CN108465488A - N- heterocycle carbines ruthenium catalyst containing imidazolium ionic liquid group and its application - Google Patents
N- heterocycle carbines ruthenium catalyst containing imidazolium ionic liquid group and its application Download PDFInfo
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- CN108465488A CN108465488A CN201810175457.4A CN201810175457A CN108465488A CN 108465488 A CN108465488 A CN 108465488A CN 201810175457 A CN201810175457 A CN 201810175457A CN 108465488 A CN108465488 A CN 108465488A
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- aryl
- carbonyl
- organic substituent
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 83
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 63
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 title claims abstract description 36
- -1 C2To C20Alkylene Chemical group 0.000 claims abstract description 103
- 239000003446 ligand Substances 0.000 claims abstract description 69
- 125000001424 substituent group Chemical group 0.000 claims abstract description 62
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims abstract description 31
- 238000005865 alkene metathesis reaction Methods 0.000 claims abstract description 26
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 85
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 40
- 125000004122 cyclic group Chemical group 0.000 claims description 32
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 29
- 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
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000000460 chlorine Chemical group 0.000 claims description 23
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 23
- 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
- 150000001721 carbon Chemical group 0.000 claims description 18
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 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
- 238000000034 method Methods 0.000 claims description 17
- 238000006467 substitution reaction Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 125000001153 fluoro group Chemical group F* 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 150000001336 alkenes Chemical class 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
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 11
- 125000000101 thioether group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 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
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 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 1
- 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
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 15
- 125000000623 heterocyclic group Chemical group 0.000 abstract 2
- 239000002585 base Substances 0.000 description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 41
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 36
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 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 22
- 230000015572 biosynthetic process Effects 0.000 description 21
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 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
- 238000004949 mass spectrometry Methods 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
- 238000003756 stirring Methods 0.000 description 12
- 239000007788 liquid Substances 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 11
- 238000006555 catalytic reaction Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229940126214 compound 3 Drugs 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229940125904 compound 1 Drugs 0.000 description 7
- 229940125898 compound 5 Drugs 0.000 description 7
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 6
- 238000002360 preparation method Methods 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
- 229940125782 compound 2 Drugs 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
- 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
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical class CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-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
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process 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
- 239000011541 reaction mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000012265 solid product Substances 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
- 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 description 3
- 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 description 3
- 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 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000071 diazene Inorganic materials 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
- 239000001301 oxygen Substances 0.000 description 3
- 125000004344 phenylpropyl group Chemical group 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-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
- 239000002253 acid Substances 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
- 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
- 238000004364 calculation method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 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
- 229910052739 hydrogen Inorganic materials 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
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 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
- 239000003643 water by type Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- HVWJIZNHPRYJPA-UHFFFAOYSA-N 1,3,5-trimethylcyclohexa-2,4-dien-1-amine Chemical compound CC1=CC(C)=CC(C)(N)C1 HVWJIZNHPRYJPA-UHFFFAOYSA-N 0.000 description 1
- 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
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- HAEQAUJYNHQVHV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylbenzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2=CC=CC=C2)C=CC=1 HAEQAUJYNHQVHV-UHFFFAOYSA-N 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
- 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
- IRDQNLLVRXMERV-UHFFFAOYSA-N CCCC[Na] Chemical group CCCC[Na] IRDQNLLVRXMERV-UHFFFAOYSA-N 0.000 description 1
- 0 CC[*@](CCCC(N(CCN1c2c(CC)cc(C)cc2C)C1[Ru](*)(Cl)(Cl)=C*)=C(C)C)(CC=CC)C(C)=[N+]I Chemical compound CC[*@](CCCC(N(CCN1c2c(CC)cc(C)cc2C)C1[Ru](*)(Cl)(Cl)=C*)=C(C)C)(CC=CC)C(C)=[N+]I 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
- 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 1
- 108010002352 Interleukin-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
- 239000006227 byproduct Substances 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 229940125773 compound 10 Drugs 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
- 229940079593 drug Drugs 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
- 239000012535 impurity Substances 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
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 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
- 239000011295 pitch Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 238000010992 reflux Methods 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
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- 238000010025 steaming Methods 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
- 238000010792 warming Methods 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)
- B01J31/2278—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
- B01J31/2265—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
-
- 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
-
- 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
-
- 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
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
Abstract
The present invention relates to the N heterocycle carbine ruthenium catalysts containing imidazolium ionic liquid group, the ruthenium catalyst is the compound with structure shown in lower formula (I)：Wherein L is neutral electron ligand, R1、R2、R3、R4、R5And R6It is each independently H, R group or the organic substituent with 1 to 20 carbon atom；R7For first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenylindan alkenylene；The R group has structure shown in lower formula (II)：The invention further relates to application of the catalyst in olefin metathesis reaction.The present invention is connected directly imidazolium ionic liquid group and N heterocyclic carbone catalysts, and imidazolium ionic liquid group is enable to be able to more effectively play its characteristic property, to reach the catalytic efficiency and catalyst stability that improve catalyst.
Description
The application be " on March 29th, 2017 " applying date, application No. is " 2017101955460 ", entitled " contain
Have the N- heterocycle carbine ruthenium catalysts and preparation method thereof of imidazolium ionic liquid group " application for a patent for invention division Shen
Please.
Technical field
The present invention relates to it is a kind of it is novel containing ionic liquid group N- heterocycle carbine ruthenium catalysts and preparation method thereof and
Using more particularly to it is a kind of being directly accessed imidazolium ionic liquid group on the N- heterocyclic carbene ligands of metal complex, this
Imidazolium ionic liquid group is just set to effectively act as improving stability and the effect of catalytic efficiency of catalyst.
Background technology
The homogeneous catalyst of olefin metathesis reaction is the important tool of Synthetic Organic Chemistry, and being widely used in various has
In machine study on the synthesis and industrial production.Wherein ruthenium homogeneous catalyst is the olefin metathesis catalyst being most widely used at present.
Research in terms of organic synthesis includes small molecule pharmacy, bio-pharmaceuticals, the preparation of organic intermediate, natural products
Synthesis, high molecular material etc..Industrial production application includes biological insecticides, personal skin or hair care articles for use, new material, system
Medicine industry etc..It has many advantages, such as：It is active high, not only to air-stable, in the presence of water, acid, alcohol or other solvents still
Very high catalytic activity so can be kept, and has very strong applicability to the various functional groups that alkene carries.
Mainly the structure with generality ruthenium catalyst is as shown in Figure 1 for it：
Although ruthenium catalyst have catalytic performance it is good many advantages, such as, there is catalyst it is of high cost and reaction after urge
Agent is difficult to the problem of removing.In order to overcome ruthenium catalyst, these are insufficient, researcher using a kind of emerging ionic liquid and
The technology that catalyst is combined can increase the activity of catalyst and extend catalyst life.So that one can only be used originally
Secondary ruthenium catalyst becomes the catalyst that can be recycled for multiple times, to achieve the purpose that reduce catalyst cost；In addition,
It is easier to detach 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 detach mesh
's.
According to the literature, ionic liquid group is connected in two kinds of different ligands.It is most common 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. it reports and imidazolium ionic liquid group IL-1 is introduced into ruthenium urges
On the positions 5- 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 in magazine SYNLETT 2008,12,1805-1808 about by same imidazoles
Ionic liquid group is introduced on the positions 3- of ruthenium catalyst C-2a；Later Chen, S-W and Lee, S-g et al. exist
Imidazolium ionic liquid group is connected on the positions 2- of catalysis C-2a by Tetrahedron 2009,65,3397-3403.About
Two kinds are that imidazolium ionic liquid group is connected on alkyl phosphorus ligand by Consorti C-S. et al., please refer to magazine
J.Org.Lett,2008,10,237-240。
This catalyst for ionic liquid group being connected to different ligands, repeatedly use performance still there is
Some difference：Ionic liquid group, which is linked into the catalyst in alkoxy benzene ligand and is typically exhibited, preferably repeatedly to be made
With number, and the catalyst being connected on alkyl phosphorus ligand can be limited by certain reactants and solvent, and otherwise its cycle is urged
Change ability declines.
Invention content
The key problem of ionic liquid and ruthenium catalyst combined technology is how to solve ionic liquid group to be catalyzed with ruthenium
Agent is exactly preferably to be combined problem with catalytic center.The two combines closer, and ionic liquid group can
Preferably guard catalyst enhances its catalytic activity and delay 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
A 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 sequence>Vinylidene ligand>Alkyl phosphorus is coordinated
Body.The binding ability sequence of above-mentioned each ligand is more readily understood that by looking back olefin metathesis reaction mechanism；Mechanism of catalytic reaction：
First, it is combination of the alkyl phosphorus ligand departing from ruthenium catalytic center, forms the intermediate with catalytic activity；Then, in this
Mesosome is reacted with the double bond on reactant olefin, and new vinylidene reactive intermediate is formed after substituted ethylene pitches ligand；Most
Afterwards, it is reacted again with the double bond of reactant olefin, generates new ruthenium catalytic center and product.It can from mechanism of catalytic reaction
Going out alkyl phosphorus ligand and vinylidene ligand all will successively be detached from ruthenium catalytic center, and only N- heterocycle carbines ligand is always
It is in conjunction.
Although (1) kind ligand i.e. vinylidene ligand and the will be connected at present containing imidazolium ionic liquid group by having
(2) it plants ligand, that is, alkyl phosphorus ligand or corresponds the report of this catalyst containing imidazolium ionic liquid on part
Road, preparation method are synthesis ligands containing imidazolium ionic liquid first, are then replaced with containing the ionic liquid ligand
The ligand of ionic liquid is free of on ruthenium catalyst accordingly, and obtains both catalyst described above.But due to
(3) kind ligand, that is, N- heterocycle carbines ligand and ruthenium catalytic center binding ability is too strong, thus in preparation use (1) and
(2) similar method uses method of the substitution of ligand containing ionic liquid without ionic liquid ligand, can not 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 been prepared on N- heterocycle carbines by further investigation containing imidazolium ionic liquid group
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 the effect detached.
Then, the present invention first aspect provide it is a kind of on N- heterocycle carbines containing imidazolium ionic liquid group
Ruthenium catalyst, the ruthenium catalyst are the compound with structure shown in formula (I)：
Wherein：
L is neutral electron ligand, and the neutrality electron ligand is selected from by C3-C20Three substitution alkyl phosphorus bases of a carbon,
C3-C20Alkoxy, the C of a carbon6-C20The aryloxy group of a carbon has C1To C20Alkyl thioether group or have C0To C20Alkane
One group of the group of the pyridyl group composition of base；
R1、R2、R3、R4、R5And R6It is each independently H, R group or first organic substitution with 1 to 20 carbon atom
Base, first organic substituent are selected from by C1-C20Alkyl, C1-C20Alkoxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20
Alkyl-carbonyl, C7-C20Aryl carbonyl, C1-C20Amide groups and C3-C8The group of cyclic group composition；R1、R2、R3、R4、R5And R6In
At least one group is R group；Preferably, R2And R3It is asynchronously H, it is further preferred that R2And R3At least one of for institute
State the first organic substituent；Also it is preferred that R4And R6It is asynchronously H, it is further preferred that R4And R6At least one of be
First organic substituent；
R7For first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenylindan alkenylene；And R7
It is not H and R group；
The R group has 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 integer of 0 to 10, 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 R11It is each independently H or the second organic substituent, 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 preparing ruthenium catalyst in second aspect, the method includes：(1) chemical combination is synthesized
Object 1；And compound 3 is synthesized by compound 2；(2) compound 4 is synthesized by compound 1 and compound 3；(3) it is synthesized by compound 4
Compound 5；(4) compound 6 is synthesized by compound 5；(5) compound 7-I is synthesized by compound 6；(6) it is synthesized by compound 7-I
Compound 7-II；(7) compound 8 or compound 9 as ruthenium catalyst are synthesized by compound 7-II；Wherein, compound 1 is to change
The structural formula for closing object 7 is as follows：
Compound 8 is selected from the group being made of following compound 8a, 8b, 8c and 8d：
The compound 9 is as follows：
The present invention provides ruthenium catalyst or second aspect of the present invention described in first aspect present invention in the third aspect
Ruthenium catalyst made from the method reacts especially in olefin metathesis using the alkene derived from vegetable oil such as cottonseed oil as instead
Object is answered to carry out the application in olefin metathesis reaction, it is preferred that the cycle applications in olefin metathesis reaction.
The present invention by imidazolium ionic liquid group with the N- heterocycle carbine ligands of ruthenium catalyst be combined to be formed it is new
Ruthenium catalyst (referred to herein as imidazolium ionic liquid base-ruthenium catalyst).This novel imidazolium ionic liquid base-ruthenium
Catalyst shows increased catalyst activity and extended catalyst life in the reaction of such as olefin metathesis, and is reacting
It is easy to detach from reaction mixture later, regenerates and recycle.
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 the ruthenium catalyst being in the prior art connected to ionic liquid group in two kinds of different ligands；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
It is obtained in base benzene ligand；The ruthenium catalyst on the right is second of imidazole ion liquid catalyst, wherein by ionic liquid base
Group is connected on 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 implementation mode
The present invention provides a kind of ruthenium containing imidazolium ionic liquid group on N- heterocycle carbines in first aspect and urges
Agent, which is characterized in that the ruthenium catalyst is the compound with structure shown in formula (I)：
Wherein：
L is neutral electron ligand, and the neutrality electron ligand is selected from by C3-C20Three substitution alkyl phosphorus bases of a carbon,
C3-C20Alkoxy, the C of a carbon6-C20The aryloxy group of a carbon has C1To C20Alkyl thioether group or have C0To C20Alkane
Base (indicates C1To C20Alkyl or H) pyridyl group composition group a group；L optionally with R7It is cyclic or not cyclic,
Such as five-membered ring or hexatomic ring.
R1、R2、R3、R4、R5And R6It is each independently H, R group or first organic substitution with 1 to 20 carbon atom
Base, first organic substituent are selected from by C1-C20Alkyl, C1-C20Alkoxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20
Alkyl-carbonyl, C7-C20Aryl carbonyl, C1-C20Amide groups and C3-C8The group of cyclic group composition；R1、R2、R3、R4、R5And R6In
At least one group is R group；Preferably, R2And R3It is asynchronously H, it is further preferred that R2And R3At least one of for institute
State the first organic substituent；R4And R6It is asynchronously H, it is further preferred that R4And R6At least one of organic taken for described first
Dai Ji；
R7For first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenylindan alkenylene；And R7
It is not H and R group；R7It is optionally cyclic or not cyclic with L, such as five-membered ring or hexatomic ring, this depend on specific L groups and
R7Group.
The R group has 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 integer of 0 to 10, 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 R11It is each independently H or the second organic substituent, second organic substituent is selected from by C1-
C20Alkyl, C6-C20Aryl and C3-C8The group of cyclic group composition.
Hereafter some specific implementation modes of the 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 ligands, such as can be selected from by C3-C20Three substitution alkyl phosphorus bases, the C of a carbon3-C20
Alkoxy, the C of a carbon6-C20One group of the group that aryloxy group, thiosubstituents group or the pyridyl group of a carbon form.
In some embodiments, L groups are C3-C20Alkyl phosphorus base, for example, have 3,4,5,6,7,8,9,10,11,
12, the alkyl phosphorus of 13,14,15,16,17,18,19 or 20 carbon atoms, such as thricyclohexyl phosphorus base (PCy3-).In addition preferred
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 tertiary butyl), n-pentyl, isopentyl,
N-hexyl, isohesyl.
In some embodiments, L groups are C3-C20Alkoxy, for example, have 3,4,5,6,7,8,9,10,11,12,
13, the alkoxy of 14,15,16,17,18,19 or 20 carbon atoms.Preferably, the alkoxy is C3-C12Alkoxy,
More preferably C3-C6Alkoxy, for example, propoxyl group, isopropoxy, n-butoxy, isobutoxy (such as sec-butoxy or
Tert-butoxy), n-pentyloxy, isoamoxy, positive hexyloxy, dissident's oxygroup.
In some embodiments, L groups are C6-C20Aryloxy group, for example, have 6,7,8,9,10,11,12,13,14,
15, the aryloxy group of 16,17,18,19 or 20 carbon atoms.Preferably, the aryloxy group is C6-C12Aryloxy group；More preferably
Be C6-C9Aryloxy group, for example, phenoxy group, benzyloxy, phenethyl oxygroup or phenylpropyl oxygroup.
In some embodiments, L groups are with C1To C12Alkyl thioether group, for example, have 1,2,3,4,5,
6, the thioether group of the alkyl of 7,8,9,10,11 or 12 carbon atoms, the more preferably alkyl with 1,2,3,4,5 or 6 carbon atom
Thioether group.
In some embodiments, L groups are with C3To C12Alkyl pyridyl group, such as with 1,2,3,4,5 or 6
The thioether group of the alkyl of a carbon atom..
In some preferred embodiments, L groups are isopropoxy and and R7Group forms 6 membered rings or tricyclohexyl phosphine
Base.
R1To R6Group
R1、R2、R3、R4、R5And R6It is each independently H, R group or first organic substitution with 1 to 20 carbon atom
Base, first organic substituent are selected from by C1-C20Alkyl, C1-C20Alkoxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20
Alkyl-carbonyl, C7-C20Aryl carbonyl, C1-C20Amide groups and C3-C8The group of cyclic group composition；R1、R2、R3、R4、R5And R6In
At least one group is R group；Preferably, R2And R3It is asynchronously H it is further preferred that R2And R3At least one of for institute
State the first organic substituent；R4And R6It is asynchronously H and R4And R6At least one of be first organic substituent；About R
Group will be described separately below.
About 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,
12, the alkyl of 13,14,15,16,17,18,19 or 20 carbon atoms, for example, methyl, ethyl, propyl, butyl, amyl, hexyl,
Heptyl, octyl, nonyl, certain herbaceous plants with big flowers base, undecyl, dodecyl, myristyl, cetyl, octadecyl or eicosyl.Institute
State alkyl be preferably methyl, ethyl, propyl, isopropyl, butyl, isopropenyl, amyl, isopentyl, hexyl or isohesyl (such as
Cyclohexyl)；Further preferably methyl, ethyl, propyl 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,
12, the alkoxy of 13,14,15,16,17,18,19 or 20 carbon atoms, for example, methoxyl group, ethyoxyl, propoxyl group, butoxy,
Amoxy, hexyloxy, oxygroup in heptan, octyloxy, nonyl epoxide, certain herbaceous plants with big flowers oxygroup, 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 oxygroup (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,
16, the aryl of 17,18,19 or 20 carbon atoms, for example, phenyl, carry 1 C1To C14The phenyl of alkyl substituent carries 2
C1To C13The phenyl of alkyl substituent carries 3 C1To C12The phenyl of alkyl substituent carries 4 C1To C11Alkyl substituent
Phenyl, carry 5 C1To C10The phenyl of alkyl substituent.Preferably, phenyl, 1 to 3 C is carried on phenyl ring1To C3Alkane
The phenyl of base, such as benzyl, phenethyl or phenylpropyl.
As first organic substituent, the C6-C20Aryloxy group be, for example, with 6,7,8,9,11,12,13,14,
15, the aryloxy group of 16,17,18,19 or 20 carbon atoms, for example, phenoxy group, carry 1 C1To C14The benzene oxygen of alkyl substituent
Base carries 2 C1To C13The phenoxy group of alkyl substituent carries 3 C1To C12The phenoxy group of alkyl substituent carries 4 C1
To C11The phenoxy group of alkyl substituent carries 5 C1To C10The phenoxy group of alkyl substituent.Preferably, phenoxy group, on phenyl ring
With 1 to 3 C1To C3Alkyl phenoxy group, such as benzyloxy, benzene ethyoxyl or phenylpropyl alcohol oxygroup.
As first organic substituent, the C2-C20Alkyl-carbonyl be, for example, with 2,3,4,5,6,7,8,9,11,
12, the alkyl-carbonyl of 13,14,15,16,17,18,19 or 20 carbon atoms, the moieties in the alkyl-carbonyl can example
Such as it is methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, certain herbaceous plants with big flowers base, undecyl, dodecyl, 14
Alkyl, cetyl or octadecyl.The alkyl is preferably methyl, ethyl, propyl, isopropyl, butyl, isopropenyl, penta
Base, isopentyl, hexyl or isohesyl (such as cyclohexyl)；Further preferably methyl, ethyl, propyl or isopropyl；Into 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,
15, the aryl carbonyl of 16,17,18,19 or 20 carbon atoms, the aryl moiety in the aryl carbonyl can have substituent group,
Such as the alkyl substituent of 1,2,3,4,5,6,7,8,9,11,12 or 13 carbon atoms is carried on phenyl ring.Preferably, the alkyl
Substituent group be methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, certain herbaceous plants with big flowers base, undecyl, dodecyl,
Tridecyl, more preferably methyl, ethyl, propyl, isopropyl, butyl, isopropenyl, amyl, isopentyl, hexyl or isohesyl
(such as cyclohexyl), it is further preferred that methyl, ethyl, propyl or isopropyl；It is even furthermore preferable that methyl or ethyl,
Most preferably methyl, that is, the C7-C20Aryl carbonyl is carbobenzoxy.
As first organic substituent, the C1-C20Amide groups for example can be not surpass in total with carbon atom number
Cross the alkyl substituent of 19 carbon atoms, for example, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl,
Certain herbaceous plants with big flowers base, undecyl, dodecyl, myristyl, cetyl or the amide groups of octadecyl substitution, preferably methyl, second
Base, propyl, butyl, amyl or the amide groups of hexyl substitution, the further preferably amide groups of methyl, ethyl or propyl substitution.
As first organic substituent, the C3-C8Cyclic group be, for example, be saturated or undersaturated three-membered ring,
Four-membered ring, five-membered ring, hexatomic ring, heptatomic ring or octatomic ring, the five-membered ring being preferably saturated, hexatomic ring or heptatomic ring.
R1、R2、R3、R4、R5And R6In 1,2,3,4,5 or 6 group can be R group；Preferably 2 groups are for example
R1And/or R5It is R group；Further preferably 1 group such as R1Or R5It is R group, most preferably, R1It is R group.
In R1、R2、R3、R4、R5And R6In, other than the group as R group, other groups preferably independently be H or
The first organic substituent with 1 to 20 carbon atom.In some embodiments, the other groups independently are H or tool
There is the alkyl of 1 to 6 carbon atom.In some preferred embodiments, the other groups independently are with 1 to 6 carbon
The alkyl of atom.In some preferred embodiments, the other groups independently are the alkane with 1 to 3 carbon atom
Base such as methyl, ethyl, propyl or isopropyl, most preferably all methyl of the other groups.
In some preferred embodiments, R1And/or R5At least one of group be R group；And R2、R3、R4With
R6At least one of be methyl, at least two be methyl, at least three be methyl or all methyl.
In some preferred embodiments, the R1For R group, remaining all methyl.
R7Group
The R7Group can be above with respect to R1、R2、R3、R4、R5And R6First 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 R6First organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenyl
Indenes alkenylene；And R7It is not H and R group.Preferably, the first organic substituent is the alkyl with 1 to 6 carbon atom,
More preferably alkyl such as methyl, ethyl, propyl or isopropyl, most preferably methyl with 1 to 3 carbon atom.The C2Extremely
C20Alkylene is preferably the alkylene of C2 to C6, for example, vinyl, acrylic, allyl, cyclobutenyl, pentenyl or hexene
Base.
In some preferred embodiments, the R7Group is selected from phenyl, isopropenyl or phenylindan alkenylene composition
Group；
In some embodiments, the R7Group can be mutual indepedent with L groups；In other embodiments, institute
State R7Group can form arbitrary cyclic group together with L groups.
R group
In the ruthenium catalyst of the present invention, R1、R2、R3、R4、R5、R6In at least one be that there is knot shown in lower formula (II)
The R group of structure：
Y group
Y can be CH2, O, S, N or the first group, first group is selected from by C6To C20Aryl, C6To C20Aryloxy group,
C2To C20Alkyl-carbonyl, C7To C20Aryl carbonyl, C1To C20Amide groups, C3-C8A group in the group of cyclic group composition.
The C6To C20Aryl, C6To C20Aryloxy group, C2To C20Alkyl-carbonyl, C7To C20Aryl carbonyl, C1To C20Amide groups and C3-C8
Cyclic group is respectively such as above with respect to R1To R6The C6To C20Aryl, C6To C20Aryloxy group, C2To C20Alkyl-carbonyl, C7Extremely
C20Aryl carbonyl, C1To C20Amide groups and C3-C8Cyclic group, details are not described herein.
In some preferred embodiments, Y can be CH2, O, S or N, more preferable Y is O or S, most preferably O.
N values
N can be integer of 0 to 10, 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, further preferably 2 to 6 integer are still more preferably 2 to 4, most preferably 4；
X group
X can be fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；Preferably, X be fluorine, chlorine, bromine,
Iodine, PF6Or BF4, it is further preferred that X is PF6Or BF4, most preferably, X PF6。
R8、R9、R10And R11Group
R8、R9、R10And R11It is each independently H or the second organic substituent, 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,
12, the alkyl of 13,14,15,16,17,18,19 or 20 carbon atoms, for example, methyl, ethyl, propyl, butyl, amyl, hexyl,
Heptyl, octyl, nonyl, certain herbaceous plants with big flowers base, undecyl, dodecyl, myristyl, cetyl, octadecyl or eicosyl.Institute
State C1-C20Alkyl is preferably methyl, ethyl, propyl, isopropyl, butyl, isopropenyl, amyl, isopentyl, hexyl or isohesyl
(such as cyclohexyl)；Further preferably methyl, ethyl, propyl 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,
16, the aryl of 17,18,19 or 20 carbon atoms, for example, phenyl, carry 1 C1To C14The phenyl of alkyl substituent carries 2
C1To C13The phenyl of alkyl substituent carries 3 C1To C12The phenyl of alkyl substituent carries 4 C1To C11Alkyl substituent
Phenyl, carry 5 C1To C10The phenyl of alkyl substituent.Preferably, phenyl, 1 to 3 C is carried on phenyl ring1To C3Alkane
The phenyl of base, such as benzyl, phenethyl or phenylpropyl.
As second organic substituent, the C3-C8Cyclic group be, for example, be saturated or undersaturated three-membered ring,
Four-membered ring, five-membered ring, hexatomic ring, heptatomic ring or octatomic ring, the five-membered ring being preferably saturated, hexatomic ring or heptatomic ring.
In some specific embodiments, the ruthenium catalyst has structure shown in above-mentioned formula (I), wherein L groups
For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1、R2、R3、R4、R5And R6
It is each independently H, organic with the R group of structure shown in above-mentioned formula (II) or described first with 1 to 20 carbon atom
Substituent group, R1、R2、R3、R4、R5And R6At least one of group be R group, R2And R3Be asynchronously H and it is at least one be described
First organic substituent；R4And R6Be asynchronously H and it is at least one be first organic substituent；Y is CH2, O, S, N or institute
State the first group；N is integer of 0 to 10；X is fluorine, chlorine, bromine, iodine, PF6、BF4、NO3、CF3SO3Or N (SO2CF3)2；R8、R9、R10
And R11It is each independently second organic substituents of H or described.
In some specific embodiments, the ruthenium catalyst has structure shown in above-mentioned formula (I), wherein L groups
For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1、R2、R3、R4、R5And R6
It is each independently H, 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 R3Be asynchronously H and it is at least one be C1-C20Alkyl；R4And R6It is asynchronously H and at least one
A is C1-C20Alkyl；Y is CH2、O、S、N；N is integer of 0 to 10；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 structure shown in above-mentioned formula (I), wherein L groups
For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1、R2、R3、R4、R5And R6
It is each independently H, 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；Preferably, R2And R3It is asynchronously H, it is further preferred that R2And R3At least one of be C1-C6
Alkyl；Also it is preferred that R4And R6It is asynchronously H, it is further preferred that R4And R6At least one of be C1-C6Alkyl；Y is
CH2、O、S、N；N is integer of 0 to 10；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 structure shown in above-mentioned formula (I), wherein L groups
For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1、R2、R3、R4、R5And R6
It is each independently R group or C with structure shown in above-mentioned formula (II)1-C6Alkyl, R1、R2、R3、R4、R5And R6In at least
One group is R group；Y is CH2、O、S、N；N is integer of 0 to 10；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 structure shown in above-mentioned formula (I), wherein L groups
For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1And/or R5For with upper
State the R group of structure shown in formula (II), R2、R3、R4And R6Methyl, ethyl, propyl, isopropyl, butyl, isopropyl each independently
Alkenyl, amyl, isopentyl or hexyl or isohesyl；Y is O or S；N is integer of 0 to 10；X is PF6Or BF4；R8、R9、R10With
R11It is each independently methyl, ethyl, propyl, isopropyl, butyl, isopropenyl, amyl, isopentyl or hexyl or isohesyl.
In some specific embodiments, the ruthenium catalyst has structure shown in above-mentioned formula (I), wherein L groups
For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1And/or R5For with upper
State the R group of structure shown in formula (II), R2、R3、R4And R6It is each independently methyl, ethyl, propyl 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 or isopropyl.
In some specific embodiments, the ruthenium catalyst has structure shown in above-mentioned formula (I), wherein L groups
For isopropoxy or or thricyclohexyl phosphino-；R7For phenyl, isopropenyl or phenylindan alkenylene；R1For with above-mentioned formula
(II) R group of structure shown in, R2、R3、R4、R5And R6It is each independently methyl；Y is O；N is 4；X is PF6；R8、R9、R10With
R11For methyl.
In some preferred embodiments of the present invention, the ruthenium catalyst is selected from following 4 representative catalysis
The compound of agent structure：
The present invention provides the synthetic method of the ruthenium catalyst described in first aspect present invention in second aspect.Using existing
Method, imidazolium ionic liquid group can not be connected at all and the strongest N- heterocycle carbines of ruthenium catalytic center bonding energy power
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,
To be unable to get the ruthenium catalyst described in first aspect present invention.For the present inventor by further investigation, having finally found can be with
Obtain the synthetic method of the ruthenium catalyst described in first aspect present invention.
In some more specific embodiments, the method for preparing the ruthenium catalyst of the invention, the method includes：
(1) compound 1 is synthesized；And compound 3 is synthesized by compound 2；
(2) compound 4 is synthesized by compound 1 and compound 3；
(3) compound 5 is synthesized by compound 4；
(4) compound 6 is synthesized by compound 5；
(5) compound 7-I is synthesized by compound 6；
(6) compound 7-II is synthesized by compound 7-I；
(7) compound 8 or compound 9 as ruthenium catalyst are synthesized by compound 7-II；
Wherein, the structural formula of compound 1 to compound 7 is as follows：
Compound 8 is selected from the group being made of following compound 8a, 8b, 8c and 8d：
The compound 9 is as follows：
In some more specific embodiments, ruthenium catalyst of the invention is carried out by following synthetic route：
More specifically, described method includes following steps for second aspect of the present invention：
(1) make 2-methylimidazole and Isosorbide-5-Nitrae-dibromobutane reaction, obtain 1- (4- brombutyls) -2-methylimidazole, i.e. chemical combination
Object 1；
(2) 4- hydroxyls -2,6- dimethylaniline, glyoxal and 1, the reaction of 3,5- trimethylanilines is made to obtain 1- (4- hydroxyls
Base -2,6- dimethyl benzene) base -2- (1,3,5- trimethylbenzene) base-second diimine, i.e. compound 2；
(3) so that compound 2 is reacted with sodium borohydride, obtain 1- (4- hydroxyls -2,6- dimethyl benzene) base -2- (1,3,5- tri-
Methylbenzene) base-ethylenediamine, i.e. compound 3；
(4) so that compound 3 is reacted with compound 1, obtain 1- (2,6- dimethyl -4- (4- (2-methylimidazole base) fourth oxygen
Base) benzene) base -2- (1,3,5- trimethylbenzene) base-ethylenediamine, i.e. compound 4；
(5) make compound 4, triethyl orthoformate and hydrochloric acid reaction, obtain 1- (2,6- dimethyl -4- (4- (2- methyl miaows
Triazole hydrochloride base) butoxy) benzene) base -3- (1,3,5- trimethylbenzene)-imidazolium chloride, i.e. compound 5；
(6) make compound 5, sodium tert-butoxide and the reaction of tertiary butyl alcohol, obtain 1- (2,6- dimethyl -4- (4- (2- methyl miaows
Oxazolyl) butoxy) benzene) base -3- (1,3,5- trimethylbenzene) -2- tertiary butyl oxygen imidazolidines, i.e. compound 6；
(7) make compound 6 and iodomethane reaction, the salt compounded of iodine imidazole ion liquid-ligand 7- being had the following structure
I, i.e. compound 7-I：
(8) make compound 7-I and hexafluorophosphoric acid silver reaction, the hexafluorophosphate (PF being had the following structure6) imidazoles
Ionic liquid-ligand 7-II, i.e. compound 7-II：
(9) the Ge Labu catalyst reactions for making compound 7-II and first generation alkoxy benzal type, obtain the ruthenium and urge
Agent.
In some preferred embodiments, the Ge Labu catalyst of the first generation alkoxy benzal type is selected from by such as
The group of lower compound C-1a, C-1b, C-1c or C-1d composition：
And
To the ruthenium catalyst be respectively selected from by compound 8a, 8b, 8c, 8d and compound 9：
The present invention provides ruthenium catalyst or second aspect of the present invention system described in first aspect present invention in the third aspect
The ruthenium catalyst obtained is reacted in olefin metathesis especially carries out alkene using the alkene derived from vegetable oil such as cottonseed oil as reactant
Application in hydrocarbon displacement reaction, it is preferred that the cycle applications in olefin metathesis reaction.
The invention is further elaborated with reference to specific embodiment, following embodiments are only to illustrate the present invention
It the purpose of scheme rather than limits.
Embodiment 1：Imidazole ion liquid-ligand, 1- (2,6- dimethyl -4- (4- (1,2- methylimidazole alkali) fourths
Oxygroup) 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 added portionwise in tetrahydrofuran (40ml) solution, and (3.0g cleans 3 times to wash with n-hexane in advance
Remove dormant oil), a large amount of bubble is released after addition immediately.Continue stirring 60 minutes until bubble-free releasing is after adding sodium hydride
Only, the clear solution in reaction is slowly then transferred to another and has been previously heated to 70 DEG C, Isosorbide-5-Nitrae-dibromo fourth is housed
In alkane (10.7g, 50mmol) and 10ml tetrahydrofuran reaction bulbs；After transfer, the reaction was continued 4 hours；Utilize TLC plate (silica gel
Thin layer) judge the terminal reacted.It is cooled to room temperature after reaction, 30ml n-hexanes is added, wash 3 times (each 30ml),
Na2SO4It is dried overnight.Then, it removes solvent using Rotary Evaporators and and using vacuum condition removal impurity, obtains slightly light
Yellow liquid product 9.0g, yield 95.7%.Product can be directly used for reacting in next step without being further purified.
C8H13BrN2High resolution mass spec calculated value：216.0262；Measured value：216.0270.
Second diimine compounds 2, i.e. 1- (4- hydroxyls -2,6- dimethyl benzene) base -2- (1,3,5- trimethylbenzene) base-second two
Imines (hereinafter sometimes simply referred to as compound 2) synthesis：
Into reaction bulb be added 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 of the acetic acid equivalent such as addition terminates reaction after complete.Filtering solution, then the 75 volume % methanol/waters with 120ml
Solution washs the yellow solid being obtained by filtration on strainer in three times, finally retains yellow solid, is dried under reduced pressure acquisition yellow
Solid 7.1g.Gained yellow solid is containing there are three types of group with imine moiety：Bis- (1,3,5- trimethylbenzenes) base-second diimines of 1,2-, 1-
(4- hydroxyl -2,6- dimethyl benzenes) base -2- (1,3,5- trimethylbenzenes) base-ethylenediamine (object), bis- (the 4- hydroxyls bases-of 1,2-
2,6- dimethyl benzenes) base-second diimine.
Ethylene diamine compound 3, i.e. 1- (4- hydroxyls -2,6- dimethyl benzene) base -2- (1,3,5- trimethylbenzene) base-ethylenediamine
The synthesis of (hereinafter sometimes referred to compound 3)：
Sodium borohydride (3.8g, 5mmol) is added in 100ml single port bottles, gained contains in being then added from the reactions above
Three kinds of second diimine yellow mixture solids (7.1g) and tetrahydrofuran (30ml).It stirs at room temperature, methanol is added dropwise in three batches (altogether
10ml is added dropwise).Reaction generates 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, add
Enter 50ml water stopped reactions, dichloromethane 30ml is then added and is washed in separatory funnel three times, removes a layer yellow solution.
After anhydrous sodium sulfate is dried, removes solvent with rotary evaporator and obtain sticky mass.Under nitrogen protection with equipped with silicon
The separation post separation of glue is followed successively by successively to the liquid sterling ethylene diamine compound of three light grays by the sequence of separation：1,
Bis- (1,3,5- trimethylbenzenes) bases-ethylenediamine of 2-, 1- (4- hydroxyl -2,6- dimethyl benzenes) base -2- (1,3,5- trimethylbenzenes) base -
Bis- (4- hydroxyl -2,6- dimethyl benzenes) bases-ethylenediamine of ethylenediamine, 1,2-.The 1- (4- hydroxyl -2,6- dimethyl benzenes) wherein purified
Base -2- (1,3,5- trimethylbenzene) base-ethylenediamine liquid, weight 1.7g.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 the conditions of nitrogen protection, 1- (4- hydroxyls -2,6- dimethyl benzene) base -2- (1,3,5- tri- is added into reaction bulb
Methylbenzene) base-ethylenediamine (6.0g, 20mmol), cesium carbonate Cs2CO3(6.8g, 22mmol) solid and the dried second of 60ml
Nitrile.It is stirred 30 minutes in room temperature oil bath, then by oil bath heating to 50 DEG C, 1- (4- brombutyls) -2-methylimidazole is added dropwise
The solution of (4.34g, 20mmol) in 20ml acetonitriles, is warming up to reflux after completion of dropwise addition, continue stirring 3 hours, utilize TLC plates
Judge the terminal of reaction.When reactant is naturally cooled to environment temperature after reaction, 30ml is added and contains 0.5g hydroxides
(3x50ml) is washed with water to neutrality in sodium water solution and toluene 30ml, fully shake, isolated organic layer；By drying, very
The lower solvent evaporated of sky, obtains the compound 4 of light gray viscous liquid, weight 7.4g, yield 86%.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 chlorides (hereinafter sometimes referred to compound 5) synthesis:
Imidazole radicals-ethylene diamine compound 4 (4.34g, 10mmol) is dissolved in 40ml toluene, primitive nail is added to the solution
Triethylenetetraminehexaacetic acid ester (6.0g) and 20% hydrochloric acid solution (3.65g).Reaction bulb equipped with distilling apparatus is heated to 80 DEG C, with reaction
Progress constantly there is solvent and by-product to be distilled out of, the terminal of reaction is judged with TLC plates, after reaction, uses reduced pressure handle instead
The distillations such as solvent are clean, and simultaneous reactions liquid becomes white solid, stood after then naturally cooling to environment temperature.To white solid
It is impregnated and is filtered with 20ml n-hexanes, retain white solid, altogether in triplicate；Lower drying is finally depressurized, canescence chemical combination is obtained
5 solid of object, weight 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- tertiary butyl oxygen imidazolidines (hereinafter sometimes referred to compound 6) synthesis：
Imidazole hydrochloride-imidazolium chloride 5 (2.0g, 3.86mmol) is added into dried reactor, 20ml is dry
It is dry to cross tetrahydrofuran and 10ml n-hexanes.Under nitrogen protection, room temperature opens stirring, by 15% sodium tert-butoxide-t-butanol solution
(3.0ml) (a concentration of 15 weight/volume % of the tertiary butyl sodium in tertiary butyl alcohol) is added drop-wise in said mixture.With dropwise addition
Carry out reaction dirty solution graduate into yellow solution, continue to react at room temperature 1-2 hours after dropwise addition, during which with TLC plates
To judge the terminal of reaction.(1x10ml) is washed with water in mixture after reaction, then dries and what is be obtained by filtration contains miaow
The solution of 6 product of oxazolyl-ligand.The solution is directly used in and is reacted in next step.C32H46N4O2High resolution mass spec calculate
Value：518.3621；Measured value：518.3598.
1- methylimidazoles ionic liquid-ligand 7,1- (2,6- dimethyl -4- (4- (1,2- methylimidazole alkali) fourths
Oxygroup) benzene) base -3- (1,3,5- trimethylbenzenes) -2- tertiary butyl oxygen imidazolidines (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 the imidazole radicals-ligand obtained from the reactions above is added, puts it in 0 DEG C of ice-water bath, is protected in nitrogen
Shield is lower to be added iodomethane CH3I(1.65g,11.6mmol).Ice-water bath then is withdrawn, reaction temperature is allowed to be maintained at room temperature, continues to stir
It mixes 2-3 hours, the terminal of reaction is judged with TLC plates.When steaming excessive CH under vacuum after reaction3I and molten
Then dried first 30ml is added in agent.Obtain the toluene solution of salt compounded of iodine 1- methylimidazoles ionic liquid-ligand 7-I.
C36H49N4O2High resolution mass spec calculated value：533.3850；Measured value：533.3861.
7-II) hexafluorophosphate (PF6) 1- methylimidazoles ionic liquid-ligand 7-II synthesis：This is a step imidazoles
The anion exchange reaction of ionic liquid.Under nitrogen protection, room gentle agitation, to obtaining ground salt compounded of iodine imidazoles in from the reactions above
Silver hexafluorophosphate (AgPF is added dropwise in the toluene solution of ionic liquid-ligand 7-I6, 1.0g, 3.96mmol) toluene solution, stir
It mixes overnight.Reaction mixture is filtered by diatomite after reaction, is washed 3 times, hexafluorophosphate (PF is obtained after dry6)
The toluene solution of 1- methylimidazoles ionic liquid-ligand 7-II.C30H43N4O2High resolution mass spec calculated value：
533.3850；Measured 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 7-II and the Ge Labu catalyst C-1a RuCl of first generation alkoxy benzal type2PCy3(=
CHC6H4OCH(CH3)2) (0.90g, 1.5mmol) be 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 impregnated and filtered more with methanol
Secondary cycle, until the raw material point (R on TLC platesfBe worth big point) disappear until, greenish solid product is dried in vacuo, miaow is obtained
Oxazolinium ion liquid-alkoxy benzal catalyst 8a, 1.0g, yield 74%.C39H52Cl2N4O2The high resolution mass spec of Ru calculates
Value：780.2511；Measured value：780.2498.1H NMR(300MHz,CDCl3)δppm:16.56 (s, 1H, Ru=CHAr), 7.48
(m, 1H, aromatic-CH), 7.46 (s, 1H, imidazolium-CH), 7.38 (s, 1H, imidazolium-CH), 7.09
(s,2H,mesityl aromatic-CH),7.00(s,2H,mesityl aromatic-CH),6.93(dd,1H,
Aromatic-CH), 6.85 (dd, 1H, aromatic-CH), 6.79 (d, 1H, aromatic-CH), 4.90 (m, 1H, (CH3)2CHOAr),4.18(m,4H,N(CH2)2N),4.08(t,2H,OCH2),4.05(t,2H,NCH2),3.77(s,3H,NCH3),
2.52(s,3H,CH3),2.48(m,12H,mesityl-CH3),2.40(s,3H,mesityl-CH3) 1.85 (m, 2H ,-
CH2CH2), 1.78 (m, 2H ,-CH2CH2-),1.27(d,6H,CH3)2CHOAr).Wherein, aromatic indicates aromatic radical,
Imidazolium indicates that imidazole radicals, Mesityl indicate mesitylene base.
B) synthesis of imidazole ion liquid-vinylidene catalyst 8b：Synthetic method is equally identical as 8a, only need to will be in reaction
First generation Ge Labu catalyst C-1a first generation type containing vinylidene as raw material Ge Labu catalyst C-1b
RuCl2(PCy3)2(=CHCH=C (CH3)2) (1.23g, 1.5mmol) replace.It is reacted and post-processing by identical with 8a,
Brown solid imidazole ion liquid-vinylidene catalyst product 8b is obtained, it is 1.10g, yield 65% to measure weight.
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 as above-mentioned 8a, only need to be by the first generation Ge Labu catalyst C-1a as raw material in reaction
With the Ge Labu catalyst C-1c RuCl of first generation type containing benzal2(PCy3)2(=CHC6H5) (1.27g, 1.5mmol) next generation
It replaces.By the identical reactions of 8a and post-processing, brown solid imidazole ion liquid-benzal catalyst product 8c is obtained, measures weight
Amount is 1.19g, yield 69%.C54H79Cl2N4The high resolution mass spec calculated value of OPRu：1002.4412；Measured value：
1002.4431。
D) synthesis of imidazole ion liquid-phenylindan Asia alkene catalyst 8d：
Synthetic method is identical as above-mentioned 8a, only need to be by the first generation Ge Labu catalyst C- as raw material in reaction
1a, with the Ge Labu catalyst C-1d RuCl of first generation Asia containing phenylindan alkenes type2(PCy3)2(=C9H6(m)C6H5)
(1.38g, 1.5mmol) is replaced.By the identical reactions of 8a and post-processing, dark brown solid product imidazol ion liquid is obtained
Body-phenylindan Asia alkene catalyst 8d, it is 1.07g, yield 57% to measure weight.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 completely same synthetic method 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 it) reacts；Then according to
7-II full terms, which carry out reaction, can obtain accordingly 2 isopropyl imidazole ionic liquid-ligand containing hexafluorophosphate；
Finally by the Ge Labu catalyst C-1a RuCl of the toluene solution of the ligand and first generation alkoxy benzal type2PCy3(=
CHC6H4OCH(CH3)2) (0.99g, 1.6mmol) reaction, by methanol impregnate and filter purification and vacuum drying, 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 synthesis of imidazole ion liquid-alkoxy benzal catalyst 12 of 4 ionic liquid group ortho position substitution of embodiment：
The synthetic route and preparation method of ortho-substituent-midbody compound 11 are with compound 1-7's described above
It prepares identical, amino phenols of the ortho position with-OH groups i.e. compound 10 has only been used to replace 2-methylimidazole as initial
Raw material will obtain the midbody compound 11 of crucial ortho position substitution after carrying out identical seven steps reaction.
The synthesis of ortho position substitution-imidazolium ionic liquid catalyst 12：By the hexafluorophosphate (PF containing 0.18mmol6)
The Ge Labu catalyst of the toluene solution (volume 20ml) and first generation alkoxy benzal type of imidazole ion liquid-ligand 11
C-1a RuCl2PCy3(=CHC6H4OCH(CH3)2) (1.30g, 2.21mmol) be added in reaction bulb together.Reaction bulb is closed
Afterwards, it is put into 80 DEG C of oil bath, stirs lower reaction 60 minutes.Reaction terminates, and is evaporated all solvents under vacuum condition, residue
It is impregnated and is filtered with methanol, until the raw material point on TLC plates disappears, greenish solid product is dried in vacuo, ortho position is obtained
Substitution-imidazolium ionic liquid catalyst 12,1.38g, yield 68.5%.
C38H50Cl2N4O2The high resolution mass spec calculated value of Ru：766.2349；Measured value：766.2335.
The catalysis reaction of 5 catalyst olefin metathesis of embodiment
The pretreatment of 1- decene and ionic liquid：1) pretreatment of 1- decene, with ultrasonoscope by the appearance equipped with 1- decene
After device degasification 30 minutes, the deoxidant (BASF AG) of 5% weight is placed into, is kept for 24 hours under the conditions of sealing and being protected from light.
Oxygen agent is removed using preceding filtering under nitrogen protection, is then bubbled about 30 minutes with nitrogen again before.2) imidazole salts from
The pretreatment of sub- liquid, using preceding at 70 DEG C, by the reaction equipped with 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquids
Bottle vacuum drying 2 hours.Then is stirring and be cooled to room temperature under nitrogen protection.
1) in the presence of no ionic liquid, the olefin metathesis operation method of 1- decene conversion ratios：
Under nitrogen protection and stirring, into the reaction bulb equipped with continuous air-blowing device and condenser pipe, 1- decene is added
(7.0g, 50mmol), then puts it into the oil bath with heating function, and after temperature reaches 60 DEG C, catalyst C- is added
2a (0.1mmol, 0.2mol%).When reaction time proceeds to 10,20,40,60,120,240 minutes, take out 0.1ml's respectively
Sample carrys out the process of observing response.Obtained sample first crosses solution of the sodium hydroxide in toluene with a 30% ethyl alcohol tertiary butyl of drop
It is reacted to terminate catalysis, then with after 5ml dilution with toluene, the content of product is analyzed with gas chromatograph (GC).As a result see
Table 1 and Fig. 3.
The calculation formula of 1- decene conversion ratios：Conversion ratio %=100%- (decene molal quantity/whole product molal quantity) X
100%
Olefin metathesis operation method in the presence of imidazolium ionic liquid：
2) 1- decene conversion ratio changes with time
Under nitrogen protection and stirring, 1- decene (7.0g, 50mmol) and 1- butyl -3- ethyl imidazol(e) hexafluoro phosphorus will be housed
The reaction bulb of hydrochlorate ionic liquid (2.0ml) mixture is put into the oil bath of heating, after temperature reaches 60 DEG C, is separately added into general
Logical catalyst C-2a and imidazolium ionic liquid-catalyst 8a (being respectively 0.1mmol, 0.2mol%).Between when reacted into
Row by 10,20,40,60,120,240 minutes when, it is separately sampled come observing response process.Obtained sample is first with a drop 30%
Ethanolic sodium hydroxide solution terminates catalysis reaction, and to use volume using silica gel treatment and again be 9:1 n-hexane and ethyl acetate
Mixed solvent elution after, analyze the content of product with gas chromatograph (GC).As a result see table 1 and Fig. 3.
1. 1- decene conversion ratios of table change with time
Reaction to the generated 9- octadecylenes of itself olefin metathesis by 1- decene：It 1) is deposited in no ionic liquid by above-mentioned
It is left in the experiment with catalyst C-2a and 8a respectively with catalyst C-2a Catalysis experiments and 2) in imidazolium ionic liquid lower,
It can be readily seen that at 60 DEG C that speed that these three are reacted all are considerably fast from its result watch 1 and Fig. 1, when proceeding to 40
Respective conversion ratio just has reached the maximum value or very close maximum value when 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, into the 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid reaction bulbs equipped with 2ml,
It is added and passes through pretreated 1- decene (7.0g, 50mmol).After the mixture is heated to 60 DEG C in oil bath, catalysis is added
(catalyst includes typical catalyst C-2a, C-2c and imidazolium ionic liquid-catalyst for agent (0.10mmol, 0.20mol%)
8a、8c).It is reacted to 40 minutes and takes out sample immediately, then cool to room temperature, the analysis of product is carried out according to above-mentioned method.
Blended product passes through with catalyst reaction system as under type is easily detached：
1. reaction mixture extracts (4 X 30ml) with toluene, combined extract liquor is obtained with Rotary Evaporators solvent evaporated
To crude product；Containing micro ion liquid crude on silica gel layer filtering, then with volume ratio be 9:1 n-hexane and ethyl acetate
Mixed solvent elution layer of silica gel be thoroughly to remove contained micro ion liquid, can obtain sterling production by distillation and rectifying
Object.
2. the regeneration of imidazolium ionic liquid catalyst reaction system：Reaction mixture toluene is extracted 3 as described above
It is secondary, i.e., as next time recycle ionic liquid catalyst systems and directly can according to this part the above (i.e. " 1- last of the ten Heavenly stems
Alkene and olefin metathesis reacting middle catalyst recycle ") identical method carries out catalysis next time and reacts.Catalyst circulation uses
Result be summarized in table 2 and Fig. 4.
Table 2. olefin metathesis reaction cycle number and conversion ratio in imidazolium ionic liquid
N.D. it indicates to be not detected, be indicated with numerical value " 0 " in Fig. 4.
Representative catalyst 8a and 8c are selected from imidazolium ionic liquid-ruthenium catalyst 8a-d, have passed through 8 times
Catalytic activity only has dropped 8% and 9% respectively after circular response；And common catalyst C-2a and C-2c is recycled in first time
Later, the conversion ratio of activity-reaction of catalyst just significantly has dropped 52-59% (second of cycle) and 80-87% (thirds
Secondary cycle).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, to make up common ruthenium catalyst well because being used only once
The deficiency of high cost of catalyst caused by and.
Claims (10)
1. a kind of ruthenium catalyst containing imidazolium ionic liquid group on N- heterocycle carbines, which is characterized in that the ruthenium is urged
Agent is the compound with structure shown in formula (I)：
Wherein：
L is neutral electron ligand, the neutrality electron ligand and R7Group is cyclic or not cyclic, and selected from by C3-C20
Three substitution alkyl phosphorus bases, the C of a carbon3-C20Alkoxy, the C of a carbon6-C20The aryloxy group of a carbon has C1To C20Alkyl sulphur
Ether has C0To C20Alkyl pyridyl group composition group a group；
R1、R2、R3、R4、R5And R6It is each independently H, R group or the first organic substituent with 1 to 20 carbon atom, and
And R1、R2、R3、R4、R5And R6At least one of group be R group, first organic substituent be selected from by C1-C20Alkyl,
C1-C20Alkoxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20Alkyl-carbonyl, C7-C20Aryl carbonyl, C1-C20Amide groups and
C3-C8The group of cyclic group composition；
R7For first organic substituent, C2To C20Alkylene, phenyl, isopropenyl or phenylindan alkenylene；And R7It is not
H and R group；
The R group has 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 integer of 0 to 10, 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 R11It is each independently H or the second organic substituent, 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 ligand, and the neutrality electron ligand is selected from by C3-C18Three substitution alkyl phosphorus bases, the C of a carbon3-C18
Alkoxy, the C of a carbon6-C18The aryloxy group of a carbon has C1To C12Alkyl thioether group or have 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；
R7For 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 R11It is each independently H or the second organic substituent, 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 ligand, and the neutrality electron ligand is selected from by C3-C18Three substitution alkyl phosphorus bases, the C of a carbon3-C6
Alkoxy, the C of a carbon6-C18The aryloxy group of a carbon has C1To C6Alkyl thioether group or have 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；
R7For 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 R11It is each independently H or the second organic substituent, 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 ligand, and the neutrality electron ligand is selected from by C3-C18Three substitution alkyl phosphorus bases, the C of a carbon3-C6
Alkoxy, the C of a carbon6-C18The aryloxy group of a carbon has C1To C3Alkyl thioether group or have 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；
R7For C1-C3Alkyl, C1-C3Alkoxy, phenyl, phenoxy group, C2-C5Alkyl-carbonyl, C7-C10Aryl carbonyl, C1-C3Amide
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 R11It is each independently H or the second organic substituent, 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, the C of a carbon3-C6Alkoxy, the C of a carbon6-C18The aryloxy group of a carbon has C1To C3
Alkyl thioether group or have C3To C6Alkyl pyridyl group 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；
R7For C1-C3Alkyl, C1-C3Alkoxy, phenyl, phenoxy group, C2-C5Alkyl-carbonyl, C7-C10Aryl carbonyl, C1-C3Amide
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 R11It is each independently H or the second organic substituent, 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 group 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. according to any one of claim 1 to 6 ruthenium catalyst, 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 the alkyl with 1 to 6 carbon atom.
8. according to any one of claim 1 to 6 ruthenium catalyst, 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 alkyl with 1 to 6 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 a carbon atom；
Preferably, L groups are CH (CH3)2O- or PCy3-；R1And R5At least one of group be R group, remaining group is only
It is on the spot H or the alkyl with 1 to 6 carbon atom, R7Group is phenyl, isopropenyl or phenylindan alkenylene；Y is O or S；n
Integer between being 2 to 6；X is fluorine, chlorine, bromine, iodine, PF6、BF4Or NO3；R8To R11It independently is H or there is 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 the alkyl with 1 to 6 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 there is 1 to 6 carbon
The alkyl of atom；
It may further be preferable that L groups are CH2(CH3)2O- or PCy3-；R1Or R5For R group, R1、R2、R3、R4、R5And R6In
Remaining group is H, methyl, ethyl, propyl 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 or isopropyl；
It is even furthermore preferable that L groups are CH2(CH3)2O- or PCy3-；R1For R group, R2、R3、R4、R5And R6For methyl, R7
Group is phenyl, isopropenyl or phenylindan alkenylene；Y is O；N is 4；X is PF6；R8To R11For methyl.
9. method according to any one of claim 1 to 8, it is characterised in that：
R2And R3It is asynchronously H, it is preferred that R2And R3At least one of be first organic substituent；And/or
R4And R6It is asynchronously H, it is preferred that R4And R6At least one of be first organic substituent.
10. ruthenium catalyst according to any one of claim 1 to 8 is reacted in olefin metathesis especially to derive from vegetable oil
Such as the application in the olefin metathesis reaction that carries out as reactant of the alkene of cottonseed oil；Preferably, in the olefin metathesis
Cycle applications in reaction.
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| CN104307571A (en) * | 2014-09-14 | 2015-01-28 | 中国科学院福建物质结构研究所 | Precious metal Carbene polymer catalysts and its preparation method and use |
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