CN110483563A - A kind of preparation method and application of novel ionic betanaphthol aldehyde schiff bases zirconium complex - Google Patents
A kind of preparation method and application of novel ionic betanaphthol aldehyde schiff bases zirconium complex Download PDFInfo
- Publication number
- CN110483563A CN110483563A CN201910843557.4A CN201910843557A CN110483563A CN 110483563 A CN110483563 A CN 110483563A CN 201910843557 A CN201910843557 A CN 201910843557A CN 110483563 A CN110483563 A CN 110483563A
- Authority
- CN
- China
- Prior art keywords
- betanaphthol
- aldehyde
- schiff bases
- zirconium
- complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000002262 Schiff base Substances 0.000 title claims abstract description 67
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 64
- 229950011260 betanaphthol Drugs 0.000 title claims abstract description 61
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 6
- 239000002904 solvent Substances 0.000 claims abstract description 49
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000706 filtrate Substances 0.000 claims abstract description 26
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 25
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 25
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 25
- -1 betanaphthol aldehyde schiff base Chemical class 0.000 claims abstract description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 11
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims abstract description 10
- 230000004224 protection Effects 0.000 claims abstract description 8
- 239000002585 base Substances 0.000 claims abstract description 7
- 230000008014 freezing Effects 0.000 claims abstract description 6
- 238000007710 freezing Methods 0.000 claims abstract description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 4
- 238000003445 Hantzsch reaction Methods 0.000 claims abstract description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 60
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 25
- XSXHWVKGUXMUQE-UHFFFAOYSA-N osmium dioxide Inorganic materials O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 claims description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 18
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical group OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical group OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 claims description 8
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 6
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 4
- YBROZCQZSRICSG-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonic acid silver Chemical compound [Ag].OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YBROZCQZSRICSG-UHFFFAOYSA-N 0.000 claims description 3
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 claims description 3
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 claims description 3
- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 claims description 3
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 3
- QZHDEAJFRJCDMF-UHFFFAOYSA-N perfluorohexanesulfonic acid Chemical group OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QZHDEAJFRJCDMF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- UJHSIDUUJPTLDY-UHFFFAOYSA-N (2-nitrophenyl)-phenylmethanone Chemical compound [O-][N+](=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 UJHSIDUUJPTLDY-UHFFFAOYSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- BQHRYSVGIDDPNP-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonic acid silver Chemical compound [Ag].OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BQHRYSVGIDDPNP-UHFFFAOYSA-N 0.000 claims description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical compound FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229930016911 cinnamic acid Natural products 0.000 claims description 2
- 235000013985 cinnamic acid Nutrition 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- OENLEHTYJXMVBG-UHFFFAOYSA-N pyridine;hydrate Chemical class [OH-].C1=CC=[NH+]C=C1 OENLEHTYJXMVBG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 125000005504 styryl group Chemical group 0.000 claims description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002841 Lewis acid Substances 0.000 abstract 1
- 150000007517 lewis acids Chemical class 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 38
- 238000010898 silica gel chromatography Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 16
- 238000000605 extraction Methods 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 3
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical class C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 2
- IKMBXKGUMLSBOT-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C(F)C(F)=C(F)C(F)=C1F IKMBXKGUMLSBOT-UHFFFAOYSA-N 0.000 description 2
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 239000011972 silica sulfuric acid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 108090000312 Calcium Channels Proteins 0.000 description 1
- 102000003922 Calcium Channels Human genes 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000002253 anti-ischaemic effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000004112 neuroprotection Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- QUJLPICXDXFRSN-UHFFFAOYSA-N scandium;trifluoromethanesulfonic acid Chemical compound [Sc].OS(=O)(=O)C(F)(F)F QUJLPICXDXFRSN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D211/84—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen directly attached to ring carbon atoms
- C07D211/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
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Abstract
The invention belongs to be catalyzed technical field of organic synthesis, and in particular to a kind of preparation method and application of novel ionic betanaphthol aldehyde schiff bases zirconium complex.Zirconium atom of the present invention and betanaphthol aldehyde schiff base ligand and water molecule coordination, two perfluor alkane (virtue) base sulfonic acid groups are respectively with covalent bond and ionic bond in conjunction with central atom zirconium.Betanaphthol aldehyde schiff bases zirconium dichloride is dissolved in solvent, and in N2Under protection, silver salt is added, is protected from light 1-4h at room temperature, is filtered, n-hexane is added in filtrate, until layering, is put into refrigerator freezing for 24 hours, betanaphthol aldehyde schiff bases zirconium complex is precipitated.Betanaphthol aldehyde schiff bases zirconium complex has high air stability and strong lewis acid, can efficient catalytic aldehyde, Hantzsch reaction synthesis Isosorbide-5-Nitrae-dihydrogen pyridine derivative of 'beta '-ketoester and ammonium acetate.
Description
Technical field
The invention belongs to be catalyzed technical field of organic synthesis, and in particular to a kind of novel ionic betanaphthol aldehyde schiff bases zirconium
The preparation method and application of complex.
Background technique
Isosorbide-5-Nitrae-dihydropyridine compound is nitrogen-containing heterocycle compound, has extensive biology and pharmacy value.Especially facing
The diseases such as cardiovascular and cerebrovascular and hypertension are treated as calcium ion channel blocker on bed, also in platelet aggregation-against, neuroprotection
And it is played an important role in terms of anti-ischemic.It is anti-by Hantzsch for synthesizing the classical way of 1,4- dihydropyridine compounds
It answers: being prepared by the ammonia condensation reaction of the aldehyde of a molecule, the 'beta '-ketoester of two molecules and a molecule.In recent years, Isosorbide-5-Nitrae-two is explored
The synthetic method of pyridinium hydroxide compound simple and effective has become the hot spot of organic synthesis field.
Currently, reported catalyst specifically includes that (1) bronsted acid catalyst: HClO4-SiO2, phenyl boric acid, PTSA,
Alumina sulfuric acid (ASA), silica sulfuric acid (SSA), HAc etc.；(2) lewis acid catalyst:
Cu(OTf)2、AlCl3·6H2O、RuCl3、CeCl3·7H2O、La2O3Deng；(3) ionic-liquid catalyst: TMGT, [EMIM] OAc
Deng；However there are still some problems for the above catalyst, if catalyst easily deliquesces, catalytic activity is low, poor selectivity, catalyst
It cannot recycle, pollute the environment, therefore, seeking a kind of new catalyst can the above-mentioned azepine of efficient catalytic
The synthesis of cycle compound is still worth us to further investigate.
Zirconium because of metal coordination ability with higher and catalytic activity and the concern by scientists.In recent years, organic zirconium
Compound has more application in organic synthesis, catalytic field, is applied especially to catalysis in olefine polymerization.However, matching containing schiff bases
The zirconium complex of body is seldom as lewis acid catalyst report.Possible cause is that the hetero atom (N, O) of ligand is matched with zirconium metal
Position, reduces the lewis acidity of zirconium central atom.It was found that introducing perfluoroalkyl (aryl) sulphur of long-chain in previous work
Acid groups can increase complex to the stability and acidity of air, be based on this theory, and in the present invention, we use betanaphthol
Aldehyde schiff bases zirconium dichloride (preparation method see document Analytica Chimica Acta, 2005,551,37) is initial former
Material goes the chlorine atom of displacement schiff bases zirconium dichloride with strong electrophilic long-chain perfluor alkane (benzene) base azochlorosulfonate acid anion, closes
At betanaphthol aldehyde schiff bases zirconium complex.And the introducing of long-chain perfluoroalkyl (aryl) increases stability and the Louis of complex
This is acid.Further, betanaphthol aldehyde schiff bases zirconium complex can synthesize Isosorbide-5-Nitrae-dihydrogen pyridine derivative with efficient catalytic.Currently,
Both at home and abroad not yet about the preparation method of betanaphthol aldehyde schiff bases zirconium complex and to catalyze and synthesize 1,4- dihydropyridine derivative
The open source literature of object and patent application.
Summary of the invention
The present invention provides a kind of preparation sides of novel ionic betanaphthol aldehyde schiff bases zirconium complex regarding to the issue above
Method and application.
In order to achieve the above object of the invention, the present invention proposes following technical proposal:
A kind of novel ionic betanaphthol aldehyde schiff bases zirconium complex:
Cationic betanaphthol aldehyde schiff bases zirconium complex (I), by zirconium atom and naphthol novolak schiff base ligand and a water
Molecule and an X coordination, another anion X-Ionic bond is formed with the cationic portion of complex；Complex structure formula
(I) as follows:
The X is perfluoro octyl sulfonic acid group OSO2C8F17, pentafluorophenyl group sulfonic acid group OSO2C6F5, perfluoro hexyl sulfonic acid
Group OSO2C6F13Or perfluoro butyl sulfonic acid group OSO2C4F9One of；
A kind of preparation method of novel ionic betanaphthol aldehyde schiff bases zirconium complex:
Betanaphthol aldehyde schiff bases zirconium dichloride is dissolved in solvent, and in N2Under protection, silver salt is added, at room temperature
It is protected from light 1-4h, is filtered, n-hexane is added in filtrate, until layering, is put into refrigerator freezing for 24 hours, precipitation complex is betanaphthol
Aldehyde schiff bases zirconium complex (I).
The solvent: tetrahydrofuran, acetone, acetonitrile, methanol or ethyl alcohol；The silver salt are as follows: perfluoro octyl sulfonic acid silver
AgOSO2C8F17, pentafluorophenyl group sulfonic acid silver AgOSO2C6F5, perfluoro hexyl sulfonic acid silver AgOSO2C6F13Or perfluoro butyl sulfonic acid silver
AgOSO2C4F9One of.
A kind of application of novel ionic betanaphthol aldehyde schiff bases zirconium complex:
Betanaphthol aldehyde schiff bases zirconium complex (I) can be catalyzed: the Hantzsch reaction preparation 1 of aldehyde, 'beta '-ketoester and ammonium acetate,
4- dihydrogen pyridine derivative.
A kind of application method of novel ionic betanaphthol aldehyde schiff bases zirconium complex:
It the use of betanaphthol aldehyde schiff bases zirconium complex (I) is catalyst, with aldehyde, 'beta '-ketoester and ammonium acetate are raw material, with normal
It uses organic solvent as reaction dissolvent, reacts 1-12h at 50-120 DEG C.After completion of the reaction, solvent is removed, methylene chloride is added
Catalyst is recycled in dilution, filtering, and filtrate is spin-dried for, and by column chromatography for separation, obtains Isosorbide-5-Nitrae-dihydrogen pyridine derivative；Its structural formula
It is as follows for (II):
R1For phenyl, p-methylphenyl, p-methoxyphenyl, p-hydroxybenzene, o-fluorophenyl, rubigan, to bromobenzene
Base, O-Nitrophenylfluorone, m-nitro base, one of 2- naphthalene, styryl, 2- furfuryl group, ethyl or propyl；R2For methyl or
One of ethyl；
The aldehyde is benzaldehyde, p-tolyl aldehyde, P-methoxybenzal-dehyde, parahydroxyben-zaldehyde, o fluorobenzaldehyde, right
Chlorobenzaldehyde, p-bromobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, 2- naphthaldehyde, cinnamic acid, furfural, propionic aldehyde or butyraldehyde
One of；
The 'beta '-ketoester is one of methyl acetoacetate or ethyl acetoacetate；
The solvent is one of tetrahydrofuran, acetonitrile, 1,2 dichloroethanes, acetone, ethyl alcohol, toluene；
The dosage of the catalyst is 1.0-10mol%；Catalyst reusable 5 times or more.
Compared with prior art the invention has the following advantages that
Method provided by the present invention is a kind of preparation method of ionic seat betanaphthol aldehyde husband's alkali zirconium complex and its urges
It is combined to 1,4- dihydrogen pyridine derivative.A new effective simple pathway is opened to prepare Isosorbide-5-Nitrae-dihydrogen pyridine derivative,
Catalyst stability is high and catalytic activity is high, and catalyst can reuse 5 times or more, and experimental implementation is easy.
Detailed description of the invention
Fig. 1 prepares the route map of betanaphthol aldehyde schiff bases zirconium complex；
Fig. 2 catalyzes and synthesizes 1,4- dihydrogen pyridine derivative.
Specific embodiment
The synthetic route of betanaphthol aldehyde schiff bases zirconium complex provided by the present invention, is shown in Fig. 1: by betanaphthol aldehyde schiff bases
Zirconium dichloride is dissolved in one of tetrahydrofuran, acetone, acetonitrile, methanol, ethyl alcohol, dichloromethane solvent, N2Under protection, to
One of perfluor alkane (virtue) base sulfonic acid silver is wherein added, is protected from light l-4h at room temperature.N-hexane is added in filtering, filtrate, directly
To layering.It is put into refrigerator freezing for 24 hours, complex is precipitated, filters to obtain yellow solid betanaphthol aldehyde schiff bases zirconium complex.
Betanaphthol aldehyde schiff bases zirconium complex is applied to catalyze and synthesize Isosorbide-5-Nitrae-dihydrogen pyridine derivative as catalyst, prepares
Isosorbide-5-Nitrae-dihydropyridine compound can foundation: by aldehyde, 'beta '-ketoester and ammonium acetate and solvent are added in reaction vessel, at 50-120 DEG C
React 1-12h.After completion of the reaction, methylene chloride is added, catalyst is recovered by filtration, filtrate is spin-dried for, and crude product is through column chromatography for separation
Obtain target compound.
Note: the above-mentioned reaction solvent is tetrahydrofuran, acetonitrile, one kind of 1,2 dichloroethanes, ethyl alcohol, toluene；It is described to urge
The dosage of agent is 1.0-10mol%；Catalyst reusable 5 times or more.
Below with reference to specific preparation example, the present invention will be further described:
One, the synthesis of novel betanaphthol aldehyde schiff bases zirconium perfluor alkane (benzene) base sulphonic acid complex
Preparation example 1
Betanaphthol aldehyde schiff bases schiff bases zirconium dichloride (1.0mmol) is dissolved in tetrahydrofuran (THF), N2Protection
Under, perfluoro octyl sulfonic acid silver (2.0mmol) is added, is protected from light 1h at room temperature.N-hexane is added in filtering, filtrate, until layering.
It is put into refrigerator freezing for 24 hours, yellow solid, yield 80% is precipitated.
Preparation example 2
Betanaphthol aldehyde schiff bases schiff bases zirconium dichloride (1.0mmol) is dissolved in acetonitrile (CH3CN in), N2Under protection, add
It is silver-colored (2.0mmol) to enter perfluorophenyl sulfonic acid, is protected from light 3h at room temperature.N-hexane is added in filtering, filtrate, until layering.It is put into
For 24 hours, yellow color solid, yield 70% is precipitated in refrigerator freezing.
Preparation example 3
Betanaphthol aldehyde schiff bases schiff bases zirconium dichloride (1.0mmol) is dissolved in acetone, N2Under protection, perfluor is added
Hexyl sulfonic acid is silver-colored (2.0mmol), is protected from light 2h at room temperature.N-hexane is added in filtering, filtrate, until layering.It is cold to be put into refrigerator
Freeze for 24 hours, yellow solid, yield 74% is precipitated.
Preparation example 4
Betanaphthol aldehyde schiff bases schiff bases zirconium dichloride (1.0mmol) is dissolved in methylene chloride, N2Under protection, it is added
Perfluoro butyl sulfonic acid is silver-colored (2.0mmol), is protected from light 4h at room temperature.N-hexane is added in filtering, filtrate, until layering.It is put into ice
Case freezes for 24 hours, and yellow solid, yield 67% is precipitated.
Two, betanaphthol aldehyde schiff bases zirconium complex catalyzes and synthesizes 1,4- dihydropyridine compound
Preparation example 1
Benzaldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro octyl sulfonic acid complex (X=OSO2C8F17)
(0.05mmol) stirs 12h at 80 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Solid catalysis is collected in extraction 3 times
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue separates with silica gel column chromatography, obtains faint yellow solid, and 2,6-
Dimethyl -4- phenyl -3,5- diethyl oxygen carbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 94%.
Preparation example 2
P-chlorobenzaldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent acetonitrile (2mL) and betanaphthol aldehyde schiff bases zirconium perfluorophenyl sulphonic acid complex (X=OSO2C6F5)
(0.05mmol) stirs 2h at 100 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Solid catalysis is collected in extraction 3 times
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue separates with silica gel column chromatography, obtains faint yellow solid, and 2,6-
Dimethyl -4- (rubigan) -3,5- diethyl oxygen carbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 95%.
Preparation example 3
P-bromobenzaldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro butyl sulphonic acid complex (X=OSO2C4F9)
(0.05mmol) stirs 12h at 80 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Solid catalysis is collected in extraction 3 times
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue separates with silica gel column chromatography, obtains faint yellow solid, and 2,6-
Dimethyl -4- (rubigan) -3,5- diethyl oxygen carbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 93%.
Preparation example 4
M-nitrobenzaldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent acetone (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro octyl sulfonic acid complex (X=OSO2C8F17)
(0.05mmol) stirs 12h at 50 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Solid catalysis is collected in extraction 3 times
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue separates with silica gel column chromatography, obtains faint yellow solid, and 2,6-
Dimethyl -4- (m-nitro base) -3,5- diethyl oxygen carbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 78%.
Preparation example 5
P-tolyl aldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), etoh solvent (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro octyl sulfonic acid complex (X=OSO2C8F17)
(0.05mmol) stirs 8h at 80 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Solid catalysis is collected in extraction 3 times
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue separates with silica gel column chromatography, obtains faint yellow solid, and 2,6-
Dimethyl -4- (p-methylphenyl) -3,5- diethyl oxygen carbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 84%.
Preparation example 6
P-methoxybenzal-dehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), acetic acid
Ammonium (1.2mmol), solvent THF (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro hexyl sulphonic acid complex (X=OSO2C6F13)
(0.05mmol) stirs 6h at 100 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Solid catalysis is collected in extraction 3 times
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue separates with silica gel column chromatography, obtains faint yellow solid, and 2,6-
Dimethyl -4- (p-methoxyphenyl) -3,5- diethyl oxygen carbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 82%.
Preparation example 7
Parahydroxyben-zaldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent 1,2- dichloroethanes (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro octyl sulfonic acid complex (X=
OSO2C8F17) (0.10mmol), 8h is stirred at 80 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Extraction 3 times is collected
Solid catalyst is to recycle, combined CH2Cl2Filtrate, revolving, residue are separated with silica gel column chromatography, obtain pale yellow colored solid
Body, 2,6- dimethyl -4- (p-hydroxybenzene) -3,5- diethyl oxygen carbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 87%.
Preparation example 8
Propionic aldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro octyl sulfonic acid complex (X=OSO2C8F17)
(0.05mmol) stirs 12h at 100 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Extraction 3 times is collected solid and is urged
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue separates with silica gel column chromatography, obtains faint yellow solid, and 2,
6- dimethyl -4- ethyl -3,5- diethyl oxygen carbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 94%.
Preparation example 9
Trans-cinnamic aldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent 1,2- methylene chloride (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro butyl sulphonic acid complex (X=
OSO2C4F9) (0.05mmol), 10h is stirred at 80 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Extraction 3 times is collected
Solid catalyst is to recycle, combined CH2Cl2Filtrate, revolving, residue are separated with silica gel column chromatography, obtain pale yellow colored solid
Body, (E) 2,6- dimethyl -4- styryl -3,5- diethyl oxygen carbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 90%.
Preparation example 10
Furfural (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro octyl sulfonic acid complex (X=OSO2C8F17)
(0.05mmol) stirs 9h at 80 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Solid catalysis is collected in extraction 3 times
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue are separated with silica gel column chromatography, obtain faint yellow solid 2,6- bis-
Methyl -4- (2- furfuryl group) -3,5- diethyl oxygen carbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 87%.
Preparation example 11
2- naphthaldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro octyl sulfonic acid complex (X=OSO2C8F17)
(0.05mmol) stirs 12h at 70 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Solid catalysis is collected in extraction 3 times
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue are separated with silica gel column chromatography, obtain faint yellow solid 2,6- bis-
Methyl -4- (2- naphthalene) -3,5- diethyl oxygen carbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 90%.
Preparation example 12
Benzaldehyde (1mmol) is added in 50mL round-bottomed flask, methyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro butyl sulphonic acid complex (X=OSO2C4F9)
(0.05mmol) stirs 12h at 90 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Solid catalysis is collected in extraction 3 times
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue separates with silica gel column chromatography, obtains faint yellow solid, and 2,6-
Dimethyl -4- phenyl -3,5- dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 91%.
Preparation example 13
P-chlorobenzaldehyde (1mmol) is added in 50mL round-bottomed flask, methyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro butyl sulphonic acid complex (X=OSO2C6F13)
(0.05mmol) stirs 10h at 80 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Solid catalysis is collected in extraction 3 times
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue separates with silica gel column chromatography, obtains faint yellow solid, and 2,6-
Dimethyl -4- (rubigan) -3,5- dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 94%.
Preparation example 14
P-tolyl aldehyde (1mmol) is added in 50mL round-bottomed flask, methyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro butyl sulphonic acid complex (X=OSO2C4F9)
(0.01mmol) stirs 1h at 100 DEG C.It is spin-dried for solvent, residue CH after reaction2Cl2Solid catalysis is collected in extraction 3 times
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue separates with silica gel column chromatography, obtains faint yellow solid, and 2,6-
Dimethyl -4- (p-methylphenyl) -3,5- dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 86%.
Preparation example 15
O-nitrobenzaldehyde (1mmol) is added in 50mL round-bottomed flask, methyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent toluene (2mL) and betanaphthol aldehyde schiff bases zirconium perfluoro octyl sulfonic acid complex (X=OSO2C8F17)
(0.05mmol) stirs 1h at 120 DEG C.It is spin-dried for solvent after reaction, residue uses CH2Cl2Extraction 3 times is collected solid and is urged
Agent is to recycle, combined CH2Cl2Filtrate, revolving, residue separates with silica gel column chromatography, obtains faint yellow solid, and 2,
6- dimethyl -4- (2- nitrobenzophenone) -3,5- dimethoxycarbonyl-Isosorbide-5-Nitrae-dihydropyridine, yield 92%.
In order to further embody the superiority of this method, following catalyst system example as a comparison is selected:
Comparative example 1
Benzaldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and zirconium chloride (0.05mmol) stir 12h at 80 DEG C.It is spin-dried for solvent after reaction,
Residue is separated with silica gel column chromatography, obtains faint yellow solid, 2,6- dimethyl -4- phenyl -3,5- diethyl oxygen carbonyls-Isosorbide-5-Nitrae-two
Pyridinium hydroxide, yield 23%.Catalyst cannot reuse.
Comparative example 2
Benzaldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and bis cyclopentadienyl zirconium dichloride (0.05mmol) stir 12h at 80 DEG C.It is spin-dried for after reaction molten
Agent, residue are separated with silica gel column chromatography, obtain faint yellow solid, 2,6- dimethyl -4- phenyl -3,5- diethyl oxygen carbonyl -1,
4- dihydropyridine, yield 41%.Catalyst cannot reuse.
Comparative example 3
Benzaldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and trifluoromethane sulfonic acid scandium (0.05mmol) stir 12h at 80 DEG C.It is spin-dried for after reaction
Solvent, residue are separated with silica gel column chromatography, obtain faint yellow solid, 2,6- dimethyl -4- phenyl -3,5- diethyl oxygen carbonyls -
Isosorbide-5-Nitrae-dihydropyridine, yield 65%.Catalyst cannot reuse.
Comparative example 4
Benzaldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and perfluoro octyl sulfonic acid (0.05mmol) stir 12h at 80 DEG C.It is spin-dried for after reaction molten
Agent, residue are separated with silica gel column chromatography, obtain faint yellow solid, 2,6- dimethyl -4- phenyl -3,5- diethyl oxygen carbonyl -1,
4- dihydropyridine, yield 27%.Catalyst cannot reuse.
Comparative example 5
Benzaldehyde (1mmol) is added in 50mL round-bottomed flask, ethyl acetoacetate (2.0mmol), ammonium acetate
(1.2mmol), solvent THF (2mL) and betanaphthol aldehyde schiff bases zirconium dichloride (0.05mmol) stir 12h at 80 DEG C.Reaction
After be spin-dried for solvent, residue is separated with silica gel column chromatography, obtains faint yellow solid, 2,6- dimethyl -4- phenyl -3,5- bis-
Carbethoxyl group-Isosorbide-5-Nitrae-dihydropyridine, yield 46%.Catalyst cannot reuse.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (6)
1. a kind of novel ionic betanaphthol aldehyde schiff bases zirconium complex, it is characterised in that:
Cationic betanaphthol aldehyde schiff bases zirconium complex (I), zirconium atom and naphthol novolak schiff base ligand and a hydrone with
And an X is coordinated to form cation, another anion X-Ionic bond is formed with the cationic portion of complex；Complex knot
Structure formula (I) is as follows:
2. a kind of novel ionic betanaphthol aldehyde schiff bases zirconium complex according to claim 1, it is characterised in that: described
X is perfluoro octyl sulfonic acid group OSO2C8F17, pentafluorophenyl group sulfonic acid group OSO2C6F5, perfluoro hexyl sulfonic acid group OSO2C6F13Or
Perfluoro butyl sulfonic acid group OSO2C4F9One of.
3. a kind of preparation method of novel ionic betanaphthol aldehyde schiff bases zirconium complex, it is characterised in that:
Betanaphthol aldehyde schiff bases zirconium dichloride is dissolved in solvent, and in N2Under protection, silver salt is added, is protected from light at room temperature
1-4h, filtering are reacted, n-hexane is added in filtrate, until layering, is put into refrigerator freezing for 24 hours, precipitation complex is betanaphthol aldehyde seat
Husband's alkali zirconium complex (I).
4. a kind of preparation method of novel ionic betanaphthol aldehyde schiff bases zirconium complex according to claim 3, feature
It is: the solvent: tetrahydrofuran, acetone, acetonitrile, methanol or ethyl alcohol；The silver salt are as follows: perfluoro octyl sulfonic acid silver
AgOSO2C8F17, pentafluorophenyl group sulfonic acid silver AgOSO2C6F5, perfluoro hexyl sulfonic acid silver AgOSO2C6F13Or perfluoro butyl sulfonic acid silver
AgOSO2C4F9One of.
5. a kind of application of novel ionic betanaphthol aldehyde schiff bases zirconium complex, it is characterised in that:
Betanaphthol aldehyde schiff bases zirconium complex (I) can be catalyzed: the Hantzsch reaction of aldehyde, 'beta '-ketoester and ammonium acetate prepares Isosorbide-5-Nitrae-two
Pyridinium hydroxide derivative.
6. a kind of application method of novel ionic betanaphthol aldehyde schiff bases zirconium complex, it is characterised in that:
It the use of betanaphthol aldehyde schiff bases zirconium complex (I) is catalyst, with aldehyde, 'beta '-ketoester and ammonium acetate are raw material, are had with common
Solvent reacts 1-12h at 50-120 DEG C as reaction dissolvent.After completion of the reaction, solvent is removed, it is dilute that methylene chloride is added
It releases, filters, recycle catalyst, filtrate is spin-dried for, and by column chromatography for separation, obtains Isosorbide-5-Nitrae-dihydrogen pyridine derivative；Its structural formula is
(II) as follows:
R1For phenyl, p-methylphenyl, p-methoxyphenyl, p-hydroxybenzene, o-fluorophenyl, rubigan, p-bromophenyl, neighbour
Nitrobenzophenone, m-nitro base, one of 2- naphthalene, styryl, 2- furfuryl group, ethyl or propyl；R2For methyl or ethyl
One of；
The aldehyde be benzaldehyde, p-tolyl aldehyde, P-methoxybenzal-dehyde, parahydroxyben-zaldehyde, o fluorobenzaldehyde, to chlorobenzene
In formaldehyde, p-bromobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, 2- naphthaldehyde, cinnamic acid, furfural, propionic aldehyde or butyraldehyde
It is a kind of；
The 'beta '-ketoester is one of methyl acetoacetate or ethyl acetoacetate；
The solvent is one of tetrahydrofuran, acetonitrile, 1,2 dichloroethanes, acetone, ethyl alcohol, toluene；
The dosage of the catalyst is 1.0-10mol%；Catalyst reusable 5 times or more.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114249635A (en) * | 2021-11-22 | 2022-03-29 | 山西医科大学 | Novel chiral (R) -binaphthol titanium complex and preparation method and application thereof |
| CN115536980A (en) * | 2022-11-07 | 2022-12-30 | 四川大学 | Schiff base transition metal complex modified ablation-resistant resin matrix material and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993019076A1 (en) * | 1992-03-20 | 1993-09-30 | Idaho Research Foundation, Inc. | θ6 METAL COMPLEXES OF 4-ARYL-1,4-DIHYDROPYRIDINES |
| CN1436172A (en) * | 2000-06-12 | 2003-08-13 | 卫材株式会社 | 1,2-dihydropyridine compounds, process for preparation of same and use thereof |
| JP2005246703A (en) * | 2004-03-02 | 2005-09-15 | Mitsubishi Paper Mills Ltd | New zinc complex and new oxo zirconium complex and thermosensitive recording material including them |
| CN104130238A (en) * | 2014-08-04 | 2014-11-05 | 河南省科学院化学研究所有限公司 | Preparation method of rotigotine |
| US20170036989A1 (en) * | 2015-08-06 | 2017-02-09 | National Chung Cheng University | Method of Manufacturing Nitrone Compound |
| CN107141249A (en) * | 2017-06-28 | 2017-09-08 | 湖南大学 | A kind of method for synthesizing 1,4 dihydrogen pyridine derivatives |
| CN107722049A (en) * | 2017-11-07 | 2018-02-23 | 山西医科大学 | A kind of preparation and its application of novel ionic double-core schiff bases titanium complex |
| CN107790186A (en) * | 2017-11-07 | 2018-03-13 | 山西医科大学 | A kind of new decamethyl Zirconocenes and its preparation method and application |
| CN110003093A (en) * | 2019-04-15 | 2019-07-12 | 陕西师范大学 | The method that bis cyclopentadienyl zirconium dichloride cooperates with benzoic acids ligand catalysis synthesis 1,4- dihydrogen pyridine derivative |
-
2019
- 2019-09-06 CN CN201910843557.4A patent/CN110483563B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993019076A1 (en) * | 1992-03-20 | 1993-09-30 | Idaho Research Foundation, Inc. | θ6 METAL COMPLEXES OF 4-ARYL-1,4-DIHYDROPYRIDINES |
| CN1436172A (en) * | 2000-06-12 | 2003-08-13 | 卫材株式会社 | 1,2-dihydropyridine compounds, process for preparation of same and use thereof |
| JP2005246703A (en) * | 2004-03-02 | 2005-09-15 | Mitsubishi Paper Mills Ltd | New zinc complex and new oxo zirconium complex and thermosensitive recording material including them |
| CN104130238A (en) * | 2014-08-04 | 2014-11-05 | 河南省科学院化学研究所有限公司 | Preparation method of rotigotine |
| US20170036989A1 (en) * | 2015-08-06 | 2017-02-09 | National Chung Cheng University | Method of Manufacturing Nitrone Compound |
| CN107141249A (en) * | 2017-06-28 | 2017-09-08 | 湖南大学 | A kind of method for synthesizing 1,4 dihydrogen pyridine derivatives |
| CN107722049A (en) * | 2017-11-07 | 2018-02-23 | 山西医科大学 | A kind of preparation and its application of novel ionic double-core schiff bases titanium complex |
| CN107790186A (en) * | 2017-11-07 | 2018-03-13 | 山西医科大学 | A kind of new decamethyl Zirconocenes and its preparation method and application |
| CN110003093A (en) * | 2019-04-15 | 2019-07-12 | 陕西师范大学 | The method that bis cyclopentadienyl zirconium dichloride cooperates with benzoic acids ligand catalysis synthesis 1,4- dihydrogen pyridine derivative |
Non-Patent Citations (3)
| Title |
|---|
| ŁUKASZ GÓRSKIA等，: "Fluoride-selective polymeric membrane electrodes based on Zr(IV)- and Al(III)-salen ionophores of various structures", 《ANALYTICA CHIMICA ACTA》 * |
| MASOUD NASR-ESFAHANI等，: "Rapid and efficient oxidation of Hantzsch 1,4-dihydropyridines with sodium periodate catalyzed by manganese (III) Schiff base complexes", 《BIOORG. MED. CHEM.》 * |
| MJNICA VICIANO等，: "Salcy-Naphthalene Cobalt Complexes as Catalysts for the Synthesis of High Molecular Weight Polycarbonates", 《CHEMCATCHEM》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114249635A (en) * | 2021-11-22 | 2022-03-29 | 山西医科大学 | Novel chiral (R) -binaphthol titanium complex and preparation method and application thereof |
| CN115536980A (en) * | 2022-11-07 | 2022-12-30 | 四川大学 | Schiff base transition metal complex modified ablation-resistant resin matrix material and preparation method and application thereof |
| CN115536980B (en) * | 2022-11-07 | 2024-01-26 | 四川大学 | Schiff base transition metal complex modified ablation-resistant resin matrix material and preparation method and application thereof |
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