CN110563769B - Ruthenium carbene olefin metathesis catalyst chelated by bidentate sulfur ligand and preparation method and application thereof - Google Patents
Ruthenium carbene olefin metathesis catalyst chelated by bidentate sulfur ligand and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000003446 ligand Substances 0.000 title claims abstract description 31
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 31
- 238000005865 alkene metathesis reaction Methods 0.000 title claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000011593 sulfur Substances 0.000 title claims abstract description 27
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 9
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 150000001875 compounds Chemical class 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- -1 ruthenium carbene olefin Chemical class 0.000 claims description 17
- 239000012265 solid product Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- 239000013522 chelant Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- NTEYQAHRPQPPMP-UHFFFAOYSA-N CO.CC(C)(C)[O-].[Na+] Chemical compound CO.CC(C)(C)[O-].[Na+] NTEYQAHRPQPPMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- HLGOWXWFQWQIBW-UHFFFAOYSA-N 1,3-bis(ethenyl)cyclopentane Chemical compound C=CC1CCC(C=C)C1 HLGOWXWFQWQIBW-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000005686 cross metathesis reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 4
- DHRQXRVZGHBRHX-UHFFFAOYSA-N [Na].[Na].S1C(SC(=C1S)S)=O Chemical compound [Na].[Na].S1C(SC(=C1S)S)=O DHRQXRVZGHBRHX-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- IVNOJHSSOXLLSM-UHFFFAOYSA-N 2-pyran-2-ylidenepyran-3-carboximidamide Chemical compound NC(=N)C1=CC=COC1=C1OC=CC=C1 IVNOJHSSOXLLSM-UHFFFAOYSA-N 0.000 description 1
- ZLSXKGYHTGRSFY-UHFFFAOYSA-N 4,5-bis(sulfanyl)-1,3-dithiol-2-one Chemical compound SC=1SC(=O)SC=1S ZLSXKGYHTGRSFY-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007350 electrophilic reaction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000003203 stereoselective catalyst Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/08—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention provides a ruthenium carbene olefin metathesis catalyst chelated by a bidentate sulfur ligand, which has the structural formula:
the preparation method is simple, and the obtained olefin metathesis catalyst has excellent catalytic activity and stereoselectivity and high structural stability, is applied to norbornene ROMP reaction, and has higher yield and better Z-selectivity.
Description
Technical Field
The invention relates to the technical field of transition metal organic catalysts, in particular to a ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelate, and a preparation method and application thereof.
Background
At present, the olefins with Z-type structures have wide application in the fields of chemistry, biology, medicine and the like, and need to be prepared by a rapid, efficient and stereoselective catalytic reaction, and the key point of the catalytic reaction is a catalyst, so that a high-activity olefin metathesis catalyst capable of effectively controlling stereoselectivity needs to be deeply researched.
Olefin metathesis is a reversible process, the Z-olefin product is mainly kinetically controlled, while the E-olefin product is mainly thermodynamically controlled, especially in the late stage of the reaction, which is often a very complex process, and it is very difficult to obtain a high-yield and Z-selective olefin metathesis product, so that the research of a high-activity olefin metathesis catalyst for effectively controlling stereoselectivity is of great significance.
Currently, great progress has been made in the search for olefin metathesis catalysts, including the mono-aryloxypyrrolidine compounds of the stereoselective catalysts Mo-and W-, for the preparation of biologically active natural products; ruthenium catalysts chelated with bidentate P ligands have Z-selectivity for ring-opening metathesis polymerization (ROMP); the ruthenium catalyst bidentate chelate of N-heterocyclic carbene (NHC) has Z-selectivity when being used for various double decomposition reactions of olefin; a ruthenium carbene catalyst with bidentate sulfur ligand chelate is used for ring-opening polymerization/ring-opening cross metathesis (ROMP/ROCM), Cross Metathesis (CM) and ring-closing metathesis (RCM) reaction of olefins, and has catalytic activity and Z-selectivity.
However, the catalytic activity and Z-selectivity of existing olefin metathesis catalysts are not high, and particularly the catalytic activity and Z-selectivity in the cross-metathesis reaction process are in need of improvement.
Therefore, it is a problem to be solved by those skilled in the art to provide a novel and highly efficient catalyst to improve the catalytic activity and Z-selectivity during cross metathesis reaction.
Disclosure of Invention
In view of the above, the invention provides a ruthenium carbene olefin metathesis catalyst chelated by a bidentate sulfur ligand, and a preparation method and application thereof, the preparation method is simple, the obtained olefin metathesis catalyst has excellent catalytic activity and stereoselectivity, and high structural stability, and the catalyst is applied to norbornene ROMP reaction and has higher yield and better Z-selectivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a ruthenium carbene olefin metathesis catalyst comprising a bidentate sulfur ligand chelate, wherein the ruthenium carbene olefin metathesis catalyst comprising a bidentate sulfur ligand chelate has the structural formula:
the beneficial effects of the preferred technical scheme are as follows: the catalyst disclosed by the invention contains the bidentate sulfur ligand, so that the repulsive force between the bidentate sulfur ligand and the N-heterocyclic carbene ligand can be increased, the ligand is forced to be away from the N-heterocyclic carbene ligand with large steric hindrance as far as possible, the intermediate transition state of the action of the catalyst and olefin is close to a triangular biconical coordination structure, and the catalytic activity of the catalyst is favorably improved; due to the space obstruction effect of the bidentate sulfur ligand, the triangular bipyramid in the intermediate transition state is more compact and crowded, the three-dimensional control capability of the intermediate in the transition state on a substituent group is facilitated, and the stereoselectivity is improved; in addition, the bidentate sulfur ligand contained in the catalyst has larger electronegativity, and can effectively reduce electrophilic reaction of nitrogen heterocyclic carbene para-sulfur atom to carbon ruthenium double bond, thereby improving the stability of the catalyst.
The invention also provides a preparation method of the ruthenium carbene olefin metathesis catalyst chelated by the bidentate sulfur ligand, which comprises the following steps:
a preparation method of ruthenium carbene olefin metathesis catalyst chelated by a bidentate sulfur ligand is characterized by comprising the following steps:
(1) dissolving a compound (I) in methanol, adding a sodium tert-butoxide methanol solution, completely reacting under stirring, filtering to remove the solvent after the reaction is finished, and drying a solid product under a vacuum condition to obtain a compound (II);
(2) adding the compound (II) and a Hoveyda-Grubbs II catalyst into a dry tetrahydrofuran solvent, completely reacting under the stirring condition, and performing vacuum filtration after the reaction is finished to pump out the solvent to obtain a brownish red solid product; adding normal hexane into the brownish red solid product, uniformly stirring to obtain a mixed solution, carrying out centrifugal separation on the mixed solution to obtain a solid product, carrying out suction filtration on the residual solid, and drying to obtain a compound (III), namely the ruthenium carbene olefin double decomposition catalyst containing the chelate of the bidentate sulfur ligand;
the chemical structural formula of the compound (I) is as follows:
the chemical structure of the compound (II) is as follows:
the chemical structural formula of the compound (III) is as follows:
preferably, the molar ratio of the compound (I) to the sodium tert-butoxide in the step (1) is (1-3): (2-6).
Preferably, the compound (I) in the step (1) is dissolved in methanol at a concentration of 0.1-0.4 mmol/mL, and a colorless solution can be formed.
Preferably, the concentration of sodium tert-butoxide in the methanol solution of sodium tert-butoxide described in step (1) is 0.1 to 0.6mmol/mL, a colorless solution can be formed.
Preferably, in the step (1), the reaction temperature is 15-30 ℃, the stirring speed is 600r/min-1000r/min, and the reaction time is 2-5 h; the reaction solution gradually changed from colorless to a deep red solution.
The beneficial effects of the preferred technical scheme are as follows: compound (II) can be obtained in a yield of more than 75%.
Preferably, the molar ratio of the Hoveyda-GrubbsII catalyst to the compound (II) in the step (2) is (1-3): (2-3).
Preferably, the Hoveyda-Grubbs II catalyst in step (2) is dissolved in dry tetrahydrofuran at a concentration of 0.01 to 0.2mmol/ml, and the compound (II) is dissolved in dry tetrahydrofuran at a concentration of 0.02 to 0.2 mmol/ml.
Preferably, the reaction temperature in the step (2) is 15-30 ℃, the stirring speed is 600r/min-1000r/min, and the reaction time is 0.5-1.5 h; the liquid-solid ratio of the added n-hexane to the brownish red solid product is 20-30 mL/g.
The beneficial effects of the preferred technical scheme are as follows: according to the preferable conditions of step (2), the compound (III) can be obtained in a yield of more than 60%.
The invention also provides an application of the ruthenium carbene olefin metathesis catalyst chelated by the bidentate sulfur ligand in the ring-opening metathesis polymerization reaction of norbornene.
Compared with the prior art, the invention discloses a ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelate and a preparation method and application thereof, and the catalyst has the following beneficial effects:
(1) the catalyst prepared by the method has high catalytic activity and high stereoselectivity, and the catalyst has excellent stability;
(2) the method disclosed by the invention has the advantages of simple steps and mild reaction conditions, can be obtained by reaction at room temperature, and has excellent development prospect;
(3) the ruthenium olefin metathesis catalyst prepared by the invention has obvious catalytic action on norbornene ROMP reaction, can improve the yield of the reaction, has better Z-selectivity, and can obtain Z-type olefin after norbornene ROMP reaction.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows the scheme of compound (III)1H-NMR spectrum;
FIG. 2 shows the scheme of compound (III)13A C-NMR spectrum;
FIG. 3 is a drawing showing a poly (1, 3-divinylcyclopentane)1H-NMR spectrum;
FIG. 4 is a drawing of poly (1, 3-divinylcyclopentane)13C-NMR spectrum.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a preparation method of a ruthenium carbene olefin metathesis catalyst chelated by a bidentate sulfur ligand, which specifically comprises the following steps:
(1) dissolving the compound (I) in methanol to form a solution with the concentration of 0.1-0.4 mmol/mL, and then, according to the molar ratio of the compound (I) to sodium tert-butoxide of (1-3): (2-6), adding a methanol solution of sodium tert-butoxide with the concentration of 0.1-0.6mmol/mL, reacting for 2-5h at the stirring speed of 600r/min-1000r/min and the temperature of 15-30 ℃, filtering to remove the solvent after the reaction is finished, and drying the obtained solid product under the vacuum condition to obtain a compound (II);
(2) according to the molar ratio of (1-3): (2-3) adding Hoveyda-GrubbsII catalyst and a compound (II) into a dried tetrahydrofuran solvent to form a reaction system with the concentration of the Hoveyda-GrubbsII catalyst being 0.01-0.2 mmol/ml and the concentration of the compound (II) being 0.02-0.2 mmol/ml, then reacting for 0.5-1.5h under the stirring condition of 600r/min-1000r/min and the temperature condition of 15-30 ℃, and after the reaction is finished, pumping the solvent by using a vacuum pump to obtain a brownish red solid product; adding n-hexane into the brownish red solid product, wherein the liquid-solid ratio of the added n-hexane to the brownish red solid product is 20-30 mL/g; uniformly stirring to obtain a mixed solution, centrifuging the mixed solution, separating out liquid, draining the residual solid, and drying to obtain a compound (III), namely the ruthenium carbene olefin double decomposition catalyst containing the bidentate sulfur ligand chelate;
the chemical structural formula of the compound (I) is as follows:
the chemical structure of the compound (II) is as follows:
the chemical structural formula of the compound (III) is as follows:
example 1
Synthesis of 1, 3-dithiol-2-one-4, 5-dithiol disodium salt (II)
1,3,4, 6-Tetrathiocyclopentene-2, 5-dione (208.3mg,1mmol) was dissolved in 5mL of methanol. To this solution was added 5mL of methanol in sodium tert-butoxide (211.4mg,2.2 mmol). The solution was stirred at 800r/min for 2 hours at room temperature, changing from colorless to deep red. After completion of the reaction, the solvent was drained and dried under vacuum to obtain red solid powder (II) (201mg, yield: 89.0%).
Example 2
Synthesis of 1, 3-dithiol-2-one-4, 5-dithiol disodium salt (II)
1,3,4, 6-Tetrathiocyclopentene-2, 5-dione (104.2mg,0.5mmol) was dissolved in 5mL of methanol. To this solution was added 5mL of methanol in sodium tert-butoxide (144.1mg,1.5 mmol). The solution was stirred at 700r/min for 3 hours at room temperature, changing from colorless to deep red. After completion of the reaction, the solvent was drained and dried under vacuum to obtain red solid powder (II) (169mg, yield: 75.0%).
Example 3
Synthesis of 1, 3-dithiol-2-one-4, 5-dithio-disodium salt (II)
1,3,4, 6-tetrathiacyclopentene-2, 5-dione (208.3mg,1mmol) was dissolved in 5mL methanol. To this solution was added 5mL of methanol in sodium tert-butoxide (240.2mg,2.5 mmol). Stirring at 900r/min for 4 hours at room temperature changed the solution from colorless to dark red. After completion of the reaction, the solvent was drained and dried in vacuo to obtain (II) as a red solid (194mg, yield: 86.0%).
Example 4
Synthesis of 1, 3-dithiol-2-one-4, 5-dithiol disodium salt (II)
1,3,4, 6-Tetrathiocyclopentene-2, 5-dione (104.2mg,0.5mmol) was dissolved in 5mL of methanol. To this solution was added 5mL of methanol in sodium tert-butoxide (288.3mg,3.0 mmol). The solution was stirred at 800r/min for 5 hours at room temperature, changing from colorless to deep red. After completion of the reaction, the solvent was drained and dried under vacuum to obtain (II) as a red solid powder (151mg, yield: 67.0%).
Example 5
Synthesis of 1, 3-dithiol-2-one-4, 5-dithiol disodium salt (II)
1,3,4, 6-Tetrathiocyclopentene-2, 5-dione (208.3mg,1mmol) was dissolved in 5mL of methanol. To this solution was added 5mL of methanol in sodium tert-butoxide (240.2mg,2.5 mmol). Stirring at 1000r/min at 30 deg.C for 4 hr to turn the solution from colorless to deep red. After completion of the reaction, the solvent was drained and dried under vacuum to obtain red solid powder (II) (192mg, yield: 85.0%).
Example 6
Synthesis of 1, 3-dithiolan-2-one-4, 5-dithiol-chelated ruthenium carbene compound (III)
Grubbs-HoveydaII catalyst (464.0mg,0.74mmol), compound II prepared in example 1 (201.0mg,0.9 mmol) was placed in a 25mL round bottom flask. 15mL of dry THF was added and stirred at 800r/min for 30min at room temperature. And after the reaction is finished, pumping the solvent by using a vacuum pump to obtain a brownish red solid. Adding n-hexane into the solid, stirring thoroughly until the color of n-hexane turns red, centrifuging the mixed solution, removing liquid, and draining the solid. Compound III was obtained as a brown solid powder (385mg, yield: 70.6%).
The synthesized compound III was detected by a nuclear magnetic resonance spectrometer, and the results are shown in FIGS. 1 to 2.
As is apparent from the results of FIGS. 1 to 2, the ruthenium complex (III)1HNMR(400MHz,CDCl3)δ14.57(s,1H),7.26(s,1H),7.08(d,J＝8.3Hz,1H),6.95(s,2H),6.79(t,J＝7.3Hz,2H),6.62(d,J＝7.3Hz,1H),6.10(s,1H),5.33(dd,J＝14.1,7.4Hz,1H),4.01–3.84(m,4H),2.44(s,6H),2.29(s,6H),2.22(s,3H),1.74(d,J＝6.7Hz,3H),1.61(s,3H),1.40(d,J＝6.5Hz,3H)；13C NMR(100MHz,CDCl3)δ216.21,201.16,154.55,141.69,136.04,130.54,129.35,127.45,124.39,122.42,118.40,115.69,83.17,51.31,31.61,24.35,22.68,21.00,14.16.
Example 7
Synthesis of 1, 3-dithiol-2-one-4, 5-dithiol chelated ruthenium carbene compound (III)
Grubbs-HoveydaII catalyst (201mg,0.32mmol) and compound II prepared in example 2 (169.0mg,0.75mmol) were placed in a 25mL round bottom flask. 15mL of dry THF was added and the mixture was stirred at 600r/min at room temperature for 1 hour. And after the reaction is finished, the solvent is pumped by a vacuum pump to be dry to obtain a brownish red solid. Adding n-hexane into the solid, stirring thoroughly until the color of n-hexane turns red, centrifuging the mixed solution, removing liquid, and draining the solid. Compound III was obtained as a brown solid powder (552mg, yield: 70.1%).
The synthesized compound III was detected by a nuclear magnetic resonance spectrometer, and the results are shown in FIGS. 1 to 2.
Example 8
Synthesis of 1, 3-dithiolan-2-one-4, 5-dithiol-chelated ruthenium carbene compound (III)
Grubbs-HoveydaII catalyst (418.6mg,0.67mmol) and compound II prepared in example 4 (151mg,0.67 mmol) were placed in a 25mL round bottom flask. 15mL of dry THF was added thereto, and the mixture was stirred at 1000r/min at room temperature for 1.5 hours. And after the reaction is finished, pumping the solvent by using a vacuum pump to obtain a brownish red solid. Adding n-hexane into the solid, stirring thoroughly until the color of n-hexane turns red, centrifuging the mixed solution, removing liquid, and draining the solid. Compound III was obtained as a brown solid powder (133mg, yield: 67.5%).
The synthesized compound III was detected by a nuclear magnetic resonance spectrometer, and the results are shown in FIGS. 1 to 2.
Example 9
Synthesis of 1, 3-dithiolan-2-one-4, 5-dithiol-chelated ruthenium carbene compound (III)
Grubbs-HoveydaII catalyst (106.4mg,0.17mmol), compound II prepared in example 5 (192mg,0.85 mmol) was placed in a 25mL round bottom flask. 15mL of dry THF was added and stirred at 30 ℃ at a rate of 800r/min for 1 hour. And after the reaction is finished, pumping the solvent by using a vacuum pump to obtain a brownish red solid. Adding n-hexane into the solid, stirring thoroughly until the color of n-hexane turns red, centrifuging the mixed solution, removing liquid, and draining the solid. Compound III was obtained as a brown solid powder (87mg, yield: 69.3%).
The synthesized compound III was detected by a nuclear magnetic resonance spectrometer, and the results are shown in FIGS. 1 to 2.
Example 10
Synthesis of catalytic product poly (1, 3-divinyl cyclopentane)
Under nitrogen, 0.1mL of CH was added to a 5mL vial containing magnetons2Cl2After a solution was added to compound III (0.7mg, 0.001mmol) prepared in example 6, 1.5mL of norbornene (94.1mg, 1.0mmol) in CH was added2Cl2And (3) solution. The solution was stirred at room temperature for 1 hour, and the solution became very viscous after the reaction was completed. Then 5mL MeOH was added and the mixture was stirred vigorously to precipitate white polynorbornene. Washing with MeOH (3X 4mL) and drying in vacuo for 24h gave the product as a white solid with a Z/E ratio of 82:18 (82.8mg, 88% yield).
The white solid product was detected by a nuclear magnetic resonance spectrometer, and the results are shown in fig. 3 to 4.
As is evident from the results of FIGS. 3-4,1HNMR(400MHz,CDCl3)δ5.22(d,J＝5.9Hz,2H),2.79(s,2H),1.93–1.87(m,1H),1.82(d,J＝13.3Hz,2H),1.36(s,2H),1.02(dd,J＝22.2,10.7Hz,1H).13C NMR(100MHz,CDCl3)δ133.8,42.7,38.6,33.2.
the Z/E ratio was determined to be 82:18 from the ratio of the peak areas in the nuclear magnetic hydrogen spectrum.
Example 11
Synthesis of catalytic product poly (1, 3-divinyl cyclopentane)
Under nitrogen, 0.1mL of CH was added to a 5mL vial containing magnetons2Cl2After a solution was added to compound III (0.35mg, 0.0005mmol) prepared in example 7, 1.5mL of norbornene (94.1mg, 1.0mmol) in CH was added2Cl2And (3) solution. The solution was stirred at room temperature for 1 hour, and after the reaction was complete the solution became very viscous. Then 5mL MeOH was added and the mixture was stirred vigorously to precipitate white polynorbornene. Washing with MeOH (3X 4mL) and drying in vacuo for 24h gave the product as a white solid with a Z/E ratio of 82:18 (71.5mg, 76% yield).
The white solid product was detected by a nuclear magnetic resonance spectrometer, and the results are shown in fig. 3 to 4.
As is evident from the results of FIGS. 3-4,1HNMR(400MHz,CDCl3)δ5.22(d,J＝5.9Hz,2H),2.79(s,2H),1.93–1.87(m,1H),1.82(d,J＝13.3Hz,2H),1.36(s,2H),1.02(dd,J＝22.2,10.7Hz,1H).13C NMR(100MHz,CDCl3)δ133.8,42.7,38.6,33.2.
the Z/E ratio was determined to be 82:18 from the ratio of the peak areas in the nuclear magnetic hydrogen spectrum.
Example 12
Synthesis of catalytic product poly (1, 3-divinyl cyclopentane)
Under nitrogen, 0.1mL of CH was added to a 5mL vial containing magnetons2Cl2After a solution was added to compound III (1.05mg, 0.0015mmol) prepared in example 9, 1.5mL of norbornene (94.1mg, 1.0mmol) in CH was added2Cl2And (3) solution. The solution was stirred at room temperature for 1 hour, and the solution became very viscous after the reaction was completed. Then 5mL MeOH was added and the mixture was stirred vigorously to precipitate white polynorbornene. Washing with MeOH (3X 4mL) and drying in vacuo for 24h gave the product as a white solid with a Z/E ratio of 82:18 (82.8mg, 88% yield).
The white solid product was detected by a nuclear magnetic resonance spectrometer, and the results are shown in fig. 3 to 4.
As is evident from the results of FIGS. 3-4,1HNMR(400MHz,CDCl3)δ5.22(d,J＝5.9Hz,2H),2.79(s,2H),1.93–1.87(m,1H),1.82(d,J＝13.3Hz,2H),1.36(s,2H),1.02(dd,J＝22.2,10.7Hz,1H).13C NMR(100MHz,CDCl3)δ133.8,42.7,38.6,33.2.
the Z/E ratio was determined to be 82:18 from the ratio of the peak areas in the nuclear magnetic hydrogen spectrum.
The embodiments are described in a progressive manner in the specification, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A ruthenium carbene olefin metathesis catalyst comprising a bidentate sulfur ligand chelate, wherein the ruthenium carbene olefin metathesis catalyst has the structural formula:
2. a preparation method of ruthenium carbene olefin metathesis catalyst chelated by a bidentate sulfur ligand is characterized by comprising the following steps:
(1) dissolving a compound (I) in methanol, adding a sodium tert-butoxide methanol solution, completely reacting under stirring, filtering to remove the solvent after the reaction is finished, and drying a solid product under a vacuum condition to obtain a compound (II);
(2) adding the compound (II) and a Hoveyda-Grubbs II catalyst into a dry tetrahydrofuran solvent, completely reacting under the stirring condition, and performing vacuum filtration after the reaction is finished to pump out the solvent to obtain a brownish red solid product; adding normal hexane into the brownish red solid product, uniformly stirring to obtain a mixed solution, carrying out centrifugal separation on the mixed solution to obtain a solid product, carrying out suction filtration on the residual solid, and drying to obtain a compound (III), namely the ruthenium carbene olefin double decomposition catalyst containing the chelate of the bidentate sulfur ligand;
the chemical structural formula of the compound (I) is as follows:
the chemical structure of the compound (II) is as follows:
the chemical structural formula of the compound (III) is as follows:
3. the method for preparing the ruthenium carbene olefin metathesis catalyst chelated with the bidentate sulfur ligand as claimed in claim 2, wherein the molar ratio of the compound (I) to the sodium tert-butoxide in the step (1) is (1-3): (2-6).
4. The method for preparing the ruthenium carbene olefin metathesis catalyst containing the chelate of a bidentate sulfur ligand according to claim 3, wherein the compound (I) in the step (1) is dissolved in the methanol at a concentration of 0.1 to 0.4 mmol/mL.
5. The method of claim 4, wherein the concentration of sodium tert-butoxide in the solution of sodium tert-butoxide in methanol in step (1) is 0.1 to 0.6 mmol/mL.
6. The method for preparing the ruthenium carbene olefin metathesis catalyst containing the chelate of the bidentate sulfur ligand as set forth in claim 5, wherein the reaction temperature in the step (1) is 15 to 30 ℃, the stirring speed is 600r/min to 1000r/min, and the reaction time is 2 to 5 hours.
7. The process of claim 2 or 6, wherein the molar ratio of Hoveyda-GrubbsII catalyst to compound (II) in step (2) is (1-3): (2-3).
8. The method of claim 7, wherein the Hoveyda-GrubbsII catalyst is dissolved in dry tetrahydrofuran at a concentration of 0.01 to 0.2mmol/ml and the compound (II) is dissolved in dry tetrahydrofuran at a concentration of 0.02 to 0.2mmol/ml in step (2).
9. The method for preparing the ruthenium carbene olefin metathesis catalyst containing the chelate of the bidentate sulfur ligand as set forth in claim 8, wherein the reaction temperature in the step (2) is 15 to 30 ℃, the stirring speed is 600r/min to 1000r/min, and the reaction time is 0.5 to 1.5 hours; the liquid-solid ratio of the added n-hexane to the brownish red solid product is 20-30 mL/g.
10. The use of a ruthenium carbene olefin metathesis catalyst having a bidentate sulfur ligand chelate as defined in claim 1 in ring opening metathesis polymerization of norbornene.
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| A 3,4-dimercapto-3-cyclobutene-1,2-dione-chelated Z-stereoretentive/stereoselective olefin metathesis;Tao Wang et al.;《Dalton Trans.》;20190402;图1、Scheme1、表1 * |
| Readily Accessible and Easily Modifiable Ru-Based Catalysts for Efficient and Z-Selective Ring-Opening Metathesis Polymerization and Ring-Opening/Cross-Metathesis;R. Kashif M. Khan et al.;《J. Am. Chem. Soc.》;20130703;Scheme 1、表1 * |
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