CN109692709B - Catalyst for olefin metathesis reaction and preparation and application methods thereof - Google Patents
Catalyst for olefin metathesis reaction and preparation and application methods thereof Download PDFInfo
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
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- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
Abstract
The invention discloses a catalyst for olefin metathesis reaction and preparation and application methods thereof, belonging to the technical field of olefin metathesis catalysis. The chemical structure of the catalyst for olefin metathesis reaction is shown as formula I:
wherein, L is aza five-membered ring carbene; x1And X2Are the same or different anions; r1When selected from hydrogen, R2Selected from the group consisting of alkoxy, alkylsulfonyl, alkylsulfinyl, silyl, hydroxy, substituted or unsubstituted hydrocarbyl; r3Is cycloalkyl, alkane or aromatic hydrocarbon; r4、R5Aryl, cycloalkyl, alkane or together form an epoxy group. The catalyst provided by the invention has the advantages of simple preparation method, small catalyst consumption, high reaction rate, stable process and environment-friendly reaction and synthesis, and is mainly applied to the industrial high-efficiency production of olefin metathesis products.
Description
Technical Field
The invention belongs to the technical field of olefin metathesis catalysis, and particularly relates to a catalyst for olefin metathesis reaction and preparation and application methods thereof.
Background
Since the 50 s of the 20 th century, the research has rapidly progressed because of the important utility of olefin metathesis products. Olefin metathesis refers to the process of cleaving and recombining carbon-carbon multiple bonds under metal catalysis. According to the change of the molecular skeleton during the reaction, cross metathesis reaction, ring-closing metathesis reaction, ring-opening metathesis polymerization reaction, ring-opening metathesis reaction may be included.
Molybdenum-based, tungsten-based catalysts are the earliest reported olefin metathesis catalysts, but they have low catalytic activity and are unstable to water and air. Ruthenium-based catalysts subsequently reported are widely used due to their high activity in different metathesis reactions, resistance to functional groups, and stability to air and water. Among the most commonly used ruthenium-based catalysts are the generation 1, generation 2, and generation 3 Gerab (Grubbs) type ruthenium catalysts (Gru-I, Gru-II, Gru-III) (Recent advances in ruthenium-based catalysts. Grubbs et al, Chem Soc Rev. DOI:10.1039/c8cs00027 a).
Particularly Gru-II, the tricyclohexylphosphine is replaced by N heterocarbene (Nheterocylic carbene) ligand, so that the catalytic activity is obviously improved, and the catalyst can be widely applied to industrial catalytic processes.
Disclosure of Invention
The invention provides a novel catalyst for olefin metathesis reaction, which is improved on the basis of a 2 nd generation Grubbs type catalyst to obtain a catalyst with a chiral diphosphine binuclear ruthenium carbene complex structure for olefin metathesis reaction.
The invention provides a catalyst for olefin metathesis reaction, which has a chemical structure shown as a formula I:
wherein the content of the first and second substances,
l is aza five-membered ring carbene;
X1and X2Are the same or different anions;
R1and R2Each independently selected from alkoxy, alkylsulfonyl, alkylsulfinyl, silyl, hydroxy, substituted or unsubstituted hydrocarbyl; or R1When selected from hydrogen, R2Selected from the group consisting of alkoxy, alkylsulfonyl, alkylsulfinyl, silyl, hydroxy, substituted or unsubstituted hydrocarbyl;
R3is cycloalkyl, alkane or aromatic hydrocarbon;
R4and R5Are identical or different aryl, cycloalkyl, straight-chain, branched-chain alkane, or R4And R5Linked together to form a cycloalkyl group.
Further, R3Is isopropyl, cyclohexyl, tert-butyl or phenyl; preferably R3Is cyclohexyl.
Further, R4、R5Each independently selected from n-propyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl or phenyl; preferably R4And R5Are all phenyl groups.
Further, X1、X2Each independently selected from the group consisting of halogen Cl, Br, or I.
Further, L is aza five-membered ring carbene, including saturated or unsaturated aza five-membered ring carbene, the structural formula is shown as formula IIa and IIb respectively,
wherein R is6、R7、R8、R9、R10Each independently selected from: hydrogen, substituted or unsubstituted primary or secondary alkyl groups, substituted or unsubstituted phenyl groups, substituted or unsubstituted naphthyl groups, substituted or unsubstituted anthracenyl groups, halogens, hydroxyl groups, mercapto groups, cyano groups, thiocyanato groups, amino groups, nitro groups, nitroso groups, sulfonic groups, oxyboronyl groups, borono groups, phosphonic groups, phosphinic groups, phospho groups, phosphino groups, and siloxy groups.
The invention also provides a preparation method of the catalyst for olefin metathesis reaction, which comprises the following steps:
a) under the protection of nitrogen, dissolving chiral primary diamine and triethylamine in tetrahydrofuran solvent, and stirring to obtain an amine solution; dissolving a corresponding disubstituted phosphine chloride compound in tetrahydrofuran serving as a solvent to obtain a phosphine chloride solution; slowly dripping a phosphine chloride solution into an amine solution for mixing reaction, draining the solvent, adding absolute ethyl alcohol for filtering, washing the solid with n-hexane, and draining to obtain a chiral diphosphine amine ligand;
b) under the protection of nitrogen, dissolving a metal ruthenium carbene complex in a solvent toluene, adding pyridine, mixing, reacting, adding n-hexane, stirring, precipitating, filtering, washing, and draining the solvent to obtain a pyridine-coordinated ruthenium carbene complex;
c) under the protection of nitrogen, dissolving the chiral diphosphine ligand obtained in the step a) in a solvent of toluene or dichloromethane, dissolving the pyridine-coordinated ruthenium carbene complex obtained in the step b) in the solvent of toluene or dichloromethane, dripping the solution into the solution of the chiral diphosphine ligand, after the reaction, draining the solvent, filtering n-hexane, and draining the obtained filtrate to obtain the chiral diphosphine-coordinated ruthenium carbene compound, namely the catalyst for olefin metathesis reaction.
Further, in the step a), the amount of the chiral primary diamine is 1 equivalent, and the amount of the triethylamine is 2-3 equivalents; in the step c), the dosage of the chiral diphosphine ligand is 1 equivalent, and the dosage of the ruthenium carbene complex coordinated by pyridine is 2 equivalents.
The invention also provides an application method of the catalyst for olefin metathesis reaction, wherein the olefin metathesis reaction comprises cross metathesis reaction, ring closing metathesis reaction, ring opening metathesis polymerization reaction and ring opening metathesis reaction.
Further, the application method comprises the following steps: after the reaction of the olefin and the catalyst in the reaction bottle, the solvent is pumped to dryness, and the product is obtained by column separation.
Further, the reaction temperature is 0-80 ℃, and the molar ratio of the catalyst to the olefin is 1: 1-100000.
The proposed catalyst for olefin metathesis reaction of the present invention has the following advantages:
the invention provides a catalyst with a chiral diphosphine binuclear ruthenium carbene complex structure, and a preparation method and an application method thereof, which are improved on the basis of a 2 nd generation Grubbs type catalyst. The catalyst has the advantages of simple preparation method, high reaction rate, small catalyst consumption, high production efficiency, stable process and uniform product molecular weight distribution, and is suitable for industrial high-efficiency production of olefin metathesis products.
Detailed Description
It should be noted that the embodiments and features of the embodiments disclosed in the present disclosure may be combined with each other without conflict.
The embodiment of the invention provides a catalyst for olefin metathesis reaction, which has a chemical structure shown as a formula I:
wherein the content of the first and second substances,
l is aza five-membered ring carbene;
X1and X2Are the same or different anions;
R1and R2Each independently selected from alkoxy, alkylsulfonyl, alkylsulfinyl, silyl, hydroxy or substituted or unsubstituted hydrocarbyl; or R1When selected from hydrogen, R2Selected from the group consisting of alkoxy, alkylsulfonyl, alkylsulfinyl, silyl, hydroxy, substituted or unsubstituted hydrocarbyl;
R3is cycloalkyl, alkane or aromatic hydrocarbon;
R4and R5Are identical or different aryl, cycloalkyl, straight-chain, branched-chain alkane, or R4And R5Linked together to form a cycloalkyl group.
The invention improves on the basis of a 2 nd generation Grubbs type ruthenium catalyst, provides a catalyst for olefin metathesis reaction, adopts chiral raw materials to synthesize a chiral PNCCNP diphosphine amine ligand, phosphorus atoms in the ligand can form coordinate bonds with ruthenium metal to finally obtain a chiral bimetallic catalyst, the bimetallic catalyst can quickly improve the reaction rate of the olefin metathesis reaction, reduce the dosage of the catalyst and improve the production efficiency, and meanwhile, the molecular weight distribution of the product is uniform, thus being suitable for the industrial high-efficiency production of olefin metathesis products.
Although the search for olefin metathesis has made great strides, there are still many challenges. Further breakthroughs are needed in terms of reaction rates, efficient utilization of catalysts, etc., to facilitate industrial applications of olefin metathesis reactions, all of which are problems to be solved.
In the prior art, researches have reported that in 2 nd generation Grubbs type ruthenium catalysts, trialkyl or triphenylphosphine ligands have different structures and properties, so that the coordination of the phosphine ligands and metal ruthenium is influenced, and the activity and the reaction rate of the catalysts are influenced. Attempts have also been made to improve the ruthenium catalysts of Grubbs 2 generation by means of phosphine ligands containing electron-withdrawing substituents, but the catalytic effect, in particular the reaction rate, is not significantly improved.
On the basis of the 2 nd generation Grubbs type ruthenium catalyst, the invention improves the catalyst by a diphosphine amine ligand doped with P-X bonds (wherein X is electronegative heteroatom) and improves the catalytic performance. The chiral double-metal catalyst is finally obtained by adopting the chiral PNCCNP diphosphine ligand to form a coordination bond with the central metal atom ruthenium, so that the structure and the property of the catalyst are changed, a better coordination effect and a synergistic effect are formed among the carbene ligand, the chiral PNCCNP diphosphine ligand and the double-central metal atom ruthenium on the catalyst, and the catalyst is acted together from the aspects of steric hindrance, electronic effect and the like, so that the reaction rate and the catalytic activity of the catalyst are improved.
In one embodiment of the invention, L is aza five-membered ring carbene, including saturated or unsaturated aza five-membered ring carbene, the structural formula of which is shown as formula IIa and IIb respectively,
wherein R is6、R7、R8、R9、R10Each independently selected from: hydrogen, substituted or unsubstituted primary or secondary alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, halogen, hydroxy, mercapto, cyano, thiocyanatoAmino, nitro, nitroso, sulfonic, oxyboron, borono, phosphonic, phosphinic, phospho, phosphino and siloxy groups. In the invention, L is aza five-membered ring carbene which is beneficial to improving the catalytic activity because of the diversity of N-heterocyclic carbene ligand sphere shapes.
In the examples of the present invention, X1、X2Each independently selected from Cl, Br or I; preferably, X1、X2Are all halogen Cl.
In one embodiment of the present invention, R1And R2Each independently selected from alkoxy, alkylsulfonyl, alkylsulfinyl, silyl, hydroxy, substituted or unsubstituted hydrocarbyl; or R1When selected from hydrogen, R2Selected from the group consisting of alkoxy, alkylsulfonyl, alkylsulfinyl, silyl, hydroxy, substituted or unsubstituted hydrocarbyl, which hydrocarbyl may be substituted with the following groups, respectively: alkyl, aryl, alkenyl, alkynyl, metallocene, halogen, nitro, nitroso, hydroxyl, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio, or amido.
Preferably, R1Is hydrogen, R2Is a substituted or unsubstituted hydrocarbyl group; more preferably, R1Is hydrogen, R2Is substituted or unsubstituted aryl; more preferably, R1Is hydrogen, R2Is phenyl.
In yet another embodiment of the present invention, R3Can be cycloalkyl, alkane or aromatic hydrocarbon, etc. Specifically, R3Can be isopropyl, cyclohexyl, tert-butyl or phenyl, etc. Preferably R3Cyclohexyl and phenyl.
In one embodiment of the present invention, R4、R5Can be aryl, cycloalkyl, alkane or R4And R5Linked together to form a cycloalkyl group, and the like. Specifically, R4、R5Is phenyl or R4、R5Together form cyclohexyl and the like.
In the embodiment of the invention, a chiral PNCCNP diphosphine ligand with a special structure is adopted to form coordination with a carbene ligand and central metal atom ruthenium, and the coordination is carried out from a space positionR on the phosphamine ligand, which co-acts with the electronic effect3、R4、R5The different types of the substituent groups, and the synergistic effect and coordination effect of the bimetallic ruthenium under the action of different substituent groups can influence the insertion of olefin molecules, thereby influencing the catalytic reaction rate.
In a preferred embodiment of the present invention, the olefin metathesis catalyst has a chemical structure represented by formula I:
wherein the content of the first and second substances,
l is aza five-membered ring carbene;
X1and X2Are the same or different anions; preferably, X1And X2Each independently selected from Cl, Br or I; more preferably, X1、X2Are all halogen Cl;
R1and R2Each independently selected from alkoxy, alkylsulfonyl, alkylsulfinyl, silyl, or hydroxy, substituted or unsubstituted hydrocarbyl; or R1When selected from hydrogen, R2Selected from the group consisting of alkoxy, alkylsulfonyl, alkylsulfinyl, silyl, hydroxy, substituted or unsubstituted hydrocarbyl, the alkyl or hydrocarbyl groups may each be substituted with: alkyl, aryl, alkenyl, alkynyl, metallocene, halogen, nitro, nitroso, hydroxyl, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio, or amido; preferably, R1Is hydrogen, R2Is a substituted or unsubstituted hydrocarbyl group; more preferably, R1Is hydrogen, R2Is substituted or unsubstituted aryl; more preferably, R1Is hydrogen, R2Is phenyl;
R3can be cycloalkyl, alkane or aromatic hydrocarbon, preferably cycloalkyl, alkane or aromatic hydrocarbon, more preferably R3Is cyclohexyl;
R4r5 is aryl, cycloalkyl, alkane; or R4And R5Linked together to form a cycloalkyl group. Preferably R4Is n-propyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl or phenyl; more preferably R4And R5 is phenyl.
The invention also provides a preparation method of the catalyst for olefin metathesis reaction, which comprises the following steps:
a) under the protection of nitrogen, 1 equivalent of chiral primary amine and 2-3 equivalents of triethylamine are dissolved in tetrahydrofuran solvent, and are stirred to obtain amine solution; dissolving 2 equivalents of disubstituted phosphine chloride in tetrahydrofuran solvent to obtain a phosphine chloride solution; mixing and reacting an amine solution and a phosphine chloride solution, draining the solvent, adding absolute ethyl alcohol, filtering, and washing the obtained solid with n-hexane to obtain a chiral diphosphine amine ligand;
the reaction formula is as follows:
b) under the protection of nitrogen, dissolving a metal ruthenium carbene complex in a solvent toluene, adding pyridine, mixing, reacting, adding n-hexane, stirring, precipitating, filtering, washing, and draining the solvent to obtain a pyridine-coordinated ruthenium carbene complex;
the reaction formula is as follows:
c) under the protection of nitrogen, dissolving 2 equivalents of the ruthenium carbene complex coordinated by pyridine obtained in the step b) in a solvent of toluene or dichloromethane, dissolving 1 equivalent of the chiral diphosphine ligand obtained in the step a) in the solvent of toluene or dichloromethane, mixing the two for reaction, draining the solvent, filtering n-hexane, and draining the obtained filtrate to obtain a chiral ruthenium carbene compound coordinated by the chiral diphosphine, namely a catalyst for olefin metathesis reaction;
the reaction formula is as follows:
it is to be noted that Cy, Py and Mes in the formula are abbreviations for cyclohexyl, pyridyl and mesityl, respectively.
Further, in the step b), the amount of the metallic ruthenium carbene complex and pyridine may be 1mmol of the metallic ruthenium carbene complex: 2-10mL pyridine.
The invention also provides an application method of the catalyst for olefin metathesis reaction, wherein the olefin metathesis reaction comprises cross metathesis reaction, ring closing metathesis reaction, ring opening metathesis polymerization reaction and ring opening metathesis reaction.
In one embodiment of the present invention, a method for using a catalyst for olefin metathesis comprises the steps of: after the reaction of the reaction raw material olefin and the catalyst in a reaction bottle, the solvent is pumped to dryness and the product is obtained by column separation, and then the ring-opening metathesis polymerization reaction product is washed by methanol to obtain the polymer. The olefin as the reaction raw material may be any olefin capable of undergoing metathesis reaction, such as diethyl diallylmalonate, norbornene, etc. The metathesis reaction may be carried out solely on one kind of olefin, or the ring-opening metathesis polymerization reaction may be carried out on two kinds of the same or different olefins.
Further, the reaction temperature is 0-80 ℃; preferably, the reaction temperature is 20-40 ℃. The temperature range is favorable for olefin metathesis reaction, and the temperature is too high or too low to be favorable for reaction.
Further, the molar ratio of catalyst to olefin is from 1:1 to 100000. For example, it may be 1:2, 1:50, 1:100, 1:1000, 1:2000, 1: 5000. 1:100000, etc. The selection of the appropriate reaction ratios for different olefin feedstocks facilitates an increase in the activity and reaction rate of the olefin metathesis reaction.
The present invention will be described in detail with reference to specific examples.
Example 1
The preparation of the olefin metathesis catalyst # 1 has the following chemical structural formula, and comprises the following steps:
a) under the protection of nitrogen, 114.19mg of (1R, 2R) -cyclohexanediamine and 303.57mg of triethylamine are added into a 50mL eggplant-shaped bottle, 15mL of tetrahydrofuran are mixed, 465.46mg of dicyclohexyl phosphine chloride is diluted by tetrahydrofuran and slowly added into the eggplant-shaped bottle dropwise, white precipitate is separated out after stirring for 8 hours, the solvent is drained, absolute ethyl alcohol is added, stirring and filtering are carried out, the solid is washed by n-hexane, the filtrate is concentrated and placed into a refrigerator for recrystallization, white solid is obtained, the liquid is transferred, and the white solid is drained to obtain the chiral diphosphine ligand.
b) Under the protection of nitrogen, placing 800mg of Gru-II ruthenium coordination compound into a 100mL eggplant-shaped bottle, adding 1mL of toluene, adding 7mL of pyridine for reaction for 10min, adding 50mL of n-hexane, stirring for 20min, separating out a green solid, filtering, washing with n-hexane, and draining to obtain a light green solid.
c) Under the protection of nitrogen, 72.74mg of the pyridine-coordinated ruthenium carbene compound obtained in the step b) is placed in a 25mL eggplant-shaped bottle and dissolved in 3mL of toluene, then 25.34mg of the monophosphine ligand obtained in the step a) is dissolved in 1mL of toluene and dropwise added into the eggplant-shaped bottle, the reaction is carried out for 10min at normal temperature, the solvent is removed, n-hexane is added, the solid is filtered, washed and dried by suction, and the reddish brown solid catalyst 1# (yield is 75mg, yield is 87%) is obtained.
Catalyst # 1 nmr was characterized as follows:
1H NMR(400MHz,Rt；in C6D6):δ19.59(s,2H),8.18(br s,4H),7.14-7.10(t,2H),6.97-6.93(t,4H),6.88-6.86(d,4H),6.24(br s,4H),3.79-3.73(t,2H),3.35-3.30(t,4H),,3.25-3.18(q,4H),,2.76(br s,12H),2.40(br s,6H),2.33(br s,6H),2.17(s,6H),2.11-2.01(m,6H),1.84(s,6H),1.64-1.53(t,22H),,1.45-1.40(br d,6H),,1.14-1.13(q,12H),,1.04-0.96(m,3H).
31P NMR(162MHz；C6D6):δ73.40(s).
example 2
The preparation of the olefin metathesis catalyst # 2 has the following chemical structural formula, and comprises the following steps:
a) under the protection of nitrogen, 212.30mg of (1S,2S) -1, 2-diphenylethylenediamine and 303.57mg of triethylamine are added into a 50mL eggplant-shaped bottle, 15mL of tetrahydrofuran are mixed, 465.46mg of dicyclohexyl phosphonium chloride is diluted by tetrahydrofuran and slowly dripped into the eggplant-shaped bottle, white precipitate is separated out after stirring for 8 hours, then the solvent is drained, anhydrous stirring and filtering are added, the solid is washed by n-hexane, the filtrate is concentrated and put into a refrigerator for recrystallization to obtain white solid, the liquid is transferred, and the white solid is drained to obtain the azaphosphine ligand.
b) The same as in example 1.
c) Under the protection of nitrogen, 72.74mg of the pyridine-coordinated ruthenium carbene compound obtained in the step b) is placed into a 25mL eggplant-shaped bottle and dissolved in 3mL of toluene, 30.24mg of the monophosphine ligand obtained in the step a) is dissolved in a small amount of toluene and is dripped into the eggplant-shaped bottle, the reaction is carried out for 5min at the temperature of 40 ℃, the solvent is removed, n-hexane is added, the solid is filtered, washed and dried by pumping, and the reddish brown solid catalyst No. 2 is obtained. (yield 62.51mg, yield 71.7%)
Catalyst # 2 nmr was characterized as follows:
1H NMR(400MHz,CDCl3)δ19.41(s,2H),7.13-7.09(t,7H),7.06-7.00(q,3H),6.96-6.92(d,7H),6.86-6.76(br m,6H),6.52-6.43(br m,3H),5.85(br s,2H),4.51-4.46(t,2H),3.39-3.33(q,2H),3.29-3.21(m,5H),3.13-3.09(t,2H),2.90-2.85(br d,7H),2.67(s,6H),2.56(br s,6H),2.39-2.33(s,4H),2.23(s,6H),2.11-2.09(m,8H),1.80(s,10H),1.64(br s,3H),1.47-1.43(m,7H),1.17-1.14(m,9H),1.01-0.95(m,6H),0.63-0.57(t,3H),0.50-0.46(d,3H),0.29-0.23(d,3H).
31P NMR(162MHz；C6D6):δ78.41(s).
example 3
a) Under the protection of nitrogen, 212.30mg of (1S,2S) -1, 2-diphenylethylenediamine and 303.57mg of triethylamine are added into a 50mL eggplant-shaped bottle, 15mL of tetrahydrofuran are mixed, 441.28mg of diphenyl phosphine chloride is diluted by tetrahydrofuran and slowly added into the eggplant-shaped bottle dropwise, after stirring for 8 hours, white precipitate is separated out, then a solvent is drained, anhydrous stirring filtration is carried out, the solid is washed by n-hexane, the filtrate is concentrated and put into a refrigerator for recrystallization, a white solid is obtained, the liquid is transferred, and the white solid is drained to obtain the azaphosphine ligand.
b) The same as in example 1.
c) Under the protection of nitrogen, 72.74mg of pyridine-coordinated ruthenium carbene compound obtained in b) is placed in a 25mL eggplant-shaped bottle and dissolved in 3mL of toluene, then 29.03mg of monophosphine ligand obtained in a) is dissolved in a small amount of toluene and is dripped in the eggplant-shaped bottle to react for 5min, the solvent is removed, n-hexane is added, and the solid is filtered, washed and dried by pumping to obtain the reddish brown solid catalyst No. 3. (yield 58.58mg, yield 68.2%)
Catalyst # 3 nmr was characterized as follows:
1H NMR(400MHz,CDCl3)δ19.09(s,2H),7.62-7.41(m,8H),7.32-7.19(m,16H),7.01-6.91(m,14H),6.74-6.66(br m,10H),6.53-6.45(br m,4H),5.80(br s,2H),3.44-3.40(m,8H),2.02(s,6H),1.94(s,8H),1.80(s,10H),1.21-1.17(m,10H)
31P NMR(162MHz；C6D6):δ67.23(s).
example 4
Carrying out double decomposition reaction on catalysts 1#, 2# and 3# when the raw material is N, N-diallyl p-toluenesulfonamide, wherein the double decomposition reaction specifically comprises the following steps:
under the protection of nitrogen, 0.005mmol of catalyst is placed in a nuclear magnetic tube, 0.5mL of deuterated benzene solvent is added, 12.56mg (0.5mmol) of N, N-diallyl-p-toluenesulfonamide raw material is added, and the whole process adopts1The reaction amount of the reaction raw materials was measured by H NMR, and the results are shown in Table 1:
TABLE 1 catalyst 1#, 2#, 3# and 2 nd generation Grubbs catalyst evaluation results
From the above experiments, catalyst # 1 and catalyst # 2 showed a faster initial reaction rate than catalyst # 3, with a long enough reaction time and a conversion rate close to 100%, and a reaction rate better than that of the Gru-II catalyst.
Example 5
Catalyst 2# in the raw material diallyl diethyl malonate carries out double decomposition reaction, which is as follows:
under the protection of nitrogen, 0.2. mu. mol of catalyst 2# and 4mL of toluene solvent were added into a 25mL eggplant-shaped bottle, 96.12mg (0.4mmol) of diethyl diallylmalonate raw material was added, reaction was carried out at 25 ℃ for 6h, the raw material was found to be completely reacted by GC detection, the solvent was drained, and the product 82.1mg was obtained after passing through a fast column, with a yield of 96.70%.
Example 6
The ring-opening metathesis polymerization reaction of the catalyst 1#, the catalyst 2# and the catalyst 3# with the raw material of norbornene is as follows:
TABLE 2 evaluation results of catalysts # 1, # 2, # 3 and Grubbs catalysts 1 and 2
Catalyst No. 1, catalyst No. 2 and catalyst No. 3 are bimetallic catalysts, that is, two metal active centers are provided, and the dosage of the catalyst is reduced by one time compared with that of a single active center catalyst. Compared with the mononuclear catalysts Gru-I and Gru-II in the prior art, the product obtained by catalysis of the bimetallic catalyst has a Polymer Dispersity Index (PDI) closer to 1, i.e. the molecular weight distribution is more uniform; in addition, the molecular weight is slightly larger than that of the catalyst in the prior art, and the cis-selectivity of the product is also improved.
The disclosure of the present invention is to be considered as exemplary only and not as restrictive, and all changes that come within the spirit and scope of the disclosure and any equivalents thereto are intended to be embraced therein.
Claims (8)
1. A method for preparing a catalyst for olefin metathesis, comprising the steps of:
a) under the protection of nitrogen, dissolving chiral primary diamine and triethylamine in tetrahydrofuran solvent, and stirring to obtain an amine solution; dissolving a corresponding disubstituted phosphine chloride compound in tetrahydrofuran serving as a solvent to obtain a phosphine chloride solution; slowly dripping a phosphine chloride solution into an amine solution for mixing reaction, draining the solvent, adding absolute ethyl alcohol for filtering, washing the solid with n-hexane, and draining to obtain a chiral diphosphine amine ligand;
b) under the protection of nitrogen, dissolving a metal ruthenium carbene complex in a solvent toluene, adding pyridine, mixing, reacting, adding n-hexane, stirring, precipitating, filtering, washing, and draining the solvent to obtain a pyridine-coordinated ruthenium carbene complex;
c) under the protection of nitrogen, dissolving the chiral diphosphine ligand obtained in the step a) in a solvent of toluene or dichloromethane, dissolving the pyridine-coordinated ruthenium carbene complex obtained in the step b) in the solvent of toluene or dichloromethane, dripping the solution into the solution of the chiral diphosphine ligand, after the reaction, draining the solvent, filtering n-hexane, and draining the obtained filtrate to obtain a chiral diphosphine-coordinated ruthenium carbene compound, namely a catalyst for olefin metathesis reaction;
the chemical structure of the catalyst for olefin metathesis reaction is shown as formula I:
wherein the content of the first and second substances,
l is aza five-membered ring carbene;
X1and X2Are the same or differentAn anion;
R1and R2Each independently selected from alkoxy, alkylsulfonyl, alkylsulfinyl, silyl, hydroxy, substituted or unsubstituted hydrocarbyl; or R1When selected from hydrogen, R2Selected from the group consisting of alkoxy, alkylsulfonyl, alkylsulfinyl, silyl, hydroxy, substituted or unsubstituted hydrocarbyl;
R3is cycloalkyl, isopropyl, cyclohexyl, tert-butyl or phenyl;
R4and R5Each independently selected from n-propyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl or phenyl, or R4And R5Linked together to form a cycloalkyl group.
2. The method of claim 1, wherein the chiral primary diamine is used in an amount of 1 equivalent and the triethylamine is used in an amount of 2 to 3 equivalents in the step a); in the step c), the dosage of the chiral diphosphine ligand is 1 equivalent, and the dosage of the ruthenium carbene complex coordinated by pyridine is 2 equivalents.
3. The method of claim 1, wherein X is1、X2Each independently selected from the group consisting of halogen Cl, Br, or I.
4. The method of claim 1, wherein L is an aza five-membered ring carbene, including saturated or unsaturated aza five-membered ring carbenes, having the structural formulas shown in formulas IIa and IIb,
wherein R is6、R7、R8、R9、R10Each independently selected from hydrogen, substituted or unsubstituted primary or secondary alkyl, substituted or unsubstituted phenyl,Substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, halogen, hydroxyl, mercapto, cyano, thiocyanato, amino, nitro, nitroso, sulfonic, oxyboroyl, borono, phosphonic, phosphinic, phospho, phosphino, and siloxy.
5. A catalyst for olefin metathesis prepared by the process of any one of claims 1 to 4.
6. The method of using a catalyst for olefin metathesis as recited in claim 5, wherein the olefin metathesis reaction includes a cross metathesis reaction, a ring closing metathesis reaction, and a ring opening metathesis reaction.
7. The method of using a catalyst for olefin metathesis according to claim 6, comprising the steps of: after the reaction of the reaction raw material olefin and the catalyst in a reaction bottle, the solvent is pumped to dryness, the product is obtained by column separation, and the product of the ring-opening metathesis polymerization reaction is washed by methanol to obtain the polymer.
8. The method of using a catalyst for olefin metathesis according to claim 6, wherein the reaction temperature is 0 to 80 ℃ and the molar ratio of the catalyst to the olefin is 1:1 to 100000.
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