an indenylidene group, substituted or not.

Load

Olefins implemented in the method according to the invention are selected from linear alpha-olefins. Preferably, the olefins are selected from linear alpha olefins having 3 to 20 carbon atoms, preferably from 4 to 14 and more preferably between 5 and 10. Examples include pentene-1, the hexene-1, heptene-1, octene-1, nonene-1 or décène-.

Linear alpha olefins may be used alone or in admixture.

The filler may for example be derived from a Fischer-Tropsch process.

Getting œuyre catalyst

The quantity of catalyst composition used for the metathesis reaction depends on a variety of factors such as the identity of reactants and reaction conditions that are employed. Therefore, the required quantity of catalyst composition is defined optimally and independently for each reaction. However, preferably, the amount of ruthenium complex relative to olefins, expressed in moles, is between 1 and 10,000 ppm, preferably between 1 and 200 ppm and particularly preferably between 1 and 100 ppm.

the method

The metathesis process of olefins according to the invention may advantageously be performed in the absence or presence of a solvent. If appropriate, solvents used according to the method of the invention may be chosen from organic solvents, protic solvents or water. Suitable solvents for the metathesis of the present invention may for example be selected from aromatic hydrocarbons such as benzene, toluene and xylenes, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, chlorinated alkanes such as dichloromethane, chloroform and 1, 2-dichloroethane, ethers such as diethyl ether and tetrahydrofuran, alcohols such as methanol and ethanol or the water. A preferred solvent is chlorobenzene. Combinations of these solvents can also be used advantageously. Any amount of solvent may advantageously be employed, but the use of at least the minimum amount required for dissolving the compound of formula (I) is preferred and such minimum amount is easily determined by one skilled in the art. The volume of the solvent can be very small relative to the volume of olefin reactants employed.

Said process for metathesis of olefins according to the invention is advantageously carried out under vigorous stirring, to the extent that it allows good contact between the reactants (which may be gaseous in some cases) and said catalyst composition.

Said process for metathesis of olefins according to the invention can advantageously be implemented under a nitrogen or argon atmosphere, preferably at atmospheric pressure. Generally, a wide temperature range can be used. Said process for metathesis of olefins according to the invention is advantageously carried out at a temperature between 0 ° C and 80 ° C, and preferably between 20 ° C and 150 ° C.

The reaction pressure is preferably between atmospheric pressure and 10 MPa (100 bar) and preferably between atmospheric pressure and 3 MPa (30 bar). If the reactant is gaseous, it is advantageously used pure or in admixture or diluted with an inert paraffin.

Said process for metathesis of olefins according to the invention can advantageously be conducted both in closed systems (batch), in open or semi-continuous system system, and with one or more reaction stages.

Generally, the reaction time or the residence time in a continuous reaction for the olefin metathesis process according to the invention is preferably from about one second to about one day, preferably about five minutes to about 10 hours. The invention will be further explained in light of the illustrative examples given below that show the benefits of catalytic compositions and method of the invention. The following examples illustrate the invention without limiting its scope.

Examples

Example 1 Process for metathesis of 1-octene with catalyst A carrying a symmetrical NHC (not according to the invention)

Metathesis of octene-1 was carried out with a symmetrical carbene complex NHC the following structure:

Figure imgf000012_0001

catalyst A

In a reaction tube equipped with a magnetic bar and under an argon atmosphere was charged with the required amount of catalyst A in solution in 0.5 mL of dichloromethane. Still under a flow of argon, 200 mg of dodecane as internal standard. Adjusting the setpoint heated to the desired temperature (50 or 80 ° C). When the set temperature is reached, is added 5 ml of octene-1, freshly distilled and filtered through basic alumina and degassed before the test, which corresponds to time t = 0 of the reaction. At the end of reaction, the reaction medium is neutralized with a few drops of butyl vinyl ether and diluted in heptane prior to analysis by gas chromatography.

The octene-1 conversion was calculated with the following formula:

((mol starting octènerl - octene mole final) / mole octene-1 start) * 100 Selectivity to tetradecene is calculated with the following formula:

((mol tetradecene * 2) / (mol 1-octene starting - mole octene-1 final)) * 100

The results after 4 hours of testing are shown in Table below.

Example 2 Process for metathesis of 1-octene with catalyst B carrying a symmetrical NHC (not according to the invention)

Figure imgf000013_0001

catalyst B

The octene-1, the metathesis reaction is carried out as in Example 1 using catalyst B instead of catalyst A.

The results after 4 hours of testing are shown in Table below.

Example 3 Process for metathesis of 1-octene with catalyst C bearing unsymmetrical NHC (according to the invention)

Figure imgf000013_0002

catalyst C

The octene-1, the metathesis reaction is carried out as in Example 1, using catalyst C instead of Catalyst A.

The results after 4 hours of testing are shown in Table below. Table: Results of the catalytic tests described in Examples 1-3

Figure imgf000014_0001

It is observed that the method according to the invention allows to obtain from octene-tetradecene (C14) with a selectivity of 99%, superior to that obtained with known catalysts. This excellent selectivity allows easier separation of the product and easy recycling of the unreacted olefin.

Claims

A method of linear alpha olefins metathesis in internal linear olefins using as a catalyst a ruthenium complex having the formula (I) below, having at least one N-heterocyclic carbene asymmetrical for which one of the nitrogen atoms carries a cycloalkyl group R 7 having a carbon number greater than 3 and the other nitrogen atom carries an aryl group R 8,
Figure imgf000015_0001
formula I
in which :
- X are identical or different and are anionic ligands,
- L is a donor ligand with 2 electrons,
- Y represents an alkylidene moiety, vinylidene, allenylidene or indenylidene, substituted or unsubstituted, Y can optionally form a ring with L,
- R 3, R 4, R 5 and R 6, identical or different, are hydrogen, halogen, alkyl, cycloalkyl, aryl or arylalkyl, each of which may be substituted by alkyl, halide, alkoxy or by phenyl optionally substituted by halide groups, alkyl or alkoxy.
The method of claim 1 wherein R 7 is a monocyclic cycloalkyl group having a carbon number between 4 and 24, or polycyclic having a carbon number between 4 and 18.
Method according to one of the preceding claims wherein R 8 is a mono- or polycyclic aromatic group having a carbon number between 6 and 20. Process according to one of the preceding claims wherein wherein R 3, R 4, R 5 and R 6 are identical or different and are selected from
- a linear or branched alkyl group having 1 to 15 carbon atoms,
- a monocyclic cycloalkyl group having 3 to 10 carbon atoms, or polycyclic having from 4 to 18 carbon atoms,
- a mono- or bicyclic aromatic group having from 6 to 20 carbon atoms,
- a linear branched arylalkyl group or carrier of a monocyclic aromatic ring having 7 to 12 carbon atoms, the aliphatic chain contains 1 or 2 carbon atoms.
Method according to one of the preceding claims wherein X is an anionic ligand selected from haiogènures, sulfates, alkyl sulfates, aryl sulfates, alkylsulfonates, arylsulfonates, the alkylsulfinates, the arylsulfinate, acyl, carbonates, carboxylates, alkoxides, phenoxides, amides and pyrolures, unsubstituted or substituted with one or more group selected from alkyl groups having 1 to 12 carbon atoms, alkoxide groups containing from 1 to 12 carbon atoms, aryl groups having from 5 to 24 carbon atoms and haiogènures, said substituent groups, except haiogènures, being themselves unsubstituted or substituted by one or more groups selected from the haiogènures, alkyl groups having 1 to 6 carbon atoms, alkoxide groups containing from 1 to 6 carbon atoms, and aryl groups.
Method according to the preceding claim wherein X is selected from haiogènures ligands, benzoates, tosylates, mesylates, trifluoromethane sulfonates, pyrolures, trifluoroacetate CF 3 CO 2, CH3CO2 acetates, alcoholates and phenolates.
Method according to one of the preceding claims wherein L is a phosphorus ligand of the formula PR '3 wherein P is a phosphorus atom and R' is selected from R and (OR) groups in which the groups R are identical or different and are selected from hydrogen, halogen, haiogènures, alkyl, cycloalkyl, aryl and arylalkyl, substituted or unsubstituted groups each having up to 20 carbon atoms, the substituents of said groups are selected from halides, alkyl groups and groups aryl having up to 20 carbon atoms, and in the case where R 'is oR, R' and R are not a hydrogen or a halide, and in the case where R 'is R, at least one R is not hydrogen or halogen.
8. Method according to the preceding claim wherein L is a tri-alkyl or tri-cycloalkyl phosphine selected from tricyclohéxylphosphines, the triisopropylphosphines and tricyclopentylphosphines, a di- alkyl phosphine or a cycloalkyl selected from di- dicyclohexylphosphines, the dicyclohexylphenylphosphines, di-tert-butylphosphines and di-tert butylchlorophosphines or tri-aryl phosphine selected from triphenylphosphine, tri (methylphenyl) phosphine, trimesitylphosphine, tri (dimethylphenyl) phosphine, tri [(trifluoromethyl) phenyl] phosphine . 9. The method of claim 1 wherein the ligands X are identical and are chosen from the chlorides or bromides ligands, L is a tricyclohexylphoshine and Y is an indenylidene group, substituted or not.
10. Method according to one of the preceding claims wherein the olefins are selected from linear alpha olefins having 3 to 20 carbon atoms, alone or mixed.
January 1. Method according to the preceding claim wherein the olefin is selected from the pentene, hexene, heptène-, octene, nonene-1 or décène-.
12. Method according to one of the preceding claims wherein the amount of ruthenium complex relative to olefins, expressed in moles, is between 1 and 0000 ppm.
13. Method according to one of the preceding claims conducted in the presence of a solvent selected from aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated alkanes, ethers, alcohols or water, alone or in admixture .
14. Method according to one of the preceding claims carried out at a temperature between 0 ° C and 180 ° C and at a pressure between atmospheric pressure and 10 MPa (100 bar).
15. A method according to any preceding claim conducted in a closed system, semi-open system or continuously system, and with one or more reaction stages.
PCT/FR2012/000458 2011-12-02 2012-11-14 Method for metathesizing linear alpha olefins using a ruthenium complex comprising an asymmetrical n-heterocyclic carbene WO2013079820A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3005049A1 (en) * 2013-04-26 2014-10-31 IFP Energies Nouvelles Process for olefin metathesis from Fischer-Tropsch cuts using a ruthenium complex comprising an N-heterocyclic diaminocarbene ASYMMETRIC

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046096A1 (en) 1999-12-21 2001-06-28 Sasol Technology (Pty) Ltd Metathesis process for converting short chain olefins to longer chain olefins
WO2007075427A1 (en) 2005-12-16 2007-07-05 Materia, Inc. Organometallic ruthenium complexes and related methods for the preparation of tetra-substituted and other hindered olefins
WO2011056874A2 (en) 2009-11-09 2011-05-12 Exxonmobil Chemical Patents Inc. Metathesis catalysts and processes for use thereof
US20110282068A1 (en) * 1998-04-06 2011-11-17 Evonik Degussa Gmbh Alkylidene complexes of ruthenium containing n-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110282068A1 (en) * 1998-04-06 2011-11-17 Evonik Degussa Gmbh Alkylidene complexes of ruthenium containing n-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis
WO2001046096A1 (en) 1999-12-21 2001-06-28 Sasol Technology (Pty) Ltd Metathesis process for converting short chain olefins to longer chain olefins
WO2007075427A1 (en) 2005-12-16 2007-07-05 Materia, Inc. Organometallic ruthenium complexes and related methods for the preparation of tetra-substituted and other hindered olefins
WO2011056874A2 (en) 2009-11-09 2011-05-12 Exxonmobil Chemical Patents Inc. Metathesis catalysts and processes for use thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BLÉCHERT ORGANOMETALLICS vol. 25, 2006, pages 25 - 28
CHEM REV vol. 110, 2010, pages 1746 - 1787

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3005049A1 (en) * 2013-04-26 2014-10-31 IFP Energies Nouvelles Process for olefin metathesis from Fischer-Tropsch cuts using a ruthenium complex comprising an N-heterocyclic diaminocarbene ASYMMETRIC
US9556296B2 (en) 2013-04-26 2017-01-31 Centre National De La Recherche Scientifique Process for metathesis of olefins obtained from Fischer-Tropsch fractions using a ruthenium complex comprising a dissymmetrical N-heterocyclic diaminocarbene

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