CN106925351B - N heterocycle carbine ruthenium catalysts containing imidazolium ionic liquid group and preparation method thereof - Google Patents

N heterocycle carbine ruthenium catalysts containing imidazolium ionic liquid group and preparation method thereof Download PDF

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CN106925351B
CN106925351B CN201710195546.0A CN201710195546A CN106925351B CN 106925351 B CN106925351 B CN 106925351B CN 201710195546 A CN201710195546 A CN 201710195546A CN 106925351 B CN106925351 B CN 106925351B
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ruthenium catalyst
organic substituent
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CN106925351A (en
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魏文灏
李冠军
袁瑞君
宋洪超
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TIANJIN 3&G CHEMTECH RESEARCH INSTITUTE Co Ltd
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    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Abstract

The present invention relates to N heterocycle carbine ruthenium catalysts containing imidazolium ionic liquid group and preparation method thereof.The ruthenium catalyst is the compound with structure shown in lower formula (I)：Wherein L is neutral electron part, R1、R2、R3、R4、R5And R6It is each independently H, R group or the organic substituent with 1 to 20 carbon atom；R7For first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenylindan alkenylene；The R group has the structure shown in lower formula (II)：The present invention, which is joined directly together imidazolium ionic liquid group with N heterocyclic carbone catalysts, to be connect, and enables imidazolium ionic liquid group to be able to more effectively play its characteristic property, so as to reach the catalytic efficiency and catalyst stability that improve catalyst.

Description

N- heterocycle carbines ruthenium catalyst and its preparation containing imidazolium ionic liquid group Method
Technical field
The present invention relates to it is a kind of it is new containing ionic liquid group N- heterocycle carbine ruthenium catalysts and preparation method thereof and Using, more particularly to it is a kind of be directly accessed imidazolium ionic liquid group on the N- heterocyclic carbene ligands of metal complex, this Imidazolium ionic liquid group is just set to effectively act as improving stability and the effect of catalytic efficiency of catalyst.
Background technology
The homogeneous catalyst of olefin metathesis reaction is the important tool of Synthetic Organic Chemistry, and being widely used in various has In machine study on the synthesis and industrial production.Wherein ruthenium homogeneous catalyst is the olefin metathesis catalyst being most widely used at present.
Research in terms of organic synthesis includes small molecule pharmacy, bio-pharmaceuticals, the preparation of organic intermediate, natural products Synthesis, high polymer material etc..Industrial production application includes biological insecticides, personal skin or hair care articles for use, new material, system Medicine industry etc..It has many advantages, such as：It is active high, not only to air-stable, in the presence of water, acid, alcohol or other solvents still Very high catalytic activity so can be kept, and there are very strong applicability in the various functional groups carried to alkene.
Mainly the structure with generality ruthenium catalyst is as shown in Figure 1 for it：
Although ruthenium catalyst has many advantages, such as catalytic performance is good, there is urged after catalyst cost height and reaction The problem of agent is difficult to remove.In order to overcome these deficiencies of ruthenium catalyst, researcher using a kind of emerging ionic liquid and The technology that catalyst is combined, the activity of catalyst can be increased and extend catalyst life.So that one can only be used originally Secondary ruthenium catalyst, become the catalyst that can be recycled for multiple times, so as to reach the purpose for reducing catalyst cost；In addition, It is easier to separate with product after the completion of reaction.The technology of early stage is used using ionic liquid as solvent, will be common catalyzed Agent is put into ionic liquid；Although obtaining some progress, effect not highly significant.Present method is by ionic liquid base Group access ruthenium catalyst on, this ruthenium catalyst realize be recycled for multiple times and post catalyst reaction be easier separate mesh 's.
According to the literature, ionic liquid group is connected in two kinds of different ligands.It is the most frequently used as shown in Fig. 2 It is the first, ionic liquid group is connected to catalyst C-2a alkoxy benzene ligand, second is to be connected to catalyst C-2b Alkyl phosphorus ligand.
The first example for being connected on alkoxy benzene ligand is introduced first：The researchers such as Yao, Q. are in magazine Angew.Chem.Int.Ed.2003,42,3395-3398. report and imidazolium ionic liquid group IL-1 is incorporated into ruthenium urged On the 5- positions of agent C-2a alkoxy benzene；Clavier, H, et al. in Chem.Commun.2004,2282-2283, have also been made It is similar to introduce；Hideaki Wakamatsu are delivered on by same imidazoles in magazine SYNLETT 2008,12,1805-1808 Ionic liquid group is incorporated on ruthenium catalyst C-2a 3- positions；Later Chen, S-W and Lee, S-g et al. exist Imidazolium ionic liquid group is connected on catalysis C-2a 2- positions by Tetrahedron 2009,65,3397-3403.On Two kinds are that imidazolium ionic liquid group is connected on alkyl phosphorus ligand by Consorti C-S. et al., refer to magazine J.Org.Lett,2008,10,237-240。
This catalyst for ionic liquid group being connected to different ligands, repeatedly use performance still there is Some difference：The catalyst that ionic liquid group is linked into alkoxy benzene ligand, which is typically exhibited, preferably repeatedly to be made With number, and the catalyst being connected on alkyl phosphorus ligand can be limited by some reactants and solvent, and otherwise its circulation is urged Change ability declines.
The content of the invention
The key problem of ionic liquid and ruthenium catalyst combined technology is that how to solve ionic liquid group to be catalyzed with ruthenium Agent is exactly preferably to be combined problem with catalytic center.Both are combined closer, and ionic liquid group just can Preferably guard catalyst, strengthen its catalytic activity and delay catalytic life；
The composition of ruthenium catalyst is as shown in Figure 2：Ruthenium (Ru) is catalytic center, removed outside two halogen radicals, also other three Individual ligand：(1) vinylidene ligand；(2) alkyl phosphorus ligand or part is corresponded；(3) N- heterocycle carbines ligand. Three ligands are N- heterocycle carbine ligands with ruthenium catalytic center binding ability order>Vinylidene ligand>Alkyl phosphorus is coordinated Body.The binding ability order of above-mentioned each part is more readily understood that by looking back olefin metathesis reaction mechanism；Mechanism of catalytic reaction： First, it is combination of the alkyl phosphorus ligand departing from ruthenium catalytic center, forms the intermediate with catalytic activity；Then, in this Mesosome is reacted with the double bond on reactant olefin, and new vinylidene reactive intermediate is formed after substituted ethylene pitches ligand；Most Afterwards, the double bond again with reactant olefin is reacted, and produces new ruthenium catalytic center and product.Can from mechanism of catalytic reaction Going out alkyl phosphorus ligand and vinylidene ligand all will successively depart from ruthenium catalytic center, and only N- heterocycle carbines ligand is all the time It is in conjunction.
Although (1) kind ligand i.e. vinylidene ligand and the will be connected at present containing imidazolium ionic liquid group by having (2) it is alkyl phosphorus ligand or the report for corresponding this catalyst containing imidazolium ionic liquid on part to plant ligand Road, its preparation method are to synthesize ligand containing imidazolium ionic liquid first, are then substituted with the ionic liquid ligand is contained The ligand of ionic liquid is free of on ruthenium catalyst accordingly, and obtains both catalyst described above.But due to (3) plant ligand be that N- heterocycle carbines ligand and ruthenium catalytic center binding ability are too strong, therefore in preparation use (1) and (2) similar method, that is, method of the substitution of ligand containing ionic liquid without ionic liquid ligand is used, can not also be obtained at present It is catalyzed to the ruthenium for containing imidazolium ionic liquid group in N- heterocycle carbine ligands.
The present inventor has been prepared on N- heterocycle carbines containing imidazolium ionic liquid group by further investigation Ruthenium catalyst.It shows that this imidazolium ionic liquid group catalyst that contains on N- heterocycle carbines has very using result Good being recycled for multiple times property and post catalyst reaction are easier the effect separated.
Then, the present invention first aspect provide it is a kind of on N- heterocycle carbines containing imidazolium ionic liquid group Ruthenium catalyst, the ruthenium catalyst are the compound with structure shown in formula (I)：
Wherein：
L is neutral electron part, and the neutral electron part is selected from by C3-C20Three substitution alkyl phosphorus bases of individual carbon, C3-C20Alkoxy, the C of individual carbon6-C20The aryloxy group of individual carbon, there is C1To C20Alkyl thioether group or there is C0To C20Alkane One group of the group of the pyridine radicals composition of base；
R1、R2、R3、R4、R5And R6It is each independently H, R group or first organic substitution with 1 to 20 carbon atom Base, first organic substituent are selected from by C1-C20Alkyl, C1-C20Alkoxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20 Alkyl-carbonyl, C7-C20Aryl carbonyl, C1-C20Amide groups and C3-C8The group of cyclic group composition；R1、R2、R3、R4、R5And R6In At least one group is R group；R2And R3It is asynchronously H and is first organic substituent；R4And R6It is asynchronously H and is First organic substituent；
R7For first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenylindan alkenylene；And R7 It is not H and R group；
The R group has the structure shown in lower formula (II)：
Wherein：
Y is CH2, O, S, N or the first group, first group is selected from by C6To C20Aryl, C6To C20Aryloxy group, C2Extremely C20Alkyl-carbonyl, C7To C20Aryl carbonyl, C1To C20Amide groups, C3-C8A group in the group of cyclic group composition；
N is 0 to 10 integer, preferably 2 to 6 integer, more preferably 2 to 4 integer；
X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；
R8、R9、R10And R11H or the second organic substituent are each independently, second organic substituent is selected from by C1- C20Alkyl, C6-C20Aryl and C3-C8The group of cyclic group composition.
The present invention provides a kind of method for preparing ruthenium catalyst in second aspect, and methods described includes：
(1) compound 1 is synthesized；It is and 2-in-1 into compound 3 by compound；
(2) compound 4 is synthesized by compound 1 and compound 3；
(3) compound 5 is synthesized by compound 4；
(4) compound 6 is synthesized by compound 5；
(5) compound 7-I is synthesized by compound 6；
(6) compound 7-II is synthesized by compound 7-I；
(7) compound 8 or compound 9 as ruthenium catalyst are synthesized by compound 7-II；
Wherein, the structural formula of compound 1 to compound 7 is as follows：
Compound 8 is selected from the group being made up of following compound 8a, 8b, 8c and 8d：
The compound 9 is as follows：
The present invention provides the ruthenium catalyst or second aspect of the present invention described in first aspect present invention in the third aspect Ruthenium catalyst made from methods described is reacted especially using the alkene derived from vegetable oil such as cottonseed oil as instead in olefin metathesis Thing is answered to carry out the application in olefin metathesis reaction, it is preferred that the cycle applications in olefin metathesis reaction.
The present invention by imidazolium ionic liquid group with the N- heterocycle carbine ligands of ruthenium catalyst be combined to be formed it is new Ruthenium catalyst (is referred to herein as imidazolium ionic liquid base-ruthenium catalyst).This new imidazolium ionic liquid base-ruthenium Catalyst shows increased catalyst activity and the catalyst life extended in the reaction of such as olefin metathesis, and is reacting Easily separated afterwards from reactant mixture, regenerate and recycle.
Brief description of the drawings
Fig. 1 shows olefin metathesis agent commonly used in the prior art, the wherein representative alkene of C-1a~d 1st generations Hydrocarbon replaces agent, and C-2a~d is the representative olefin metathesis agent of 2nd generation.
Fig. 2 is shown is connected to the ruthenium catalyst in two kinds of different ligands by ionic liquid group in the prior art；The left side Ruthenium catalyst be the first catalyst containing imidazole ion liquid, wherein ionic liquid group to be connected to catalyst C-2a alcoxyl Obtained in base benzene ligand；The ruthenium catalyst on the right is second of imidazole ion liquid catalyst, wherein by ionic liquid base Group is connected on ruthenium catalyst C-2b alkyl phosphorus ligand and obtained.
Fig. 3 shows what different ruthenium catalysts changed with time for the conversion ratio of olefin metathesis reaction raw materials 1- decene Diagram.
Fig. 4 shows that different ruthenium catalysts are used for the conversion ratio of olefin metathesis reaction raw materials 1- decene with the change of cycle-index The diagram of change.
Embodiment
The present invention provides a kind of ruthenium containing imidazolium ionic liquid group on N- heterocycle carbines in first aspect and urged Agent, it is characterised in that the ruthenium catalyst is the compound with structure shown in formula (I)：
Wherein：
L is neutral electron part, and the neutral electron part is selected from by C3-C20Three substitution alkyl phosphorus bases of individual carbon, C3-C20Alkoxy, the C of individual carbon6-C20The aryloxy group of individual carbon, there is C1To C20Alkyl thioether group or there is C0To C20Alkane Base (represents C1To C20Alkyl or H) pyridine radicals composition group a group；L optionally with R7It is cyclic or not cyclic, Such as five-membered ring or hexatomic ring.
R1、R2、R3、R4、R5And R6It is each independently H, R group or first organic substitution with 1 to 20 carbon atom Base, first organic substituent are selected from by C1-C20Alkyl, C1-C20Alkoxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20 Alkyl-carbonyl, C7-C20Aryl carbonyl, C1-C20Amide groups and C3-C8The group of cyclic group composition；R1、R2、R3、R4、R5And R6In At least one group is R group；R2And R3It is asynchronously H and is first organic substituent；R4And R6It is asynchronously H and is First organic substituent；
R7For first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenylindan alkenylene；And R7 It is not H and R group；R7It is optionally cyclic or not cyclic with L, such as five-membered ring or hexatomic ring, this depend on specific L groups and R7Group.
The R group has the structure shown in lower formula (II)：
Wherein：
Y is CH2, O, S, N or the first group, first group is selected from by C6To C20Aryl, C6To C20Aryloxy group, C2Extremely C20Alkyl-carbonyl, C7To C20Aryl carbonyl, C1To C20Amide groups, C3-C8A group in the group of cyclic group composition；
N is 0 to 10 integer, preferably 2 to 6 integer, more preferably 2 to 4 integer；
X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；
R8、R9、R10And R11H or the second organic substituent are each independently, second organic substituent is selected from by C1- C20Alkyl, C6-C20Aryl and C3-C8The group of cyclic group composition.
Hereafter some embodiments of ruthenium catalyst described to the first aspect of the present invention are carried out more particularly It is bright.
L groups
L groups are neutral electron parts, such as can be selected from by C3-C20Three substitution alkyl phosphorus bases, the C of individual carbon3-C20 Alkoxy, the C of individual carbon6-C20One group of the group that aryloxy group, thiosubstituents group or the pyridine radicals of individual carbon form.
In some embodiments, L groups are C3-C20Alkyl phosphorus base, for example, with 3,4,5,6,7,8,9,10,11, 12nd, the alkyl phosphorus of 13,14,15,16,17,18,19 or 20 carbon atoms, such as thricyclohexyl phosphorus base (PCy3-).It is preferable in addition It is that the alkyl in the alkyl phosphorus is C3-C12Straight chained alkyl or branched-alkyl, more preferably C3-C6Straight chained alkyl or branch Change alkyl, for example, n-propyl, isopropyl, normal-butyl, isopropenyl (such as sec-butyl or tert-butyl group), n-pentyl, isopentyl, N-hexyl, isohesyl.
In some embodiments, L groups are C3-C20Alkoxy, for example, with 3,4,5,6,7,8,9,10,11,12, 13rd, the alkoxy of 14,15,16,17,18,19 or 20 carbon atoms.Preferably, the alkoxy is C3-C12Alkoxy, More preferably C3-C6Alkoxy, for example, propoxyl group, isopropoxy, n-butoxy, isobutoxy (such as sec-butoxy or Tert-butoxy), n-pentyloxy, isoamoxy, positive hexyloxy, dissident's epoxide.
In some embodiments, L groups are C6-C20Aryloxy group, for example, with 6,7,8,9,10,11,12,13,14, 15th, the aryloxy group of 16,17,18,19 or 20 carbon atoms.Preferably, the aryloxy group is C6-C12Aryloxy group；More preferably Be C6-C9Aryloxy group, for example, phenoxy group, benzyloxy, phenethyl epoxide or phenylpropyl epoxide.
In some embodiments, L groups are with C1To C12Alkyl thioether group, for example, with 1,2,3,4,5, 6th, the thioether group of the alkyl of 7,8,9,10,11 or 12 carbon atoms, the more preferably alkyl with 1,2,3,4,5 or 6 carbon atom Thioether group.
In some embodiments, L groups are with C3To C12Alkyl pyridine radicals, such as with 1,2,3,4,5 or 6 The thioether group of the alkyl of individual carbon atom..
In some preferred embodiments, L groups are isopropoxy and and R7Group forms 6 yuan of rings or tricyclohexyl phosphine Base.
R1To R6Group
R1、R2、R3、R4、R5And R6It is each independently H, R group or first organic substitution with 1 to 20 carbon atom Base, first organic substituent are selected from by C1-C20Alkyl, C1-C20Alkoxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20 Alkyl-carbonyl, C7-C20Aryl carbonyl, C1-C20Amide groups and C3-C8The group of cyclic group composition；R1、R2、R3、R4、R5And R6In At least one group is R group；R2And R3It is asynchronously H and is first organic substituent；R4And R6It is asynchronously H and is First organic substituent；On R group, will separately describe below.
On the first organic substituent
As first organic substituent, the C1-C20Alkyl be, for example, with 1,2,3,4,5,6,7,8,9,11, 12nd, the alkyl of 13,14,15,16,17,18,19 or 20 carbon atoms, for example, methyl, ethyl, propyl group, butyl, amyl group, hexyl, Heptyl, octyl group, nonyl, certain herbaceous plants with big flowers base, undecyl, dodecyl, myristyl, cetyl, octadecyl or eicosyl.Institute State alkyl be preferably methyl, ethyl, propyl group, isopropyl, butyl, isopropenyl, amyl group, isopentyl, hexyl or isohesyl (such as Cyclohexyl)；Further preferably methyl, ethyl, propyl group or isopropyl；Further preferably methyl or ethyl, most preferably Be methyl.
As first organic substituent, the C1-C20Alkoxy be, for example, with 1,2,3,4,5,6,7,8,9,11, 12nd, the alkoxy of 13,14,15,16,17,18,19 or 20 carbon atoms, for example, methoxyl group, ethyoxyl, propoxyl group, butoxy, Amoxy, hexyloxy, epoxide in heptan, octyloxy, nonyl epoxide, certain herbaceous plants with big flowers epoxide, hendecane epoxide, dodecyloxy, tetradecyloxyaniline, ten Six alkoxies, octadecane epoxide or eicosane epoxide.The C1-C20Alkoxy is preferably methoxyl group, ethyoxyl, propoxyl group, different Propoxyl group, butoxy, isopropyl alkenyloxy group, amoxy, isoamoxy, hexyloxy or dissident's epoxide (such as cyclohexyl)；Further Preferably methoxyl group, ethyoxyl, propoxyl group or isopropoxy；Further preferably methoxy or ethoxy, most preferably It is methoxyl group.
As first organic substituent, the C6-C20Aryl be, for example, with 6,7,8,9,11,12,13,14,15, 16th, the aryl of 17,18,19 or 20 carbon atoms, for example, phenyl, with 1 C1To C14The phenyl of alkyl substituent, with 2 C1To C13The phenyl of alkyl substituent, with 3 C1To C12The phenyl of alkyl substituent, with 4 C1To C11Alkyl substituent Phenyl, with 5 C1To C10The phenyl of alkyl substituent.Preferably, phenyl, carry 1 to 3 C on phenyl ring1To C3Alkane The phenyl of base, such as benzyl, phenethyl or phenylpropyl.
As first organic substituent, the C6-C20Aryloxy group be, for example, with 6,7,8,9,11,12,13,14, 15th, the aryloxy group of 16,17,18,19 or 20 carbon atoms, for example, phenoxy group, with 1 C1To C14The benzene oxygen of alkyl substituent Base, with 2 C1To C13The phenoxy group of alkyl substituent, with 3 C1To C12The phenoxy group of alkyl substituent, with 4 C1 To C11The phenoxy group of alkyl substituent, with 5 C1To C10The phenoxy group of alkyl substituent.Preferably, phenoxy group, on phenyl ring With 1 to 3 C1To C3Alkyl phenoxy group, such as benzyloxy, benzene ethyoxyl or phenylpropyl alcohol epoxide.
As first organic substituent, the C2-C20Alkyl-carbonyl be, for example, with 2,3,4,5,6,7,8,9,11, 12nd, the alkyl-carbonyl of 13,14,15,16,17,18,19 or 20 carbon atoms, the moieties in the alkyl-carbonyl can example Such as it is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, certain herbaceous plants with big flowers base, undecyl, dodecyl, 14 Alkyl, cetyl or octadecyl.The alkyl is preferably methyl, ethyl, propyl group, isopropyl, butyl, isopropenyl, penta Base, isopentyl, hexyl or isohesyl (such as cyclohexyl)；Further preferably methyl, ethyl, propyl group or isopropyl；Enter one Step is preferably methyl or ethyl, most preferably methyl.
As first organic substituent, the C7-C20Aryl carbonyl be, for example, with 7,8,9,11,12,13,14, 15th, the aryl carbonyl of 16,17,18,19 or 20 carbon atoms, the aryl moiety in the aryl carbonyl can have substituent, Such as the alkyl substituent of 1,2,3,4,5,6,7,8,9,11,12 or 13 carbon atoms is carried on phenyl ring.Preferably, the alkyl Substituent be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, certain herbaceous plants with big flowers base, undecyl, dodecyl, Tridecyl, more preferably methyl, ethyl, propyl group, isopropyl, butyl, isopropenyl, amyl group, isopentyl, hexyl or isohesyl (such as cyclohexyl), it is further preferred that methyl, ethyl, propyl group or isopropyl；It is even furthermore preferable that methyl or ethyl, Most preferably methyl, i.e. the C7-C20Aryl carbonyl is carbobenzoxy.
As first organic substituent, the C1-C20Amide groups for example can be not surpass altogether with carbon number Cross the alkyl substituent of 19 carbon atoms, for example, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, Certain herbaceous plants with big flowers base, undecyl, dodecyl, myristyl, cetyl or the amide groups of octadecyl substitution, preferably methyl, second Base, propyl group, butyl, amyl group or the amide groups of hexyl substitution, the amide groups that more preferably methyl, ethyl or propyl group substitute.
As first organic substituent, the C3-C8Cyclic group be, for example, saturation or undersaturated three-membered ring, Five-membered ring, hexatomic ring or the heptatomic ring of four-membered ring, five-membered ring, hexatomic ring, heptatomic ring or octatomic ring, preferably saturation.
R1、R2、R3、R4、R5And R6In 1,2,3,4,5 or 6 group can be R group；Preferably 2 groups are for example R1And/or R5It is R group；Further preferably 1 group such as R1Or R5It is R group, most preferably, R1It is R group.
In R1、R2、R3、R4、R5And R6In, in addition to the group as R group, other groups preferably independently for H or The first organic substituent with 1 to 20 carbon atom.In some embodiments, the other groups independently are H or tool There is the alkyl of 1 to 6 carbon atom.In some preferred embodiments, the other groups independently are with 1 to 6 carbon The alkyl of atom.In some preferred embodiments, the other groups independently are the alkane with 1 to 3 carbon atom Base such as methyl, ethyl, propyl group or isopropyl, most preferably all methyl of the other groups.
In some preferred embodiments, R1And/or R5In at least one group be R group；And R2、R3、R4With R6In it is at least one be methyl, at least two be methyl, at least three be methyl or all methyl.
In some preferred embodiments, the R1For R group, remaining all methyl.
R7Group
The R7Group can be above with respect to R1、R2、R3、R4、R5And R6Described the first organic substituent, C2To C20Alkene Alkyl, phenyl, isopropenyl or phenylindan alkenylene；And R7It is not H and R group.Preferably, the R7Group can be Above with respect to R1、R2、R3、R4、R5And R6Described the first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenyl Indenes alkenylene；And R7It is not H and R group.Preferably, the first organic substituent is the alkyl with 1 to 6 carbon atom, More preferably there is alkyl such as methyl, ethyl, propyl group or the isopropyl, most preferably methyl of 1 to 3 carbon atom.The C2Extremely C20Alkylene is preferably C2 to C6 alkylene, for example, vinyl, acrylic, pi-allyl, cyclobutenyl, pentenyl or hexene Base.
In some preferred embodiments, the R7Group is selected from phenyl, isopropenyl or phenylindan alkenylene composition Group；
In some embodiments, the R7Group can be separate with L groups；In other embodiments, institute State R7Group can form any cyclic group together with L groups.
R group
In the ruthenium catalyst of the present invention, R1、R2、R3、R4、R5、R6In at least one be to have to tie shown in lower formula (II) The R group of structure：
Y group
Y can be CH2, O, S, N or the first group, first group is selected from by C6To C20Aryl, C6To C20Aryloxy group, C2To C20Alkyl-carbonyl, C7To C20Aryl carbonyl, C1To C20Amide groups, C3-C8A group in the group of cyclic group composition. The C6To C20Aryl, C6To C20Aryloxy group, C2To C20Alkyl-carbonyl, C7To C20Aryl carbonyl, C1To C20Amide groups and C3-C8 Cyclic group is respectively as described above for R1To R6Described C6To C20Aryl, C6To C20Aryloxy group, C2To C20Alkyl-carbonyl, C7Extremely C20Aryl carbonyl, C1To C20Amide groups and C3-C8Cyclic group, it will not be repeated here.
In some preferred embodiments, Y can be CH2, O, S or N, more preferably Y is O or S, most preferably O.
N values
N can be 0 to 10 integer, for example, 0,1,2,3,4,5,6,7,8,9 or 10, preferably 2 to 10 integer, more Preferably 2 to 8 integer, more preferably 2 to 6 integer, it is still more preferably 2 to 4, most preferably 4；
X group
X can be fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；Preferably, X be fluorine, chlorine, bromine, Iodine, PF6Or BF4, it is further preferred that X is PF6Or BF4, most preferably, X PF6。
R8、R9、R10And R11Group
R8、R9、R10And R11H or the second organic substituent are each independently, second organic substituent is selected from by C1- C20Alkyl, C6-C20Aryl and C3-C8The group of cyclic group composition.
As second organic substituent, the C1-C20Alkyl be, for example, with 1,2,3,4,5,6,7,8,9,11, 12nd, the alkyl of 13,14,15,16,17,18,19 or 20 carbon atoms, for example, methyl, ethyl, propyl group, butyl, amyl group, hexyl, Heptyl, octyl group, nonyl, certain herbaceous plants with big flowers base, undecyl, dodecyl, myristyl, cetyl, octadecyl or eicosyl.Institute State C1-C20Alkyl is preferably methyl, ethyl, propyl group, isopropyl, butyl, isopropenyl, amyl group, isopentyl, hexyl or isohesyl (such as cyclohexyl)；Further preferably methyl, ethyl, propyl group or isopropyl；Further preferably methyl or ethyl, most Preferably methyl.
As second organic substituent, the C6-C20Aryl be, for example, with 6,7,8,9,11,12,13,14,15, 16th, the aryl of 17,18,19 or 20 carbon atoms, for example, phenyl, with 1 C1To C14The phenyl of alkyl substituent, with 2 C1To C13The phenyl of alkyl substituent, with 3 C1To C12The phenyl of alkyl substituent, with 4 C1To C11Alkyl substituent Phenyl, with 5 C1To C10The phenyl of alkyl substituent.Preferably, phenyl, carry 1 to 3 C on phenyl ring1To C3Alkane The phenyl of base, such as benzyl, phenethyl or phenylpropyl.
As second organic substituent, the C3-C8Cyclic group be, for example, saturation or undersaturated three-membered ring, Five-membered ring, hexatomic ring or the heptatomic ring of four-membered ring, five-membered ring, hexatomic ring, heptatomic ring or octatomic ring, preferably saturation.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1、R2、R3、R4、R5And R6 It is each independently H, organic with the R group of structure shown in above-mentioned formula (II) or described first with 1 to 20 carbon atom Substituent, R1、R2、R3、R4、R5And R6In at least one group be R group, R2And R3It is asynchronously H and is described first organic Substituent；R4And R6It is asynchronously H and is first organic substituent；Y is CH2, the group of O, S, N or described first；N is 0 To 10 integer；X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；R8、R9、R10And R11Independently of one another For the organic substituents of H or described second.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1、R2、R3、R4、R5And R6 It is each independently H, there is the R group or C of structure shown in above-mentioned formula (II)1-C20Alkyl, R1、R2、R3、R4、R5And R6In extremely A few group is R group, R2And R3It is asynchronously H and is C1-C20Alkyl；R4And R6It is asynchronously H and is C1-C20Alkyl；Y It is CH2、O、S、N；N is 0 to 10 integer；X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；R8、R9、 R10And R11It is each independently H or C1-C20Alkyl.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1、R2、R3、R4、R5And R6 It is each independently H, there is the R group or C of structure shown in above-mentioned formula (II)1-C6Alkyl, R1、R2、R3、R4、R5And R6In extremely A few group is R group, R2And R3It is asynchronously H and is C1-C6Alkyl；R4And R6It is asynchronously H and is C1-C6Alkyl；Y is CH2、O、S、N；N is 0 to 10 integer；X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；R8、R9、R10 And R11It is each independently H or C1-C6Alkyl.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1、R2、R3、R4、R5And R6 It is each independently R group or C with structure shown in above-mentioned formula (II)1-C6Alkyl, R1、R2、R3、R4、R5And R6In at least One group is R group；Y is CH2、O、S、N；N is 0 to 10 integer；X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N(SO2CF3)2；R8、R9、R10And R11It is each independently C1-C6Alkyl.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1And/or R5For with upper State the R group of structure shown in formula (II), R2、R3、R4And R6Methyl, ethyl, propyl group, isopropyl, butyl, isopropyl independently of one another Alkenyl, amyl group, isopentyl or hexyl or isohesyl；Y is O or S；N is 0 to 10 integer；X is PF6Or BF4；R8、R9、R10With R11It is each independently methyl, ethyl, propyl group, isopropyl, butyl, isopropenyl, amyl group, isopentyl or hexyl or isohesyl.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1And/or R5For with upper State the R group of structure shown in formula (II), R2、R3、R4And R6It is each independently methyl, ethyl, propyl group or isopropyl；Y be O or S；N is 2 to 6 integer；X is PF6Or BF4；R8、R9、R10And R11It is each independently methyl, ethyl, propyl group or isopropyl.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1For with above-mentioned formula (II) R group of structure shown in, R2、R3、R4、R5And R6It is each independently methyl；Y is O；N is 4；X is PF6；R8、R9、R10With R11For methyl.
In some preferred embodiments of the present invention, the ruthenium catalyst is selected from following 4 representative catalysis The compound of agent structure：
The present invention provides the synthetic method of the ruthenium catalyst described in first aspect present invention in second aspect.Using existing Method, imidazolium ionic liquid group can not be connected to the N- heterocycle carbine most strong with ruthenium catalytic center bonding energy power at all In coordination, because ruthenium is not only connected in the coordination of N- heterocycle carbines, equally also it is easily connected on imidazolium ionic liquid group, So as to which the ruthenium catalyst described in first aspect present invention can not be obtained.For the present inventor by further investigation, have found finally can be with Obtain the synthetic method of the ruthenium catalyst described in first aspect present invention.
In some more specifically embodiment, the method for preparing the ruthenium catalyst of the invention, methods described includes：
(1) compound 1 is synthesized；It is and 2-in-1 into compound 3 by compound；
(2) compound 4 is synthesized by compound 1 and compound 3；
(3) compound 5 is synthesized by compound 4；
(4) compound 6 is synthesized by compound 5；
(5) compound 7-I is synthesized by compound 6；
(6) compound 7-II is synthesized by compound 7-I；
(7) compound 8 or compound 9 as ruthenium catalyst are synthesized by compound 7-II；
Wherein, the structural formula of compound 1 to compound 7 is as follows：
Compound 8 is selected from the group being made up of following compound 8a, 8b, 8c and 8d：
The compound 9 is as follows：
In some more specifically embodiment, ruthenium catalyst of the invention is carried out by following synthetic route：
More specifically, second aspect of the present invention methods described comprises the following steps：
(1) make 2-methylimidazole and Isosorbide-5-Nitrae-dibromobutane reaction, obtain 1- (4- brombutyls) -2-methylimidazole, i.e. chemical combination Thing 1；
(2) make 4- hydroxyls -2,6- dimethylaniline, glyoxal and 1, the reaction of 3,5- trimethylanilines, obtain 1- (4- hydroxyls Base -2,6- dimethyl benzene) base -2- (1,3,5- trimethylbenzene) base-second diimine, i.e. compound 2；
(3) compound 2 is reacted with sodium borohydride, obtain 1- (4- hydroxyls -2,6- dimethyl benzene) base -2- (1,3,5- tri- Methylbenzene) base-ethylenediamine, i.e. compound 3；
(4) compound 3 is reacted with compound 1, obtain 1- (2,6- dimethyl -4- (4- (2-methylimidazole base) fourth oxygen Base) benzene) base -2- (1,3,5- trimethylbenzene) base-ethylenediamine, i.e. compound 4；
(5) make compound 4, triethyl orthoformate and hydrochloric acid reaction, obtain 1- (2,6- dimethyl -4- (4- (2- methyl miaows Triazole hydrochloride base) butoxy) benzene) base -3- (1,3,5- trimethylbenzene)-imidazolium chloride, i.e. compound 5；
(6) make compound 5, sodium tert-butoxide and the reaction of tert-butyl group alcohol, obtain 1- (2,6- dimethyl -4- (4- (2- methyl miaows Oxazolyl) butoxy) benzene) base -3- (1,3,5- trimethylbenzene) -2- tert-butyl group oxygen imidazolidines, i.e. compound 6；
(7) make compound 6 and iodomethane reaction, obtain the salt compounded of iodine imidazole ion liquid-ligand 7- with following structure I, i.e. compound 7-I：
(8) make compound 7-I and hexafluorophosphoric acid silver reaction, obtain the hexafluorophosphate (PF with following structure6) imidazoles Ionic liquid-ligand 7-II, i.e. compound 7-II：
(9) make compound 7-II and the first generation alkoxy benzal type Ge Labu catalyst reactions, obtain the ruthenium and urge Agent.
In some preferred embodiments, the Ge Labu catalyst of the first generation alkoxy benzal type is selected from by such as The group of lower compound C-1a, C-1b, C-1c or C-1d composition：
And To the ruthenium catalyst be respectively selected from by compound 8a, 8b, 8c, 8d and compound 9：
The present invention provides ruthenium catalyst or the second aspect of the present invention system described in first aspect present invention in the third aspect The ruthenium catalyst obtained reacts in olefin metathesis carries out alkene especially using the alkene derived from vegetable oil such as cottonseed oil as reactant Application in hydrocarbon displacement reaction, it is preferred that the cycle applications in olefin metathesis reaction.
The invention is further elaborated with reference to specific embodiment, following embodiments are only to illustrate the present invention The purpose of scheme rather than limit.
Embodiment 1：Imidazole ion liquid-ligand, 1- (2,6- dimethyl -4- (4- (1,2- methylimidazole alkali) fourths Epoxide) benzene) base -3- (1,3,5- trimethylbenzenes) -2- methyl oxygen imidazolidines synthesis
Bromobutyl imidazolium compounds 1 is the synthesis of 1- (4- brombutyls) -2-methylimidazole (abbreviation compound 1)：
Under conditions of the protection of room temperature, stirring and nitrogen, to being placed with 2-methylimidazole (4.2g, 50mmol) and dried 60 weight % sodium hydrides solids are added portionwise in tetrahydrofuran (40ml) solution and (3.0g, clean 3 times with n-hexane in advance to wash Remove Dormant oils), substantial amounts of bubble is released after addition immediately.Continue stirring 60 minutes until bubble-free releasing is after adding sodium hydride Only, the clear solution in reaction is slowly then transferred to another and has been previously heated to 70 DEG C, equipped with Isosorbide-5-Nitrae-dibromo fourth In alkane (10.7g, 50mmol) and 10ml tetrahydrofuran reaction bulbs；After transfer, continue reaction 4 hours；Utilize TLC plate (silica gel Thin layer) judge reaction terminal.Reaction is cooled to room temperature after terminating, add 30ml n-hexanes, washes 3 times (each 30ml), Na2SO4It is dried overnight.Then, using Rotary Evaporators remove solvent and and go the removal of impurity using vacuum condition, obtain slightly light Yellow liquid product 9.0g, yield 95.7%.Product need not be further purified, and can be directly used for reacting in next step. C8H13BrN2High resolution mass spec calculated value：216.0262；Measured value：216.0270.
Second diimine compounds 2, i.e. 1- (4- hydroxyls -2,6- dimethyl benzene) base -2- (1,3,5- trimethylbenzene) base-second two Imines (hereinafter sometimes simply referred to as compound 2) synthesis：
Into reaction bulb add 4- hydroxyl -2,6- dimethylanilines (4.4g), 40% glyoxal (4.3g) aqueous solution and 1,3,5- trimethylaniline (4.0g), then add 50 volume % isopropanol/waters (50ml) and 13% volume acetic acid/isopropanol (10 Drop), reaction 4h is stirred at room temperature, reaction solution gradually becomes yellow solution, with TLC plates (10 volume % ethyl acetate/just oneself Alkane) come judge reaction whether reach terminal (how judging), product would indicate that three yellow spottings on the tlc plate.Reaction The sodium hydroxide solution terminating reaction of the acetic acid equivalent such as addition after complete.Filtering solution, then the 75 volume % methanol/waters with 120ml Solution washs the yellow solid being filtrated to get on filter screen in three times, finally retains yellow solid, is dried under reduced pressure acquisition yellow Solid 7.1g.Gained yellow solid contains three kinds of group with imine moiety：1,2- double (1,3,5- trimethylbenzenes) base-second diimine, 1- (4- hydroxyl -2,6- dimethyl benzenes) base -2- (1,3,5- trimethylbenzenes) base-ethylenediamine (object), 1,2- pairs (4- hydroxyls base - 2,6- dimethyl benzenes) base-second diimine.
Ethylene diamine compound 3, i.e. 1- (4- hydroxyls -2,6- dimethyl benzene) base -2- (1,3,5- trimethylbenzene) base-ethylenediamine The synthesis of (hereinafter sometimes referred to compound 3)：
Sodium borohydride (3.8g, 5mmol) is added in 100ml single port bottles, middle gained from the reactions above is then added and contains Three kinds of second diimine yellow mixture solids (7.1g) and tetrahydrofuran (30ml).Stir at room temperature, methanol is added dropwise in three batches (altogether 10ml is added dropwise).Reaction produces hydrogen, and heat release.Reaction about 5h is stirred at room temperature, solution graduates into faint yellow straight by yellow To near colorless, judge whether reaction reaches terminal with TLC plates (25 volume % ethyl acetate/n-hexane).After reaction terminates, add Enter 50ml water stopped reactions, then add dichloromethane 30ml and washed in separatory funnel three times, remove a layer yellow solution. After anhydrous sodium sulfate drying, remove solvent with rotary evaporator and obtain sticky mass.Use under nitrogen protection and silicon is housed The separation post separation of glue, successively to the liquid sterling ethylene diamine compound of three light grays, it is followed successively by by the order of separation：1, Double (1,3,5- trimethylbenzenes) bases-ethylenediamine of 2-, 1- (4- hydroxyl -2,6- dimethyl benzenes) base -2- (1,3,5- trimethylbenzenes) base - Double (4- hydroxyl -2,6- dimethyl benzenes) bases-ethylenediamine of ethylenediamine, 1,2-.The 1- (4- hydroxyl -2,6- dimethyl benzenes) wherein purified Base -2- (1,3,5- trimethylbenzene) base-ethylenediamine liquid, weight 1.7g.C19H26N2O high resolution mass spec calculated value： 298.2045；Measured value：298.2056.
Imidazole radicals-ethylene diamine compound 4,1- (2,6- dimethyl -4- (4- (2-methylimidazole base) butoxy) benzene) base -2- The synthesis of (1,3,5- trimethylbenzenes) base-ethylenediamine (hereinafter sometimes referred to compound 4)：
Under nitrogen protective condition, 1- (4- hydroxyls -2,6- dimethyl benzene) base -2- (1,3,5- tri- is added into reaction bulb Methylbenzene) base-ethylenediamine (6.0g, 20mmol), cesium carbonate Cs2CO3(6.8g, 22mmol) solid and the dried second of 60ml Nitrile.Stirred 30 minutes in room temperature oil bath, then by oil bath heating to 50 DEG C, 1- (4- brombutyls) -2-methylimidazole is added dropwise The solution of (4.34g, 20mmol) in 20ml acetonitriles, is warming up to backflow after completion of dropwise addition, continue stirring 3 hours, utilize TLC plates Judge the terminal of reaction.Reactant is naturally cooled into environment temperature after reaction terminates, 30ml is added and contains 0.5g hydroxides (3x50ml) is washed with water to neutrality in sodium water solution and toluene 30ml, fully shake, isolated organic layer；By drying, very The lower solvent evaporated of sky, obtains the compound 4 of light gray viscous liquid, weight 7.4g, yield 86%.C27H38N4O high score Resolution mass spectrum calculated value：434.3046；Measured value：434.3061.
Imidazole hydrochloride-imidazolium chloride 5,1- (2,6- dimethyl -4- (4- (2-methylimidazole hydrochloric acid alkali) fourth oxygen Base) benzene) base -3- (1,3,5- trimethylbenzenes)-imidazolium chlorides (hereinafter sometimes referred to compound 5) synthesis:
Imidazole radicals-ethylene diamine compound 4 (4.34g, 10mmol) is dissolved in 40ml toluene, primitive nail is added to the solution Triethylenetetraminehexaacetic acid ester (6.0g) and 20% hydrochloric acid solution (3.65g).Reaction bulb equipped with distilling apparatus is heated to 80 DEG C, with reaction Progress constantly there is solvent and accessory substance to be distilled out of, the terminal of reaction is judged with TLC plates, after reaction, uses reduced pressure handle instead The distillations such as solvent are clean, and simultaneous reactions liquid is changed into white solid, stood after then naturally cooling to environment temperature.To white solid Soaked and filtered with 20ml n-hexanes, retain white solid, altogether in triplicate；Lower drying is finally depressurized, obtains canescence chemical combination The solid of thing 5, weight 4.1g, yield 80.3%.C28H37N4O high resolution mass spec calculated value：445.2967；Measured value： 445.2954。
Imidazole radicals-ligand 6,1- (2,6- dimethyl -4- (4- (2-methylimidazole base) butoxy) benzene) base -3- (1,3, 5- trimethylbenzenes) -2- tert-butyl group oxygen imidazolidines (hereinafter sometimes referred to compound 6) synthesis：
Imidazole hydrochloride-imidazolium chloride 5 (2.0g, 3.86mmol) is added into dried reactor, 20ml is done It is dry to cross tetrahydrofuran and 10ml n-hexanes.Under nitrogen protection, room temperature opens stirring, by 15% sodium tert-butoxide-t-butanol solution (3.0ml) (concentration of the tert-butyl group sodium in tert-butyl group alcohol is 15 weight/volume %) is added drop-wise in said mixture.With dropwise addition Carry out react dirty solution graduate into yellow solution, continue to react 1-2 hours at room temperature after dropwise addition, during which with TLC plates To judge the terminal of reaction.Reaction terminates rear mixture and (1x10ml) is washed with water, and then dries and what is be filtrated to get contains miaow The solution of the product of oxazolyl-ligand 6.The solution is directly used in and reacted in next step.C32H46N4O2High resolution mass spec calculate Value：518.3621；Measured value：518.3598.
1- methylimidazoles ionic liquid-ligand 7,1- (2,6- dimethyl -4- (4- (1,2- methylimidazole alkali) fourths Epoxide) benzene) base -3- (1,3,5- trimethylbenzenes) -2- tert-butyl group oxygen imidazolidines (hereinafter sometimes referred to compound 7) synthesis：
7-I) salt compounded of iodine 1- methylimidazoles ionic liquid-ligand 7-I synthesis：To advance second through in dried reaction bulb The solution of the compound 6 of the imidazole radicals-ligand obtained from the reactions above is added, is put it in 0 DEG C of ice-water bath, is protected in nitrogen Shield is lower to add iodomethane CH3I(1.65g,11.6mmol).Ice-water bath then is withdrawn, allows reaction temperature to be maintained at room temperature, continues to stir 2-3 hours are mixed, the terminal of reaction is judged with TLC plates.Excessive CH is steamed under vacuum after reaction terminates3I and molten Agent, then add dried first 30ml.Obtain salt compounded of iodine 1- methylimidazoles ionic liquid-ligand 7a toluene solution. C36H49N4O2High resolution mass spec calculated value：533.3850；Measured value：533.3861.
7-II) hexafluorophosphate (PF6) 1- methylimidazoles ionic liquid-ligand 7b synthesis：This be a step imidazoles from The anion exchange reaction of sub- liquid.In nitrogen protection, under the gentle agitation of room, to obtain in from the reactions above ground salt compounded of iodine imidazoles from Sub- liquid-ligand 7a toluene solution, hexafluorophosphoric acid silver (AgPF is added dropwise6, 1.0g, 3.96mmol) toluene solution, stirring Overnight.Reaction is filtered reactant mixture by diatomite after terminating, and is washed 3 times, and hexafluorophosphate (PF is obtained after drying6)1- Methylimidazole ionic liquid-ligand 7b toluene solution.C30H43N4O2High resolution mass spec calculated value：533.3850；Survey Value：533.3841.
The synthesis of 2 imidazolium ionic liquids of embodiment-catalyst is as follows：
A) imidazole ion liquid-alkoxy benzal catalyst 8a synthesis：Hexafluorophosphate (PF will be contained6) imidazol ion Liquid-ligand 7b toluene solution and the Ge Labu catalyst C-1a RuCl of first generation alkoxy benzal type2PCy3(= CHC6H4OCH(CH3)2) (0.90g, 1.5mmol) is added in reaction bulb.By reaction bulb it is closed after, be put into 80 DEG C of oil bath, stir Mix lower reaction 40-60 minutes.Reaction terminates, and is evaporated all solvents under vacuum condition, and residue is soaked and filtered more with methanol Secondary circulation, until the raw material point (R on TLC platesfBe worth big point) disappear untill, greenish solid product is dried in vacuo, obtains miaow Oxazolinium ion liquid-alkoxy benzal catalyst 8a, 1.0g, yield 74%.C39H52Cl2N4O2Ru high resolution mass spec calculates Value：780.2511；Measured value：780.2498.1H NMR(300MHz,CDCl3)δppm:16.56 (s, 1H, Ru=CHAr), 7.48 (m, 1H, aromatic-CH), 7.46 (s, 1H, imidazolium-CH), 7.38 (s, 1H, imidazolium-CH), 7.09 (s,2H,mesityl aromatic-CH),7.00(s,2H,mesityl aromatic-CH),6.93(dd,1H, Aromatic-CH), 6.85 (dd, 1H, aromatic-CH), 6.79 (d, 1H, aromatic-CH), 4.90 (m, 1H, (CH3)2CHOAr),4.18(m,4H,N(CH2)2N),4.08(t,2H,OCH2),4.05(t,2H,NCH2),3.77(s,3H,NCH3), 2.52(s,3H,CH3),2.48(m,12H,mesityl-CH3),2.40(s,3H,mesityl-CH3) 1.85 (m, 2H ,- CH2CH2-), 1.78 (m, 2H ,-CH2CH2-),1.27(d,6H,CH3)2CHOAr).Wherein, aromatic represents aromatic radical, Imidazolium represents imidazole radicals, and Mesityl represents mesitylene base.
B) imidazole ion liquid-vinylidene catalyst 8b synthesis：Synthetic method is equally identical with 8a, only need to be by reaction First generation Ge Labu catalyst C-1a first generation type containing vinylidene as raw material Ge Labu catalyst C-1b RuCl2(PCy3)2(=CHCH=C (CH3)2) (1.23g, 1.5mmol) replace.By reacting and post-processing with 8a identicals, Brown solid imidazole ion liquid-vinylidene catalyst product 8b is obtained, it is 1.10g to measure weight, yield 65%. C52H81Cl2N4OPRu high resolution mass spec calculated value：980.4569；Measured value：980.4582.
C) imidazole ion liquid-benzal catalyst 8c synthesis：
Synthetic method is identical with above-mentioned 8a, only need to be using the first generation Ge Labu catalyst C-1a as raw material in reaction With the Ge Labu catalyst C-1c RuCl of first generation type containing benzal2(PCy3)2(=CHC6H5) (1.27g, 1.5mmol) next generation Replace.React and post-process by 8a identicals, obtain brown solid imidazole ion liquid-benzal catalyst product 8c, measure weight Measure as 1.19g, yield 69%.C54H79Cl2N4OPRu high resolution mass spec calculated value：1002.4412；Measured value： 1002.4431。
D) imidazole ion liquid-phenylindan Asia alkene catalyst 8d synthesis：
Synthetic method is identical with above-mentioned 8a, only need to be using the first generation Ge Labu catalyst C- as raw material in reaction 1a, with the Ge Labu catalyst C-1d RuCl of first generation Asia containing phenylindan alkenes type2(PCy3)2(=C9H6(m)C6H5) (1.38g, 1.5mmol) is replaced.React and post-process by 8a identicals, obtain dark brown solid product imidazol ion liquid Body-phenylindan Asia alkene catalyst 8d, it is 1.07g to measure weight, yield 57%.C62H83Cl2N4OPRu high resolution mass spec meter Calculation value：1102.4725；Measured value：1102.4703.
The synthesis of embodiment 3.1- isopropylimdazoles ionic liquid-alkoxy benzal catalyst 9：
According to the synthetic method completely same from compound 7-I to catalyst 8a, catalyst 9 is obtained.Specific step is： Iso-Propyl iodide (the CH of equivalent is used in 7-I reactions first3)2CHI replaces its iodomethane (CH3I) react；Then according to 7-II full terms, which carry out reaction, can obtain accordingly 2 isopropyl imidazole ionic liquid-ligand containing hexafluorophosphate； Finally by the toluene solution of the ligand and the Ge Labu catalyst C-1a RuCl of first generation alkoxy benzal type2PCy3(= CHC6H4OCH(CH3)2) (0.99g, 1.6mmol) reaction, the purification and vacuum drying soaked and filtered by methanol, obtain green Color solid product 1- isopropylimdazoles ionic liquid-alkoxy benzal catalyst 9, weight 1.1g, yield 81%. C41H56Cl2N4O2Ru high resolution mass spec calculated value：808.2818；Measured value：808.2829.
The catalyst olefin metathesis catalytic reaction of embodiment 4
The pretreatment of 1- decene and ionic liquid：1) pretreatment of 1- decene, with ultrasonoscope by the appearance equipped with 1- decene After device degasification 30 minutes, the deoxidant (BASF AG) of 5% weight is placed into, is kept for 24 hours under the conditions of sealing and lucifuge. Oxygen agent is removed using preceding filtering under nitrogen protection, then using preceding again with nitrogen bubble about 30 minutes.2) imidazole salts from The pretreatment of sub- liquid, using preceding at 70 DEG C, by the reaction equipped with 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquids Bottle vacuum drying 2 hours.Then room temperature is cooled under stirring and nitrogen protection.
1) in the presence of without ionic liquid, the olefin metathesis operation method of 1- decene conversion ratios：
In the case where nitrogen is protected and is stirred, into the reaction bulb equipped with continuous air-blowing device and condenser pipe, 1- decene is added (7.0g, 50mmol), then puts it into the oil bath with heating function, after temperature reaches 60 DEG C, adds catalyst C- 2a (0.1mmol, 0.2mol%).When reaction time proceeds to 10,20,40,60,120,240 minutes, take out 0.1ml's respectively Sample carrys out the process of observing response.Obtained sample first crosses solution of the sodium hydroxide in toluene with a 30% ethanol tert-butyl group of drop To terminate catalytic reaction, then with after 5ml dilution with toluene, the content of product is analyzed with gas chromatograph (GC).As a result see Table 1 and Fig. 3.
The calculation formula of 1- decene conversion ratios：Conversion ratio %=100%- (decene molal quantity/whole products molal quantity) X 100%
The olefin metathesis operation method in the presence of imidazolium ionic liquid：
2) 1- decene conversion ratio changes with time
In the case where nitrogen is protected and is stirred, 1- decene (7.0g, 50mmol) and 1- butyl -3- ethyl imidazol(e) hexafluoro phosphorus will be housed The reaction bulb of hydrochlorate ionic liquid (2.0ml) mixture is put into the oil bath of heating, after temperature reaches 60 DEG C, is separately added into general Logical catalyst C-2a and imidazolium ionic liquid-catalyst 8a (being respectively 0.1mmol, 0.2mol%).Enter between when reacted Row by 10,20,40,60,120,240 minutes when, it is separately sampled come observing response process.Obtained sample is first with a drop 30% Ethanolic sodium hydroxide solution terminates catalytic reaction, then with volume is by silica gel treatment and again 9:1 n-hexane and ethyl acetate Mixed solvent elution after, analyze the content of product with gas chromatograph (GC).As a result see table 1 and Fig. 3.
Table 1.1- decene conversion ratios change with time
Reaction to generating 9- octadecylenes by itself olefin metathesis of 1- decene：1) deposited by above-mentioned without ionic liquid Left lower with catalyst C-2a Catalysis experiments and 2) in imidazolium ionic liquid in the experiment with catalyst C-2a and 8a respectively, It is all considerably fast that these three speed reacted are can be readily seen that at 60 DEG C from its result watch 1 and Fig. 1, when proceeding to 40 Respective conversion ratio just has been maxed out value or very close maximum during minute.Therefore the reaction time one in testing below Rule is chosen to be 40 minutes.
3) 1- decene recycles with olefin metathesis reacting middle catalyst
Under nitrogen protection, into the 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid reaction bulbs equipped with 2ml, Add the 1- decene (7.0g, 50mmol) by pretreatment.After the mixture is heated to 60 DEG C in oil bath, catalysis is added (catalyst includes typical catalyst C-2a, C-2c and imidazolium ionic liquid-catalyst for agent (0.10mmol, 0.20mol%) 8a、8c).It is reacted to 40 minutes and takes out sample immediately, be subsequently cooled to room temperature, the analysis of product is carried out according to above-mentioned method.
Blended product is easily separated with catalyst reaction system by following manner：
1. reactant mixture extracts (4 X 30ml) with toluene, the extract of merging is obtained with Rotary Evaporators solvent evaporated To crude product；Containing micro ion liquid crude on silica gel layer filtering, then with volume ratio be 9:1 n-hexane and ethyl acetate Mixed solvent elution layer of silica gel be thoroughly to remove contained micro ion liquid, can obtain sterling production by distillation and rectifying Thing.
2. the regeneration of imidazolium ionic liquid catalyst reaction system：Reactant mixture is extracted 3 with toluene as described above It is secondary, i.e., as next time recycle ionic liquid catalyst systems and directly can according to this part the above (i.e. " 1- last of the ten Heavenly stems Alkene and olefin metathesis reacting middle catalyst recycle ") identical method carries out catalytic reaction next time.Catalyst recycles Result be summarized in table 2 and Fig. 4.
Table 2. olefin metathesis reaction cycle number and conversion ratio in imidazolium ionic liquid
N.D. represent to be not detected by, represented in Fig. 4 with numerical value " 0 ".
Representative catalyst 8a and 8c are selected from imidazolium ionic liquid-ruthenium catalyst 8a-d, have passed through 8 times Catalytic activity only have dropped 8% and 9% respectively after circular response；And common catalyst C-2a and C-2c circulates in first time Afterwards, the conversion ratio of activity-reaction of catalyst just significantly have dropped 52-59% (second of circulation) and 80-87% the (the 3rd Secondary circulation).From the above result that it is observed that：It is this that imidazolium ionic liquid is connected to the coordination of ruthenium catalyst N- heterocycle carbines New imidazolium ionic liquid-ruthenium catalyst, such as catalyst 8a-d on body is recyclable well in olefin metathesis reaction performance Usability.
This new imidazolium ion liquid that imidazolium ionic liquid group is connected to ruthenium catalyst N- heterocycle carbine ligands Body group and ruthenium catalyst, it can be recycled for multiple times, so as to make up common ruthenium catalyst well because being used only once The high deficiency of catalyst cost caused by and.

Claims (21)

1. a kind of ruthenium catalyst containing imidazolium ionic liquid group on N- heterocycle carbines, it is characterised in that the ruthenium is urged Agent is the compound with structure shown in formula (I)：
Wherein：
L is neutral electron part, the neutral electron part and R7Group is cyclic or not cyclic, and selected from by C3-C18 Three substitution alkyl phosphorus bases, the C of individual carbon3-C6The alkoxy of individual carbon and there is C3To C6One of group of pyridine radicals composition of alkyl Group；
R1、R2、R3、R4、R5And R6It is each independently H, R group or the first organic substituent, the first organic substituent choosing Free C1-C6Alkyl and C1-C6The group of alkoxy composition；R1、R2、R3、R4、R5And R6In 1 or 2 group be R group；R2And R3 For first organic substituent；R4And R6For first organic substituent；
R7For first organic substituent, C2To C7Alkylene, phenyl or phenylindan alkenylene；And R7It is not H and R group；
The R group has the structure shown in lower formula (II)：
Wherein：
Y is O or S；
N is 0 to 10 integer；
X is PF6、BF4Or N (SO2CF3)2；
R8、R9、R10And R11H or the second organic substituent are each independently, second organic substituent is C1-C6Alkyl.
2. ruthenium catalyst according to claim 1, it is characterised in that：
N is 2 to 6 integer.
3. ruthenium catalyst according to claim 1, it is characterised in that：
N is 2 to 4 integer.
4. ruthenium catalyst according to claim 1, it is characterised in that：
The neutral electron part is with C3To C6Alkyl pyridine radicals；
First organic substituent is selected from by C1-C3Alkyl and C1-C3The group of alkoxy composition；
R7For C1-C3Alkyl, C1-C3Alkoxy, C2To C7Alkylene, phenyl or phenylindan alkenylene；
N is 2 to 4 integer；
Second organic substituent is C1-C3Alkyl.
5. ruthenium catalyst according to claim 1, it is characterised in that：
L is C3-C18Three substitution alkyl phosphorus bases, the C of individual carbon3-C6The alkoxy of individual carbon and there is C3To C6Alkyl pyridine radicals group Into group a group；
First organic substituent is selected from by C1-C3Alkyl and C1-C3The group of alkoxy composition；
R7For C1-C3Alkyl, C1-C3Alkoxy, C2To C7Alkylene, phenyl or phenylindan alkenylene；
N is 2 to 4 integer；
Second organic substituent is C1-C3Alkyl.
6. ruthenium catalyst according to claim 5, it is characterised in that：
R7It is phenyl, isopropenyl or phenylindan Asia alkene.
7. ruthenium catalyst according to claim 1, it is characterised in that：
R1、R2、R3、R4、R5And R6In 2 groups be R group.
8. ruthenium catalyst according to claim 1, it is characterised in that：
R1And R5It is R group.
9. ruthenium catalyst according to claim 1, it is characterised in that：
R1、R2、R3、R4、R5And R6In 1 group be R group.
10. ruthenium catalyst according to claim 1, it is characterised in that：
R1Or R5It is R group.
11. ruthenium catalyst according to claim 1, it is characterised in that：
L groups are CH (CH3)2O- or PCy3-；
R1And R5In at least one group be R group, remaining group independently is H, R group or with 1 to 6 carbon atom Alkyl；
R7Group is phenyl, isopropenyl or phenylindan alkenylene；
N is the integer between 2 to 6；
X is PF6Or BF4；And/or
R8And R11It independently is H or the alkyl with 1 to 6 carbon atom.
12. ruthenium catalyst according to claim 1, it is characterised in that：
L groups are CH (CH3)2O- or PCy3-；
R1And R5In at least one group be R group, remaining group independently is H or the alkyl with 1 to 6 carbon atom；
R7Group is phenyl, isopropenyl or phenylindan alkenylene；
N is the integer between 2 to 6；
X is PF6Or BF4；
R8To R11It independently is H or the alkyl with 1 to 6 carbon atom.
13. ruthenium catalyst according to claim 1, it is characterised in that：
L groups are CH2(CH3)2O- or PCy3-；
R1Or R5For R group, R1、R2、R3、R4、R5And R6In remaining group be H, methyl, ethyl, propyl group or isopropyl；
R7Group is phenyl, isopropenyl or phenylindan alkenylene；
N is the integer between 2 to 4；
X is PF6Or BF4；
R8To R11It independently is H, methyl, ethyl, propyl group or isopropyl.
14. ruthenium catalyst according to claim 1, it is characterised in that：
L groups are CH2(CH3)2O- or PCy3-；
R1For R group, R2、R3、R4、R5And R6For methyl；
R7Group is phenyl, isopropenyl or phenylindan alkenylene；
Y is O；
N is 4；
X is PF6；
R8To R11For methyl.
15. according to the ruthenium catalyst described in claim 1,4 or 5, it is characterised in that：
The C2To C7Alkylene is isopropenyl.
16. ruthenium catalyst according to any one of claim 1 to 3, it is characterised in that：
The ruthenium catalyst is selected from the group being made up of following compound 8a, 8b, 8c, 8d and compound 9：
A kind of 17. method for preparing ruthenium catalyst, it is characterised in that methods described includes：
(1) compound 1 is synthesized；It is and 2-in-1 into compound 3 by compound；
(2) compound 4 is synthesized by compound 1 and compound 3；
(3) compound 5 is synthesized by compound 4；
(4) compound 6 is synthesized by compound 5；
(5) compound 7-I is synthesized by compound 6；
(6) compound 7-II is synthesized by compound 7-I；
(7) compound 8 or compound 9 as ruthenium catalyst are synthesized by compound 7-II；
Wherein, the structural formula of compound 1 to compound 7 is as follows：
Compound 8 is selected from the group being made up of following compound 8a, 8b, 8c and 8d：
The compound 9 is as follows：
18. application of the ruthenium catalyst in olefin metathesis reaction according to any one of claim 1 to 16.
19. application according to claim 18, it is characterised in that the olefin metathesis is to be made with the alkene derived from vegetable oil The olefin metathesis carried out for reactant.
20. application according to claim 19, it is characterised in that the vegetable oil is cottonseed oil.
21. the application according to any one of claim 18 to 20, it is characterised in that the application is to be put in the alkene The cycle applications changed in reaction.
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