CN106939026A - A kind of preparation and its application of ruthenium metal olefin metathesis catalyst - Google Patents
A kind of preparation and its application of ruthenium metal olefin metathesis catalyst Download PDFInfo
- Publication number
- CN106939026A CN106939026A CN201710139013.0A CN201710139013A CN106939026A CN 106939026 A CN106939026 A CN 106939026A CN 201710139013 A CN201710139013 A CN 201710139013A CN 106939026 A CN106939026 A CN 106939026A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- solvent
- reaction
- olefin metathesis
- alkyl
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 142
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000005865 alkene metathesis reaction Methods 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims description 31
- 150000001336 alkenes Chemical group 0.000 claims abstract description 42
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 12
- 230000000977 initiatory effect Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 126
- 238000006243 chemical reaction Methods 0.000 claims description 105
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 75
- -1 nitro, amino Chemical class 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 37
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 150000002431 hydrogen Chemical class 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000005292 vacuum distillation Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 229910052794 bromium Inorganic materials 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 16
- 229910052740 iodine Inorganic materials 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 150000002170 ethers Chemical class 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- YIKMRTHKLRXOBU-UHFFFAOYSA-N bromomethane;triphenylphosphane Chemical compound BrC.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YIKMRTHKLRXOBU-UHFFFAOYSA-N 0.000 claims description 10
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 230000004044 response Effects 0.000 claims description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 7
- 230000021736 acetylation Effects 0.000 claims description 7
- 238000006640 acetylation reaction Methods 0.000 claims description 7
- 229940113088 dimethylacetamide Drugs 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 150000008282 halocarbons Chemical class 0.000 claims description 7
- 150000001350 alkyl halides Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 150000002825 nitriles Chemical group 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- 238000007239 Wittig reaction Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000005864 Sulphur Chemical group 0.000 claims description 2
- 238000005917 acylation reaction Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 238000004220 aggregation Methods 0.000 claims description 2
- 238000011938 amidation process Methods 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 24
- 150000001993 dienes Chemical class 0.000 abstract description 20
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 abstract description 9
- 239000003814 drug Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 150000001923 cyclic compounds Chemical class 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 113
- 239000000543 intermediate Substances 0.000 description 74
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 63
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 38
- 239000000047 product Substances 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000012043 crude product Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 0 Cc1cc(C)c(*(C=CN2c3c(C)cc(C)cc3C)C2=*(Cl)Cl)c(C)c1 Chemical compound Cc1cc(C)c(*(C=CN2c3c(C)cc(C)cc3C)C2=*(Cl)Cl)c(C)c1 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000006798 ring closing metathesis reaction Methods 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 239000001119 stannous chloride Substances 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 5
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical group ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- REXUYBKPWIPONM-UHFFFAOYSA-N 2-bromoacetonitrile Chemical compound BrCC#N REXUYBKPWIPONM-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 150000002678 macrocyclic compounds Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 239000011984 grubbs catalyst Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 125000006178 methyl benzyl group Chemical group 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 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
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- 240000000203 Salix gracilistyla Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- GNHQSAUHXKRQMC-UHFFFAOYSA-N benzene;chlorine Chemical compound [Cl].C1=CC=CC=C1 GNHQSAUHXKRQMC-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
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- 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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/04—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with only hydrogen atoms, halogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D225/00—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom
- C07D225/02—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom not condensed with other rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- 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
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- 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
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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Abstract
The invention discloses a kind of ruthenium metal olefin metathesis catalyst of new alkene part and ruthenium Cabbeen formation and its application.The present invention is initiation material from the salicylide containing substituted radical that is simple in construction, being easy to get, and facile syntheesis obtains required alkene part, and the alkene part carries out ligand exchange with catalyst precarsor again, that is, obtains corresponding new metal ruthenium catalyst.Such catalyst efficiently promoting olefin metathesis can be reacted, and cyclic compound and catalysis dicyclopentadiene progress ring opening metathesis polymerization are obtained for being catalyzed the cultural care of multiple types alkadienes.This method raw material is easy to get, simple to operate, and process stabilizing is environment-friendly, is adapted to amplification production, to prepare various big ring class drug molecules and super performance macromolecular material there is provided a kind of good thinking and method using this olefin metathesis catalyst.
Description
Technical field
The invention is related to a kind of preparation method and applications of olefin metathesis catalyst, particularly a kind of ruthenium metal catalytic
The preparation method of agent and its catalysis alkadienes substrate carry out cultural care in and catalysis dicyclopentadiene opened
The application of ring metathesis polymerization reaction.
Technical background
In recent decades, the research of olefin metathesis reaction is because its synthetic product is in fields such as medicine, agricultural chemicals and materials
Substantial worth and obtain rapid development.And cyclization double decomposition (Ring-closing metathesis, abbreviation RCM) is reacted
It is a kind of important kind of olefin metathesis reaction, because of its distinguishing feature in terms of various macrocycle molecules are synthesized, has obtained
Increasing concern.It makes compound cyclization there is provided the important of synthesis of cyclic organic compound by building carbon-to-carbon double bond
Means.At present, some macrocyclic compounds are applied as medicine in clinic, and more macrocyclic compounds are then
It is among the corresponding medicament research and development stage (Nature, 2008,7,608-624).Ring-opening metathesis polymerization (Ring-opening
Metathesis polymerization, abbreviation ROMP) reaction be olefin metathesis reaction another important kind.The neck
The research in domain is concentrated mainly on the ROMP catalysts of synthesizing efficient and prepares multi-functional new material side based on ROMP reactions
Face (Macromolecules, 2012,45,4447-4453), researchers investigated large quantities of tools using ROMP reactions
There are the novel high polymer material of excellent properties, such as polydicyclopentadiene, polynorbornene and polycyclic octene etc..
The catalyst of olefin metathesis reaction generates a variety of types by development for many years, and Cabbeen type is catalyzed
Agent is the most important RCM catalyst of current research and development.In this kind of catalyst, most important and application it is most be
Schrock catalyst (J.Am.Chem.Soc.1990,112,3875-3886) and Grubbs catalyst (Bioorganic＆
Medicinal Chemistry, 2001,9 (1), 199-209) and the Hoveyda- that is modified Grubbs catalyst
Grubbs catalyst, Grela catalyst and ZhanShi catalyst.The present invention has synthesized the new ruthenium metal olefin polymerization of a class
It is simultaneously applied in catalysis alkadienes substrate progress cultural care by catalyst.
The content of the invention
It is contemplated that be initiation material from the enough salicylides simply replaced of knot, required for easily obtaining
Alkene part, resulting alkene part carries out ligand exchange with catalyst precarsor again can access corresponding New Ruthenium metal catalytic
Agent.Such catalyst efficiently promoting olefin metathesis can be reacted, and cyclization double decomposition is carried out for various catalysis alkadienes substrates
The big ring class organic molecule of reaction synthesis, can also be used for catalysis dicyclopentadiene polymerisation and obtains high performance polymer material
Material.This method raw material is easy to get, simple to operate, and process stabilizing is environment-friendly, is adapted to amplification production, is that alkene part and ruthenium Cabbeen are urged
Agent and prepare big cyclic agent molecule using this olefin metathesis catalyst and super performance macromolecular material is provided
A kind of good thinking and method.
The invention provides a kind of ruthenium metal olefin metathesis catalyst, it is characterised in that：Concrete structure formula is as follows：
Wherein, R1For hydrogen, alkyl, aryl；
R2For hydrogen, alkyl, aryl；
R3For hydrogen, alkyl, aryl；
R4For hydrogen, alkyl, aryl；
R5For hydrogen, alkyl, aryl；
R1' it is hydrogen, alkyl, aryl；
R2' it is hydrogen, alkyl, aryl；
R3' it is hydrogen, alkyl, aryl；
R4' it is hydrogen, alkyl, aryl；
R5' it is hydrogen, alkyl, aryl；
R7For hydrogen, alkyl, aryl；
L is halogen；
Y is oxygen or sulphur；
Z1For any on phenyl ring or several substituted halogens (preferably：Chlorine, bromine, iodine), nitro, amino, aryl, alkyl, alkane
Epoxide；
Z2For hydrogen, alkyl, aryl.
Abovementioned alkyl preferably is selected from the straight or branched alkyl that carbon number is no more than 6, such as：Methyl, ethyl, propyl group, together with two
Methyl (- CH (CH3)2)、-C(CH3)3,-pentane ,-n-hexane etc.；
Above-mentioned alkoxy preferably is selected from the alkoxy that carbon atom is no more than 6, such as：-OCH3,-OC2H5,-OC3H8,-OC4H9；
Above-mentioned aryl is preferably phenyl, benzyl, p-methylphenyl, p-methoxyphenyl, an aminomethyl phenyl, meta-methoxy benzene
Base, p-hydroxybenzene, to methyl-benzyl, to methoxy-benzyl, a methyl-benzyl, meta-methoxy benzyl etc.；
Above-mentioned R1、R2、R3、R4、R5、R1‘、R2‘、R3‘、R4‘、R5' for substituent that is identical or differing.
Above-mentioned Z1The preferably dibasic group of meta or ortho position.
Further, present invention also offers the preparation method of above-mentioned ruthenium metal olefin metathesis catalyst, its feature exists
In being realized by following steps：
Step 1: will be exposed in hydroxyl exposed in substituted salicylide or 2- thiosalicylic aldehyde by nitrile compounds
It is sulfhydryl protected；
Wherein, the structure of nitrile compounds is as follows：
The X1For electron-withdrawing group, such as：Halogen is (preferably：Chlorine, bromine, iodine), hydroxyl etc.；
The Y is oxygen or sulphur atom；
Step 2: by the carbonyl alkenyl in substituted salicylide；
The olefination is preferably Wittig reactions.
Step 3: the cyano group introduced in step one is obtained into amide compound by reduction and acylation reaction；
Amidation reagent employed in amidated process is the compound shown in following structure：
The X3For electron-withdrawing group, such as：Halogen is (preferably：Chlorine, bromine, iodine), hydroxyl etc.；
Step 4: the product of step 3 and catalyst precarsor reaction are obtained into target product.
The catalyst precarsor is generally Grubbs 2ndCatalyst precarsor.
Further, a kind of preparation method for ruthenium metal olefin metathesis catalyst that the present invention is provided, its specific work
Skill step is as follows：
Step 1-1, substituted salicylide, solvent, highly basic and nitrile compounds are added into reactor, be stirred at room temperature uniform
Afterwards, at a temperature of 20-80 DEG C, react 0.5-20 hours；
Above-mentioned highly basic is selected from sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, diisopropyl ethyl amine, potassium tert-butoxide, tertiary fourth
Sodium alkoxide, sodium hydride, hydrofining；It preferably is selected from the inorganic bases such as potassium carbonate, cesium carbonate or triethylamine, diisopropyl ethyl amine etc. organic
Alkali.
Above-mentioned solvent is selected from nitrile solvents, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), ether
Class solvent, alkane solvents, toluene, chlorobenzene, alkyl halide；It preferably is selected from acetonitrile, N,N-dimethylformamide, N, N- dimethylacetamides
Amine, dimethyl sulfoxide (DMSO) equal solvent.The mass ratio of the solvent and substituted salicylic aldehydes is preferably 5-10:1.
The reaction temperature is preferably 50-60 DEG C；
The reaction time has appropriate adjustment according to differential responses raw material, and its terminal is judged with prosecutor formula in TLC or other
Substituted salicylide raw material reaction, which is finished, to be defined.
Intermediate compound I is obtained after step 1-2, extractive reaction liquid, the solvent for removing organic phase；
Extraction agent is selected from the reagents such as esters, ethers, halogenated hydrocarbons, toluene, preferably is selected from the esters such as ethyl acetate, methyl acetate molten
Agent, its consumption is 3-4 times of the overall accumulated amount of reaction solution, in order to improve the effect of extraction, also can select the water of 1-2 times of volume,
To wash organic layer at least 2 times.
The structural formula of the intermediate compound I is as follows：
Step 2-1, intermediate compound I is dissolved in after solvent, adds triphenylphosphine bromomethane, after cooling, into reaction solution in batches
Highly basic is added, at a temperature of -10-120 DEG C, is reacted 0.5-20 hours, Wittig reactions are completed；
Above-mentioned highly basic is selected from sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, diisopropyl ethyl amine, potassium tert-butoxide, tertiary fourth
Sodium alkoxide, sodium hydride, hydrofining, tert-butyl lithium；It preferably is selected from potassium tert-butoxide, sodium tert-butoxide, sodium hydride.
Above-mentioned solvent is selected from nitrile solvents, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), ether
Class solvent, alkane solvents, toluene, chlorobenzene, alkyl halide；It preferably is selected from the ethers such as methyl tertiary butyl ether(MTBE), ether or tetrahydrofuran molten
Agent.The solvent and the mass ratio of intermediate compound I are preferably 10-15:1.
The temperature of the reaction is preferably -10-0 DEG C；
The reaction time has appropriate adjustment according to differential responses raw material, and its terminal is judged with prosecutor formula in TLC or other
Intermediate compound I raw material reaction, which is finished, to be defined.
Step 2-2, treat intermediate compound I after completion of the reaction, remove solvent, add water, extractive reaction liquid removes the molten of organic phase
Intermediate II is obtained after agent；
Extraction agent is selected from the reagents such as esters, ethers, halogenated hydrocarbons, toluene, preferably is selected from the halos such as dichloromethane, chloroform
Hydrocarbon.Its consumption is 3-4 times of the overall accumulated amount of reaction solution, in order to improve the effect of extraction, also can select the water of 1-2 times of volume,
To wash organic layer at least 2 times.
Step 3-1, intermediate II is dissolved in after solvent, in being added under less than 0 DEG C of cryogenic conditions after reducing agent, in -10-
At a temperature of 120 DEG C, react 0.5-20 hours, be amino by cyano reduction；
Above-mentioned solvent is selected from nitrile solvents, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), ether
Class solvent, alkane solvents, toluene, chlorobenzene, alkyl halide；It preferably is selected from ether solvent；Most preferably from methyl tertiary butyl ether(MTBE), ether,
Tetrahydrofuran or 1,4- dioxane) etc. ether solvents.The solvent and the mass ratio of intermediate II are preferably 5-15:1.
Reaction temperature is preferably -10-0 DEG C；
The reducing agent may be selected from it is any can be by the reagent that cyano reduction is amino, preferably borine tetrahydrofuran solution, hydrogen
Change lithium aluminium etc..
After the completion of step 3-2, reaction, reaction is quenched with acid, column chromatography obtains intermediate III；
The acid is preferably inorganic acid, such as：Hydrochloric acid or sulfuric acid etc.；Its concentration is preferably 7-85% acid.
The eluant, eluent selected in the column chromatography procedure preferably is selected from esters, ethers, ketone, alkane；It preferably is selected from ethyl acetate, second
The ester solution of sour methyl esters etc., and carbon number are not more than 8 alkane.
The eluant, eluent is most preferably ethyl acetate and n-hexane/pentane/hexamethylene/pentamethylene=1:0.5-5.
Step 3-3, intermediate III is dissolved in after solvent, adds acetylation reagent, highly basic, it is anti-at a temperature of 0-10 DEG C
Answer 0.5-20 hours, occur amidation process；
Above-mentioned solvent is selected from nitrile solvents, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), ether
Class solvent, alkane solvents, toluene, chlorobenzene, alkyl halide；It preferably is selected from the halogenated hydrocarbon solvents such as dichloromethane, chloroform.The solvent
Mass ratio with intermediate III is preferably 5-15:1.
The acetylation reagent is preferably chloroacetic chloride or acetic anhydride；
The organic base is preferably triethylamine, diisopropyl ethyl amine, potassium tert-butoxide, sodium tert-butoxide etc., most preferably three second
Amine or diisopropyl ethyl amine；
Step 3-4, after completion of the reaction, reaction is quenched with acid, dries and removes after solvent, obtains alkene part；
The acid is preferably inorganic acid, such as：Hydrochloric acid or sulfuric acid etc.；Its concentration is preferably 7-85% acid.
Step 4-1, catalyst precarsor and alkene part be dissolved in after solvent, add catalyst, at a temperature of 30-50 DEG C,
Reaction 2-4 hours；
Above-mentioned solvent is selected from nitrile solvents, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), ether
Class solvent, alkane solvents, toluene, chlorobenzene, alkyl halide；The solvent is preferably n-hexane, normal heptane, petroleum ether, toluene, chlorine
Benzene, tetrahydrofuran and dichloromethane etc., the solvent of optimization is toluene and dichloromethane；The solvent and catalyst precarsor added
Ratio in 3mL:1g to 10mL:Between 1g, the ratio of optimization is 5mL:1g.
The catalyst is selected from metallic catalyst, preferably is selected from sub- ketone of iodate etc..
Step 4-2, elimination solid, remove after solvent, are recrystallized to give final catalyst.
The solid is generally the inorganic salts solid after the completion of reaction；
Before final catalyst is separated out, preferably by system be cooled to 0-20 DEG C place 1-2 hours after, then will wherein precipitate
The contaminant filter gone out is removed.Then vacuum distillation removes solvent therein again, adds good solvent and poor solvent carries out crystallization
After obtain final product dark green solid.
The good solvent may be selected from the ester solvents such as the halogenated hydrocarbons such as dichloromethane and chloroform, ethyl acetate and methyl acetate, should
Poor solvent may be selected from the alcoholic solvents such as methanol, ethanol and isopropanol, ether solvents and ketone solvent.
The volume ratio of the good solvent and poor solvent is 1:5 to 1:Between 20, most preferred volume ratio is 1:10,
And the ratio of crystallization solvent for use cumulative volume and used catalyst precursor is in 5mL:1g to 20mL:Between 1g.Separating out final production
Required recrystallization temperature is between 0-30 DEG C during thing crystal, and the crystallization time is between 1 hour to 5 hours.
Further, the preparation method for a kind of ruthenium metal olefin metathesis catalyst that the present invention is provided, also with so
The characteristics of：I.e., the mol ratio of salicylide, highly basic and nitrile compounds is 1:1.0-2.5:1.0-2.5；It is preferably in a proportion of 1:1.2-
1.5:1.0-1.5；
The mol ratio of intermediate compound I, highly basic and triphenylphosphine bromomethane is 1:1.0-2.5:1.0-2.5；It is preferably in a proportion of 1:
1.2-1.5:1.0-1.5；
Intermediate II, the mol ratio of reducing agent are 1:2-3；
Intermediate III, acetylation reagent, the mol ratio of highly basic are 1:1.0-2.5:1.0-2.5；It is preferably in a proportion of 1:1.0-
1.2:1.3-1.5；
Catalyst precarsor, the mol ratio of alkene part are 1:1-2.5；It is preferably in a proportion of 1:1.0-1.2.
Further, a kind of ruthenium metal olefin metathesis catalyst for providing of the present invention, also with it is such the characteristics of：I.e.,
Above-mentioned ruthenium metal olefin metathesis catalyst is the compound shown in one of following structure：
Wherein, above-mentioned X1Selected from F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；
Above-mentioned X2Selected from F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt。
When ruthenium metal olefin metathesis catalyst is constituted above, its preferred preparation method is as follows：I.e., it is above-mentioned
New Ruthenium metal olefin metathesis catalyst preparation method, it is characterised in that include following five steps：
A. from the salicylide of substitutionWill be exposed in salicylide molecule by being reacted with bromoacetonitrile
Hydroxyl protection gets up to obtain intermediate compound I, and its structural formula is：
Intermediate compound I
Wherein, X1,X2=F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；Y=O, S；
B. intermediate compound I made from step A is obtained into alkene intermediates II with Wittig reagent reactings again, its structural formula
For：
Intermediate II
Wherein, X1,X2=F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；Y=O, S；
C. the cyano group in intermediate II made from step B is carried out into reduction with reducing agent again turns into amino, so that in obtaining
Mesosome III, its structure is
Intermediate III
Wherein, X1,X2=F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；Y=O, S；
D. the amino in intermediate III made from step C is protected with acetyl group again and obtains required alkene and match somebody with somebody
Body, its structural formula is
Wherein, X1,X2=F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；Y=O, S；
E. by the alkene part obtained in step D and catalyst precarsor Grubbs2ndReacted and obtained claims 1
In described new catalyst
Wherein, X1,X2=F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；Y=O, S.
Above-mentioned steps A specific preparation process is as follows：
Substituted salicylide, solvent, highly basic and bromoacetonitrile are added into reactor, is stirred at room temperature uniformly, then be slowly heated
Temperature reaches 50-60 DEG C in into reactor, is continually maintained in the thermotonus until the bigcatkin willow aldehyde reaction that raw material replaces is finished.So
Substantial amounts of ethyl acetate is added in backward reactor, then organic phase is repeatedly washed with water.Finally organic layer drying solvent is spin-dried for
After obtain intermediate compound I
Wherein, X1,X2=F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；Y=O, S；
Highly basic used in reaction system can be that the inorganic bases such as potassium carbonate, cesium carbonate can also be that triethylamine or two are different
The organic bases such as ethylamine.
Solvent used in above-mentioned steps A can be acetonitrile, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and
The mass ratio of dimethyl sulfoxide (DMSO) etc., solvent and raw material substituted salicylic aldehydes is 5:1-10:1, the acetic acid second added after completion of the reaction
The volume of ester is 3-4 times of reaction solution cumulative volume, and to be about the clear water agitator treating organic layer 3-4 of 1 times of volume of reaction solution
It is secondary.
Above-mentioned steps B specific preparation process is as follows：
Intermediate compound I and solvent are added in reaction bulb together, at room temperature stirring and dissolving, then add triphenylphosphine bromine first
Alkane.After cooling, then highly basic, which is added portionwise, into reaction solution occurs Wittig reactions.When intermediate compound I after completion of the reaction, will
Solvent is evaporated and then adds water, then is extracted product with dichloromethane, and intermediate is obtained after then dichloromethane is evaporated
II。
Wherein, X1,X2=F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；Y=O, S；
The highly basic used in reaction system can be potassium tert-butoxide, sodium tert-butoxide, sodium hydride etc., highly basic and substrate intermediate
The ratio of the amount of I material is 1.2:1-1.5:1.
The preparation method of above-mentioned ruthenium metal olefin metathesis catalyst, it is characterised in that molten used in being reacted in step B
Agent can be methyl tertiary butyl ether(MTBE), ether or tetrahydrofuran, and the mass ratio of solvent and substrate intermediate compound I is 10:1-15:1.
The ratio of the amount of triphenylphosphine bromomethane and the material of intermediate compound I is 1.0:1-1.5:1, the temperature of reaction is maintained at -10-0
℃。
Above-mentioned steps C specific preparation process is as follows：
Intermediate II is dissolved in ether solvent (methyl tertiary butyl ether(MTBE), ether, tetrahydrofuran or Isosorbide-5-Nitrae-dioxane etc.),
Then the (- 10-0 DEG C) cyano group added in reducing agent reduction intermediate II molecular structure are amino under cryogenic.Wherein institute
Reducing agent can be borine tetrahydrofuran solution either lithium aluminium hydride, and the amount of reducing agent used is substrate intermediate II
2-3 equivalents.After the completion of reaction, reaction is quenched with watery hydrochloric acid.The product Intermediate III crossed after silicagel column purifying reduction, it is used
Eluant, eluent is ethyl acetate：N-hexane=1:1.
Above-mentioned steps D specific preparation process is as follows：
Obtained intermediate III after reduction is added into reactor, stirring and dissolving after methylene chloride is added, so
After add acetylation reagent (chloroacetic chloride or acetic anhydride) and organic base (triethylamine or diisopropyl ethyl amine) stirring reaction.
The temperature wherein reacted is 0-10 DEG C, and the acetylation reagent of addition is the 1.0-1.2 equivalents of intermediate III, the organic base of addition
It is the 1.3-1.5 equivalents of substrate intermediate III.Instead
Watery hydrochloric acid washing reaction liquid is used after should finishing, the alkene part removed required for being obtained after solvent is dried
Wherein, X1,X2=F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；Y=O, S；
Above-mentioned steps E specific preparation process is as follows：
By catalyst precarsor and prepare the alkene part required for some catalystAdd to reaction
In device, stirring and dissolving after solvent is added, then, the sub- ketone stirring reaction of iodate is added.The mistake after catalyst precarsor has reacted
The New Ruthenium metal olefin for by product recrystallize required for purification is obtained again after inorganic salts solid, solvent evaporated is filtered to gather
Close catalyst；
Wherein, X, Y=F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；Y=O, S；
The ratio between amount of material of above-mentioned catalyst precarsor and alkene part is 1:1 to 1:Between 2.5, wherein the ratio optimized is
1:1.2。
The preparation method of above-mentioned ruthenium metal olefin metathesis catalyst, solvent used can be n-hexane, normal heptane, stone
Oily ether, toluene, chlorobenzene, tetrahydrofuran and dichloromethane etc., the solvent of optimization is toluene and dichloromethane；The solvent that is added and
Catalyst precarsor Grubbs2ndRatio in 3ml:1g to 10ml:Between 1g, the ratio of optimization is 5ml:1g.
The preparation method of above-mentioned ruthenium metal olefin metathesis catalyst, the reaction temperature carried out is between 30-50 DEG C, instead
Between seasonable between 2-4 hours.
The preparation method of above-mentioned ruthenium metal olefin metathesis catalyst, it is necessary to by system before final catalyst is separated out
Be cooled to 0-20 DEG C place 1 to 2 hours after, then by the contaminant filter being wherein settled out remove.Then vacuum distillation removes it again
In solvent, add after good solvent and poor solvent carry out crystallization and obtain final product dark green solid.
The preparation method of above-mentioned ruthenium metal olefin metathesis catalyst, what is added when separating out final product crystal is benign
Solvent can be dichloromethane, chloroform and ethyl acetate, and poor solvent can be methanol, ethanol and isopropanol etc..
The preparation method of above-mentioned ruthenium metal olefin metathesis catalyst, the good solvent and not when separating out final product crystal
The volume ratio of good solvent is 1:5 to 1:Between 20, wherein the volume ratio for comparing optimization is 1:10, and crystallization solvent for use is total
Volume and the ratio of used catalyst precursor are in 5ml:1g to 20ml:Between 1g.
The preparation method of above-mentioned ruthenium metal olefin metathesis catalyst, the required crystallization temperature when separating out final product crystal
Degree is between 0-30 DEG C, and the crystallization time is between 1 hour to 5 hours.
In addition, present invention also offers a kind of above-mentioned application process of ruthenium metal olefin metathesis catalyst, its feature exists
In：Above-mentioned ruthenium metal olefin metathesis catalyst is applied to alkene cultural care, the alkene cultural care
Substrate be diolefin compound.
Further, above-mentioned a kind of application process of ruthenium metal olefin metathesis catalyst that the present invention is provided, also has
So the characteristics of：I.e., step A, diolefin compound is dissolved in solvent, under conditions of protection gas shielded, by ruthenium metal alkene
Hydrocarbon metathesis catalyst is added portionwise in reactor, and olefin metathesis reaction occurs at a temperature of 30-80 DEG C；
After the completion of step B, question response, remove solvent or product is obtained by vacuum distillation.
Above-mentioned solvent can be n-hexane, normal heptane, petroleum ether, toluene, chlorobenzene, tetrahydrofuran and dichloromethane etc., excellent
The solvent aromatic solvent or halogenated hydrocarbons of change, most preferably toluene and dichloromethane；
Specific method is：Metathesis catalyst is added portionwise in reactor under conditions of the protection bubble such as drum nitrogen,
And promote cultural care to reactor heated for controlling temperature.Whether completed with TLC monitoring reactions, reaction will be molten after being fully completed
Agent vacuum distillation is removed.Product obtained by reaction can also be purified under conditions of high vacuum vacuum distillation.
Further, above-mentioned a kind of application process of ruthenium metal olefin metathesis catalyst that the present invention is provided, also has
So the characteristics of：I.e., the mass ratio of above-mentioned diolefin compound and ruthenium metal olefin metathesis catalyst is 1000:0.1-
0.3.The concentration of above-mentioned catalyst solution is 0.1-1g/L.
Further, above-mentioned a kind of application process of ruthenium metal olefin metathesis catalyst that the present invention is provided, also has
So the characteristics of：I.e., above-mentioned diolefin compound is the compound shown in following structure：
Further, above-mentioned a kind of application process of ruthenium metal olefin metathesis catalyst that the present invention is provided, is applied to
It is catalyzed dicyclopentadiene and carries out ring opening metathesis polymerization, specific application process is as follows：Dicyclopentadiene is added into polymerization to hold
In device, then catalyst is dissolved and is added dropwise in dicyclopentadiene in a solvent, catalyst solution is stirred equal when being added dropwise
It is even.Then stop stirring and heating the dicyclopentadiene polymerization of initiation catalyst.
Above-mentioned solvent can be normal heptane, toluene, chlorobenzene, acetone, isopropanol, dioxane, tetrahydrofuran and dichloromethane
Alkane, dichloroethanes etc., most preferably the solvent aromatic solvent or halogenated hydrocarbons of optimization, toluene and dichloromethane；
Further, above-mentioned a kind of application process of ruthenium metal olefin metathesis catalyst that the present invention is provided, also has
So the characteristics of：I.e., the mass ratio of dicyclopentadiene and ruthenium the metal olefin metathesis catalyst is 1000:0.1-
0.55, the heating-up temperature for triggering the polymerization of catalyst dicyclopentadiene is 50-70 DEG C, and the polymerization initiation time is 5-10 minutes.
The effect of the present invention and effect：
The present invention, as raw material, is designed from substituted salicylic aldehydes simple and easy to get and is prepared for a series of different substituents
Alkene part ruthenium catalyst, the activity of catalyst is determined by different substituents, is that it is closed in catalysis alkadienes substrate
The application of ring metathesis reaction provides multiple choices.
In addition, the present invention by a series of metal ruthenium catalysts be used for be catalyzed alkadienes substrate carry out cultural care with
And catalysis dicyclopentadiene is carried out in ring opening metathesis polymerization, activity is high, catalyst amount is few, to various functional group tolerances
The simple clean, post processing of good, reaction is simple, the big rule available for various big ring class drug molecules and super performance macromolecular material
Mould is produced.
Embodiment
Embodiment 1
Ruthenium metal olefin metathesis catalyst 1# preparation method
Include following five steps：
A. from the salicylide of substitutionBy being reacted with bromoacetonitrile by hydroxyl exposed in salicylide molecule
Protect and obtain intermediate compound I, its structural formula is：
Intermediate compound I
3- cresotinic acid aldehyde 200g and 1L DMFs, stirring and dissolving are added into 2L reaction bulb.Again to
200g bromoacetonitriles and 100g potassium carbonate are slowly added in the reaction bulb, stirring reaction is continued after being heated to 60 DEG C.Monitored by TLC
To raw material reaction it is complete after, reaction solution is poured into 4L ethyl acetate, then blunge washing three times, add water 4L every time.Add nothing
Aqueous sodium persulfate is dried, and filters and depressurizes and divides exactly after solvent, obtains product crude product 240g, yield 75%.
B. intermediate compound I made from step A is obtained into alkene intermediates II with Wittig reagent reactings again, its structural formula
For：
Intermediate II
By the salicylide intermediate compound I of protection250g and triphenylphosphine bromomethane 400g are added to 10L together
In reaction bulb, solvents tetrahydrofurane 5L is added.Cooling down to being slowly added portionwise potassium tert-butoxide 100g after 0 DEG C again.Reaction
Removal of solvent under reduced pressure after end, adds 5L water dissolves.After being extracted with 10L dichloromethane, anhydrous sodium sulfate drying, filtering are steamed
Alkene part crude product is obtained after dry solvent, then intermediate II is obtained after vacuum distillation is purified
Yellow oily liquid 210g, yield 88%.
C. the cyano group in intermediate II made from step B is carried out into reduction with reducing agent again turns into amino, so that in obtaining
Mesosome III, its structure is
Intermediate III
By intermediate II500 grams add in the tetrahydrofuran that 5L are dried, then under nitrogen protection 0 DEG C
When be slowly added to 100 grams of tetrahydrochysene lithium aluminium powder in batches into system.Add rear temperature and be warmed to room temperature rear stirring reaction after 5 hours
TLC detection raw material reactions are finished.Reaction is filtered to remove solid after 0 DEG C adds water and is quenched with ethyl acetate.Vacuum distillation removes four
Product is extracted with ethyl acetate out after hydrogen furans.Divide after liquid solvent evaporated, product obtains pure by silica gel column chromatography separating-purifying
410 grams of product, yield 90%.
D. the amino in intermediate III made from step C is protected with acetyl group again and obtains required alkene and match somebody with somebody
Body, its structural formula is
By intermediate III200 grams are dissolved in 1 liter of dichloromethane, and 90 grams of triethylamine and second are added at 0 DEG C
80 grams of acyl chlorides, stirring reaction washs organic layer with saturated aqueous ammonium chloride 3 times after 2 hours.Liquid drying is divided to obtain institute after being spin-dried for
230 grams of the alkene part needed, yield 90%.
Step E specific preparation process is as follows：
By catalyst precarsor 620g and alkene part340g is added into 10L reactors, adds solvent
Dichloromethane 5L, adds stannous chloride 150g, and 30 DEG C of heating responses to raw material disappears under nitrogen protective condition, is cooled to room
Temperature, filters out impurity.Filtrate decompression is boiled off after toluene, is added dichloromethane 100mL and methanol 5L and is separated out product catalyst solid,
Final catalyst is obtained after filtering drying330g, yield 65%.
1H NMR(300.18MHz,22℃,CDCl3,Me4Si):δ=11.17 (s, 1H), 8.04 (s, 1H), 7.70 (s,
1H),7.44(s,1H),6.76(s,4H),5.34(m,1H),3.83(s,1H),3.51(m,2H),3.33(m,2H),3.22(s,
4H), (d, J=7.8Hz, the 6H) ppm. of 2.34 (s, 3H), 2.66 (s, 3H), 2.22 (s, 12H), 1.35
Ruthenium metal olefin metathesis catalyst 1# application
The specific implementation step that ruthenium catalyst catalysis diene carries out cultural care is as follows：To 500mL reactors
Middle addition diene substrate 10g.The dichloromethane solution of catalyst is prepared, 100mg catalyst solids are dissolved in 10mL dichloromethane,
A certain amount of addition reaction solution is taken after stirring.Reactor is heated to 40 DEG C, nitrogen bubble is blasted into reactor solution and is put
Go out, TLC detections are evaporated off solvent and pure product is obtained with high vacuum vacuum distillation after completion of the reaction.
It is the situation of the various alkadienes substrate cultural cares of the catalyst in following table：
Embodiment 2
Ruthenium metal olefin metathesis catalyst 2# preparation method
Include following five steps：
A. from the salicylide of substitutionBy being reacted with bromoacetonitrile by hydroxyl exposed in salicylide molecule
Base, which is protected, obtains intermediate compound I, and its structural formula is：
Intermediate compound I
Substituted salicylide 200g and 1L DMSO, stirring and dissolving are added into 2L reaction bulb.Delay again into the reaction bulb
It is slow to add 250g bromoacetonitriles and 100g potassium carbonate, continue stirring reaction after being heated to 80 DEG C.Monitored by TLC complete to raw material reaction
Afterwards, reaction solution is poured into 4L ethyl acetate, then washing three times of blunging, add water 4L every time.Anhydrous sodium sulfate is added to carry out
Dry, filter and depressurize and divide exactly after solvent, obtain product crude product 265g.
B. intermediate compound I made from step A is obtained into alkene intermediates II with Wittig reagent reactings again, its structural formula
For：
Intermediate II
By the salicylide intermediate compound I of protection265g and triphenylphosphine bromomethane 450g are added to together
In 10L reaction bulbs, solvent dioxane 5L is added.Cooling down to being slowly added portionwise potassium tert-butoxide 120g after 0 DEG C again.Instead
Removal of solvent under reduced pressure after should terminating, adds 5L water dissolves.After being extracted with 10L chloroforms, anhydrous sodium sulfate drying, filtering are evaporated
Alkene part crude product is obtained after solvent, then intermediate II is obtained after vacuum distillation is purified
Oily liquids 230g.
C. the cyano group in intermediate II made from step B is carried out into reduction with reducing agent again turns into amino, so that in obtaining
Mesosome III, its structure is
Intermediate III
By intermediate II500 grams add in the tetrahydrofuran that 4L are dried, and then under nitrogen protection 0
DEG C when be slowly added to 100 grams of sodium borohydride (being dissolved in 1L tetrahydrofurans) in batches into system.Add after rear temperature is warmed to room temperature and stir
TLC detections raw material reaction after reacting 5 hours is mixed to finish.Reaction is filtered to remove solid after 0 DEG C adds water and is quenched with ethyl acetate.
Product is extracted with ethyl acetate out after removing tetrahydrofuran in vacuum distillation.Divide after liquid solvent evaporated, product passes through silica gel column chromatography
Separating-purifying obtains 460 grams of pure product.
D. the amino in intermediate III made from step C is protected with acetyl group again and obtains required alkene and match somebody with somebody
Body, its structural formula is
By intermediate III200 grams are dissolved in 1 liter of dichloromethane, and diisopropyl ethyl is added at 0 DEG C
100 grams of 120 grams of amine and chloroacetic chloride, stirring reaction wash organic layer with saturated aqueous ammonium chloride 3 times after 3 hours.Liquid is divided to dry
245 grams required of alkene part is obtained after being spin-dried for.
Step E specific preparation process is as follows：
By catalyst precarsor 680g and alkene part340g is added into 10L reactors, is added
Methylene chloride 5L, adds stannous chloride 150g, and 60 DEG C of heating responses to raw material disappears under nitrogen protective condition, is cooled to
Room temperature, filters out impurity.Filtrate decompression is boiled off after toluene, is added dichloromethane 100mL and methanol 5L precipitation product catalysts and is consolidated
Final catalyst is obtained after body, filtering drying361g。
1H NMR(300.18MHz,22℃,CDCl3,Me4Si):δ=11.37 (s, 1H), 8.10 (s, 1H), 7.70 (s,
2H),6.84(s,2H),6.76(s,4H),5.42(s,2H),4.10(t,2H),3.51(t,2H),2.87(m,4H),2.15(s,
3H),1.84(s,3H),1.20(d,24H)ppm.
Ruthenium metal olefin metathesis catalyst 2# application
The specific implementation step that ruthenium catalyst catalysis diene carries out cultural care is as follows：To 500mL reactors
Middle addition diene substrate 10g.The dichloromethane solution of catalyst is prepared, 100mg catalyst solids are dissolved in 10mL dichloromethane,
A certain amount of addition reaction solution is taken after stirring.Reactor is heated to 60 DEG C, nitrogen bubble is blasted into reactor solution and is put
Go out, TLC detections are evaporated off solvent and pure product is obtained with high vacuum vacuum distillation after completion of the reaction.
It is the situation of the various alkadienes substrate cultural cares of the catalyst in following table：
Embodiment 3,
Ruthenium metal olefin metathesis catalyst 3# preparation method
3- methyl -4- methoxyl groups-salicylide 200g and 1L DMF, stirring and dissolving is added into 2L reaction bulb.Again to this
200g 2- methyl bromoacetonitriles and 100g sodium carbonate are slowly added in reaction bulb, stirring reaction is continued after being heated to 40 DEG C.Pass through
TLC monitor to raw material reaction it is complete after, reaction solution is poured into 4L methyl acetates, then blunge washing three times, add water 4L every time.
Add anhydrous sodium sulfate to be dried, filter and depressurize and divide exactly after solvent, obtain intermediate compound I product crude product 260g.
By the salicylide intermediate compound I of protection, 260g and triphenylphosphine bromomethane 500g are added in 10L reaction bulbs together,
Add solvent toluene 5L.Cooling down to being slowly added portionwise sodium tert-butoxide 150g after 0 DEG C again.Reaction is removed under reduced pressure after terminating
Solvent, adds 5L water dissolves.After being extracted with 10L chloroforms, anhydrous sodium sulfate drying, filtering obtain alkene part after solvent evaporated
Crude product, then obtain intermediate II after vacuum distillation is purified240g。
By intermediate II500 grams add in the tetrahydrofuran that 5L is dried, then under nitrogen protection
It is slowly added to 100 grams of tetrahydrochysene lithium aluminium powder at 0 DEG C in batches into system.Add rear temperature and be warmed to room temperature rear stirring reaction 6 hours
TLC detects that raw material reaction is finished afterwards.Reaction is filtered to remove solid after 0 DEG C adds water and is quenched with ethyl acetate.Vacuum distillation is removed
Product is extracted with ethyl acetate out after tetrahydrofuran.Divide after liquid solvent evaporated, product is obtained by silica gel column chromatography separating-purifying
Pure product435 grams.
By intermediate III200 grams are dissolved in 1 liter of dichloromethane, and 90 grams of triethylamine is added at 0 DEG C
With 80 grams of chloroacetic chloride, stirring reaction washs organic layer with saturated aqueous ammonium chloride 3 times after 4 hours.Liquid drying is divided to be obtained after being spin-dried for
To 245 grams required of alkene part.
By catalyst precarsor 700g and alkene part350g is added into 10L reactors, adds solvent
Chloroform 5L, adds stannous chloride 150g, and 50 DEG C of heating responses to raw material disappears under nitrogen protective condition, is cooled to room temperature, mistake
Filter out impurity.Filtrate decompression is boiled off after toluene, is added chloroform 100mL and ethanol 1L and is separated out product catalyst solid, filtering drying
Final catalyst is obtained afterwards369g。
1H NMR(300.18MHz,22℃,CDCl3,Me4Si):δ=12.07 (s, 1H), 8.03 (s, 1H), 6.90 (s,
1H),6.71(s,4H),6.66(s,1H),6.76(s,4H),4.49(m,1H),3.83(s,3H),3.61(m,2H),3.24(s,
4H),2.34(s,6H),2.15(s,3H),2.12(s,3H),1.84(s,3H),1.40(d,24H)ppm. Ruthenium metal olefin is answered Decomposition catalyst 3# application
The specific implementation step that ruthenium catalyst catalysis diene carries out cultural care is as follows：To 1000mL reactors
Middle addition diene substrate 10g.The toluene solution of catalyst is prepared, 300mg catalyst solids are dissolved in 60mL toluene, stirred
After take a certain amount of addition reaction solution.Reactor is heated to 80 DEG C, nitrogen bubble is blasted into reactor solution and is released, TLC inspections
Survey is evaporated off solvent and pure product is obtained with high vacuum vacuum distillation after completion of the reaction.
It is the situation of the various alkadienes substrate cultural cares of the catalyst in following table：
Embodiment 4,
Ruthenium metal olefin metathesis catalyst 4# preparation
Added into 2L reaction bulb to phenyl salicylic aldehyde 200g and 1L DMF, stirring and dissolving.Again to
Be slowly added to 300g bromoacetonitriles and 150g potassium carbonate in the reaction bulb, room temperature reaction to TLC monitor to raw material reaction it is complete after, will be anti-
Liquid is answered to pour into 4L ethyl acetate/chloroform (80/20), then washing three times of blunging, add water 4L every time.Add anhydrous sodium sulfate
It is dried, filters and depressurize and divide exactly after solvent, obtain productCrude product 265g.
By the salicylide intermediate compound I of protection250g and triphenylphosphine bromomethane 300g are added to together
In 10L reaction bulbs, solvents tetrahydrofurane 5L is added.Cooling down to being slowly added portionwise potassium tert-butoxide 130g after 0 DEG C again.Instead
Removal of solvent under reduced pressure after should terminating, adds 5L water dissolves.After being extracted with 10L dichloromethane, anhydrous sodium sulfate drying, filtering,
Alkene part crude product is obtained after solvent evaporated, then intermediate II is obtained after vacuum distillation is purifiedOily liquid
Body 225g.
By intermediate II500 grams add in the tetrahydrofuran that 5L are dried, and then under nitrogen protection 0
DEG C when be slowly added to 120 grams of tetrahydrochysene lithium aluminium powder in batches into system.Add rear temperature and be warmed to room temperature rear stirring reaction after 5 hours
TLC detection raw material reactions are finished.Reaction is filtered to remove solid after 0 DEG C adds water and is quenched with ethyl acetate.Vacuum distillation removes four
Product is extracted with ethyl acetate out after hydrogen furans.Divide after liquid solvent evaporated, product obtains pure by silica gel column chromatography separating-purifying
435 grams of product.
By intermediate III200 grams are dissolved in 1 liter of dichloromethane, and 130 grams of triethylamine is added at 0 DEG C
With 250 grams of acetic anhydride, stirring reaction washs organic layer with saturated aqueous ammonium chloride 3 times after 5 hours.Point liquid is dried be spin-dried for after
Obtain 230 grams required of alkene part.
By catalyst precarsor 600g and alkene part400g is added into 10L reactors, is added
Methylene chloride 5L, adds stannous chloride 180g, and 30 DEG C of heating responses to raw material disappears under nitrogen protective condition, is cooled to
Room temperature, filters out impurity.Filtrate decompression is boiled off after toluene, is added dichloromethane 100mL and methanol 5L precipitation product catalysts and is consolidated
Final catalyst is obtained after body, filtering drying360g。
1H NMR(300.18MHz,22℃,CDCl3,Me4Si):δ=12.01 (s, 1H), 8.13 (s, 1H), 7.80 (s,
1H),7.68(d,1H),7.51(m,4H),7.41(d,1H),7.05(d,1H),6.66(s,4H),5.43(s,2H),4.10(t,
2H),3.53(t,2H),2.34(s,6H),2.12(s,12H),1.84(s,3H)ppm.
Ruthenium metal olefin metathesis catalyst 4# application
The specific implementation step that ruthenium catalyst catalysis diene carries out cultural care is as follows：To 500mL reactors
Middle addition diene substrate 10g.The dichloromethane solution of catalyst is prepared, 150mg catalyst solids are dissolved in 10mL dichloromethane,
A certain amount of addition reaction solution is taken after stirring.Reactor is heated to 40 DEG C, nitrogen bubble is blasted into reactor solution and is put
Go out, TLC detections are evaporated off solvent and pure product is obtained with high vacuum vacuum distillation after completion of the reaction.
Embodiment 5,
Ruthenium metal olefin metathesis catalyst 5# preparation
Added into 2L reaction bulb to 2- thiosalicylic aldehyde 100g and 1L DMFs, stirring and dissolving.Again
Be slowly added to 120g bromoacetonitriles and 80g potassium carbonate into the reaction bulb, room temperature reaction to TLC monitor to raw material reaction it is complete after, will
Reaction solution is poured into 4L ethyl acetate, then with saturated common salt water washing three times, every time plus saturated aqueous common salt 4L.Add anhydrous slufuric acid
Sodium is dried, and filters and depressurizes and divide exactly after solvent, obtains productCrude product 155g.
By the salicylide intermediate compound I of protection155g and triphenylphosphine bromomethane 180g are added to together
In 5L reaction bulbs, solvents tetrahydrofurane 2L is added.Cooling down to being slowly added portionwise potassium tert-butoxide 130g after 0 DEG C again.Instead
Removal of solvent under reduced pressure after should terminating, adds 1L water dissolves.After being extracted with 10L dichloromethane, anhydrous sodium sulfate drying, filtering,
Alkene part crude product is obtained after solvent evaporated, then intermediate II is obtained after vacuum distillation is purifiedOily liquid
Body 120g.
By intermediate II100 grams add in the tetrahydrofuran that 1L are dried, and then under nitrogen protection 0
DEG C when be slowly added to 50 grams of tetrahydrochysene lithium aluminium powder in batches into system.Add rear temperature and be warmed to room temperature rear stirring reaction after 5 hours
TLC detection raw material reactions are finished.Reaction is filtered to remove solid after 0 DEG C adds water and is quenched with ethyl acetate.Vacuum distillation removes four
Product is extracted with ethyl acetate out after hydrogen furans.Divide after liquid solvent evaporated, product obtains pure by silica gel column chromatography separating-purifying
105 grams of product.
By intermediate III100 grams are dissolved in 1 liter of dichloromethane, and 60 grams of triethylamine is added at 0 DEG C
With 90 grams of acetic anhydride, stirring reaction washs organic layer with saturated aqueous ammonium chloride 3 times after 5 hours.Liquid drying is divided to be obtained after being spin-dried for
To 20 grams required of alkene ligand 1.
By catalyst precarsor 300g and alkene part100g is added into 10L reactors, is added
Methylene chloride 5L, adds stannous chloride 60g, and 30 DEG C of heating responses to raw material disappears under nitrogen protective condition, is cooled to
Room temperature, filters out impurity.Filtrate decompression is boiled off after toluene, is added dichloromethane 100mL and methanol 1.5L and is separated out product catalyst
Final catalyst is obtained after solid, filtering drying160g。
1H NMR(300.18MHz,22℃,CDCl3,Me4Si):δ=11.01 (s, 1H), 8.03 (s, 1H), 6.69 (m,
4H),3.54(t,2H),3.41(t,2H),3.29(s,4H),2.37(s,6H),2.10(s,12H),1.80(s,3H)ppm.
Ruthenium metal olefin metathesis catalyst 5# application
The specific implementation step that ruthenium catalyst catalysis diene carries out cultural care is as follows：To 500mL reactors
Middle addition diene substrate 10g.Preparing catalyst, (mass ratio of diolefin compound and catalyst is 1000:0.1-0.3 model
Enclose interior selection) dichloromethane solution, 120mg catalyst solids are dissolved in 10mL dichloromethane, are taken after stirring a certain amount of
Add reaction solution.Reactor is heated to 40 DEG C, nitrogen bubble is blasted into reactor solution and is released, TLC detection reactions are finished
Solvent is evaporated off afterwards and pure product is obtained with high vacuum vacuum distillation.
The response data of different catalysts consumption and different diene substrates is as follows：
Application in catalyst 1-5# catalysis dicyclopentadiene polymerisations
10g dicyclopentadienes are added in aggregation container, then by the catalyst (mass ratio of dicyclopentadiene and catalyst
Example is 1000:In the range of 1-5 select) dissolve and be added dropwise in dicyclopentadiene in 10ml dichloromethane, while be added dropwise while incite somebody to action
Catalyst solution stirs, and then stops stirring and heating the dicyclopentadiene polymerization of initiation catalyst.
The data of catalysis dicyclopentadiene polymerisation are shown in below table：
Claims (10)
1. a kind of ruthenium metal olefin metathesis catalyst, it is characterised in that：Concrete structure formula is as follows：
Wherein, R1For hydrogen, alkyl, aryl；
R2For hydrogen, alkyl, aryl；
R3For hydrogen, alkyl, aryl；
R4For hydrogen, alkyl, aryl；
R5For hydrogen, alkyl, aryl；
R1' it is hydrogen, alkyl, aryl；
R2' it is hydrogen, alkyl, aryl；
R3' it is hydrogen, alkyl, aryl；
R4' it is hydrogen, alkyl, aryl；
R5' it is hydrogen, alkyl, aryl；
R7For hydrogen, alkyl, aryl；
L is halogen；
Y is oxygen or sulphur；
Z1For any on phenyl ring or times several substituted halogens, nitro, amino, aryl, alkyl, alkoxy；
Z2For hydrogen, alkyl, aryl.
2. a kind of preparation method of ruthenium metal olefin metathesis catalyst as claimed in claim 1, it is characterised in that by walking as follows
It is rapid to realize：
Step 1: by nitrile compounds by hydroxyl exposed in substituted salicylide or 2- thiosalicylic aldehyde or sulfhydryl protected
Come；
Step 2: by the carbonyl alkenyl in substituted salicylide；
Step 3: the cyano group introduced in step one is obtained into amide compound by reduction and acylation reaction；
Step 4: the product of step 3 and catalyst precarsor reaction are obtained into target product.
3. a kind of preparation method of ruthenium metal olefin metathesis catalyst as claimed in claim 2, it is characterised in that：Concrete technology
Step is as follows：
Step 1-1, substituted salicylide, solvent, highly basic and nitrile compounds are added into reactor, be stirred at room temperature it is uniform after,
At a temperature of 20-80 DEG C, react 0.5-20 hours；
Intermediate compound I is obtained after step 1-2, extractive reaction liquid, the solvent for removing organic phase；
Step 2-1, intermediate compound I is dissolved in after solvent, adds triphenylphosphine bromomethane, after cooling, be added portionwise into reaction solution
Highly basic, at a temperature of -10-120 DEG C, reacts 0.5-20 hours, completes Wittig reactions；
Step 2-2, treat intermediate compound I after completion of the reaction, remove solvent, add after water, extractive reaction liquid, the solvent for removing organic phase
Obtain intermediate II；
Step 3-1, intermediate II is dissolved in after solvent, in being added under less than 0 DEG C of cryogenic conditions after reducing agent, in -10-120
At a temperature of DEG C, react 0.5-20 hours, be amino by cyano reduction；
After the completion of step 3-2, reaction, reaction is quenched with acid, column chromatography obtains intermediate III；
Step 3-3, intermediate III is dissolved in after solvent, adds acetylation reagent, highly basic, reacted at a temperature of 0-10 DEG C
0.5-20 hours, occurs amidation process；
Step 3-4, after completion of the reaction, reaction is quenched with acid, dries and removes after solvent, obtains alkene part；
Step 4-1, catalyst precarsor and alkene part be dissolved in after solvent, add catalyst, at a temperature of 30-50 DEG C, reaction
2-4 hours；
Step 4-2, elimination solid, remove after solvent, are recrystallized to give final catalyst.
4. a kind of preparation method of ruthenium metal olefin metathesis catalyst as claimed in claim 3, it is characterised in that：
The highly basic be selected from sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, diisopropyl ethyl amine, potassium tert-butoxide, sodium tert-butoxide,
Sodium hydride, hydrofining；
It is molten that the solvent is selected from nitrile solvents, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), ethers
Agent, alkane solvents, toluene, chlorobenzene, alkyl halide；
The acid is inorganic acid；
The reagent of the extraction is selected from esters, ethers, halogenated hydrocarbons, toluene；
The mol ratio of the substituted salicylic aldehydes, highly basic and nitrile compounds is 1:1.0-2.5:1.0-2.5；
The mol ratio of the intermediate compound I, highly basic and triphenylphosphine bromomethane is 1:1.0-2.5:1.0-2.5；
The intermediate II, the mol ratio of reducing agent are 1:2-3；
The intermediate III, acetylation reagent, the mol ratio of highly basic are 1:1.0-2.5:1.0-2.5；
The catalyst precarsor, the mol ratio of alkene part are 1:1-2.5.
5. a kind of ruthenium metal olefin metathesis catalyst as described in claim 1-4 is any, it is characterised in that：
The ruthenium metal olefin metathesis catalyst is the compound shown in one of following structure：
Wherein, the X1Selected from F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；
The X2Selected from F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt。
6. a kind of ruthenium metal olefin metathesis catalyst is in alkene cultural care as described in claim 1-5 is any
Using, it is characterised in that：
The substrate of the alkene cultural care is diolefin compound；
Specific application process is as follows：
Step A, diolefin compound is dissolved in solvent, under conditions of protection gas shielded, ruthenium metal olefin metathesis is urged
Agent is added portionwise in reactor, and olefin metathesis reaction occurs at a temperature of 30-80 DEG C；
After the completion of step B, question response, remove solvent or product is obtained by vacuum distillation.
7. application as claimed in claim 6, it is characterised in that：
The diolefin compound is 1000 with the mass ratio of ruthenium metal olefin metathesis catalyst:1-5.
8. application as claimed in claim 6, it is characterised in that：
The diolefin compound is the compound shown in following structure：
9. a kind of ruthenium metal olefin metathesis catalyst is in catalysis dicyclopentadiene polymerisation as described in claim 1-5 is any
In application, it is characterised in that：
Specific application process is as follows：Dicyclopentadiene is added in aggregation container, then dissolved catalyst simultaneously in a solvent
It is added dropwise in dicyclopentadiene, catalyst solution stirs when being added dropwise, then stops stirring and heating initiation catalyst
It is catalyzed dicyclopentadiene polymerization.
10. application as claimed in claim 9, it is characterised in that：
The dicyclopentadiene is 1000 with the mass ratio of ruthenium metal olefin metathesis catalyst:0.1-0.5；
The heating-up temperature for triggering catalyst dicyclopentadiene to polymerize is 50-70 DEG C, and the polymerization initiation time is 5-10 points
Clock.
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| CN107641165A (en) * | 2017-08-08 | 2018-01-30 | 上海克琴科技有限公司 | Metal ruthenium catalyst DREAM 2nd and its application in alkene cyclization double decomposition and dicyclopentadiene polymerisation |
| CN107722243A (en) * | 2017-11-02 | 2018-02-23 | 克琴新材料科技（上海）有限公司 | A kind of lightweight is modified dicyclopentadiene material and preparation method thereof |
| CN107828004A (en) * | 2017-11-02 | 2018-03-23 | 克琴新材料科技（上海）有限公司 | A kind of environmental protection flame retardant dicyclopentadiene material and preparation method thereof |
| CN109225334A (en) * | 2018-07-20 | 2019-01-18 | 吉林化工学院 | A kind of ruthenium olefin metathesis catalyst and its preparation method and application with ortho position steric hindrance structure |
| CN111732681A (en) * | 2020-07-02 | 2020-10-02 | 张玉清 | Bi-component latent metal carbene catalytic system, dicyclopentadiene polymeric bi-material system and polydicyclopentadiene composite material |
| CN113000066A (en) * | 2021-01-09 | 2021-06-22 | 河南大学 | Z-selective ruthenium carbene olefin metathesis catalyst, and preparation method and application thereof |
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| CN107641165A (en) * | 2017-08-08 | 2018-01-30 | 上海克琴科技有限公司 | Metal ruthenium catalyst DREAM 2nd and its application in alkene cyclization double decomposition and dicyclopentadiene polymerisation |
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| CN113000066A (en) * | 2021-01-09 | 2021-06-22 | 河南大学 | Z-selective ruthenium carbene olefin metathesis catalyst, and preparation method and application thereof |
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Denomination of invention: Preparation and application of a ruthenium metal olefin metathesis catalyst Effective date of registration: 20231218 Granted publication date: 20200320 Pledgee: Industrial Bank Co.,Ltd. Shanghai Jinshan Branch Pledgor: SHANGHAI COACHCHEM TECHNOLOGY CO.,LTD. Registration number: Y2023980071859 |