CN104356165A - Novel N-heterocyclic carbene ruthenium catalyst containing electron donating group and preparation method thereof - Google Patents
Novel N-heterocyclic carbene ruthenium catalyst containing electron donating group and preparation method thereof Download PDFInfo
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- CN104356165A CN104356165A CN201410611863.2A CN201410611863A CN104356165A CN 104356165 A CN104356165 A CN 104356165A CN 201410611863 A CN201410611863 A CN 201410611863A CN 104356165 A CN104356165 A CN 104356165A
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- fragrant
- aryl
- alkyl
- base
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- 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 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 title abstract description 26
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title abstract description 15
- 229910052707 ruthenium Inorganic materials 0.000 title abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 40
- 150000002148 esters Chemical class 0.000 claims description 32
- 229910052736 halogen Inorganic materials 0.000 claims description 26
- 150000002367 halogens Chemical class 0.000 claims description 26
- 150000002466 imines Chemical class 0.000 claims description 22
- 150000001412 amines Chemical class 0.000 claims description 20
- 150000003568 thioethers Chemical class 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 125000000524 functional group Chemical group 0.000 claims description 17
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 16
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 16
- 150000001299 aldehydes Chemical class 0.000 claims description 16
- 150000001408 amides Chemical class 0.000 claims description 16
- 150000001718 carbodiimides Chemical class 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 150000002576 ketones Chemical class 0.000 claims description 16
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical compound OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 150000003573 thiols Chemical class 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 150000004982 aromatic amines Chemical class 0.000 claims description 12
- -1 aryl sulfonic acid Chemical compound 0.000 claims description 12
- 125000005110 aryl thio group Chemical group 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 10
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 10
- 150000008430 aromatic amides Chemical class 0.000 claims description 10
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 10
- 125000004104 aryloxy group Chemical group 0.000 claims description 10
- 150000003949 imides Chemical class 0.000 claims description 10
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 10
- 125000005555 sulfoximide group Chemical group 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910000074 antimony hydride Inorganic materials 0.000 claims description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical compound [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 43
- 239000000243 solution Substances 0.000 description 37
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 26
- 239000007787 solid Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000004949 mass spectrometry Methods 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 6
- 229910000071 diazene Inorganic materials 0.000 description 6
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 229940117389 dichlorobenzene Drugs 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 3
- 229910052622 kaolinite Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FJIIWDFMQNNIOH-UHFFFAOYSA-N 1,3-dimethyl-5-propan-2-yloxybenzene Chemical compound CC(C)OC1=CC(C)=CC(C)=C1 FJIIWDFMQNNIOH-UHFFFAOYSA-N 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 2
- MKFDNRRBDDXYFM-QPJJXVBHSA-N 1-propan-2-yloxy-2-[(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1OC(C)C MKFDNRRBDDXYFM-QPJJXVBHSA-N 0.000 description 2
- BEJOYKHTBKOSGB-UHFFFAOYSA-N 2,6-dimethyl-4-propan-2-yloxyaniline Chemical compound CC(C)OC1=CC(C)=C(N)C(C)=C1 BEJOYKHTBKOSGB-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- NYPYPOZNGOXYSU-UHFFFAOYSA-N 3-bromopyridine Chemical compound BrC1=CC=CN=C1 NYPYPOZNGOXYSU-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- HFUDDBYHCAJNHS-UHFFFAOYSA-N [Ru].BrC1=CC=CN=C1 Chemical compound [Ru].BrC1=CC=CN=C1 HFUDDBYHCAJNHS-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- GHPHCACQRYSXSS-UHFFFAOYSA-N ruthenium;tricyclohexylphosphane Chemical compound [Ru].C1CCCCC1P(C1CCCCC1)C1CCCCC1 GHPHCACQRYSXSS-UHFFFAOYSA-N 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 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 description 1
- QPVRKFOKCKORDP-UHFFFAOYSA-N 1,3-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC(C)(O)CC=C1 QPVRKFOKCKORDP-UHFFFAOYSA-N 0.000 description 1
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical class CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
Classifications
-
- 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 System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—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
- 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
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
Abstract
The invention provides a novel N-heterocyclic carbene ruthenium catalyst containing an electron donating group and a preparation method thereof. The preparation method comprises the step of linking the electron donating group with an N-heterocyclic carbine ligand based on the original structure of the N-heterocyclic carbene ruthenium catalyst, so as to greatly increase the electron donating ability of the N-heterocyclic carbine ligand, improve the catalytic efficiency and the structural stability of the catalyst.
Description
Technical field
The invention relates to a kind of novel N-heterocycle carbine ruthenium catalyst and preparation method thereof, particularly relate to a kind of N-heterocycle carbine ruthenium catalyst being connected to electron donating group on the imidazolidyl of metal complex, this kind of catalyzer can demonstrate high activity in replacement(metathesis)reaction.
Background technology
Lattice granny rag catalyzer is the important tool of Synthetic Organic Chemistry, is widely used in organic synthesis research and industrial production.It is the olefin metathesis catalyst be most widely used at present.Industrial production application comprises the aspects such as biotic pesticide, individual skin or hair care articles for use, novel material, pharmaceutical industry.It has plurality of advantages: active high, not only to air-stable, under water, acid, alcohol or other solvents exist, still can keep catalytic activity, and to alkene with various functional groups have very strong tolerance.Owing to accessing the N-heterocyclic carbene ligand to have stronger electron donation and more high stability than Phosphine ligands on ruthenium metal ion, therefore this s-generation ruthenium catalyst, than the first-generation, there is higher activity and selectivity and better stability.The electron donation that N-heterocyclic carbene ligand is stronger just, makes its catalytic activity improve two orders of magnitude, as can be seen here N-heterocyclic carbene ligand its structure and electronic effect will directly have influence on the performance of catalyzer.
A large amount of s-generation catalyzer containing various dissimilar N-heterocyclic carbene ligand is in the news.Such as: W.A.Herrmann is reported in magazine " Tetrahedron Letters " 40 (1999) 4787-4790 and J.Huang and is reported in J.Am.Chem.Soc.121 (1999), the imidazolines Cabbeen of 2674-2678; RH Grubbs, Authorization Notice No. CN1213032C imidazolidine-based metal carbene catalyzer; The N-heterocyclic carbene ligand (application number: CN200710194494.1) containing different number and position nitrogen of WA Herman report; RH Grubbs report replace the N-heterocyclic carbene ligand (application number: CN200980119030.1) of skeleton with having; The chirality six-membered heterocycle carbene precursor compound (application number: 201410037647.1) of Sun Zhihua report.And various dissimilar part.Such as: Hoveyda-Grubbs catalyzer: Hoveyda is reported in magazine " J.Am.Chem.Soc. " 122 (2000) 8168-8179; And other people patent FR2947189; WO0214376; Pyridines catalyzer: Wen-zhen Zhang " Eur.J.Org.chem. " 2007 5345-5352.Current application is maximum, the widest N-heterocycle carbine of research mainly contains: pentacyclic imidazole type Cabbeen, imidazoline type Cabbeen, 1,2,4-triazole type, thiazole type and benzothiazole type etc., also comprise the atypia N-heterocycle carbines such as tetra-atomic ring, six-ring, seven-membered ring.
Although N-heterocyclic carbene ligand and metal complex thereof have achieved above-mentioned achievement, the stability and the catalytic activity that improve constantly catalyzer have been the problems that numerous researcher constantly explores.Although emphasize again and again in current report N-heterocyclic carbene ligand excellence give Electronic Performance, but rarely have report to how to propose to improve in its structure to strengthen its electron donation further, and nearly all imidazolidyl having determined the N-heterocyclic carbene ligand of structure all only relates to the replacement of simple alkyl, aryl or halogenated aryl, and author be surprised to find electron donating group is accessed further N-heterocyclic carbene ligand imidazolidyl on the activity of such catalyzer can be made greatly to improve.
Summary of the invention
The invention, on the basis of existing research, provides a kind of novel N-heterocyclic carbenes ruthenium catalyst containing electron donating group, for having the compound of formula (I) structure,
Wherein:
X
1and X
2be anion ligand independently of one another;
Ln is neutral to electron donor ligand, wherein n=1 or 2, represent that L part is one, represent that L part is two during n=2, and these two parts can be identical or different as n=1;
R
1, R
2, R
3, R
4, R
5, R
6be H or be selected from C independently of one another
1-C
20alkyl, C
2-C
20the rare base of chain, C
2-C
20alkynyl, aryl, C
1-C
20carboxylicesters, C
1-C
20alkoxyl group, C
2-C
20the rare oxygen base of chain, C
2-C
20alkynyloxy base, aryloxy, alkoxy carbonyl, C
1-C
20alkylthio, arylthio, C
1-C
20alkyl sulphonyl, arylsulfonyl, aryl amine, fragrant imido grpup, arylamine alkylsulfonyl, fragrant sulfimide base, fragrant sulfuryl, arylamine sulfuryl, fragrant sulfoximide base, fragrant urea groups, aromatic amide, fragrant imide and C
1-C
20the substituting group of Alkylsulfinyl, or R
3and R
4form cycloalkyl or aryl together, or R
5or R
6form any cyclic group together with Ln, above-mentioned substituting group is not substituted or is selected from following one or more replacements: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen;
And wherein,
R
1, R
2at least one is selected from aryloxy, arylthio, arylsulfonyl, aryl amine, fragrant imido grpup, arylamine alkylsulfonyl, fragrant sulfimide base, fragrant sulfuryl, arylamine sulfuryl, fragrant sulfoximide base, fragrant urea groups, aromatic amide, fragrant imide, and substituting group is selected from following one or more replacement or forms cyclic group following together between any two and above substituting group: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen.
In preferred versions more of the present invention, R
1, R
2at least one, be preferably two, have the structure of following formula (II),
Wherein:
R
7, R
8, R
9, R
10, R
11be H or be selected from C independently of one another
1-C
20alkyl, C
2-C
20the rare base of chain, C
2-C
20alkynyl, aryl, C
1-C
20carboxylicesters, C
1-C
20alkoxyl group, C
2-C
20the rare oxygen base of chain, C
2-C
20alkynyloxy base, aryloxy, alkoxy carbonyl, C
1-C
20alkylthio, arylthio, C
1-C
20alkyl sulphonyl, arylsulfonyl, aryl amine, fragrant imido grpup, arylamine alkylsulfonyl, fragrant sulfimide base, fragrant sulfuryl, arylamine sulfuryl, fragrant sulfoximide base, fragrant urea groups, aromatic amide, fragrant imide and C
1-C
20the substituting group of Alkylsulfinyl, or form cycloalkyl or aryl arbitrarily each other, above-mentioned substituting group is not substituted or is selected from following one or more replacements: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen;
And wherein,
R
7, R
8, R
11in at least one is YRx, wherein, Y is O, S or NH, and Rx is H or is selected from following one or more replacement or forms cyclic group following together between any two and above substituting group: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen.
In the present invention further preferred version, R
7, R
8, R
9, R
10, R
11in at least three be substituted, be selected from C
1-C
20alkyl, C
2-C
20the rare base of chain, C
2-C
20alkynyl, aryl, C
1-C
20carboxylicesters, C
1-C
20alkoxyl group, C
2-C
20the rare oxygen base of chain, C
2-C
20alkynyloxy base, aryloxy, alkoxy carbonyl, C
1-C
20alkylthio, arylthio, C
1-C
20alkyl sulphonyl, arylsulfonyl, aryl amine, fragrant imido grpup, arylamine alkylsulfonyl, fragrant sulfimide base, fragrant sulfuryl, arylamine sulfuryl, fragrant sulfoximide base, fragrant urea groups, aromatic amide, fragrant imide and C
1-C
20the substituting group of Alkylsulfinyl, above-mentioned substituting group is not substituted or is selected from following one or more replacements: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen;
And the R be substituted
7, R
8or R
11in at least one is YRx, wherein, Y is O, S or NH, and Rx is H or is selected from following one or more replacement or forms cyclic group following together between any two and above substituting group: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen.
In the present invention also further preferred version, R
7for YRx, wherein, Y is O, S or NH, and Rx is H or is selected from following one or more replacements: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen; R
8and R
11for H; R
9, R
10be substituted, be selected from C
1-C
20alkyl, C
2-C
20the rare base of chain, C
2-C
20alkynyl, aryl, C
1-C
20carboxylicesters, C
1-C
20alkoxyl group, C
2-C
20the rare oxygen base of chain, C
2-C
20alkynyloxy base, aryloxy, alkoxy carbonyl, C
1-C
20alkylthio, arylthio, C
1-C
20alkyl sulphonyl, arylsulfonyl, aryl amine, fragrant imido grpup, arylamine alkylsulfonyl, fragrant sulfimide base, fragrant sulfuryl, arylamine sulfuryl, fragrant sulfoximide base, fragrant urea groups, aromatic amide, fragrant imide and C
1-C
20the substituting group of Alkylsulfinyl.
In further preferred embodiments of the present invention, R
7for YRx, wherein, Y is O, S or NH, and Rx is H or is selected from C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl; R
8and R
11for H; R
9, R
10be substituted, be selected from C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl.
Wherein, in preferred versions more of the present invention,
X
1and X
2be H, halogen or be selected from C independently of one another
1-C
20alkyl, aryl, C
1-C
20alkoxide, aryl oxide, C
3-C
20alkyldiketonate, aryldiketonate, C
1-C
20carboxylate radical, aryl sulfonic acid root, C
1-C
20alkyl azochlorosulfonate, C
1-C
20alkylthio, arylthio, C
1-C
20alkyl sulphonyl, C
1-C
20the substituting group of Alkylsulfinyl, above-mentioned substituting group is not substituted or is selected from C
1-C
10alkyl, C
1-C
10one or more parts of alkoxyl group, aryl and halogen replace;
Further, above-mentioned X
1and X
2be preferably halogen, CF independently of one another
3cO
2, CH
3cO
2, CFH
2cO
2, (CH
3)
3cO, (CF
3)
2(CH
3) CO, (CF
3) (CH
3)
2cO, PhO, MeO, EtO, tosylate, methanesulfonic are followed or trifluoromethanesulfonic acid is followed.
Wherein, in preferred versions more of the present invention,
L in Ln
1or L
2two parts all can independently selected from PR
ar
br
cphosphine (wherein R
a, R
b, R
cbe aryl or C independently of one another
1-C
10alkyl), N-heterocycle, ether, amine, imines, alcohol, mercaptan, thioether, carboxylic compound, carbonyl compound, stibine, arsine, nitrile, above-mentioned substituting group is not substituted or is selected from following one or more replacements: C
1-C
5alkyl, C
1-C
5alkoxyl group, aryl and halogen;
Further, L in Ln
1or L
2two parts all can independently preferably from-P (cyclohexyl)
3,-P (cyclopentyl)
3,-P (sec.-propyl)
3,-P (phenyl)
3, N-heterocycle, ether, amine, imines, alcohol, mercaptan, thioether, carboxylic compound, carbonyl compound, above-mentioned substituting group is not substituted or is selected from following one or more replacements: C
1-C
5alkyl, C
1-C
5alkoxyl group, aryl and halogen, and L
2two parts identical.
Wherein, in preferred versions more of the present invention,
R
5for H, and R
6for phenyl or vinyl, formed with Ln or do not form cyclic group, and R
6in substituting group be not substituted or be selected from following one or more replacements: C
1-C
5alkyl, C
1-C
5alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen;
Further, above-mentioned R
6be preferably phenyl or vinyl, or formed with L or do not form cyclic group.
Preferably, compound of the present invention is selected from following several:
Novel N-heterocyclic carbenes ruthenium catalyst provided by the invention such as, owing to having accessed the group containing pushing away electronic action, the L in above-claimed cpd on N-heterocycle
apart, the phenyl ring be connected is connected to the O atom that electronegativity is larger with N on imidazolidyl, and the electronic cloud on phenyl ring is offset to imidazolidyl, significantly enhance N-heterocyclic carbene ligand give Electronic Performance.In addition, in order to make the structure stablizing this electron donating group, electron donating group face position or the enterprising step of a position carbon atom replaces, improve group sterically hindered, reach the object of the offset effect of electronic cloud on firm phenyl ring.
Embodiment
Be further elaborated the invention below in conjunction with specific embodiment, following embodiment is only the object of elaboration the present invention program but not limits.
two (4-isopropoxy-2,6-3,5-dimethylphenyl)-imidazolium chloride of synthesis 1,3-of embodiment 1 ligand
4-isopropoxy-2,6-dimethylaniline synthesis: by 4-amino-3 in the glove box of isolated air, 5-xylenol (1.27g, the sodium hydride (0.60g, 15mmol) of 10mmol) He 60% joins in dimethyl formamide (DMF, the 15ml) solvent that 4A molecular sieve drying crosses, there is exothermic phenomenon, add salt of wormwood (0.34g, 2.46mmol) and bromo propane (2.67g, 19mmol) again in 50ml two-mouth bottle.Under argon shield; reflux condensate device is housed; reaction 22 hours under reaction flask stirs at 50 degrees Celsius; judge whether to reach reaction end with TLC plate; react and added bromo propane (0.85g) after 4 hours; reaction soln becomes Vandyke brown from light brown, then reaction overnight, and final reaction terminates to leave standstill cooling.Reaction soln after leaving standstill is filtered, filtrate is poured in separating funnel, then get methylene dichloride (DCM) solution of 15ml and 0.5ml aqueous sodium hydroxide solution to carry out separatory and leave standstill 30min, then lower floor's brown solution is taken out, in separating funnel, again add 30ml DCM and 60ml water extract the former funnel aqueous solution three times at the middle and upper levels, retain lower floor's solution, then together with merging with above-mentioned brown solution, then in merging solution, add frozen water and DCM utilizes separating funnel to carry out extraction three times, retain brown solution.In brown solution, add anhydrous magnesium sulfate carry out drying, drying is about filtered after 4 hours, eventually passes after silica gel chromatographic column is separated and goes to revolve steaming, obtain brown solution 1.21g, yield 63.7%.
1H NMR(400MH，CDCl
3)：ppm6.60(s，Ar-m，2H)，4.40(i-Pr-CH，Septet，J＝6.0，1H)，3.30(Ar-NH
2，s，broad，2H)，2.20(Ar-CH
3，s，6H)，1.32(i-Pr-CH3，d，J＝6.0，6H)。
13C NMR(400MH，CDCl
3)：d 158.0，133.9，125.4，116.8，70.1，46.6，21.9，19.5。C
11h
17n
2the high resolution mass spec calculated value of O: 179.1310; Observed value: 179.1321.
1, two (the 4-isopropoxy-2 of 2-, 6-dimethyl benzene) base-second diimine synthesis: in the reaction flask of 100ml, add 4-isopropoxy-2,6-xylidine (8.0g), oxalic dialdehyde (8.0g) add 50% isopropanol/water (50ml) and 13% acetic acid/Virahol (2) again, at room temperature stirring reaction 4h, reaction solution is yellowing solution gradually, judge whether reaction reaches terminal with TLC plate, add 2ml sodium hydroxide solution after having reacted and stop side reaction generation.Filtering solution, then divide by 75% methanol/water solution of 120ml and wash yellow solid above three times, under drying under reduced pressure, obtain yellow solid, 6.2g, yield 75%.
1h NMR (400MH, CDCl
3): ppm 8.13 (N=CH, s, 2H), 6.66 (Ar-m, s, 4H), 4.55 (i-Pr-CH, q, J=6.0,2H), 2.18 (Ar-CH
3, s, 12H), 1.36 (i-Pr-CH
3, d, J=6.0,12H).
Two (4-isopropoxy-2, the 6-dimethyl benzene) base of 1,2--quadrol synthesis: in 50ml single port bottle, NaBH4 (0.19g, 5mmol) is added in methanol solvate (3ml), produce exothermic phenomenon, and releasing hydrogen gas.Subsequently 1, two (the 4-isopropoxy-2 of 2-, 6-dimethyl benzene) base-second diimine (0.35g, 1mmol) being dissolved into THF (7ML) adds in reaction flask, at room temperature stirring reaction 5h, judge whether reaction reaches terminal with TLC plate, solution colour graduates into faint yellow by yellow, get 15mlDCM and 50ml water to extract solution take off a layer weak yellow liquid in separating funnel, then carry out rotary evaporation and become sticky mass, add 3ml methyl alcohol and 4ml water again, then titration 1ml concentrated hydrochloric acid is under cryostat, release white gas, release amount of heat, yellow solution is white, then filter, retain white solid, finally carry out drying under decompression, obtain white solid 0.27g.
1H NMR(400MH，CDCl
3)：ppm 6.54(Ar-m，s，4H)，4.53(i-Pr-CH，t，J＝6.0，2H)，4.15(NH-CH
2，s，4H)，2.57(Ar-CH
3，s，12H)，1.33(i-Pr，d，J＝6.4，12H)。
13C NMR(400MH，CDCl
3)：δ158.0，133.9，125.4，116.8，70.1，46.6，21.9，19.5。
1, two (the 4-isopropoxy-2 of 3-, 6-3,5-dimethylphenyl) synthesis of-imidazolium chloride: in 50ml reaction flask, add 1, two (the 4-isopropoxy-2 of 2-, 6-dimethyl benzene) base-quadrol (0.27g) and TEOF (0.81ml), be dissolved in 3ml ethanol, at ambient pressure, water distilling apparatus is housed, reaction flask is at 110 degrees Celsius of lower stirring reaction 6h, judge whether reaction is complete with TLC plate (16% methanol/ethyl acetate), after reaction terminates, use reduced pressure instead clean for the ethanol distillation of solvent and generation, reaction solution is made to become white solid, carry out cooling subsequently to leave standstill.In white solid, add 20ml normal hexane to its washing three times, then filter, retain white solid, finally carry out drying under decompression.Obtain white solid 0.20g.
1H NMR(400MH，CDCl
3)：ppm 9.17(N-CH＝N，s，1H)，6.58(Ar-m，J＝5.2，4H)，4.51(N-CH
2，s，2H)，4.48(i-Pr，J＝6.0，2H)，3.71(N-CH
2，2H)，2.34(Ar-CH
3，s，12H)，1.30(i-Pr-CH
3，dd，J
1＝6.4，J
2＝6.0，12H)。
13C NMR(400MH，CDCl
3)
13C NMR(400MH，CDCl
3)δ164.0，158.6，157.4，137.6，136.8，130.7，125.3，115.7，70.0，52.2，43.6，22.0，18.7，18.4。C
25h
35clN
2o
2high resolution mass spec calculated value: 430.2387; Observed value: 430.2369.
synthesis 1-[(1，3，5-trimethyl-benzene) the base]-3-of embodiment 2 ligand ([4-isopropoxy-2,6-dimethyl benzene) base]-
imidazolium chloride
1-(1, 3, 5-Three methyl Benzene) base-2-(4-isopropoxy-2, 6-dimethyl benzene) synthesis of base-second diimine: add 4-isopropoxy-2 in reaction flask, 6-xylidine (4g), oxalic dialdehyde (8g) and three equal monomethylanilines (4g), add 50% isopropanol/water (50ml) and 13% acetic acid/Virahol (10) again, at room temperature stirring reaction 4h, reaction solution is yellowing solution gradually, judge whether reaction reaches terminal with TLC plate (10% ethyl acetate/normal hexane), resultant will demonstrate three yellow spottings on the tlc plate.A small amount of sodium hydroxide solution termination reaction is added after having reacted.Filtering solution, then divide by 75% methanol/water solution of 120ml and wash yellow solid above three times, finally retain yellow solid, under drying under reduced pressure, obtain yellow solid, 7.13g.Gained yellow solid contains three group with imine moiety: 1,2-two (1,3,5-Three methyl Benzene) base-second diimine, 1-(1,3,5-Three methyl Benzene) base-2-(4-isopropoxy-2,6-dimethyl benzene) base-quadrol, 1, two (4-isopropoxy-2, the 6-dimethyl benzene) base-second diimine of 2-.The ratio that its proportions and two aromatic amines add has close relationship.
1-(1,3,5-Three methyl Benzene) base-2-(4-isopropoxy-2,6-dimethyl benzene) synthesis of base-quadrol: in 100ml single port bottle, add sodium borohydride (3.8g, 5mmol), add gained yellow solid subsequently and contain three group with imine moiety (7.0g, 1mmol) and tetrahydrofuran (THF) (30ml).Stirred at ambient temperature, in three batches dropping methyl alcohol 10ml altogether.Reaction produces hydrogen and heat release.At room temperature stirring reaction is about 5h, judges whether reaction reaches terminal, and solution colour graduates into faint yellow by yellow with TLC plate (25% ethyl acetate/normal hexane).After reaction terminates, add 50ml water and carry out stopped reaction, add methylene dichloride 30ml subsequently and wash three times in separating funnel, take off a layer yellow solution.After anhydrous sodium sulphate drying, with rotatory evaporator except desolventizing obtains sticky mass.Three liquid amine compound of light gray of successively attaining the Way are separated: 1 through silica gel chromatography post, 2-two (1,3,5-Three methyl Benzene) base-quadrol, 1-(1,3,5-Three methyl Benzene) base-2-(4-isopropoxy-2,6-dimethyl benzene) base-quadrol, 1, two (4-isopropoxy-2, the 6-dimethyl benzene) base-quadrol of 2-.By 1-(1，3，5-trimethyl-benzene) base-2-(the 4-isopropoxy-2 of purifying, 6-dimethyl benzene) base-quadrol is dissolved in 10ml methyl alcohol and 3ml water, then titration 1.0ml concentrated hydrochloric acid under cryostat, releases white gas, releases amount of heat.Gained white solid product, after filtration, washing, decompression under carry out drying, obtain the hydrochloride 0.7g that white solid is quadrol.C
22h
33clN
2the high resolution mass spec calculated value of O: 376.2281; Observed value: 376.2293.
1-[(1, 3, 5-Three methyl Benzene) base]-3-([4-isopropoxy-2, 6-dimethyl benzene) base] synthesis of-imidazolium chloride: in 50ml reaction flask, add 1-(1, 3, 5-Three methyl Benzene) base-2-(4-isopropoxy-2, 6-dimethyl benzene) base-quadrol (0.38g) and TEOF (0.81ml), be dissolved in 3ml ethanol, at ambient pressure, water distilling apparatus is housed, reaction flask is at 110 degrees Celsius of lower stirring reaction 6h, judge whether reaction is complete with TLC plate, after reaction terminates, use reduced pressure instead clean for the ethanol distillation of solvent and generation, reaction solution is made to become white solid, carry out cooling subsequently to leave standstill.In white solid, add 20ml normal hexane to its washing three times, then filter, retain white solid, finally carry out drying under decompression.Obtain white solid 0.30g.C
23h
31clN
2the high resolution mass spec calculated value of O: 386.2125; Observed value: 386.2136.
Adopt method and the route of above-mentioned synthesis, use the aromatic amine that two different, different two aromatic base-second diimine, quadrol and imidazolium chloride can be prepared easily through reaction and separation processes such as condensation, reduction, Cheng Huan.
the synthesis of embodiment 3 catalyzer
Two (4-isopropoxy-2,6-3,5-dimethylphenyl)-2-(imidazolidine subunit) (dichlorobenzene methylene radical) (tricyclohexyl phosphine) ruthenium of the synthesis of catalyzer D-1: 1,3-; In the glove box of isolated air, by the potassium hexamethyldisilazide (KHMDS of 0.7M at toluene solvant, 1.7ml, 1.2mmol, 1.2 equivalents) solution, 1,3-two (4-isopropoxy-2,6-3,5-dimethylphenyl)-imidazolium chloride (430mg, 1.0mmol, 1.0 equivalents) and toluene (5ml) join in the reactor of 50ml.Gained mixture adds RuCl after at room temperature stirring 5 minutes
2(PCy
3)
2(=CHC
6h
5) (823mg, 1.0mmol, 1.0 equivalents).Then take out glove box, reaction mixture is under the nitrogen, 70 DEG C of conditions of air-isolation, and stir 40 minutes, solution becomes dark brown solution.Reaction end TLC plate judges.After reacting completely, concetrated under reduced pressure.Added by anhydrous hexane in brown residue, this mixture at room temperature stirs 20 minutes.Pressure reducing and steaming solvent obtains burgundy precipitation, and with methyl alcohol, then use hexanes wash.If necessary by chromatography over CC catalyzer.C
50h
73cl
2n
2o
2the high resolution mass spec calculated value of PRu: 936.3830; Observed value: 936.3801.
The synthesis of catalyzer D-2: use and the identical method of Kaolinite Preparation of Catalyst D-1.Just use RuCl
2(PCy
3)
2[=CHCH=C (CH
3)
2] replace RuCl
2(PCy
3)
2(=CHC
6h
5); Under 80 DEG C of conditions, stir 50 minutes.Through underpressure distillation, obtain pure burgundy catalyzer with after methyl alcohol, hexanes wash, by column chromatography.C
48h
75cl
2n
2o
2the high resolution mass spec calculated value of PRu: 914.3987; Observed value: 914.3996.
The synthesis, (1 of catalyzer D-3,3-pair-(4-isopropoxy-2,6-3,5-dimethylphenyl)-2-imidazolidine subunit) dichloro (adjacent isopropoxy α-tolylene) closes ruthenium: in glove box, by catalyzer D-1 (937mg, 1.0mmol, 1.0 equivalents), 1-isopropoxy-2-(1-propenyl) benzene (352.5mg, 2.0mmol, 2.0 equivalents) and dry toluene (10ml) join in 20ml reactor.Glove box is taken out after obturaging.Under 40 DEG C of conditions, stir 4 hours, brown solution becomes sap green, judges reaction end with TLC plate.After reaction terminates, through underpressure distillation, with after methyl alcohol, hexanes wash, obtain pure dark green solid.Green pure catalyzer is obtained through column chromatography.C
35h
46cl
2n
2o
3the high resolution mass spec calculated value of Ru: 714.1929; Observed value: 714.1933.
The synthesis, (1 of catalyzer D-4, two (the 4-isopropoxy-2 of 3-, 6-3,5-dimethylphenyl)-2-(imidazolidine subunit) (dichlorobenzene methylene radical) (3-bromopyridine) ruthenium: by catalyzer D-1 (469mg, 0.5mmol, 1.0 equivalents), 3-bromopyridine (3.0ml, 31mmol, 60.0 equivalents) join in 20ml reactor, without the need to any solvent.Glove box is taken out after obturaging.At ambient temperature, stir 40 minutes, brown solution becomes green, judges reaction end with TLC plate.After reaction terminates, through underpressure distillation, with after methyl alcohol, hexanes wash, obtain pure dark green solid.Obtain green catalyst.C
42h
48br
2cl
2n
4the high resolution mass spec calculated value of OR u: 970.0565; Observed value: 970.0560.
Respectively by the method with Kaolinite Preparation of Catalyst D-1 to D-4, can prepare equally and have different two aromatic base catalyzer, concrete example is as follows.
The synthesis of catalyst S-1: 1-[(1，3，5-trimethyl-benzene) base]-3-(4-isopropoxy-2,6-dimethyl benzene) base] (dichlorobenzene methylene radical) (tricyclohexyl phosphine) ruthenium; In the glove box of isolated air, by the potassium hexamethyldisilazide (KHMDS of 0.7M at toluene solvant, 1.6ml, 1.1mmol, 1.1 equivalents) solution, 1-[(1,3,5-Three methyl Benzene) base]-3-([4-isopropoxy-2,6-dimethyl benzene) base]-imidazolium chloride (387mg, 1.0mmol, 1.0 equivalents) and toluene (5ml) joins in the reactor of 50ml.Gained mixture adds RuCl after at room temperature stirring 5 minutes
2(PCy
3)
2(=CHC
6h
5) (823mg, 1.0mmol, 1.0 equivalents).Then take out glove box, reaction mixture is under the nitrogen, 70 DEG C of conditions of air-isolation, and stir 40 minutes, solution becomes dark brown solution.Reaction end TLC plate judges.After reacting completely, concetrated under reduced pressure.Added by anhydrous hexane in brown residue, this mixture at room temperature stirs 20 minutes.Pressure reducing and steaming solvent obtains burgundy precipitation, and with methyl alcohol, then use hexanes wash.If necessary by chromatography over CC catalyzer.C
48h
69cl
2n
2the high resolution mass spec calculated value of OPRu: 892.3568; Observed value: 892.3574.
The synthesis of catalyst S-2: use and the identical method of Kaolinite Preparation of Catalyst S-1.Just use RuCl
2(PCy
3)
2[=CHCH=C (CH
3)
2] (800mg) replace RuCl
2(PCy
3)
2(=CHC
6h
5); Under 80 DEG C of conditions, stir 50 minutes.Through underpressure distillation, obtain pure burgundy catalyzer with after methyl alcohol, hexanes wash, by column chromatography.C
46h
71cl
2n
2the high resolution mass spec calculated value of OPRu: 870.3725; Observed value: 870.3730.
The synthesis of catalyst S-3,1-[(1,3,5-Three methyl Benzene) base]-3-[(4-isopropoxy-2,6-dimethyl benzene) base] dichloro (adjacent isopropoxy α-tolylene) closes ruthenium: in glove box, by catalyst S-1 (893mg, 1.0mmol, 1.0 equivalents), 1-isopropoxy-2-(1-propenyl) benzene (352.5mg, 2.0mmol, 2.0 equivalents) and dry toluene (10ml) join in 20ml reactor.Glove box is taken out after obturaging.Under 50 DEG C of conditions, stir 5 hours, brown solution becomes sap green, judges reaction end with TLC plate.After reaction terminates, through underpressure distillation, with after methyl alcohol, hexanes wash, obtain pure dark green solid.Green pure catalyzer is obtained through column chromatography.C
33h
42cl
2n
2o
2the high resolution mass spec calculated value of Ru: 670.1667; Observed value: 670.1660.
The synthesis of catalyst S-4,1-[(1,3,5-Three methyl Benzene) base]-3-[(4-isopropoxy-2,6-dimethyl benzene) base] (dichlorobenzene methylene radical) (3-bromopyridine) ruthenium: by catalyst S-1 (442mg, 0.5mmol, 1.0 equivalents), 3-bromopyridine (3.0ml, 31mmol, 60.0 equivalents) join in 20ml reactor, without the need to any solvent.Glove box is taken out after obturaging.At ambient temperature, stir 40 minutes, brown solution becomes green, judges reaction end with TLC plate.After reaction terminates, through underpressure distillation, with after methyl alcohol, hexanes wash, obtain pure dark green solid.Obtain green catalyst.C
40h
44br
2cl
2n
4the high resolution mass spec calculated value of ORu: 926.0302; Observed value: 926.0315.
embodiment 4 catalyst reaction example
In glove box, N, the N-diallyl-solution of PTS (0.70mmol, 190mg) in the toluene of 35ml is mixed with ruthenium catalyst D-3 prepared by the present invention, stir at 45 DEG C.Analyzed by GC.
Ruthenium catalyst D-3 consumption is 0.05mol%, observes the conversion of 99% after 10 minutes.Ruthenium catalyst D-3 consumption is 0.01mol%, observes the conversion of 97% after 30 minutes.Under the existence of complex compound 6 (0.005mol%), observe the conversion of 94% after 180 minutes.
Claims (9)
1. there is a compound for formula (I) structure,
Wherein:
X
1and X
2be anion ligand independently of one another;
Ln is neutral to electron donor ligand, n=1 or 2;
R
1, R
2, R
3, R
4, R
5, R
6be H or be selected from C independently of one another
1-C
20alkyl, C
2-C
20the rare base of chain, C
2-C
20alkynyl, aryl, C
1-C
20carboxylicesters, C
1-C
20alkoxyl group, C
2-C
20the rare oxygen base of chain, C
2-C
20alkynyloxy base, aryloxy, alkoxy carbonyl, C
1-C
20alkylthio, arylthio, C
1-C
20alkyl sulphonyl, arylsulfonyl, aryl amine, fragrant imido grpup, arylamine alkylsulfonyl, fragrant sulfimide base, fragrant sulfuryl, arylamine sulfuryl, fragrant sulfoximide base, fragrant urea groups, aromatic amide, fragrant imide and C
1-C
20the substituting group of Alkylsulfinyl, or R
3and R
4form cycloalkyl or aryl together, or R
5or R
6form any cyclic group together with Ln, above-mentioned substituting group is not substituted or is selected from following one or more replacements: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen;
And wherein,
R
1, R
2at least one is selected from aryloxy, arylthio, arylsulfonyl, aryl amine, fragrant imido grpup, arylamine alkylsulfonyl, fragrant sulfimide base, fragrant sulfuryl, arylamine sulfuryl, fragrant sulfoximide base, fragrant urea groups, aromatic amide, fragrant imide, and substituting group is selected from following one or more replacement or forms cyclic group following together between any two and above substituting group: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen.
2. compound according to claim 1, is characterized in that, described R
1, R
2at least one, be preferably two, have the structure of following formula (II),
Wherein:
R
7, R
8, R
9, R
10, R
11be H or be selected from C independently of one another
1-C
20alkyl, C
2-C
20the rare base of chain, C
2-C
20alkynyl, aryl, C
1-C
20carboxylicesters, C
1-C
20alkoxyl group, C
2-C
20the rare oxygen base of chain, C
2-C
20alkynyloxy base, aryloxy, alkoxy carbonyl, C
1-C
20alkylthio, arylthio, C
1-C
20alkyl sulphonyl, arylsulfonyl, aryl amine, fragrant imido grpup, arylamine alkylsulfonyl, fragrant sulfimide base, fragrant sulfuryl, arylamine sulfuryl, fragrant sulfoximide base, fragrant urea groups, aromatic amide, fragrant imide and C
1-C
20the substituting group of Alkylsulfinyl, or form cycloalkyl or aryl arbitrarily each other, above-mentioned substituting group is not substituted or is selected from following one or more replacements: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen;
And wherein,
R
7, R
8, R
11in at least one is YRx, wherein, Y is O, S or NH, and Rx is H or is selected from following one or more replacement or forms cyclic group following together between any two and above substituting group: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen.
3. compound according to claim 2, is characterized in that, R
7, R
8, R
9, R
10, R
11in at least three be substituted, be selected from C
1-C
20alkyl, C
2-C
20the rare base of chain, C
2-C
20alkynyl, aryl, C
1-C
20carboxylicesters, C
1-C
20alkoxyl group, C
2-C
20the rare oxygen base of chain, C
2-C
20alkynyloxy base, aryloxy, alkoxy carbonyl, C
1-C
20alkylthio, arylthio, C
1-C
20alkyl sulphonyl, arylsulfonyl, aryl amine, fragrant imido grpup, arylamine alkylsulfonyl, fragrant sulfimide base, fragrant sulfuryl, arylamine sulfuryl, fragrant sulfoximide base, fragrant urea groups, aromatic amide, fragrant imide and C
1-C
20the substituting group of Alkylsulfinyl, above-mentioned substituting group is not substituted or is selected from following one or more replacements: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen;
And the R be substituted
7, R
8or R
11in at least one is YRx, wherein, Y is O, S or NH, and Rx is H or is selected from following one or more replacement or forms cyclic group following together between any two and above substituting group: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen.
4. compound according to claim 2, is characterized in that, R
7for YRx, wherein, Y is O, S or NH, and Rx is H or is selected from following one or more replacements: C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen; R
8and R
11for H; R
9, R
10be substituted, be selected from C
1-C
20alkyl, C
2-C
20the rare base of chain, C
2-C
20alkynyl, aryl, C
1-C
20carboxylicesters, C
1-C
20alkoxyl group, C
2-C
20the rare oxygen base of chain, C
2-C
20alkynyloxy base, aryloxy, alkoxy carbonyl, C
1-C
20alkylthio, arylthio, C
1-C
20alkyl sulphonyl, arylsulfonyl, aryl amine, fragrant imido grpup, arylamine alkylsulfonyl, fragrant sulfimide base, fragrant sulfuryl, arylamine sulfuryl, fragrant sulfoximide base, fragrant urea groups, aromatic amide, fragrant imide and C
1-C
20the substituting group of Alkylsulfinyl.
5. compound according to claim 2, is characterized in that, R
7for YRx, wherein, Y is O, S or NH, and Rx is H or is selected from C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl; R
8and R
11for H; R
9, R
10be substituted, be selected from C
1-C
10alkyl, C
1-C
10alkoxyl group, aryl.
6. the compound according to any one of claim 1-5, is characterized in that,
X
1and X
2be H, halogen or be selected from C independently of one another
1-C
20alkyl, aryl, C
1-C
20alkoxide, aryl oxide, C
3-C
20alkyldiketonate, aryldiketonate, C
1-C
20carboxylate radical, aryl sulfonic acid root, C
1-C
20alkyl azochlorosulfonate, C
1-C
20alkylthio, arylthio, C
1-C
20alkyl sulphonyl, C
1-C
20the substituting group of Alkylsulfinyl, above-mentioned substituting group is not substituted or is selected from C
1-C
10alkyl, C
1-C
10one or more parts of alkoxyl group, aryl and halogen replace;
L in Ln
1or L
2two parts all can independently selected from PR
ar
br
cphosphine, N-heterocycle, ether, amine, imines, alcohol, mercaptan, thioether, carboxylic compound, carbonyl compound, stibine, arsine, nitrile, above-mentioned substituting group is not substituted or is selected from following one or more replacements: C
1-C
5alkyl, C
1-C
5alkoxyl group, aryl and halogen; Wherein R
a, R
h, R
cbe aryl or C independently of one another
1-C
10alkyl;
R
5for H; And R
6for phenyl or vinyl, formed with Ln or do not form cyclic group, and R
6in substituting group be not substituted or be selected from following one or more replacements: C
1-C
5alkyl, C
1-C
5alkoxyl group, aryl and be selected from the functional group of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imines, acid amides, nitro, carboxylic acid, disulphide, carbonic ether, isocyanic ester, carbodiimide, carbalkoxy, carbamate and halogen.
7. the compound according to any one of claim 1-5, is characterized in that,
X
1and X
2be preferably halogen, CF independently of one another
3cO
2, CH
3cO
2, CFH
2cO
2, (CH
3)
3cO, (CF
3)
2(CH
3) CO, (CF
3) (CH
3)
2cO, PhO, MeO, EtO, tosylate, methanesulfonic are followed or trifluoromethanesulfonic acid is followed;
L in Ln
1or L
2two parts all can independently preferably from-P (cyclohexyl)
3,-P (cyclopentyl)
3,-P (sec.-propyl)
3,-P (phenyl)
3, N-heterocycle, ether, amine, imines, alcohol, mercaptan, thioether, carboxylic compound, carbonyl compound, above-mentioned substituting group is not substituted or is selected from following one or more replacements: C
1-C
5alkyl, C
1-C
5alkoxyl group, aryl and halogen, and L
2two parts identical;
R
5for H; And R
6for phenyl or vinyl, formed with L or do not form cyclic group.
8. compound according to claim 1, is characterized in that, N-heterocyclic carbene ligand is selected from following:
。
9. compound according to claim 1, is characterized in that, is selected from following:
。
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| CN105541548A (en) * | 2016-01-07 | 2016-05-04 | 神华集团有限责任公司 | Preparation method of methyl alcohol and diol |
| CN109863138A (en) * | 2016-08-19 | 2019-06-07 | 优美科股份公司及两合公司 | Olefin metathesis catalyst |
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| CN106831305B (en) * | 2015-12-31 | 2018-02-23 | 天津斯瑞吉高新科技研究院有限公司 | A kind of method that long-chain olefin is prepared by medium chain alkene |
| CN110975939A (en) * | 2019-12-19 | 2020-04-10 | 华东师范大学 | Ethylene carbonate hydrogenation heterogeneous catalyst, and preparation method and application thereof |
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| DE102007039526A1 (en) * | 2007-08-21 | 2009-02-26 | Lanxess Deutschland Gmbh | Catalyst systems and their use for metathesis reactions |
| CN104356165A (en) * | 2014-11-03 | 2015-02-18 | 天津斯瑞吉高新科技研究院有限公司 | Novel N-heterocyclic carbene ruthenium catalyst containing electron donating group and preparation method thereof |
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| CN104844662A (en) * | 2014-11-03 | 2015-08-19 | 天津斯瑞吉高新科技研究院有限公司 | Novel N-heterocyclic carbene ruthenium catalyst containing electron donating group and preparation method thereof |
| CN107629091A (en) * | 2014-11-03 | 2018-01-26 | 天津斯瑞吉高新科技研究院有限公司 | A kind of N heterocycle carbine ruthenium catalysts containing electron donating group and preparation method thereof |
| CN107629091B (en) * | 2014-11-03 | 2020-05-15 | 天津斯瑞吉高新科技研究院有限公司 | N-heterocyclic carbene ruthenium catalyst containing electron donating group and preparation method thereof |
| CN105541548A (en) * | 2016-01-07 | 2016-05-04 | 神华集团有限责任公司 | Preparation method of methyl alcohol and diol |
| CN109863138A (en) * | 2016-08-19 | 2019-06-07 | 优美科股份公司及两合公司 | Olefin metathesis catalyst |
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