CN106925351A - N heterocycle carbine ruthenium catalysts containing imidazolium ionic liquid group and preparation method thereof - Google Patents
N heterocycle carbine ruthenium catalysts containing imidazolium ionic liquid group and preparation method thereof Download PDFInfo
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- CN106925351A CN106925351A CN201710195546.0A CN201710195546A CN106925351A CN 106925351 A CN106925351 A CN 106925351A CN 201710195546 A CN201710195546 A CN 201710195546A CN 106925351 A CN106925351 A CN 106925351A
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- aryl
- carbonyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 140
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 85
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 58
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 125000000623 heterocyclic group Chemical group 0.000 title abstract 3
- -1 C2To C20Alkylene Chemical group 0.000 claims abstract description 97
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 60
- 125000001424 substituent group Chemical group 0.000 claims abstract description 60
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 47
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims abstract description 31
- 230000007935 neutral effect Effects 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 78
- 239000002585 base Substances 0.000 claims description 64
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 46
- 125000004122 cyclic group Chemical group 0.000 claims description 32
- 150000001721 carbon Chemical group 0.000 claims description 30
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 26
- 238000005865 alkene metathesis reaction Methods 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 23
- 239000000460 chlorine Chemical group 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 22
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 229910021188 PF6 Inorganic materials 0.000 claims description 19
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 18
- 238000006467 substitution reaction Methods 0.000 claims description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 17
- 229910052794 bromium Inorganic materials 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 125000001153 fluoro group Chemical group F* 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 12
- 125000004104 aryloxy group Chemical group 0.000 claims description 11
- 229940125904 compound 1 Drugs 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 11
- 229940126214 compound 3 Drugs 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 229940125898 compound 5 Drugs 0.000 claims description 9
- 125000000101 thioether group Chemical group 0.000 claims description 9
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- HPJGEESDHAUUQR-SKGSPYGFSA-N (2s)-2-[[(2s)-5-(diaminomethylideneamino)-2-[[(2s)-1-[(2s)-5-(diaminomethylideneamino)-2-[[(2s)-2-[[(2s)-3-naphthalen-2-yl-2-(3-pyridin-3-ylpropanoylamino)propanoyl]amino]-3-phenylpropanoyl]amino]pentanoyl]pyrrolidine-2-carbonyl]amino]pentanoyl]amino]buta Chemical compound NC(=O)C[C@@H](C(N)=O)NC(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H]1CCCN1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H](NC(=O)[C@H](CC=1C=C2C=CC=CC2=CC=1)NC(=O)CCC=1C=NC=CC=1)CC1=CC=CC=C1 HPJGEESDHAUUQR-SKGSPYGFSA-N 0.000 claims description 5
- LJIOTBMDLVHTBO-CUYJMHBOSA-N (2s)-2-amino-n-[(1r,2r)-1-cyano-2-[4-[4-(4-methylpiperazin-1-yl)sulfonylphenyl]phenyl]cyclopropyl]butanamide Chemical compound CC[C@H](N)C(=O)N[C@]1(C#N)C[C@@H]1C1=CC=C(C=2C=CC(=CC=2)S(=O)(=O)N2CCN(C)CC2)C=C1 LJIOTBMDLVHTBO-CUYJMHBOSA-N 0.000 claims description 5
- FRJJJAKBRKABFA-TYFAACHXSA-N (4r,6s)-6-[(e)-2-[6-chloro-4-(4-fluorophenyl)-2-propan-2-ylquinolin-3-yl]ethenyl]-4-hydroxyoxan-2-one Chemical compound C(\[C@H]1OC(=O)C[C@H](O)C1)=C/C=1C(C(C)C)=NC2=CC=C(Cl)C=C2C=1C1=CC=C(F)C=C1 FRJJJAKBRKABFA-TYFAACHXSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 235000012343 cottonseed oil Nutrition 0.000 claims description 3
- 239000002385 cottonseed oil Substances 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- VNAFWALXWOAPCK-UHFFFAOYSA-N 1-phenyl-2,3-dihydro-1h-indene Chemical compound C1CC2=CC=CC=C2C1C1=CC=CC=C1 VNAFWALXWOAPCK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 6
- 125000003386 piperidinyl group Chemical group 0.000 claims 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims 2
- 125000006773 (C2-C7) alkylcarbonyl group Chemical group 0.000 claims 2
- RRELDGDKULRRDM-UHFFFAOYSA-N 6-[2-chloro-4-nitro-5-(oxan-4-yloxy)anilino]-3,4-dihydro-1H-quinolin-2-one Chemical compound [O-][N+](=O)c1cc(Cl)c(Nc2ccc3NC(=O)CCc3c2)cc1OC1CCOCC1 RRELDGDKULRRDM-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 125000005012 alkyl thioether group Chemical group 0.000 claims 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 description 53
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 38
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 32
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 18
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000006555 catalytic reaction Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 12
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000004949 mass spectrometry Methods 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 9
- 150000002732 mesitylenes Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 8
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical class CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000002118 epoxides Chemical class 0.000 description 6
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 5
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 150000005224 alkoxybenzenes Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 4
- 229910000071 diazene Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 4
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- STGHLTWHGUBZKV-UHFFFAOYSA-N N1CNCC1.[O] Chemical class N1CNCC1.[O] STGHLTWHGUBZKV-UHFFFAOYSA-N 0.000 description 3
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- BGXZIBSLBRKDTP-UHFFFAOYSA-N methyl 9-(4-chloroanilino)-[1,3]thiazolo[5,4-f]quinazoline-2-carboximidate Chemical compound C12=C3SC(C(=N)OC)=NC3=CC=C2N=CN=C1NC1=CC=C(Cl)C=C1 BGXZIBSLBRKDTP-UHFFFAOYSA-N 0.000 description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HVWJIZNHPRYJPA-UHFFFAOYSA-N 1,3,5-trimethylcyclohexa-2,4-dien-1-amine Chemical class CC1=CC(C)=CC(C)(N)C1 HVWJIZNHPRYJPA-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- PNCJGBTZSPZHGY-UHFFFAOYSA-N 1h-imidazol-1-ium;dichloride Chemical compound [Cl-].[Cl-].[NH2+]1C=CN=C1.[NH2+]1C=CN=C1 PNCJGBTZSPZHGY-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- ZKYGURGLVHDMAB-UHFFFAOYSA-N CN1C=NC=C1.[I] Chemical class CN1C=NC=C1.[I] ZKYGURGLVHDMAB-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005129 aryl carbonyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000004693 imidazolium salts Chemical class 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DGBNUTJYQXQLSV-UHFFFAOYSA-N 1h-triazol-1-ium;chloride Chemical compound Cl.C1=CNN=N1 DGBNUTJYQXQLSV-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- YZPNFYQRPJKWFJ-UHFFFAOYSA-N 2-methyl-1h-imidazol-1-ium;chloride Chemical compound Cl.CC1=NC=CN1 YZPNFYQRPJKWFJ-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- CETTVSBMYQKFRL-UHFFFAOYSA-O 3-(4-bromobutyl)-1h-imidazol-3-ium Chemical class BrCCCC[N+]=1C=CNC=1 CETTVSBMYQKFRL-UHFFFAOYSA-O 0.000 description 1
- GCWYXRHXGLFVFE-UHFFFAOYSA-N 4-hydroxy-2,6-dimethylaniline Chemical class CC1=CC(O)=CC(C)=C1N GCWYXRHXGLFVFE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910017744 AgPF6 Inorganic materials 0.000 description 1
- YXYKIXHQDOQFFJ-UHFFFAOYSA-N C(CCCCCCCCCCC)ON(C1=CC=CC=C1)OCCCCCCCCCCCCCC Chemical compound C(CCCCCCCCCCC)ON(C1=CC=CC=C1)OCCCCCCCCCCCCCC YXYKIXHQDOQFFJ-UHFFFAOYSA-N 0.000 description 1
- LYIAUOYTTMJKPH-UHFFFAOYSA-N CC(O)(C)C.CC(C)(C)[O-].[Na+] Chemical compound CC(O)(C)C.CC(C)(C)[O-].[Na+] LYIAUOYTTMJKPH-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010002352 Interleukin-1 Proteins 0.000 description 1
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 description 1
- 229910014332 N(SO2CF3)2 Inorganic materials 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N N-undecane Natural products CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- JGHWDXKOTVBHKQ-UHFFFAOYSA-N N1C=NC=C1.[I] Chemical class N1C=NC=C1.[I] JGHWDXKOTVBHKQ-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- YAVVGPBYBUYPSR-UHFFFAOYSA-N benzene;oxygen Chemical compound [O].C1=CC=CC=C1 YAVVGPBYBUYPSR-UHFFFAOYSA-N 0.000 description 1
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 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
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
-
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- 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)
- B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
-
- 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
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2291—Olefins
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- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- 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
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- 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
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
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- 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
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Abstract
The present invention relates to N heterocycle carbine ruthenium catalysts containing imidazolium ionic liquid group and preparation method thereof.The ruthenium catalyst is the compound with structure shown in lower formula (I)：Wherein L is neutral electron part, R1、R2、R3、R4、R5And R6It is each independently H, R group or with 1 to 20 organic substituent of carbon atom；R7It is first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenylindan alkenylene；The R group has the structure shown in lower formula (II)：The present invention is joined directly together imidazolium ionic liquid group with N heterocyclic carbone catalysts and connects, and enables imidazolium ionic liquid group to be able to more effectively play its characteristic property, and the catalytic efficiency and catalyst stability of catalyst are improve so as to reach.
Description
Technical field
The present invention relates to it is a kind of it is new containing ionic liquid group N- heterocycle carbine ruthenium catalysts and preparation method thereof and
Using, more particularly to it is a kind of be directly accessed imidazolium ionic liquid group on the N- heterocyclic carbene ligands of metal complex, this
Imidazolium ionic liquid group is just set to effectively act as the effect of the stability and catalytic efficiency of raising catalyst.
Background technology
The homogeneous catalyst of olefin metathesis reaction is the important tool of Synthetic Organic Chemistry, and being widely used in various has
In machine study on the synthesis and industrial production.Wherein ruthenium homogeneous catalyst is the olefin metathesis catalyst being most widely used at present.
Research in terms of organic synthesis includes small molecule pharmacy, bio-pharmaceuticals, the preparation of organic intermediate, natural products
Synthesis, macromolecular material etc..Industrial production application including biological insecticides, personal skin or hair care articles for use, new material, system
The aspects such as medicine industry.It has many advantages, such as：It is active high, not only to air-stable, in the presence of water, acid, alcohol or other solvents still
So catalysis activity very high can be kept, and there are very strong applicability in the various functional groups carried to alkene.
It mainly has the structure of generality ruthenium catalyst as shown in Figure 1：
Although many advantages, such as ruthenium catalyst has catalytic performance good, urged after there is catalyst high cost and reaction
Agent is difficult to the problem for removing.In order to overcome ruthenium catalyst, these are not enough, researcher using a kind of emerging ionic liquid and
The technology that catalyst is combined, can increase the activity and extension catalyst life of catalyst.So that one can only be used originally
Secondary ruthenium catalyst, becomes the catalyst that can be recycled for multiple times, and the purpose of catalyst cost is reduced so as to reach；In addition,
It is easier to separate with product after the completion of reaction.The technology of early stage is used using ionic liquid as solvent, will be common catalyzed
Agent is put into ionic liquid；Although obtaining some progress, effect not highly significant.Present method is by ionic liquid base
Group access ruthenium catalyst on, this ruthenium catalyst realize be recycled for multiple times and post catalyst reaction be easier separate mesh
's.
According to the literature, ionic liquid group is connected in two kinds of different ligands.It is the most frequently used as shown in Fig. 2
It is the first, ionic liquid group is connected to the alkoxy benzene ligand of catalyst C-2a, second is to be connected to catalyst C-2b
Alkyl phosphorus ligand.
The first example for being connected on alkoxy benzene ligand is introduced first：The researchers such as Yao, Q. are in magazine
Angew.Chem.Int.Ed.2003,42,3395-3398. report and imidazolium ionic liquid group IL-1 is incorporated into ruthenium urges
On the 5- positions of the alkoxy benzene of agent C-2a；Clavier, H, et al. in Chem.Commun.2004,2282-2283, have also been made
It is similar to introduce；Hideaki Wakamatsu are delivered on by same imidazoles in magazine SYNLETT 2008,12,1805-1808
Ionic liquid group is incorporated on the 3- positions of ruthenium catalyst C-2a；Later Chen, S-W and Lee, S-g et al. exist
Be connected to imidazolium ionic liquid group on the 2- positions of catalysis C-2a by Tetrahedron 2009,65,3397-3403.On
Two kinds is that be connected to imidazolium ionic liquid group on alkyl phosphorus ligand by Consorti C-S. et al., refers to magazine
J.Org.Lett,2008,10,237-240。
This catalyst for ionic liquid group being connected to different ligands, still exists performance is repeatedly used
Some difference：The catalyst that ionic liquid group is linked into alkoxy benzene ligand is typically exhibited preferably repeatedly to be made
With number of times, and the catalyst being connected on alkyl phosphorus ligand can be limited by some reactants and solvent, and otherwise its circulation is urged
Change ability declines.
The content of the invention
Ionic liquid is how to solve ionic liquid group to be catalyzed with ruthenium with the key problem of ruthenium catalyst combined technology
Agent is exactly preferably to be combined problem with catalytic center.It is tightr that both combine, and ionic liquid group just can
Preferably guard catalyst, strengthens its catalysis activity and postpones catalytic life；
The composition of ruthenium catalyst is as shown in Figure 2：Ruthenium (Ru) is catalytic center, removes outside two halogen radicals, also other three
Individual ligand：(1) vinylidene ligand；(2) alkyl phosphorus ligand or part is corresponded；(3) N- heterocycle carbines ligand.
Three ligands are N- heterocycle carbine ligands with ruthenium catalytic center binding ability order>Vinylidene ligand>Alkyl phosphorus is coordinated
Body.By looking back binding ability that olefin metathesis reaction mechanism is more readily understood that above-mentioned each part sequentially；Mechanism of catalytic reaction：
First, it is combination of the alkyl phosphorus ligand departing from ruthenium catalytic center, forms the intermediate with catalysis activity；Then, in this
Mesosome is reacted with the double bond on reactant olefin, and new vinylidene reactive intermediate is formed after substituted ethylene fork ligand；Most
Afterwards, the double bond again with reactant olefin is reacted, and produces new ruthenium catalytic center and product.Can from mechanism of catalytic reaction
Going out alkyl phosphorus ligand and vinylidene ligand all will successively depart from ruthenium catalytic center, and only N- heterocycle carbines ligand is all the time
It is in conjunction.
Ligand i.e. vinylidene ligand and the are planted although having will be connected on (1st) containing imidazolium ionic liquid group at present
(2) ligand is planted to be alkyl phosphorus ligand or correspond this report containing imidazolium ionic liquid catalyst on part
Road, its preparation method is to synthesize ligand containing imidazolium ionic liquid first, is then replaced with the ionic liquid ligand is contained
The corresponding ligand without ionic liquid on ruthenium catalyst, and obtain both catalyst described above.But, due to
(3) plant ligand be N- heterocycle carbines ligand too strong with ruthenium catalytic center binding ability, therefore in preparation use (1) and
(2) similar method, i.e., replace the method without ionic liquid ligand using ligand containing ionic liquid, cannot also obtain at present
It is catalyzed to the ruthenium for containing imidazolium ionic liquid group in N- heterocycle carbine ligands.
The present inventor has prepared and has contained imidazolium ionic liquid group on N- heterocycle carbines by further investigation
Ruthenium catalyst.It shows that this imidazolium ionic liquid group catalyst that contains on N- heterocycle carbines has very using result
Good being recycled for multiple times property and post catalyst reaction is easier separate effect.
Then, the present invention contains imidazolium ionic liquid group there is provided a kind of in first aspect on N- heterocycle carbines
Ruthenium catalyst, the ruthenium catalyst is the compound with structure shown in formula (I)：
Wherein：
L is neutral electron part, and the neutral electron part is selected from by C3-C20Three substitution alkyl phosphorus bases of individual carbon,
C3-C20The alkoxy of individual carbon, C6-C20The aryloxy group of individual carbon, with C1To C20Alkyl thioether group or with C0To C20Alkane
One group of the group of the pyridine radicals composition of base；
R1、R2、R3、R4、R5And R6It is each independently H, R group or with 1 to 20 the first of carbon atom organic substitution
Base, first organic substituent is selected from by C1-C20Alkyl, C1-C20Alkoxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20
Alkyl-carbonyl, C7-C20Aryl carbonyl, C1-C20Amide groups and C3-C8The group of cyclic group composition；R1、R2、R3、R4、R5And R6In
At least one group is R group；R2And R3It is asynchronously H and be first organic substituent；R4And R6Asynchronously H and to be
First organic substituent；
R7It is first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenylindan alkenylene；And R7
It is not H and R group；
The R group has the structure shown in lower formula (II)：
Wherein：
Y is CH2, O, S, N or the first group, first group is selected from by C6To C20Aryl, C6To C20Aryloxy group, C2Extremely
C20Alkyl-carbonyl, C7To C20Aryl carbonyl, C1To C20Amide groups, C3-C8A group in the group of cyclic group composition；
N is 0 to 10 integer, preferably 2 to 6 integer, more preferably 2 to 4 integer；
X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；
R8、R9、R10And R11H or the second organic substituent are each independently, second organic substituent is selected from by C1-
C20Alkyl, C6-C20Aryl and C3-C8The group of cyclic group composition.
The present invention provides a kind of method for preparing ruthenium catalyst in second aspect, and methods described includes：
(1) compound 1 is synthesized；And it is 2-in-1 into compound 3 by compound；
(2) compound 4 is synthesized by compound 1 and compound 3；
(3) compound 5 is synthesized by compound 4；
(4) compound 6 is synthesized by compound 5；
(5) compound 7-I is synthesized by compound 6；
(6) compound 7-II is synthesized by compound 7-I；
(7) synthesized as the compound 8 or compound 9 of ruthenium catalyst by compound 7-II；
Wherein, compound 1 is as follows to the structural formula of compound 7：
Compound 8 is selected from the group being made up of following compound 8a, 8b, 8c and 8d：
The compound 9 is as follows：
The present invention provides the ruthenium catalyst or second aspect present invention described in first aspect present invention in the third aspect
Ruthenium catalyst obtained in methods described is reacted especially to derive from the alkene of vegetable oil such as cottonseed oil as anti-in olefin metathesis
Application in answering thing and carrying out olefin metathesis reaction, it is preferred that the cycle applications in olefin metathesis reaction.
Imidazolium ionic liquid group is combined to form new by the present invention with the N- heterocycle carbine ligands of ruthenium catalyst
Ruthenium catalyst (is referred to herein as imidazolium ionic liquid base-ruthenium catalyst).This new imidazolium ionic liquid base-ruthenium
Catalyst shows the catalyst life of increased catalyst activity and extension in the reaction of such as olefin metathesis, and in reaction
Easily separated from reactant mixture afterwards, regenerate and recycle.
Brief description of the drawings
Fig. 1 shows olefin metathesis agent commonly used in the prior art, the wherein representative alkene of C-1a~d 1st generations
Hydrocarbon replaces agent, and C-2a~d is the representative olefin metathesis agent of 2nd generation.
Fig. 2 shows and ionic liquid group is connected into the ruthenium catalyst in two kinds of different ligands in the prior art；The left side
Ruthenium catalyst be the first catalyst containing imidazole ion liquid, wherein ionic liquid group to be connected to the alcoxyl of catalyst C-2a
Obtained in base benzene ligand；The ruthenium catalyst on the right is second imidazole ion liquid catalyst, wherein by ionic liquid base
Group is connected on the alkyl phosphorus ligand of ruthenium catalyst C-2b and obtains.
Fig. 3 shows what different ruthenium catalysts changed with time for the conversion ratio of olefin metathesis reaction raw materials 1- decene
Diagram.
Fig. 4 shows that different ruthenium catalysts are used for the conversion ratio of olefin metathesis reaction raw materials 1- decene with the change of cycle-index
The diagram of change.
Specific embodiment
The present invention is urged in first aspect there is provided a kind of ruthenium containing imidazolium ionic liquid group on N- heterocycle carbines
Agent, it is characterised in that the ruthenium catalyst is the compound with structure shown in formula (I)：
Wherein：
L is neutral electron part, and the neutral electron part is selected from by C3-C20Three substitution alkyl phosphorus bases of individual carbon,
C3-C20The alkoxy of individual carbon, C6-C20The aryloxy group of individual carbon, with C1To C20Alkyl thioether group or with C0To C20Alkane
Base (represents C1To C20Alkyl or H) pyridine radicals composition group a group；L optionally with R7It is cyclic or not cyclic,
Such as five-membered ring or hexatomic ring.
R1、R2、R3、R4、R5And R6It is each independently H, R group or with 1 to 20 the first of carbon atom organic substitution
Base, first organic substituent is selected from by C1-C20Alkyl, C1-C20Alkoxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20
Alkyl-carbonyl, C7-C20Aryl carbonyl, C1-C20Amide groups and C3-C8The group of cyclic group composition；R1、R2、R3、R4、R5And R6In
At least one group is R group；R2And R3It is asynchronously H and be first organic substituent；R4And R6Asynchronously H and to be
First organic substituent；
R7It is first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenylindan alkenylene；And R7
It is not H and R group；R7It is optionally cyclic with L or not cyclic, such as five-membered ring or hexatomic ring, this depend on specific L groups and
R7Group.
The R group has the structure shown in lower formula (II)：
Wherein：
Y is CH2, O, S, N or the first group, first group is selected from by C6To C20Aryl, C6To C20Aryloxy group, C2Extremely
C20Alkyl-carbonyl, C7To C20Aryl carbonyl, C1To C20Amide groups, C3-C8A group in the group of cyclic group composition；
N is 0 to 10 integer, preferably 2 to 6 integer, more preferably 2 to 4 integer；
X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；
R8、R9、R10And R11H or the second organic substituent are each independently, second organic substituent is selected from by C1-
C20Alkyl, C6-C20Aryl and C3-C8The group of cyclic group composition.
Hereafter some specific embodiments of ruthenium catalyst described to the first aspect of the present invention are carried out more particularly
It is bright.
L groups
L groups are neutral electron parts, for example, can be selected from by C3-C20Three substitution alkyl phosphorus bases of individual carbon, C3-C20
The alkoxy of individual carbon, C6-C20One group of the group of the aryloxy group, thiosubstituents group or pyridine radicals composition of individual carbon.
In some embodiments, L groups are C3-C20Alkyl phosphorus base, for example, with 3,4,5,6,7,8,9,10,11,
12nd, 13,14,15,16,17,18, the 19 or 20 alkyl phosphorus of carbon atom, such as thricyclohexyl phosphorus base (PCy3-).It is preferred in addition
It is that the alkyl in the alkyl phosphorus is C3-C12Straight chained alkyl or branched-alkyl, more preferably C3-C6Straight chained alkyl or branch
Change alkyl, for example, n-propyl, isopropyl, normal-butyl, isopropenyl (such as sec-butyl or the tert-butyl group), n-pentyl, isopentyl,
N-hexyl, isohesyl.
In some embodiments, L groups are C3-C20Alkoxy, for example, with 3,4,5,6,7,8,9,10,11,12,
13rd, 14,15,16,17,18,19 or 20 alkoxies of carbon atom.Preferably, the alkoxy is C3-C12Alkoxy,
More preferably C3-C6Alkoxy, for example, propoxyl group, isopropoxy, n-butoxy, isobutoxy (for example sec-butoxy or
Tert-butoxy), n-pentyloxy, isoamoxy, positive hexyloxy, dissident's epoxide.
In some embodiments, L groups are C6-C20Aryloxy group, for example, with 6,7,8,9,10,11,12,13,14,
15th, 16,17,18,19 or 20 aryloxy group of carbon atom.Preferably, the aryloxy group is C6-C12Aryloxy group；More preferably
Be C6-C9Aryloxy group, for example, phenoxy group, benzyloxy, phenethyl epoxide or phenylpropyl epoxide.
In some embodiments, L groups are with C1To C12Alkyl thioether group, for example, with 1,2,3,4,5,
6th, 7,8,9,10,11 or 12 thioether groups of the alkyl of carbon atom, more preferably with 1,2,3,4,5 or 6 alkyl of carbon atom
Thioether group.
In some embodiments, L groups are with C3To C12Alkyl pyridine radicals, such as with 1,2,3,4,5 or 6
The thioether group of the alkyl of individual carbon atom..
Some preferred embodiment in, L groups be isopropoxy and and R7Group forms 6 yuan of rings or tricyclohexyl phosphine
Base.
R1To R6Group
R1、R2、R3、R4、R5And R6It is each independently H, R group or with 1 to 20 the first of carbon atom organic substitution
Base, first organic substituent is selected from by C1-C20Alkyl, C1-C20Alkoxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20
Alkyl-carbonyl, C7-C20Aryl carbonyl, C1-C20Amide groups and C3-C8The group of cyclic group composition；R1、R2、R3、R4、R5And R6In
At least one group is R group；R2And R3It is asynchronously H and be first organic substituent；R4And R6Asynchronously H and to be
First organic substituent；On R group, will separately describe below.
On the first organic substituent
As first organic substituent, the C1-C20Alkyl be, for example, with 1,2,3,4,5,6,7,8,9,11,
12nd, 13,14,15,16,17,18,19 or 20 alkyl of carbon atom, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl,
Heptyl, octyl group, nonyl, certain herbaceous plants with big flowers base, undecyl, dodecyl, myristyl, cetyl, octadecyl or eicosyl.Institute
State alkyl preferably methyl, ethyl, propyl group, isopropyl, butyl, isopropenyl, amyl group, isopentyl, hexyl or isohesyl (for example
Cyclohexyl)；Further preferably methyl, ethyl, propyl group or isopropyl；Further preferably methyl or ethyl, most preferably
Be methyl.
As first organic substituent, the C1-C20Alkoxy be, for example, with 1,2,3,4,5,6,7,8,9,11,
12nd, 13,14,15,16,17,18,19 or 20 alkoxies of carbon atom, such as methoxyl group, ethyoxyl, propoxyl group, butoxy,
Amoxy, hexyloxy, epoxide in heptan, octyloxy, nonyl epoxide, certain herbaceous plants with big flowers epoxide, hendecane epoxide, dodecyloxy, tetradecyloxyaniline, ten
Six alkoxies, octadecane epoxide or eicosane epoxide.The C1-C20Alkoxy is preferably methoxyl group, ethyoxyl, propoxyl group, different
Propoxyl group, butoxy, isopropyl alkenyloxy group, amoxy, isoamoxy, hexyloxy or dissident's epoxide (such as cyclohexyl)；Further
Preferably methoxyl group, ethyoxyl, propoxyl group or isopropoxy；Further preferably methoxy or ethoxy, most preferably
It is methoxyl group.
As first organic substituent, the C6-C20Aryl be, for example, with 6,7,8,9,11,12,13,14,15,
16th, 17,18,19 or 20 aryl of carbon atom, such as phenyl, with 1 C1To C14The phenyl of alkyl substituent, with 2
C1To C13The phenyl of alkyl substituent, with 3 C1To C12The phenyl of alkyl substituent, with 4 C1To C11Alkyl substituent
Phenyl, with 5 C1To C10The phenyl of alkyl substituent.Preferably, 1 to 3 C is carried on phenyl, phenyl ring1To C3Alkane
The phenyl of base, such as benzyl, phenethyl or phenylpropyl.
As first organic substituent, the C6-C20Aryloxy group be, for example, with 6,7,8,9,11,12,13,14,
15th, 16,17,18,19 or 20 aryloxy group of carbon atom, such as phenoxy group, with 1 C1To C14The benzene oxygen of alkyl substituent
Base, with 2 C1To C13The phenoxy group of alkyl substituent, with 3 C1To C12The phenoxy group of alkyl substituent, with 4 C1
To C11The phenoxy group of alkyl substituent, with 5 C1To C10The phenoxy group of alkyl substituent.Preferably, on phenoxy group, phenyl ring
With 1 to 3 C1To C3Alkyl phenoxy group, such as benzyloxy, benzene ethyoxyl or phenylpropyl alcohol epoxide.
As first organic substituent, the C2-C20Alkyl-carbonyl be, for example, with 2,3,4,5,6,7,8,9,11,
12nd, 13,14,15,16,17,18,19 or 20 alkyl-carbonyls of carbon atom, the moieties in the alkyl-carbonyl can be with example
Such as it is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, certain herbaceous plants with big flowers base, undecyl, dodecyl, 14
Alkyl, cetyl or octadecyl.The alkyl is preferably methyl, ethyl, propyl group, isopropyl, butyl, isopropenyl, penta
Base, isopentyl, hexyl or isohesyl (such as cyclohexyl)；Further preferably methyl, ethyl, propyl group or isopropyl；Enter one
Step is preferably methyl or ethyl, most preferably methyl.
As first organic substituent, the C7-C20Aryl carbonyl be, for example, with 7,8,9,11,12,13,14,
15th, 16,17,18,19 or 20 aryl carbonyls of carbon atom, the aryl moiety in the aryl carbonyl can have substitution base,
Such as on the phenyl ring alkyl substituent with 1,2,3,4,5,6,7,8,9,11,12 or 13 carbon atoms.Preferably, the alkyl
Substitution base be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, certain herbaceous plants with big flowers base, undecyl, dodecyl,
Tridecyl, more preferably methyl, ethyl, propyl group, isopropyl, butyl, isopropenyl, amyl group, isopentyl, hexyl or isohesyl
(such as cyclohexyl), it is further preferred that methyl, ethyl, propyl group or isopropyl；It is even furthermore preferable that methyl or ethyl,
Most preferably methyl, i.e. the C7-C20Aryl carbonyl is carbobenzoxy.
As first organic substituent, the C1-C20Amide groups for example can be not surpass altogether with carbon number
Cross 19 alkyl substituents of carbon atom, for example, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl,
The amide groups of certain herbaceous plants with big flowers base, undecyl, dodecyl, myristyl, cetyl or octadecyl substitution, preferably methyl, second
The amide groups of base, propyl group, butyl, amyl group or hexyl substitution, the more preferably amide groups of methyl, ethyl or propyl group substitution.
As first organic substituent, the C3-C8Cyclic group be, for example, saturation or undersaturated three-membered ring,
The five-membered ring of four-membered ring, five-membered ring, hexatomic ring, heptatomic ring or octatomic ring, preferably saturation, hexatomic ring or heptatomic ring.
R1、R2、R3、R4、R5And R6In 1,2,3,4,5 or 6 groups can be R group；Preferably 2 groups are for example
R1And/or R5It is R group；Further preferably 1 group such as R1Or R5It is R group, most preferably, R1It is R group.
In R1、R2、R3、R4、R5And R6In, in addition to the group as R group, other groups preferably independently for H or
With 1 to 20 the first organic substituent of carbon atom.In some embodiments, the other groups independently are H or tool
There is 1 to 6 alkyl of carbon atom.Some preferred embodiment in, the other groups independently are with 1 to 6 carbon
The alkyl of atom.In some preferred implementation methods, the other groups independently are with 1 to 3 alkane of carbon atom
Base such as methyl, ethyl, propyl group or isopropyl, the most preferably described all methyl of other groups.
Some preferred embodiment in, R1And/or R5At least one of group be R group；And R2、R3、R4With
R6At least one of for methyl, at least two be methyl, at least three be methyl or all methyl.
Some preferred embodiment in, the R1It is R group, remaining all methyl.
R7Group
The R7Group can be above with respect to R1、R2、R3、R4、R5And R6Described the first organic substituent, C2To C20Alkene
Alkyl, phenyl, isopropenyl or phenylindan alkenylene；And R7It is not H and R group.Preferably, the R7Group can be
Above with respect to R1、R2、R3、R4、R5And R6Described the first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenyl
Indenes alkenylene；And R7It is not H and R group.Preferably, the first organic substituent be with 1 to 6 alkyl of carbon atom,
More preferably there is 1 to 3 alkyl such as methyl, ethyl, propyl group or the isopropyl, most preferably methyl of carbon atom.The C2Extremely
C20Alkylene is preferably the alkylene of C2 to C6, for example, vinyl, acrylic, pi-allyl, cyclobutenyl, pentenyl or hexene
Base.
Some preferred embodiment in, the R7Group is selected from phenyl, isopropenyl or phenylindan alkenylene composition
Group；
In some embodiments, the R7Group can be separate with L groups；In other implementation methods, institute
State R7Group can form any cyclic group together with L groups.
R group
In ruthenium catalyst of the invention, R1、R2、R3、R4、R5、R6In at least one be with shown in lower formula (II) tie
The R group of structure：
Y group
Y can be CH2, O, S, N or the first group, first group is selected from by C6To C20Aryl, C6To C20Aryloxy group,
C2To C20Alkyl-carbonyl, C7To C20Aryl carbonyl, C1To C20Amide groups, C3-C8A group in the group of cyclic group composition.
The C6To C20Aryl, C6To C20Aryloxy group, C2To C20Alkyl-carbonyl, C7To C20Aryl carbonyl, C1To C20Amide groups and C3-C8
Cyclic group is respectively as described above for R1To R6Described C6To C20Aryl, C6To C20Aryloxy group, C2To C20Alkyl-carbonyl, C7Extremely
C20Aryl carbonyl, C1To C20Amide groups and C3-C8Cyclic group, will not be repeated here.
Some preferred embodiment in, Y can be CH2, O, S or N, more preferably Y is O or S, most preferably O.
N values
N can be 0 to 10 integer, for example, 0,1,2,3,4,5,6,7,8,9 or 10, preferably 2 to 10 integer, more
Preferably 2 to 8 integer, more preferably 2 to 6 integer is still more preferably 2 to 4, most preferably 4；
X group
X can be fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；Preferably, X be fluorine, chlorine, bromine,
Iodine, PF6Or BF4, it is further preferred that X is PF6Or BF4, most preferably, X is PF6。
R8、R9、R10And R11Group
R8、R9、R10And R11H or the second organic substituent are each independently, second organic substituent is selected from by C1-
C20Alkyl, C6-C20Aryl and C3-C8The group of cyclic group composition.
As second organic substituent, the C1-C20Alkyl be, for example, with 1,2,3,4,5,6,7,8,9,11,
12nd, 13,14,15,16,17,18,19 or 20 alkyl of carbon atom, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl,
Heptyl, octyl group, nonyl, certain herbaceous plants with big flowers base, undecyl, dodecyl, myristyl, cetyl, octadecyl or eicosyl.Institute
State C1-C20Alkyl is preferably methyl, ethyl, propyl group, isopropyl, butyl, isopropenyl, amyl group, isopentyl, hexyl or isohesyl
(such as cyclohexyl)；Further preferably methyl, ethyl, propyl group or isopropyl；Further preferably methyl or ethyl, most
Preferably methyl.
As second organic substituent, the C6-C20Aryl be, for example, with 6,7,8,9,11,12,13,14,15,
16th, 17,18,19 or 20 aryl of carbon atom, such as phenyl, with 1 C1To C14The phenyl of alkyl substituent, with 2
C1To C13The phenyl of alkyl substituent, with 3 C1To C12The phenyl of alkyl substituent, with 4 C1To C11Alkyl substituent
Phenyl, with 5 C1To C10The phenyl of alkyl substituent.Preferably, 1 to 3 C is carried on phenyl, phenyl ring1To C3Alkane
The phenyl of base, such as benzyl, phenethyl or phenylpropyl.
As second organic substituent, the C3-C8Cyclic group be, for example, saturation or undersaturated three-membered ring,
The five-membered ring of four-membered ring, five-membered ring, hexatomic ring, heptatomic ring or octatomic ring, preferably saturation, hexatomic ring or heptatomic ring.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups
It is isopropoxy or or thricyclohexyl phosphino-；R7It is phenyl, isopropenyl or phenylindan alkenylene；R1、R2、R3、R4、R5And R6
It is each independently H, with the R group of structure shown in above-mentioned formula (II) or described the first of carbon atom organic with 1 to 20
Substitution base, R1、R2、R3、R4、R5And R6At least one of group be R group, R2And R3Asynchronously for H and for described first organic
Substitution base；R4And R6It is asynchronously H and be first organic substituent；Y is CH2, the group of O, S, N or described first；N is 0
To 10 integer；X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；R8、R9、R10And R11Independently of one another
It is the organic substituents of H or described second.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups
It is isopropoxy or or thricyclohexyl phosphino-；R7It is phenyl, isopropenyl or phenylindan alkenylene；R1、R2、R3、R4、R5And R6
It is each independently H, R group or C with structure shown in above-mentioned formula (II)1-C20Alkyl, R1、R2、R3、R4、R5And R6In extremely
A few group is R group, R2And R3It is asynchronously H and be C1-C20Alkyl；R4And R6It is asynchronously H and be C1-C20Alkyl；Y
It is CH2、O、S、N；N is 0 to 10 integer；X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；R8、R9、
R10And R11It is each independently H or C1-C20Alkyl.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups
It is isopropoxy or or thricyclohexyl phosphino-；R7It is phenyl, isopropenyl or phenylindan alkenylene；R1、R2、R3、R4、R5And R6
It is each independently H, R group or C with structure shown in above-mentioned formula (II)1-C6Alkyl, R1、R2、R3、R4、R5And R6In extremely
A few group is R group, R2And R3It is asynchronously H and be C1-C6Alkyl；R4And R6It is asynchronously H and be C1-C6Alkyl；Y is
CH2、O、S、N；N is 0 to 10 integer；X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；R8、R9、R10
And R11It is each independently H or C1-C6Alkyl.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups
It is isopropoxy or or thricyclohexyl phosphino-；R7It is phenyl, isopropenyl or phenylindan alkenylene；R1、R2、R3、R4、R5And R6
It is each independently R group or C with structure shown in above-mentioned formula (II)1-C6Alkyl, R1、R2、R3、R4、R5And R6In at least
One group is R group；Y is CH2、O、S、N；N is 0 to 10 integer；X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or
N(SO2CF3)2；R8、R9、R10And R11It is each independently C1-C6Alkyl.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups
It is isopropoxy or or thricyclohexyl phosphino-；R7It is phenyl, isopropenyl or phenylindan alkenylene；R1And/or R5It is with upper
State the R group of structure shown in formula (II), R2、R3、R4And R6Methyl, ethyl, propyl group, isopropyl, butyl, isopropyl independently of one another
Alkenyl, amyl group, isopentyl or hexyl or isohesyl；Y is O or S；N is 0 to 10 integer；X is PF6Or BF4；R8、R9、R10With
R11It is each independently methyl, ethyl, propyl group, isopropyl, butyl, isopropenyl, amyl group, isopentyl or hexyl or isohesyl.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups
It is isopropoxy or or thricyclohexyl phosphino-；R7It is phenyl, isopropenyl or phenylindan alkenylene；R1And/or R5It is with upper
State the R group of structure shown in formula (II), R2、R3、R4And R6It is each independently methyl, ethyl, propyl group or isopropyl；Y be O or
S；N is 2 to 6 integer；X is PF6Or BF4；R8、R9、R10And R11It is each independently methyl, ethyl, propyl group or isopropyl.
In some specific embodiments, the ruthenium catalyst has the structure shown in above-mentioned formula (I), wherein, L groups
It is isopropoxy or or thricyclohexyl phosphino-；R7It is phenyl, isopropenyl or phenylindan alkenylene；R1It is with above-mentioned formula
(II) R group of structure shown in, R2、R3、R4、R5And R6It is each independently methyl；Y is O；N is 4；X is PF6；R8、R9、R10With
R11It is methyl.
It is more of the invention preferred embodiment in, the ruthenium catalyst be selected from following 4 representative catalysis
The compound of agent structure：
The present invention provides the synthetic method of the ruthenium catalyst described in first aspect present invention in second aspect.Using existing
Method, imidazolium ionic liquid group cannot be connected to the N- heterocycle carbine most strong with ruthenium catalytic center bonding energy power at all
In coordination, because ruthenium is not only connected in the coordination of N- heterocycle carbines, equally also it is easily connected on imidazolium ionic liquid group,
So as to the ruthenium catalyst described in first aspect present invention cannot be obtained., by further investigation, have found finally can be with for the present inventor
Obtain the synthetic method of the ruthenium catalyst described in first aspect present invention.
In some more specifically implementation method, the method for preparing the ruthenium catalyst of the invention, methods described includes：
(1) compound 1 is synthesized；And it is 2-in-1 into compound 3 by compound；
(2) compound 4 is synthesized by compound 1 and compound 3；
(3) compound 5 is synthesized by compound 4；
(4) compound 6 is synthesized by compound 5；
(5) compound 7-I is synthesized by compound 6；
(6) compound 7-II is synthesized by compound 7-I；
(7) synthesized as the compound 8 or compound 9 of ruthenium catalyst by compound 7-II；
Wherein, compound 1 is as follows to the structural formula of compound 7：
Compound 8 is selected from the group being made up of following compound 8a, 8b, 8c and 8d：
The compound 9 is as follows：
In some more specifically implementation method, ruthenium catalyst of the invention is carried out by following synthetic route：
More specifically, second aspect present invention methods described comprises the following steps：
(1) react 2-methylimidazole and Isosorbide-5-Nitrae-dibromobutane, obtain 1- (4- brombutyls) -2-methylimidazole, i.e. chemical combination
Thing 1；
(2) 4- hydroxyl -2 are made, 6- dimethylanilines, glyoxal and 1,3,5- trimethylanilines reaction obtain 1- (4- hydroxyls
Base -2,6- dimethyl benzenes) base -2- (1,3,5- trimethylbenzene) base-second diimine, i.e. compound 2；
(3) compound 2 is reacted with sodium borohydride, obtain 1- (4- hydroxyl -2,6- dimethyl benzenes) base -2- (1,3,5- tri-
Methylbenzene) base-ethylenediamine, i.e. compound 3；
(4) compound 3 is reacted with compound 1, obtain 1- (2,6- dimethyl -4- (4- (2-methylimidazole base) fourth oxygen
Base) benzene) base -2- (1,3,5- trimethylbenzene) base-ethylenediamine, i.e. compound 4；
(5) make compound 4, triethyl orthoformate and hydrochloric acid reaction, obtain 1- (2,6- dimethyl -4- (4- (2- methyl miaows
Triazole hydrochloride base) butoxy) benzene) base -3- (1,3,5- trimethylbenzene)-imidazolium chloride, i.e. compound 5；
(6) react compound 5, sodium tert-butoxide and tert-butyl group alcohol, obtain 1- (2,6- dimethyl -4- (4- (2- methyl miaows
Oxazolyl) butoxy) benzene) base -3- (1,3,5- trimethylbenzene) -2- tert-butyl group oxygen imidazolidines, i.e. compound 6；
(7) make compound 6 and iodomethane reaction, obtain the salt compounded of iodine imidazole ion liquid-ligand 7- with following structure
I, i.e. compound 7-I：
(8) make compound 7-I and hexafluorophosphoric acid silver reaction, obtain the hexafluorophosphate (PF with following structure6) imidazoles
Ionic liquid-ligand 7-II, i.e. compound 7-II：
(9) make the Ge Labu catalyst reactions of compound 7-II and first generation alkoxy benzal type, obtain the ruthenium and urge
Agent.
Some preferred embodiment in, the Ge Labu catalyst of the first generation alkoxy benzal type is selected from by such as
The group of lower compound C-1a, C-1b, C-1c or C-1d composition：
And the ruthenium catalyst for obtaining is respectively selected from by compound 8a, 8b, 8c, 8d and compound 9：
The present invention provides the ruthenium catalyst or second aspect present invention system described in first aspect present invention in the third aspect
The ruthenium catalyst for obtaining especially carries out alkene to derive from the alkene of vegetable oil such as cottonseed oil in olefin metathesis reaction as reactant
Application in hydrocarbon displacement reaction, it is preferred that the cycle applications in olefin metathesis reaction.
The invention is further elaborated with reference to specific embodiment, following embodiments are only to illustrate the present invention
The purpose of scheme rather than limit.
Embodiment 1：Imidazole ion liquid-ligand, 1- (2,6- dimethyl -4- (4- (1,2- methylimidazole alkali) fourths
Epoxide) benzene) base -3- (1,3,5- trimethylbenzenes) -2- methyl oxygen imidazolidines synthesis
Bromobutyl imidazolium compounds 1 is the synthesis of 1- (4- brombutyls) -2-methylimidazole (abbreviation compound 1)：
Under conditions of room temperature, stirring and nitrogen protection, to being placed with 2-methylimidazole (4.2g, 50mmol) and dried
60 weight % sodium hydrides solids are dividedly in some parts in tetrahydrofuran (40ml) solution, and (3.0g cleans 3 times to wash with n-hexane in advance
Remove Dormant oils), substantial amounts of bubble is released after addition immediately.Continue to stir 60 minutes until bubble-free releasing is after adding sodium hydride
Only, the clear solution in reaction is lentamente then transferred to another and has been previously heated to 70 DEG C, equipped with Isosorbide-5-Nitrae-dibromo fourth
In alkane (10.7g, 50mmol) and 10ml tetrahydrofuran reaction bulbs；After transfer, continue to react 4 hours；Using TLC plate (silica gel
Thin layer) judge reaction terminal.Reaction is cooled to room temperature after terminating, add 30ml n-hexanes, washes 3 times (each 30ml),
Na2SO4Dried overnight.Then, using Rotary Evaporators remove solvent and and using vacuum condition go the removal of impurity, obtain slightly light
Yellow liquid product 9.0g, yield is 95.7%.Product need not be further purified, and can be directly used for next step reaction.
C8H13BrN2High resolution mass spec calculated value：216.0262；Measured value：216.0270.
Second diimine compounds 2, i.e. 1- (4- hydroxyl -2,6- dimethyl benzenes) base -2- (1,3,5- trimethylbenzene) base-second two
Imines (hereinafter sometimes simply referred to as compound 2) synthesizes：
To in reaction bulb add 4- hydroxyl -2,6- dimethylanilines (4.4g), 40% glyoxal (4.3g) aqueous solution and
1,3,5- trimethylaniline (4.0g), then add 50 volume % isopropanol/waters (50ml) and 13% volume acetic acid/isopropanol (10
Drop), reaction 4h is stirred at room temperature, reaction solution gradually becomes yellow solution, with TLC plates (10 volume % ethyl acetate/just oneself
Alkane) come judge reaction whether reach terminal (how judging), product would indicate that three yellow spottings on the tlc plate.Reaction
The sodium hydroxide solution terminating reaction of the acetic acid equivalent such as addition after complete.Filtering solution, then with the 75 volume % methanol/waters of 120ml
Solution washs the yellow solid being filtrated to get on filter screen in three times, finally retains yellow solid, is dried under reduced pressure acquisition yellow
Solid 7.1g.Gained yellow solid contains three kinds of group with imine moiety：1,2- double (1,3,5- trimethylbenzenes) base-second diimine, 1-
(4- hydroxyl -2,6- dimethyl benzenes) base -2- (1,3,5- trimethylbenzenes) base-ethylenediamine (object), 1,2- pair (4- hydroxyls base -
2,6- dimethyl benzenes) base-second diimine.
Ethylene diamine compound 3, i.e. 1- (4- hydroxyl -2,6- dimethyl benzenes) base -2- (1,3,5- trimethylbenzene) base-ethylenediamine
The synthesis of (hereinafter sometimes referred to compound 3)：
Sodium borohydride (3.8g, 5mmol) is added in 100ml single port bottles, middle gained from the reactions above is subsequently added and is contained
Three kinds of second diimine yellow mixture solid (7.1g) and tetrahydrofuran (30ml).Stir at room temperature, methyl alcohol is added dropwise in three batches (altogether
10ml is added dropwise).Reaction produces hydrogen, and heat release.Reaction about 5h is stirred at room temperature, solution graduates into faint yellow straight by yellow
To near colorless, judge whether reaction reaches terminal with TLC plates (25 volume % ethyl acetate/n-hexane).After reaction terminates, plus
Enter 50ml water stopped reactions, be subsequently added dichloromethane 30ml and washed in separatory funnel three times, remove a layer yellow solution.
By after anhydrous sodium sulfate drying, removing solvent with rotary evaporator and obtaining sticky mass.Under nitrogen protection with equipped with silicon
The separation post separation of glue, successively to the sterling ethylene diamine compound that three light grays are liquid, is followed successively by by separate order：1,
Double (1,3,5- trimethylbenzenes) bases-ethylenediamine of 2-, 1- (4- hydroxyl -2,6- dimethyl benzenes) base -2- (1,3,5- trimethylbenzenes) base -
Double (4- hydroxyl -2,6- dimethyl benzenes) bases-ethylenediamine of ethylenediamine, 1,2-.The 1- (4- hydroxyl -2,6- dimethyl benzenes) for wherein purifying
Base -2- (1,3,5- trimethylbenzene) base-ethylenediamine liquid, weight is 1.7g.C19H26N2The high resolution mass spec calculated value of O：
298.2045；Measured value：298.2056.
Imidazole radicals-ethylene diamine compound 4,1- (2,6- dimethyl -4- (4- (2-methylimidazole base) butoxy) benzene) base -2-
The synthesis of (1,3,5- trimethylbenzenes) base-ethylenediamine (hereinafter sometimes referred to compound 4)：
Under nitrogen protective condition, to addition 1- (4- hydroxyl -2,6- dimethyl benzenes) base -2- (1,3,5- tri- in reaction bulb
Methylbenzene) base-ethylenediamine (6.0g, 20mmol), cesium carbonate Cs2CO3(6.8g, 22mmol) solid and the dried second of 60ml
Nitrile.Stirred 30 minutes in room temperature oil bath, then by oil bath heating to 50 DEG C, 1- (4- brombutyls) -2-methylimidazole is added dropwise
The solution of (4.34g, 20mmol) in 20ml acetonitriles, is warmed up to backflow after completion of dropwise addition, continue to stir 3 hours, using TLC plates
Judge the terminal of reaction.Reactant is naturally cooled into environment temperature after reaction terminates, adds 30ml to contain 0.5g hydroxides
Sodium water solution and toluene 30ml, fully shake, isolated organic layer are washed with water (3x50ml) to neutrality；By drying, very
The lower solvent evaporated of sky, obtains the compound 4 of light gray viscous liquid, and weight is 7.4g, yield 86%.C27H38N4The high score of O
Resolution mass spectrum calculated value：434.3046；Measured value：434.3061.
Imidazole hydrochloride-imidazolium chloride 5,1- (2,6- dimethyl -4- (4- (2-methylimidazole hydrochloric acid alkali) fourth oxygen
Base) benzene) base -3- (1,3,5- trimethylbenzenes)-imidazolium chloride (hereinafter sometimes referred to compound 5) synthesis:
Imidazole radicals-ethylene diamine compound 4 (4.34g, 10mmol) is dissolved in 40ml toluene, primitive nail is added to the solution
Triethylenetetraminehexaacetic acid ester (6.0g) and 20% hydrochloric acid solution (3.65g).The reaction bulb that will be equipped with distilling apparatus is heated to 80 DEG C, with reaction
Carrying out constantly there is solvent and accessory substance to be distilled out of, the terminal of reaction is judged with TLC plates, after reaction, uses reduced pressure handle instead
The distillation such as solvent is clean, and simultaneous reactions liquid is changed into white solid, is stood after then naturally cooling to environment temperature.To white solid
Soaked with 20ml n-hexanes and filtered, retain white solid, altogether in triplicate；Drying under finally depressurizing, obtains canescence chemical combination
The solid of thing 5, weight is 4.1g, yield 80.3%.C28H37N4The high resolution mass spec calculated value of O：445.2967；Measured value：
445.2954。
Imidazole radicals-ligand 6,1- (2,6- dimethyl -4- (4- (2-methylimidazole base) butoxy) benzene) base -3- (1,3,
5- trimethylbenzenes) -2- tert-butyl group oxygen imidazolidine (hereinafter sometimes referred to compound 6) synthesis：
To imidazole hydrochloride-imidazolium chloride 5 (2.0g, 3.86mmol) is added in dried reactor, 20ml does
It is dry to cross tetrahydrofuran and 10ml n-hexanes.Under nitrogen protection, room temperature opens stirring, by 15% sodium tert-butoxide-t-butanol solution
During (3.0ml) (concentration of the tert-butyl group sodium in tert-butyl group alcohol is 15 weight/volume %) is added drop-wise to said mixture.With dropwise addition
Carrying out reaction dirty solution graduate into yellow solution, continue to react at room temperature 1-2 hours after dropwise addition, period uses TLC plates
To judge the terminal of reaction.Reaction terminates rear mixture and washes (1x10ml) with water, and what is then dried and be filtrated to get contains miaow
The solution of the product of oxazolyl-ligand 6.The solution is directly used in next step reaction.C32H46N4O2High resolution mass spec calculate
Value：518.3621；Measured value：518.3598.
1- methylimidazoles ionic liquid-ligand 7,1- (2,6- dimethyl -4- (4- (1,2- methylimidazole alkali) fourths
Epoxide) benzene) base -3- (1,3,5- trimethylbenzenes) -2- tert-butyl group oxygen imidazolidine (hereinafter sometimes referred to compound 7) synthesis：
7-I) the synthesis of salt compounded of iodine 1- methylimidazoles ionic liquid-ligand 7-I：To advance second through in dried reaction bulb
The solution of the compound 6 of imidazole radicals-ligand that addition is obtained from the reactions above, puts it in 0 DEG C of ice-water bath, is protected in nitrogen
Shield is lower to add iodomethane CH3I(1.65g,11.6mmol).Ice-water bath then is withdrawn, allows reaction temperature to be maintained at room temperature, continue to stir
Mix 2-3 hours, the terminal of reaction is judged with TLC plates.Excessive CH is steamed under vacuum after reaction terminates3I and molten
Agent, is subsequently adding dried first 30ml.Obtain the toluene solution of salt compounded of iodine 1- methylimidazoles ionic liquid-ligand 7a.
C36H49N4O2High resolution mass spec calculated value：533.3850；Measured value：533.3861.
7-II) hexafluorophosphate (PF6) 1- methylimidazoles ionic liquid-ligand 7b synthesis：This be a step imidazoles from
The anion exchange reaction of sub- liquid.In nitrogen protection, under the gentle agitation of room, to obtain in from the reactions above ground salt compounded of iodine imidazoles from
The toluene solution of sub- liquid-ligand 7a, is added dropwise hexafluorophosphoric acid silver (AgPF6, 1.0g, 3.96mmol) toluene solution, stirring
Overnight.Reaction is filtered reactant mixture by diatomite after terminating, and is washed 3 times, and hexafluorophosphate (PF is obtained after drying6)1-
The toluene solution of methylimidazole ionic liquid-ligand 7b.C30H43N4O2High resolution mass spec calculated value：533.3850；Survey
Value：533.3841.
The synthesis of 2 imidazolium ionic liquids of embodiment-catalyst is as follows：
A) synthesis of imidazole ion liquid-alkoxy benzal catalyst 8a：Hexafluorophosphate (PF will be contained6) imidazol ion
The toluene solution of liquid-ligand 7b and the Ge Labu catalyst C-1a RuCl of first generation alkoxy benzal type2PCy3(=
CHC6H4OCH(CH3)2) (0.90g, 1.5mmol) is added in reaction bulb.By reaction bulb it is closed after, be put into 80 DEG C of oil bath, stir
Mix lower reaction 40-60 minutes.Reaction terminates, and is evaporated all solvents under vacuum condition, and residue is soaked and filtered many with methyl alcohol
Secondary circulation, until the raw material point (R on TLC platesfThe big point of value) disappear untill, greenish solid product is vacuum dried, obtain miaow
Oxazolinium ion liquid-alkoxy benzal catalyst 8a, 1.0g, yield 74%.C39H52Cl2N4O2The high resolution mass spec of Ru is calculated
Value：780.2511；Measured value：780.2498.1H NMR(300MHz,CDCl3)δppm:16.56 (s, 1H, Ru=CHAr), 7.48
(m, 1H, aromatic-CH), 7.46 (s, 1H, imidazolium-CH), 7.38 (s, 1H, imidazolium-CH), 7.09
(s,2H,mesityl aromatic-CH),7.00(s,2H,mesityl aromatic-CH),6.93(dd,1H,
Aromatic-CH), 6.85 (dd, 1H, aromatic-CH), 6.79 (d, 1H, aromatic-CH), 4.90 (m, 1H, (CH3)2CHOAr),4.18(m,4H,N(CH2)2N),4.08(t,2H,OCH2),4.05(t,2H,NCH2),3.77(s,3H,NCH3),
2.52(s,3H,CH3),2.48(m,12H,mesityl-CH3),2.40(s,3H,mesityl-CH3) 1.85 (m, 2H ,-
CH2CH2-), 1.78 (m, 2H ,-CH2CH2-),1.27(d,6H,CH3)2CHOAr).Wherein, aromatic represents aromatic radical,
Imidazolium represents imidazole radicals, and Mesityl represents mesitylene base.
B) synthesis of imidazole ion liquid-vinylidene catalyst 8b：Synthetic method is equally identical with 8a, only need to be by reaction
The first generation Ge Labu catalyst C-1a as raw material with the first generation containing vinylidene type Ge Labu catalyst C-1b
RuCl2(PCy3)2(=CHCH=C (CH3)2) (1.23g, 1.5mmol) replace.React and post-process by with 8a identicals,
Brown solid imidazole ion liquid-vinylidene catalyst product 8b is obtained, weight is measured for 1.10g, yield 65%.
C52H81Cl2N4The high resolution mass spec calculated value of OPRu：980.4569；Measured value：980.4582.
C) synthesis of imidazole ion liquid-benzal catalyst 8c：
Synthetic method is identical with above-mentioned 8a, only need to be using the first generation Ge Labu catalyst C-1a as raw material in reaction
With Ge Labu catalyst C-1c RuCl of the first generation containing benzal type2(PCy3)2(=CHC6H5) (1.27g, 1.5mmol) next generation
Replace.Reacted by 8a identicals and post-processed, obtain brown solid imidazole ion liquid-benzal catalyst product 8c, measure weight
It is 1.19g to measure, yield 69%.C54H79Cl2N4The high resolution mass spec calculated value of OPRu：1002.4412；Measured value：
1002.4431。
D) synthesis of the sub- alkene catalyst 8d of imidazole ion liquid-phenylindan：
Synthetic method is identical with above-mentioned 8a, only need to be using the first generation Ge Labu catalyst C- as raw material in reaction
1a, with Ge Labu catalyst C-1d RuCl of the first generation containing phenylindan Asia alkenes type2(PCy3)2(=C9H6(m)C6H5)
(1.38g, 1.5mmol) replaces.Reacted by 8a identicals and post-processed, obtain dark brown solid product imidazol ion liquid
Body-phenylindan Asia alkene catalyst 8d, measures weight for 1.07g, yield 57%.C62H83Cl2N4The high resolution mass spec meter of OPRu
Calculation value：1102.4725；Measured value：1102.4703.
The synthesis of embodiment 3.1- isopropylimdazoles ionic liquid-alkoxy benzal catalyst 9：
According to the synthetic method completely same from compound 7-I to catalyst 8a, catalyst 9 is obtained.Specific step is：
Iso-Propyl iodide (the CH of equivalent is used in 7-I reactions first3)2CHI replaces its iodomethane (CH3I) react；Then according to
7-II full terms carry out reaction and can obtain corresponding 2 isopropyl imidazole ionic liquid-ligand containing hexafluorophosphate；
Finally by the toluene solution of the ligand and the Ge Labu catalyst C-1a RuCl of first generation alkoxy benzal type2PCy3(=
CHC6H4OCH(CH3)2) (0.99g, 1.6mmol) reaction, by methyl alcohol immersion and the purification and vacuum drying of filtering, obtain green
Color solid product 1- isopropylimdazoles ionic liquid-alkoxy benzal catalyst 9, weight 1.1g, yield 81%.
C41H56Cl2N4O2The high resolution mass spec calculated value of Ru：808.2818；Measured value：808.2829.
The catalyst olefin metathesis catalytic reaction of embodiment 4
The pretreatment of 1- decene and ionic liquid：1) pretreatment of 1- decene, the appearance of 1- decene is will be equipped with ultrasonoscope
After device degasification 30 minutes, the deoxidant (BASF AG) of 5% weight is placed into, kept for 24 hours under the conditions of sealing and lucifuge.
Using the preceding removal deoxidant of filtering under nitrogen protection, then using preceding again with nitrogen bubble about 30 minutes.2) imidazole salts from
The pretreatment of sub- liquid, using preceding at 70 DEG C, will be equipped with the reaction of 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquids
Bottle vacuum drying 2 hours.Then room temperature is cooled under stirring and nitrogen protection.
1) in the presence of without ionic liquid, the olefin metathesis operation method of 1- decene conversion ratios：
In the case where nitrogen is protected and is stirred, in the reaction bulb equipped with continuous air-blowing device and condenser pipe, 1- decene is added
(7.0g, 50mmol), then puts it into the oil bath with heating function, after temperature reaches 60 DEG C, adds catalyst C-
2a (0.1mmol, 0.2mol%).When reaction time proceeds to 10,20,40,60,120,240 minutes, take out 0.1ml's respectively
Sample carrys out the process of observing response.The sample for obtaining first crosses solution of the NaOH in toluene with a 30% ethanol tert-butyl group of drop
To terminate catalytic reaction, then with 5ml dilution with toluene after, the content of product is analyzed with gas chromatograph (GC).Result see
Table 1 and Fig. 3.
The computing formula of 1- decene conversion ratios：Conversion ratio %=100%- (decene molal quantity/whole product molal quantity) X
100%
The olefin metathesis operation method in the presence of imidazolium ionic liquid：
2) 1- decene conversion ratio changes with time
In the case where nitrogen is protected and is stirred, 1- decene (7.0g, 50mmol) and 1- butyl -3- ethyl imidazol(e) hexafluoro phosphorus are will be equipped with
The reaction bulb of hydrochlorate ionic liquid (2.0ml) mixture is put into the oil bath of heating, after temperature reaches 60 DEG C, is separately added into general
Logical catalyst C-2a and imidazolium ionic liquid-catalyst 8a (respectively 0.1mmol, 0.2mol%).Enter between when reacted
Row by 10,20,40,60,120,240 minutes when, it is separately sampled come observing response process.The sample for obtaining is first with a drop 30%
Ethanolic sodium hydroxide solution terminates catalytic reaction, then with volume is by silica gel treatment and again 9:1 n-hexane and ethyl acetate
Mixed solvent drip washing after, the content of product is analyzed with gas chromatograph (GC).Result is see table 1 and Fig. 3.
Table 1.1- decene conversion ratios change with time
Reaction to generating 9- octadecylenes by itself olefin metathesis of 1- decene：1) deposited without ionic liquid by above-mentioned
Left in the experiment with catalyst C-2a and 8a respectively in lower use catalyst C-2a Catalysis experiments and 2) in imidazolium ionic liquid,
Speed that these three reactions are can be readily seen that at 60 DEG C from its result watch 1 and Fig. 1 are all considerably fast, when proceeding to 40
Respective conversion ratio just has been maxed out value or closely maximum during minute.Therefore the reaction time one in testing below
Rule is chosen to be 40 minutes.
3) 1- decene is recycled with olefin metathesis reacting middle catalyst
Under nitrogen protection, in the 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid reaction bulbs equipped with 2ml,
Add the 1- decene (7.0g, 50mmol) by pretreatment.When the mixture is heated to after 60 DEG C in oil bath, catalysis is added
(catalyst includes typical catalyst C-2a, C-2c and imidazolium ionic liquid-catalyst for agent (0.10mmol, 0.20mol%)
8a、8c).It is reacted to 40 minutes and takes out sample immediately, be subsequently cooled to room temperature, the analysis of product is carried out according to above-mentioned method.
Blended product is easily separated with catalyst reaction system by following manner：
1. reactant mixture extracts (4 X 30ml) with toluene, and the extract Rotary Evaporators solvent evaporated of merging is obtained
To crude product；Crude on silica gel layer filtering containing micro ion liquid, then be 9 with volume ratio:1 n-hexane and ethyl acetate
Mixed solvent drip washing layer of silica gel be thoroughly to remove contained micro ion liquid, can obtain sterling by distillation and rectifying produces
Thing.
2. the regeneration of imidazolium ionic liquid catalyst reaction system：Reactant mixture is extracted 3 with toluene as described above
It is secondary, i.e., as recycle ionic liquid catalyst systems next time and directly can according to this part the above (i.e. " 1- last of the ten Heavenly stems
Alkene and olefin metathesis reacting middle catalyst are recycled ") identical method carries out catalytic reaction next time.Catalyst is recycled
Result be summarized in table 2 and Fig. 4.
Table 2. olefin metathesis reaction cycle number of times and conversion ratio in imidazolium ionic liquid
N.D. represent and be not detected by, represented with numerical value " 0 " in Fig. 4.
Representative catalyst 8a and 8c is selected from imidazolium ionic liquid-ruthenium catalyst 8a-d, be have passed through 8 times
Catalysis activity only have dropped 8% and 9% respectively after circular response；And common catalyst C-2a and C-2c is circulated in first time
Afterwards, the conversion ratio of the activity-reaction of catalyst just significantly have dropped 52-59% (second circulation) and 80-87% the (the 3rd
Secondary circulation).From the above result that it is observed that：It is this that imidazolium ionic liquid is connected to the coordination of ruthenium catalyst N- heterocycle carbines
New imidazolium ionic liquid-ruthenium catalyst, such as catalyst 8a-d on body is recyclable well in olefin metathesis reaction performance
Usability.
This new imidazolium ion liquid that imidazolium ionic liquid group is connected to ruthenium catalyst N- heterocycle carbine ligands
Body group and ruthenium catalyst, can be recycled for multiple times, so as to make up common ruthenium catalyst well because being used only once
And the deficiency of the catalyst high cost for causing.
Claims (10)
1. it is a kind of to contain the ruthenium catalyst of imidazolium ionic liquid group on N- heterocycle carbines, it is characterised in that the ruthenium is urged
Agent is the compound with structure shown in formula (I)：
Wherein：
L is neutral electron part, the neutral electron part and R7Group is cyclic or not cyclic, and selected from by C3-C20
Three substitution alkyl phosphorus bases of individual carbon, C3-C20The alkoxy of individual carbon, C6-C20The aryloxy group of individual carbon, with C1To C20Alkyl sulphur
Ether or with C0To C20Alkyl pyridine radicals composition group a group；
R1、R2、R3、R4、R5And R6It is each independently H, R group or with 1 to 20 the first organic substituent of carbon atom, institute
The first organic substituent is stated to be selected from by C1-C20Alkyl, C1-C20Alkoxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20Alkyl oxycarbonyl
Base, C7-C20Aryl carbonyl, C1-C20Amide groups and C3-C8The group of cyclic group composition；R1、R2、R3、R4、R5And R6In at least one
Individual group is R group；R2And R3It is asynchronously H and be first organic substituent；R4And R6Asynchronously for H and be described the
One organic substituent；
R7It is first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenylindan alkenylene；And R7It is not
H and R group；
The R group has the structure shown in lower formula (II)：
Wherein：
Y is CH2, O, S, N or the first group, first group is selected from by C6To C20Aryl, C6To C20Aryloxy group, C2To C20Alkane
Base carbonyl, C7To C20Aryl carbonyl, C1To C20Amide groups, C3-C8A group in the group of cyclic group composition；
N is 0 to 10 integer, preferably 2 to 6 integer, more preferably 2 to 4 integer；
X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；
R8、R9、R10And R11H or the second organic substituent are each independently, second organic substituent is selected from by C1-C20Alkane
Base, C6-C20Aryl and C3-C8The group of cyclic group composition.
2. ruthenium catalyst according to claim 1, it is characterised in that：
L is neutral electron part, and the neutral electron part is selected from by C3-C18Three substitution alkyl phosphorus bases of individual carbon, C3-C18
The alkoxy of individual carbon, C6-C18The aryloxy group of individual carbon, with C1To C12Alkyl thioether group or with C3To C12Alkyl pyrrole
One group of the group of piperidinyl composition；
R1、R2、R3、R4、R5And R6It is each independently H, R group or the first organic substituent, the first organic substituent choosing
Free C1-C12Alkyl, C1-C12Alkoxy, C6-C18Aryl, C6-C18Aryloxy group, C2-C18Alkyl-carbonyl, C7-C19Aryl carbonyl,
C1-C18Amide groups and C3-C8The group of cyclic group composition；
R7It is C1-C12Alkyl, C1-C12Alkoxy, C6-C18Aryl, C6-C18Aryloxy group, C2-C18Alkyl-carbonyl, C7-C19Aryl carbonyl
Base, C1-C18Amide groups, C3-C8Cyclic group, C2To C12Alkylene, phenyl, isopropenyl or phenylindan alkenylene；
Y is CH2, O, S, N or the first group, first group is selected from by C6To C18Aryl, C6To C18Aryloxy group, C2To C13Alkane
Base carbonyl, C7To C19Aryl carbonyl, C1To C12Amide groups, C3-C8A group in the group of cyclic group composition；
N is 2 to 6 integer；
X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；
R8、R9、R10And R11H or the second organic substituent are each independently, second organic substituent is selected from by C1-C12Alkane
Base, C6-C18Aryl and C3-C8The group of cyclic group composition.
3. ruthenium catalyst according to claim 1, it is characterised in that：
L is neutral electron part, and the neutral electron part is selected from by C3-C18Three substitution alkyl phosphorus bases of individual carbon, C3-C6
The alkoxy of individual carbon, C6-C18The aryloxy group of individual carbon, with C1To C6Alkyl thioether group or with C3To C6Alkyl pyrrole
One group of the group of piperidinyl composition；
R1、R2、R3、R4、R5And R6It is each independently H, R group or the first organic substituent, the first organic substituent choosing
Free C1-C6Alkyl, C1-C6Alkoxy, C6-C12Aryl, C6-C12Aryloxy group, C2-C7Alkyl-carbonyl, C7-C13Aryl carbonyl, C1-
C6Amide groups and C5-C7The group of cyclic group composition；
R7It is C1-C6Alkyl, C1-C6Alkoxy, C6-C12Aryl, C6-C12Aryloxy group, C2-C7Alkyl-carbonyl, C7-C13Aryl carbonyl,
C1-C6Amide groups, C5-C7Cyclic group, C2To C7Alkylene, phenyl, isopropenyl or phenylindan alkenylene；
Y is CH2, O, S, N or the first group, first group is selected from by C6To C12Aryl, C6To C12Aryloxy group, C2To C13Alkane
Base carbonyl, C7To C13Aryl carbonyl, C1To C6Amide groups, C5-C7A group in the group of cyclic group composition；
N is 2 to 4 integer；
X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；
R8、R9、R10And R11H or the second organic substituent are each independently, second organic substituent is selected from by C1-C6Alkane
Base, C6-C12Aryl and C5-C7The group of cyclic group composition.
4. ruthenium catalyst according to claim 1, it is characterised in that：
L is neutral electron part, and the neutral electron part is selected from by C3-C18Three substitution alkyl phosphorus bases of individual carbon, C3-C6
The alkoxy of individual carbon, C6-C18The aryloxy group of individual carbon, with C1To C3Alkyl thioether group or with C3To C6Alkyl pyrrole
One group of the group of piperidinyl composition；
R1、R2、R3、R4、R5And R6It is each independently H, R group or the first organic substituent, the first organic substituent choosing
Free C1-C3Alkyl, C1-C3Alkoxy, phenyl, phenoxy group, C2-C5Alkyl-carbonyl, C7-C10Aryl carbonyl, C1-C3Amide groups and
C5-C7The group of cyclic group composition；
R7It is C1-C3Alkyl, C1-C3Alkoxy, phenyl, phenoxy group, C2-C5Alkyl-carbonyl, C7-C10Aryl carbonyl, C1-C3Acid amides
Base, C5-C7Cyclic group, C2To C7Alkylene, phenyl, isopropenyl or phenylindan alkenylene；
Y is CH2, O, S, N or the first group, first group is selected from by C6To C9Aryl, C6To C9Aryloxy group, C2To C5Alkyl
Carbonyl, C7To C10Aryl carbonyl, C1To C3Amide groups, C5-C7A group in the group of cyclic group composition；
N is 2 to 4 integer；
X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；
R8、R9、R10And R11H or the second organic substituent are each independently, second organic substituent is selected from by C1-C3Alkane
Base, C6-C9Aryl and C5-C7The group of cyclic group composition.
5. ruthenium catalyst according to claim 1, it is characterised in that：
L is C3-C18Three substitution alkyl phosphorus bases of individual carbon, C3-C6The alkoxy of individual carbon, C6-C18The aryloxy group of individual carbon, with C1To C3
Alkyl thioether group or with C3To C6Alkyl pyridine radicals composition group a group；
R1、R2、R3、R4、R5And R6It is each independently H, R group or the first organic substituent, the first organic substituent choosing
Free C1-C3Alkyl, C1-C3Alkoxy, phenyl, phenoxy group, C2-C5Alkyl-carbonyl, C7-C10Aryl carbonyl, C1-C3Amide groups and
C5-C7The group of cyclic group composition；
R7It is C1-C3Alkyl, C1-C3Alkoxy, phenyl, phenoxy group, C2-C5Alkyl-carbonyl, C7-C10Aryl carbonyl, C1-C3Acid amides
Base, C5-C7Cyclic group, C2To C7Alkylene, phenyl, isopropenyl or phenylindan alkenylene；It is further preferred that R7Be phenyl,
Isopropenyl or phenylindan Asia alkene；
Y is CH2, O, S, N or the first group, first group is selected from by C6To C9Aryl, C6To C9Aryloxy group, C2To C5Alkyl
Carbonyl, C7To C10Aryl carbonyl, C1To C3Amide groups, C5-C7A group in the group of cyclic group composition；
N is 2 to 4 integer；
X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；
R8、R9、R10And R11H or the second organic substituent are each independently, second organic substituent is selected from by C1-C3Alkane
Base, C6-C9Aryl and C5-C7The group of cyclic group composition.
6. ruthenium catalyst according to claim 1, it is characterised in that：
R1、R2、R3、R4、R5And R6In 1,2,3,4,5 or 6 groups be R group；Preferably 2 group such as R1And R5It is R
Group；Most preferably 1 group such as R1Or R5It is R group.
7. the ruthenium catalyst according to any one of claim 1 to 6, it is characterised in that：
L groups are CH (CH3)2O- or PCy3-；
R1And R5At least one of group be R group, remaining group independently is H, R group or with 1 to 6 carbon atom
Alkyl；
R7Group is phenyl, isopropenyl or phenylindan alkenylene；
Y is CH2, O, S or N；
N is the integer between 2 to 6；
X is fluorine, chlorine, bromine, iodine, PF6、BF4Or NO3；And/or
R8And R11It independently is H or with 1 to 6 alkyl of carbon atom.
8. the ruthenium catalyst according to any one of claim 1 to 6, it is characterised in that：
L groups are CH (CH3)2O- or PCy3-；R1And R5At least one of group be R group, remaining group independently is H, R
Group or with 1 to 6 alkyl of carbon atom；R7Group is phenyl, isopropenyl or phenylindan alkenylene；Y is CH2, O, S or
N；N is the integer between 2 to 6；X is fluorine, chlorine, bromine, iodine, PF6、BF4Or NO3；And/or R8And R11It independently is H or with 1 to 6
The alkyl of individual carbon atom；
Preferably, L groups are CH (CH3)2O- or PCy3-；R1And R5At least one of group be R group, remaining group is only
On the spot for H or with 1 to 6 alkyl of carbon atom, R7Group is phenyl, isopropenyl or phenylindan alkenylene；Y is O or S；n
It is the integer between 2 to 6；X is fluorine, chlorine, bromine, iodine, PF6、BF4Or NO3；R8To R11It independently is H or with 1 to 6 carbon atom
Alkyl；
It is further preferred that L groups are CH (CH3)2O- or PCy3-；R1And R5At least one of group be R group, remaining group
It independently is H or with 1 to 6 alkyl of carbon atom, R7Group is phenyl, isopropenyl or phenylindan alkenylene；Y be O or
S；N is the integer between 2 to 6；X is fluorine, chlorine, bromine, iodine, PF6、BF4Or NO3；R8To R11It independently is H or with 1 to 6 carbon
The alkyl of atom；
It may further be preferable that L groups are CH2(CH3)2O- or PCy3-；R1Or R5It is R group, R1、R2、R3、R4、R5And R6In
Remaining group is H, methyl, ethyl, propyl group or isopropyl, R7Group is phenyl, isopropenyl or phenylindan alkenylene；Y be O or
S；N is the integer between 2 to 4；X is PF6Or BF4；R8To R11It independently is H, methyl, ethyl, propyl group or isopropyl；
It is even furthermore preferable that L groups are CH2(CH3)2O- or PCy3-；R1It is R group, R2、R3、R4、R5And R6It is methyl, R7
Group is phenyl, isopropenyl or phenylindan alkenylene；Y is O；N is 4；X is PF6；R8To R11It is methyl；
Most preferably, the ruthenium catalyst is selected from the group being made up of following compound 8a, 8b, 8c, 8d and compound 9：
9. a kind of method for preparing ruthenium catalyst, it is characterised in that methods described includes：
(1) compound 1 is synthesized；And it is 2-in-1 into compound 3 by compound；
(2) compound 4 is synthesized by compound 1 and compound 3；
(3) compound 5 is synthesized by compound 4；
(4) compound 6 is synthesized by compound 5；
(5) compound 7-I is synthesized by compound 6；
(6) compound 7-II is synthesized by compound 7-I；
(7) synthesized as the compound 8 or compound 9 of ruthenium catalyst by compound 7-II；
Wherein, compound 1 is as follows to the structural formula of compound 7：
Compound 8 is selected from the group being made up of following compound 8a, 8b, 8c and 8d：
The compound 9 is as follows：
10. ruthenium catalyst according to any one of claim 1 to 8 reacts especially to derive from vegetable oil in olefin metathesis
The olefin metathesis that the alkene of such as cottonseed oil is carried out as reactant react in application；Preferably, in the olefin metathesis
Cycle applications in reaction.
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| CN109012751A (en) * | 2018-08-17 | 2018-12-18 | 浙江工业大学 | A kind of application with Cabbeen-palladium structure catalyst and its in selective hydrogenation of acetylene reaction |
| CN114341402A (en) * | 2019-09-05 | 2022-04-12 | 国立大学法人东京大学 | Method and apparatus for producing ammonia |
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| CN109012751A (en) * | 2018-08-17 | 2018-12-18 | 浙江工业大学 | A kind of application with Cabbeen-palladium structure catalyst and its in selective hydrogenation of acetylene reaction |
| CN109012751B (en) * | 2018-08-17 | 2021-06-04 | 浙江工业大学 | Catalyst with carbene-palladium structure and application thereof in selective hydrogenation reaction of acetylene |
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