CN112452317B - 一种表面改性的二氧化硅微球催化剂、制备方法及应用 - Google Patents
一种表面改性的二氧化硅微球催化剂、制备方法及应用 Download PDFInfo
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- CN112452317B CN112452317B CN202011333483.9A CN202011333483A CN112452317B CN 112452317 B CN112452317 B CN 112452317B CN 202011333483 A CN202011333483 A CN 202011333483A CN 112452317 B CN112452317 B CN 112452317B
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- silicon dioxide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000004005 microsphere Substances 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- -1 diketone compound Chemical class 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 238000006713 insertion reaction Methods 0.000 claims description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 229940125898 compound 5 Drugs 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002253 acid Substances 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 125000005594 diketone group Chemical group 0.000 abstract description 5
- 238000009830 intercalation Methods 0.000 abstract description 5
- 230000002687 intercalation Effects 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 150000004756 silanes Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 239000012230 colorless oil Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 239000003480 eluent Substances 0.000 description 7
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 4
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 229940125773 compound 10 Drugs 0.000 description 4
- 229940125797 compound 12 Drugs 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- DMIIMPQQPXUKOO-UHFFFAOYSA-N 5-methylcyclohexane-1,3-dione Chemical compound CC1CC(=O)CC(=O)C1 DMIIMPQQPXUKOO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- XWMWRWORUNGQNO-UHFFFAOYSA-N COC1=CC(=C(C=C1)S)C1=CC=CC=C1 Chemical compound COC1=CC(=C(C=C1)S)C1=CC=CC=C1 XWMWRWORUNGQNO-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical class [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
本发明公开了一种表面改性的二氧化硅微球催化剂、制备方法及应用。该催化剂由二氧化硅微球经过酸、碱或金属负载制得无孔的表面改性的二氧化硅微球催化剂。以α‑重氮酯和二酮类、胺类、硫酚类、环状二酮类、硅烷类化合物为起始原料,用不同的二氧化硅微球作催化剂,在加热条件下实现C‑H、N‑H、S‑H、O‑H、C‑C和Si‑H插入反应。该方法的二氧化硅微球作为催化剂,可重复利用,经济环保,制备简单,兼容多种化学键的构筑,合成反应原子利用效率高,可以实现克级规模反应。
Description
技术领域
本发明涉及催化剂、制备方法及用途,特别涉及一种表面改性的二氧化硅微球催化剂、制备方法及应用。
背景技术
二氧化硅(SiO2)纳米材料在化学合成、生物医药、电子、光学等领域具有广泛的应用。随着其应用领域和功能的不同,分类也有所不同,按颗粒尺寸来分,有纳米级、亚微米级和微米级等;按形貌来分,又有多孔、球形等种类,所以其粒径和形貌的多变性及可调控性,决定了二氧化硅(SiO2)纳米材料的多功能性。其中合成二氧化硅微球最著名的方法是由等人最先报道的正硅酸乙酯(TEOS)在碱性体系中发生水解和缩聚反应的溶胶-凝胶法。这种方法原料简单,反应条件可控,易于操作,被认为是制备单分散二氧化硅最为简单和有效的方法。因此,通过调节反应条件可以得到大小相同的无孔二氧化硅微球,将其作为固相材料以实现非均相催化成为一个重要的研究方向。
重氮化合物作为一类重要的卡宾前体,可以发生C-H(Angew.Chem.Int.Ed.,2018,57:8927)、N-H(Chem.Sci.2016,7,1104)、S-H(Chem.Sci.,2015,6,2488)、O-H(J.Am.Chem.Soc.2020,142,10557)、Si-H(Org.Lett.2018,20,6544)等插入反应,为构建各种药物分子、天然产物以及生物活性分子提供了有效的手段。这些报道都存在一个或多个缺点,例如原料不易得、反应条件苛刻、催化剂不可重复利用或不能进行克级反应。
发明内容
发明目的:本发明目的是提供一种经过酸、碱、金属表面改性的二氧化硅微球催化剂。
本发明另一目的是提供所述表面改性的二氧化硅微球催化剂制备方法和应用。
技术方案:本发明提供一种表面改性的二氧化硅微球催化剂,由二氧化硅微球经过酸、碱或金属负载制得无孔的表面改性的二氧化硅微球催化剂。
进一步地,所述酸为盐酸、硫酸、高氯酸、磷酸、硝酸、三氟甲磺酸中的一种或几种的混合物。
进一步地,所述碱为碳酸钠、碳酸氢钠、磷酸二氢钠、磷酸钾、碳酸铯、碳酸钾、醋酸钠中的一种或几种的混合物。
所述的表面改性的二氧化硅微球催化剂的制备方法,包括如下步骤:
(1)二氧化硅微球的制备:
将乙醇、去离子水、氨水混合搅拌,得到混合溶液A;将乙醇、正硅酸乙酯混合搅拌,得到混合溶液B;将混合溶液B加入混合溶液A内,室温搅拌,洗涤,干燥,得到二氧化硅微球;
(2)酸负载于二氧化硅微球:
将二氧化硅微球浸泡于酸溶液中,后过滤,用去离子水洗涤至中性或不洗涤,抽真空,即得酸改性二氧化硅微球,记作SMSI;
(3)碱负载于二氧化硅微球:
将二氧化硅微球浸泡于碱溶液中,后过滤,用去离子水洗涤至中性,抽真空,即得碱改性二氧化硅微球,记作SMSII;
(4)金属负载于二氧化硅微球:
取二氧化硅微球,加入乙醇,滴加偶联剂,搅拌,反应结束后,用乙醇和去离子水依次洗涤,干燥,得到改性后的二氧化硅微球;取改性后的二氧化硅微球、可溶性金属盐,加入去离子水后烘烤,经洗涤过滤后,抽真空,得到金属负载的二氧化硅微球,记做SMSIII。
进一步地,所述可溶性金属盐为三水硝酸铜、九水硝酸铁、硝酸银、氯化钴中的一种或几种的混合物。
进一步地,所述偶联剂为3-氨基丙基三乙氧基硅烷、缩水甘油醚氧基丙基三甲氧基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三乙氧基硅烷、巯丙基三甲(乙)氧基硅烷中的一种或几种的混合物。
所述的表面改性的二氧化硅微球催化剂的应用,以α-重氮酯类化合物7和二酮类化合物8、胺类化合物9、硫酚类化合物10、环状二酮类化合物11或硅烷类化合物12为起始原料,使用表面改性的二氧化硅微球催化剂,在加热条件下,实现C-H、N-H、S-H、O-H、C-C和Si-H插入反应,生成三羰基化合物1、α-氨基酯2、α-硫基酯3、α-氧基酯4、1,4-二酮化合物5、α-硅烷基酯6。优选地、所述α-重氮酯类化合物7与二酮类化合物8的摩尔比为1∶6;所述α-重氮酯类化合物7与胺类化合物9的摩尔比为1∶4;所述α-重氮酯类化合物7与硫酚类化合物10的摩尔比为1∶1;所述α-重氮酯类化合物7与环状二酮类化合物11的摩尔比为1∶6;所述α-重氮酯类化合物7与硅烷类化合物12的摩尔比为1∶12。
合成路线如下:
用酸负载的二氧化硅微球(SMSI)催化α-重氮酯类化合物7和二酮类化合物8在加热条件下实现C-H插入反应,生成三羰基化合物1;
用酸负载的二氧化硅微球(SMSI)催化α-重氮酯类化合物7和胺类化合物9在加热条件下实现C-N插入反应,生成α-氨基酯2;
用酸负载的二氧化硅微球(SMSI)催化α-重氮酯7和硫酚类化合物10在加热条件下实现C-S插入反应,生成α-硫基酯3;
用酸负载的二氧化硅微球(SMSI)催化α-重氮酯7和环状二酮类化合物11在加热条件下实现C-O插入反应,生成α-氧基酯4;
用碱负载的二氧化硅微球(SMSII)催化α-重氮酯7和二酮类化合物8在加热条件下实现C-C插入反应,生成l,4-二酮化合物5;
用金属负载的二氧化硅微球(SMSIII)催化α-重氮酯7和硅烷类化合物12在加热条件下实现C-Si插入反应,生成α-硅烷基酯6;
其中,R1选自苯基、含有卤素、甲基或甲氧基取代的芳基;
R2为碳原子数为1-4的烷基、烯丙基或苄基;
R3为苯基、含有卤素、甲基或甲氧基取代的芳基;
R4为苯基、含有卤素、甲基或甲氧基取代的芳基;
R5为苯基、含有卤素、甲基或甲氧基取代的芳基;
R6为苯基、含有卤素、甲基或甲氧基取代的芳基;
R7为烷基;
R8为甲基、苯基、乙氧基、异丙基、含有卤素、甲基或甲氧基取代的芳基;
R9为甲基、苯基、乙氧基、异丙基、含有卤素、甲基或甲氧基取代的芳基。
进一步地,反应溶剂为二氯甲烷、1,2-二氯乙烷、四氢呋喃、丙酮、N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、甲苯、1,4-二氧六环中的一种或几种的混合物。
进一步地,所述α-重氮酯类化合物7于反应溶剂中的摩尔浓度为0.05~1.0M。优先地,所述溶剂为l,2-二氯乙烷,所述α-重氮酯类化合物于反应溶剂中的摩尔浓度为0.1M。
进一步地,所述α-重氮酯类化合物7和二酮类化合物8、胺类化合物9、硫酚类化合物10、环状二酮类化合物11与硅烷类化合物12的摩尔比为2∶1~1∶15。
有益效果:本发明的二氧化硅微球催化剂,以α-重氮化合物为原料,利用该催化剂,在加热条件下,实现C-H、N-H、S-H、O-H、C-C和Si-H插入反应。原料便宜易得,催化剂制备工艺简单,催化剂可高效回收利用、经济环保,反应条件温和、效率高,反应可达到克级规模,具有实际应用价值。
具体实施方式
本实施例的改性二氧化硅微球催化剂的制备,包括如下步骤:
1)二氧化硅微球的制备:
吸取15-20mL的乙醇于200mL的圆底烧瓶,然后吸取20-25mL的去离子水,之后加5-15mL28%的氨水,室温搅拌,得到混合溶液A;吸取40-50mL的乙醇于200mL的圆底烧瓶,然后加入3-5mL正硅酸乙酯,室温搅拌,得到混合溶液B;将混合溶液B快速加入混合溶液A内,室温搅拌1-2h,经洗涤后,干燥,得到二氧化硅微球。
2)酸负载于二氧化硅微球:
将二氧化硅微球浸泡于酸水溶液中,25-50℃下浸泡12-30h,经过滤后,用去离子水洗涤至中性或不洗涤,得到各种表面改性的二氧化硅微球,例如,SMSI-a1(HClO4处理后的二氧化硅微球,洗涤至中性)、SMSI-b1(H2SO4处理后的二氧化硅微球,洗涤至中性)、SMSI-c1(CF3SO3H处理后的二氧化硅微球,洗涤至中性)、SMSI-d1(H3PO4处理后的二氧化硅微球,洗涤至中性)、SMSI-e1(HCl处理后的二氧化硅微球,洗涤至中性)、SMSI-f1(HNO3处理后的二氧化硅微球,洗涤至中性)、SMSI-a2(HClO4处理后的二氧化硅微球,未洗涤)、SMSI-b2(H2SO4处理后的二氧化硅微球,未洗涤)、
3)碱负载于二氧化硅微球:
将二氧化硅微球浸泡于碱水溶液中,25-50℃下浸泡12-30h,经过滤后,用去离子水洗涤至中性,得到各种表面改性的二氧化硅微球,例如,SMSII-a1(NaHCO3处理后的二氧化硅微球)、SMSII-b1(NaH2PO4处理后的二氧化硅微球)、SMSII-c1(Na2CO3处理后的二氧化硅微球)、SMSII-d1(K3PO4处理后的二氧化硅微球)、SMSII-e1(Cs2CO3处理后的二氧化硅微球)、SMSII-f1(K2CO3处理后的二氧化硅微球)、SMSII-g1(CH3COONa处理后的二氧化硅微球)。
4)金属负载于二氧化硅微球:
称取2-4g二氧化硅微球,然后加入100-150mL乙醇于200mL的圆底烧瓶,滴加3-6mL的偶联剂,80℃搅拌12-36h;反应结束后,冷却至室温,之后用乙醇和去离子水依次洗涤,干燥,得到改性后的二氧化硅微球;称取0.5-1g改性后的二氧化硅微球、50-600mg的可溶性金属盐于100mL的水热合成釜中,加入50-80mL去离子水,置于100-150℃烘箱烘1-2天,经洗涤过滤后,抽真空,得到金属负载的二氧化硅微球,例如,SMSIII-a1(三水合硝酸铜处理后的二氧化硅微球)、SMSIII-b1(九水合硝酸铁处理后的二氧化硅微球)、SMSIII-c1(硝酸银处理后的二氧化硅微球)、SMSIII-d1(氯化钴处理后的二氧化硅微球)。
实施例1
在室温条件下,依次称取苯基重氮乙酸乙酯7a(0.5mmol)、二苯甲酰基甲烷8a(3mmol)、SMSI-a2(HClO4处理后的二氧化硅微球,未洗涤)(30mg)于25mL Schlenk反应瓶中,在空气氛围下,加入1,2-二氯乙烷5mL,在室温下搅拌5分钟,放入80℃的油浴中反应3小时。反应结束后,将混合物冷却至室温,减压下除去挥发组份,然后用硅胶柱层析分离(洗脱液为石油醚(60-90℃)/乙酸乙酯,v/v=10∶1),得到白色固体目标产物1a(132mg,收率68%)。目标产物通过核磁共振谱测定得到确认。
实施例2
在室温条件下,依次称取苯基重氮乙酸甲酯7b(0.5mmol)、二苯甲酰基甲烷8a(3mmol)、SMSI-a1(HClO4处理后的二氧化硅微球,洗涤至中性)(30mg)于25mL Schlenk反应瓶中,在空气氛围下,加入四氢呋喃5mL,在室温下搅拌5分钟,放入70℃的油浴中反应2小时。反应结束后,将混合物冷却至室温,减压下除去挥发组份,然后用硅胶柱层析分离(洗脱液为石油醚(60-90℃)/乙酸乙酯,v/v=10∶1),得到白色固体目标产物1b(147mg,收率79%)。目标产物通过核磁共振谱测定得到确认。
实施例3
在室温条件下,依次称取苯基重氮乙酸乙酯7a(0.5mmol),苯胺9a(2mmol)、SMSI-b2(H2SO4处理后的二氧化硅微球,未洗涤)(40mg)于25mL Schlenk反应瓶中,在空气氛围下,加入丙酮5mL,在室温下搅拌3分钟,放入50℃的油浴中反应1小时。反应结束后,将混合物冷却至室温,减压下除去挥发组份,然后用硅胶柱层析分离(洗脱液为石油醚(60-90℃)/乙酸乙酯,v/v=5∶1),得到黄色固体目标产物2a(103mg,收率81%)。目标产物通过核磁共振谱测定得到确认。
实施例4
在室温条件下,依次称取苯基重氮乙酸乙酯7a(0.5mmol),对甲苯硫酚10a(0.5mmol)、SMSI-c1(CF3SO3H处理后的二氧化硅微球,洗涤至中性)(30mg)于25mL Schlenk反应瓶中,在空气氛围下,加入1,2-二氯乙烷5mL,在室温下搅拌5分钟,放入70℃的油浴中反应0.5小时。反应结束后,减压下除去挥发组份,然后用硅胶柱层析分离(洗脱液为石油醚(60-90℃)/乙酸乙酯,v/v=20∶1),得到无色油状目标产物3a(124mg,收率87%)。目标产物通过核磁共振谱测定得到确认。
实施例5
在室温条件下,依次称取苯基重氮乙酸甲酯7b(0.5mmol),对甲氧基苯硫酚10b(2.0mmol)、SMSI-f1(HNO3处理后的二氧化硅微球,洗涤至中性)(30mg)于25mL Schlenk反应瓶中,在空气氛围下,加入1,2-二氯乙烷5mL,在室温下搅拌5分钟,放入70℃的油浴中反应1小时。反应结束后,减压下除去挥发组份,然后用硅胶柱层析分离(洗脱液为石油醚(60-90℃)/乙酸乙酯,v/v=20∶1),得到无色油状目标产物3b(113mg,收率78%)。目标产物通过核磁共振谱测定得到确认。
实施例6
在室温条件下,依次称取苯基重氮乙酸乙酯7a(0.5mmol),5-甲基环己烷-1,3-二酮11a(3mmol)、SMSI-b2(H2SO4处理后的二氧化硅微球,未洗涤)(50mg)于25mL Schlenk反应瓶中,在空气氛围下,加入1,2-二氯乙烷5mL,在室温下搅拌2分钟,放入60℃的油浴中反应3小时。反应结束后,将混合物冷却至室温,减压下除去挥发组份,然后用硅胶柱层析分离(洗脱液为石油醚(60-90℃)/乙酸乙酯,v/v=2∶1),得到无色油状目标产物4a(129mg,收率89%)。目标产物通过核磁共振谱测定得到确认。
实施例7
在室温条件下,依次称取苯基重氮乙酸苄酯7c(0.5mmol),5-甲基环己烷-1,3-二酮11a(3mmol)、SMSI-a2(HClO4处理后的二氧化硅微球,未洗涤)(50mg)于25mL Schlenk反应瓶中,在空气氛围下,加入甲苯5mL,在室温下搅拌2分钟,放入60℃的油浴中反应4小时。反应结束后,将混合物冷却至室温,减压下除去挥发组份,然后用硅胶柱层析分离(洗脱液为石油醚(60-90℃)/乙酸乙酯,v/v=2∶1),得到无色油状目标产物4b(149mg,收率85%)。目标产物通过核磁共振谱测定得到确认。
实施例8
在室温条件下,依次称取苯基重氮乙酸甲酯7b(0.5mmol)、二苯甲酰基甲烷8a(3mmol)、SMSII-a1(NaHCO3处理后的二氧化硅微球,洗涤至中性)(40mg)于25mL Schlenk反应瓶中,在空气氛围下,加入丙酮5mL,在室温下搅拌2分钟,放入70℃的油浴中反应14小时。反应结束后,将混合物冷却至室温,减压下除去挥发组份,然后用硅胶柱层析分离(洗脱液为石油醚(60-90℃)/乙酸乙酯,v/v=10∶1),得到无色油状目标产物5a(119mg,收率64%)。目标产物通过核磁共振谱测定得到确认。
实施例9
在室温条件下,依次称取苯基重氮乙酸甲酯7b(0.5mmol),三乙基硅烷12a(6mmol)、SMSIII-b1(九水合硝酸铁处理后的二氧化硅微球)于25mL Schlenk反应管中,在空气氛围下,加入DMF 5mL,在室温下搅拌5分钟,放入65℃的油浴中反5小时。反应结束后,减压下除去挥发组份,然后用硅胶柱层析分离(洗脱液为石油醚(60-90℃)/乙酸乙酯,v/v=10∶1),得到无色油状目标产物6a(119mg,收率90%)。目标产物通过核磁共振谱测定得到确认。
前述典型化合物表征数据
C-H插入反应产物(1a),白色固体,1H NMR(400MHz,CDCl3)δ7.96(dd,J=8.5,1.2Hz,2H),7.68(dd,J=8.5,1.1Hz,2H),7.53-7.47(m,1H),7.46-7.40(m,1H),7.36(t,J=7.7Hz,2H),7.30-7.27(m,4H),7.18(t,J=7.4Hz,2H),7.14-7.08(m,1H),6.13(d,J=11.2Hz,1H),4.83(d,J=11.2Hz,1H),4.26-4.06(m,2H),1.19(t,J=7.1Hz,3H).13C{1H}NMR(100MHz,CDCl3)δ194.65,194.29,172.71,136.64,136.35,135.31,133.55,133.45,128.88,128.84,128.77,128.74,128.61,128.57,127.94,61.55,60.89,52.64,14.06.
N-H插入反应产物(2a),黄色固体,1H NMR(400MHz,CDCl3)δ7.54(d,J=7.2Hz,2H),7.36(dt,J=14.2,6.9Hz,3H),7.15(t,J=7.9Hz,2H),6.73(t,J=7.3Hz,1H),6.60(d,J=7.8Hz,2H),5.10(s,1H),5.01(s,1H),4.31-4.12(m,2H),1.24(t,J=7.1Hz,3H).13C{1H}NMR(100MHz,CDCl3)δ171.91,146.09,137.82,129.31,128.90,128.30,127.30,118.11,113.49,61.90,60.87,14.12.
S-H插入反应产物(3a),无色油状,1H NMR(400MHz,CDCl3)δ7.51-7.43(m,2H),7.36-7.29(m,5H),7.09(d,J=7.9Hz,2H),4.87(s,1H),4.21-4.07(m,2H),2.33(s,3H),1.19(t,J=7.1Hz,3H).13C{1H}NMR(100MHz,CDCl3)δ170.55,138.33,135.88,133.36,130.05,129.75,128.64,128.58,128.23,61.67,56.82,21.19,14.04.
O-H插入反应产物(4a),无色油状,1H NMR(400MHz,CDCl3)δ7.47-7.41(m,2H),7.38-7.30(m,3H),5.41(d,J=7.8Hz,1H),5.25(d,J=4.1Hz,1H),4.21-4.05(m,2H),2.64-2.45(m,1H),2.42-2.11(m,3H),2.08-1.91(m,1H),1.16(td,J=7.1,1.9Hz,3H),1.04(t,J=6.1Hz,3H).13C{1H}NMR(100MHz,CDCl3)δ199.31,175.46,175.42,168.16,168.12,133.85,129.37,128.85,127.08,127.06,103.82,78.16,78.03,61.96,61.93,44.95,36.92,36.90,28.66,28.62,20.76,20.73,13.91.
C-C插入反应产物(5a),无色油状,1H NMR(400MHz,CDCl3)δ7.95-7.90(m,2H),7.67-7.62(m,2H),7.55-7.50(m,1H),7.48-7.44(m,2H),7.42(t,J=7.7Hz,2H),7.37-7.34(m,1H),7.32(t,J=7.5Hz,2H),7.28-7.25(m,1H),7.24-7.20(m,2H),4.21(d,J=17.6Hz,1H),3.85(d,J=17.6Hz,1H),3.72(s,3H).13C{1H}NMR(100MHz,CDCl3)δ196.93,195.50,170.94,138.38,136.64,136.10,133.30,132.37,130.49,129.07,128.64,128.20,127.86,127.82,127.72,65.18,52.75,49.25.
Si-H插入反应产物(6a),无色油状,1H NMR(400MHz,CDCl3)δ7.28(d,J=7.3Hz,2H),7.20(t,J=7.6Hz,2H),7.09(t,J=7.3Hz,1H),3.60(s,3H),3.46(s,1H),0.83(t,J=7.9Hz,9H),0.56-0.48(m,6H).13C{1H}NMR(100MHz,CDCl3)δ173.79,136.67,128.59,128.24,125.68,51.45,42.87,7.15,2.81。
Claims (6)
2.根据权利要求1所述的表面改性的二氧化硅微球催化剂的应用,其特征在于:所述碱为碳酸钠、碳酸氢钠、磷酸二氢钠、磷酸钾、碳酸铯、碳酸钾、醋酸钠中的一种或几种的混合物。
3.根据权利要求1所述的表面改性的二氧化硅微球催化剂的应用,其特征在于:所述插入反应的反应溶剂为二氯甲烷、1,2-二氯乙烷、四氢呋喃、丙酮、N,N-二甲基甲酰胺 (DMF)、二甲基亚砜 (DMSO)、甲苯、1,4-二氧六环中的一种或几种的混合物。
4.根据权利要求1所述的表面改性的二氧化硅微球催化剂的应用,其特征在于:所述α-重氮酯类化合物7于反应溶剂中的摩尔浓度为0.05~1.0 M。
5.根据权利要求1所述的表面改性的二氧化硅微球催化剂的应用,其特征在于:所述α-重氮酯类化合物7和二酮类化合物8的摩尔比为2:1~1:15。
6.一种权利要求1所述的表面改性的二氧化硅微球催化剂的应用,其特征在于:所述表面改性的二氧化硅微球催化剂的制备方法包括如下步骤:
(1)二氧化硅微球的制备:
将乙醇、去离子水、氨水混合搅拌,得到混合溶液A;将乙醇、正硅酸乙酯混合搅拌,得到混合溶液B;将混合溶液B加入混合溶液A内,室温搅拌,洗涤,干燥,得到二氧化硅微球;
(2)碱负载于二氧化硅微球:
将二氧化硅微球浸泡于碱溶液中,后过滤,用去离子水洗涤至中性,抽真空,即得碱改性二氧化硅微球,记作SMSII。
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