CN111470991A - Synthetic method of aminoanisole compound - Google Patents
Synthetic method of aminoanisole compound Download PDFInfo
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- CN111470991A CN111470991A CN201910062773.5A CN201910062773A CN111470991A CN 111470991 A CN111470991 A CN 111470991A CN 201910062773 A CN201910062773 A CN 201910062773A CN 111470991 A CN111470991 A CN 111470991A
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- alkaline earth
- earth metal
- carbon
- nickel
- composite material
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- -1 aminoanisole compound Chemical class 0.000 title claims abstract description 43
- 238000010189 synthetic method Methods 0.000 title claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 125
- 239000002114 nanocomposite Substances 0.000 claims abstract description 84
- 239000000463 material Substances 0.000 claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 62
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 51
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- 238000006722 reduction reaction Methods 0.000 claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- POIOOCHMXHKUHV-UHFFFAOYSA-N [nitro-[nitro(phenyl)methoxy]methyl]benzene Chemical class C=1C=CC=CC=1C([N+](=O)[O-])OC([N+]([O-])=O)C1=CC=CC=C1 POIOOCHMXHKUHV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 239000011258 core-shell material Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract 6
- 239000011148 porous material Substances 0.000 claims description 30
- 238000009826 distribution Methods 0.000 claims description 21
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000013335 mesoporous material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 6
- WGYFINWERLNPHR-UHFFFAOYSA-N 3-nitroanisole Chemical compound COC1=CC=CC([N+]([O-])=O)=C1 WGYFINWERLNPHR-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- CFBYEGUGFPZCNF-UHFFFAOYSA-N 2-nitroanisole Chemical compound COC1=CC=CC=C1[N+]([O-])=O CFBYEGUGFPZCNF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- RTZOGYCMIMOVHU-UHFFFAOYSA-N 4-methoxy-2-methyl-1-nitrobenzene Chemical compound COC1=CC=C([N+]([O-])=O)C(C)=C1 RTZOGYCMIMOVHU-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910052705 radium Inorganic materials 0.000 claims description 3
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 80
- 238000010438 heat treatment Methods 0.000 description 36
- 239000000047 product Substances 0.000 description 31
- 239000010410 layer Substances 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 15
- 239000000376 reactant Substances 0.000 description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 10
- 229910052573 porcelain Inorganic materials 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000000197 pyrolysis Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 150000002815 nickel Chemical class 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000012456 homogeneous solution Substances 0.000 description 7
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 6
- 239000004312 hexamethylene tetramine Substances 0.000 description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 229940078494 nickel acetate Drugs 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- PRLDILURXJMICQ-UHFFFAOYSA-N 4-[(4-aminophenyl)methoxymethyl]aniline Chemical compound C1=CC(N)=CC=C1COCC1=CC=C(N)C=C1 PRLDILURXJMICQ-UHFFFAOYSA-N 0.000 description 3
- GMPKIPWJBDOURN-UHFFFAOYSA-N Methoxyamine Chemical compound CON GMPKIPWJBDOURN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- NOXMVNQTYSBCJC-UHFFFAOYSA-N CC(C=C(COCC(C=C1)=CC(C)=C1N)C=C1)=C1N Chemical compound CC(C=C(COCC(C=C1)=CC(C)=C1N)C=C1)=C1N NOXMVNQTYSBCJC-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- QDWGWHMTZIAPOE-UHFFFAOYSA-N [N+](=O)([O-])C1=CC=C(C=C1C)COCC=1C=C(C(=CC=1)[N+](=O)[O-])C Chemical compound [N+](=O)([O-])C1=CC=C(C=C1C)COCC=1C=C(C(=CC=1)[N+](=O)[O-])C QDWGWHMTZIAPOE-UHFFFAOYSA-N 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- GOJFAKBEASOYNM-UHFFFAOYSA-N 2-(2-aminophenoxy)aniline Chemical class NC1=CC=CC=C1OC1=CC=CC=C1N GOJFAKBEASOYNM-UHFFFAOYSA-N 0.000 description 1
- PHQAPVZFVVIONO-UHFFFAOYSA-N COC1=CC=CC=C1C(=O)C=CN Chemical compound COC1=CC=CC=C1C(=O)C=CN PHQAPVZFVVIONO-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000725 suspension Substances 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
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/398—
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
-
- B01J35/69—
Abstract
The invention provides a synthetic method of an amino anisole compound, which comprises the following steps: the carbon-coated nickel nano composite material containing alkaline earth metal is used as a catalyst to catalyze the nitrobenzyl ether compounds to carry out hydrogenation reduction reaction in the hydrogen atmosphere; the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, and the inner core is nickel nano particles. The method adopts the carbon-coated nickel nanocomposite containing alkaline earth metal as a catalyst, the carbon material and nickel nanoparticles act synergistically to produce a good catalytic effect, the alkaline earth metal of the shell layer further synergistically improves the catalytic performance of the material, and the carbon-coated nickel nanocomposite is used for hydrogenation reduction synthesis of an amino phenyl ether compound from a nitrobenzyl ether compound and has excellent activity, selectivity and safety.
Description
Technical Field
The invention relates to the field of catalysis, and particularly relates to a synthesis method of an amino anisole compound.
Background
The amino-phenyl ether compound can be widely applied to dye industry, medicine industry and perfume intermediates. The traditional industrial production method is a chemical reduction method, and the nitro-anisole is usually prepared by reducing nitro-anisole by iron powder or sodium sulfide. The method has simple process, but has the defects of heavy three-waste pollution, high cost, poor quality and the like. Compared with a chemical reduction method, the catalytic hydrogenation reduction method has the advantages of good product quality, high yield, simple process and the like, is concerned, and is an environment-friendly green process.
At present, the catalyst for catalyzing hydrogenation reaction of nitrobenzyl ether mainly takes noble metal catalysts such as platinum (Pt), palladium (Pd) and rhodium (Rh) as the main catalyst. The Pt and Pd noble metal catalysts have the advantages of high catalytic activity, mild reaction conditions and the like, but the noble metal catalysts have high price and cost, and the loss of noble metals has great harm to the environment, so the application of the noble metal catalysts in industrial production is limited. Non-noble metal catalysts, such as nickel, also have a series of problems in practical production application, such as easy agglomeration in the preparation process, easy elution in the catalytic hydrogenation process, poor stability, great potential safety hazard, and the like.
From the above, it is known that the development of a hydrogenation reduction catalyst which is stable in air and has excellent catalytic performance for the hydrogenation reduction of nitroanisole to synthesize the aminoacrylanisole is a problem to be solved in the art.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention provides a method for synthesizing an amino phenyl ether compound, which adopts a carbon-coated nickel nano composite material containing alkaline earth metal as a catalyst, wherein the nano composite material is formed by coating nickel nano particles with a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen to form a core-shell structure, a carbon material and the nickel nano particles play a role in a synergistic manner, a good catalytic effect is generated, the alkaline earth metal of the shell layer is further synergistic to improve the catalytic performance of the material, and the carbon-coated nickel nano particle is used for synthesizing the amino phenyl ether compound by hydrogenation reduction of the nitro phenyl methyl ether compound and has excellent activity, selectivity and safety.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a synthetic method of an amino anisole compound, which comprises the following steps:
the carbon-coated nickel nano composite material containing alkaline earth metal is used as a catalyst to catalyze the nitrobenzyl ether compounds to carry out hydrogenation reduction reaction in the hydrogen atmosphere;
the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, and the inner core is nickel nano particles.
According to an embodiment of the present invention, the nitrobenzyl ethers further comprise a substituent on the benzene ring, wherein the substituent is selected from C1-20One or more of alkyl, cycloalkyl and aryl.
According to an embodiment of the present invention, wherein the nitroanisole compound is selected from one or more of o-nitroanisole, p-nitroanisole, m-nitroanisole and 3-methyl-4-nitroanisole.
According to an embodiment of the present invention, the catalyst accounts for 1% to 50%, preferably 5% to 30% of the weight of the nitrobenzyl ethers.
According to one embodiment of the present invention, wherein the temperature of the hydrogenation reduction reaction is 50 ℃ to 120 ℃.
According to one embodiment of the present invention, wherein the pressure of the hydrogen gas is 0.5 to 2 MPa.
According to an embodiment of the present invention, the nitrobenzyl ethers and the catalyst are mixed in a solvent, and then subjected to a hydrogenation reduction reaction, wherein the solvent is one or more selected from alcohols, ethers, alkanes and water.
According to one embodiment of the present invention, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak. Optionally, the nanocomposite is a mesoporous material having two or more mesopore distribution peaks. Optionally, the nanocomposite material has a mesopore distribution peak in a pore size range of 2nm to 7nm and a pore size range of 8nm to 20nm, respectively. Optionally, wherein the mesopore material has a proportion of mesopore volume of more than 50%, preferably more than 80%, of the total pore volume.
According to an embodiment of the present invention, wherein the alkaline earth metal content is 0.1 at% to 3 at%, preferably 0.2 at% to 2 at%, in terms of atomic percentage; the carbon content is 65 at% to 95 at%, preferably 74 at% to 91 at%; the nickel content is 0.1 at% to 10 at%, preferably 1 at% to 8 at%; the oxygen content is 1 at% to 20 at%, preferably 4 at% to 15 at%; the nitrogen content is 1 at% to 10 at%, preferably 1 at% to 5 at%.
According to the invention, the sum of the contents of the individual components in the nanocomposite material is 100 at%.
According to one embodiment of the present invention, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm.
According to an embodiment of the present invention, the particle size of the core-shell structure is 1nm to 200nm, preferably 3nm to 100nm, more preferably 4nm to 50 nm.
According to an embodiment of the invention, wherein the alkaline earth metal is selected from one or more of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra).
The invention has the beneficial effects that:
the invention provides a synthesis method of an amino anisole compound, which uses a nano composite material of carbon-coated nickel containing alkaline earth metal as a catalyst to carry out hydrogenation reduction on a nitroanisole compound, and because the catalyst material contains a graphitized carbon layer/metal core-shell structure, no pore channel or defect which can enable reactants to approach the center of nickel exists, so that the nickel material of an inner core is very stable, does not self-ignite, is resistant to acid corrosion, has low danger, and is suitable for storage and transportation, thereby ensuring the use safety of the composite material. The catalyst material disclosed by the invention is very stable, free of spontaneous combustion, resistant to oxidation and acid corrosion, low in risk and suitable for storage and transportation, so that the safety of the synthetic process of the amino anisole compound is ensured.
The carbon-coated nickel nanocomposite containing alkaline earth metal shows good repeatability, high activity and high selectivity in the reaction of catalytically reducing nitrobenzyl ether compounds into amino-phenyl-ether compounds, and the nickel coated in the graphitized carbon layer has a penetration effect, so that the electronic state of the alkaline earth metal loaded on the surface of the graphitized carbon layer is influenced, and a synergistic effect is exerted, so that the nanocomposite has good catalytic performance; in addition, the nano composite material has stronger magnetism, and can be conveniently used for separating a catalyst by utilizing the magnetism or used for processes such as a magnetic stabilization bed and the like.
Drawings
FIG. 1 is a photograph showing the magnetic properties of the alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIG. 2 is a TEM image of an alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIG. 3 is an XRD pattern of an alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIGS. 4a and 4b respectively show N of the alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 12Adsorption-desorption isotherms and BJH pore size distribution curves;
FIG. 5 is a TEM image of an alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2;
FIG. 6 is an XRD pattern of an alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2;
fig. 7 is a BJH pore size distribution curve of the alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
The numerical ranges of the invention include the numbers defining the range. The phrase "comprising" is used herein as an open-ended term substantially equivalent to the word "including, but not limited to," and the phrase "comprising" has a corresponding meaning. As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a thing" includes more than one such thing, including all embodiments and variations substantially as hereinbefore described and with reference to the examples and drawings. Any terms not directly defined herein should be understood to have meanings associated with them as commonly understood in the art of the present invention. The following terms as used throughout this specification should be understood to have the following meanings unless otherwise indicated.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
Term(s) for
The term "alkyl" is defined herein as a straight or branched chain alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and the like.
The term "cycloalkyl" is defined herein as an alkyl group connected by single bonds and constituting a ring, such as cyclohexyl.
The term "aryl" is defined herein as a functional group or substituent derived from a simple aromatic ring, such as benzyl.
The term "nitrobenzyl ether compounds" refers to compounds wherein at least one hydrogen atom on the phenyl ring is substituted with a nitro group and the other hydrogen atoms are substituted with a methoxy group, and includes nitrobenzyl ethers wherein the phenyl ring has no substituents other than methoxy and nitro groups, and nitrobenzyl ethers wherein at least one of the other hydrogen atoms on the phenyl ring is substituted with a group other than methoxy and nitro groups.
The term "graphitized carbon layer" means a carbon structure in which a layered structure is clearly observed under a high-resolution transmission electron microscope, not an amorphous structure, and the interlayer distance is about 0.34 nm. The composite material formed after the graphitized carbon layer is coated with the nickel nano particles is spherical or quasi-spherical.
The term "mesoporous" is defined as a pore having a pore diameter in the range of 2 to 50 nm. Pores with a pore size of less than 2nm are defined as micropores and pores with a pore size of more than 50nm are defined as macropores.
The term "mesoporous material" is defined as a porous material comprising a mesoporous channel structure.
The terms "alkaline earth metal", "nitrogen" and "oxygen" in the "graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen" refer to alkaline earth metal elements, nitrogen elements and oxygen elements, wherein the "alkaline earth metal content" of the nanocomposite refers to the content of the alkaline earth metal elements, the "nitrogen content" refers to the content of the nitrogen elements, the "oxygen content" refers to the content of the oxygen elements, and specifically refers to the content of the alkaline earth metal elements, nitrogen elements and oxygen elements in various forms contained in the formed graphitized carbon layer during the preparation of the carbon-coated nanocomposite, the "alkaline earth metal content" is the total content of all forms of alkaline earth metal elements, the "nitrogen content" is the total content of all forms of nitrogen elements, and the "oxygen content" is the total content of all forms of oxygen elements. The "alkaline earth metal content", "nitrogen content" and "oxygen content" were measured by XPS method.
The term "mesopore distribution peak" refers to a mesopore distribution peak on a pore distribution curve calculated from a desorption curve according to the Barrett-Joyner-Halenda (BJH) method.
The term "TOF" is defined herein as the amount of a reactant converted per unit time by a single active metal atom, and TOF measures the rate at which a catalyst catalyzes a reaction and indicates the intrinsic activity of the catalyst.
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the invention are analytically pure, and all reagents are commercially available.
The XRD diffractometer adopted by the invention is an XRD-6000X-ray powder diffractometer (Shimadzu Japan), and the XRD test conditions are Cu target, K α ray (the wavelength lambda is 0.154nm), tube voltage is 40kV, tube current is 200mA, and scanning speed is 10 degrees (2 theta)/min.
The high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100(HRTEM) (Nippon electronics Co., Ltd.), and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200 kV.
The X-ray photoelectron spectrum analyzer (XPS) is an ESCA L ab220i-X L type electron spectrum analyzer which is produced by VG scientific company and is provided with Avantage V5.926 software, the X-ray photoelectron spectrum analyzer has the analysis and test conditions that an excitation source is monochromized A1K α X-rays, the power is 330W, and the basic vacuum is 3 × 10 during analysis and test-9mbar. In addition, the electron binding energy was corrected with the C1s peak (284.6eV), and the late peak processing software was XPSPEAK.
BET test method: in the invention, the pore structure property of a sample is measured by a Quantachrome AS-6B type analyzer, the specific surface area and the pore volume of the catalyst are obtained by a Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
In the invention, the composition of the gas is obtained by on-line gas chromatography analysis, and the chromatographic type is as follows: agilent GC7890B, accuracy 10-6. And introducing test gas into the chromatogram from the sample inlet, separating by using a chromatographic column, and calculating the percentage of each gas component by integrating each chromatographic peak.
In the invention, after the average particle diameter of the metal nanoparticles is divided into peaks by an XRD (X-ray diffraction) pattern, the average particle diameter is calculated according to the Sherle formula: d ═ k γ/(B cos θ) was calculated. Wherein k is Scherrer constant, k is 0.89; b is half-height width; theta is the diffraction angle, unit radian; gamma is the x-ray wavelength, 0.154054 nm.
The invention provides a synthetic method of an amino anisole compound, which comprises the following steps: the carbon-coated nickel nano composite material containing alkaline earth metal is used as a catalyst to catalyze the nitrobenzyl ether compounds to carry out hydrogenation reduction reaction in the hydrogen atmosphere; the chemical reaction equation is exemplified as follows,
the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, and the inner core is nickel nano particles.
In some embodiments, the nitrobenzophenone compound further contains a substituent on the benzene ring, and the substituent R is selected from C1-20The above substitution may be mono-substitution or poly-substitution, such as p-nitroanisole, m-nitroanisole or 3-methyl-4-nitroanisole.
In some embodiments, the catalyst accounts for 1% to 50%, preferably 5% to 30% of the mass of the nitrobenzyl ethers.
In some embodiments, the temperature in which the hydrogenation reduction reaction is carried out is generally in the range of 50 ℃ to 120 ℃.
In some embodiments, the pressure of the hydrogen gas therein is generally in the range of 0.5MPa to 2 MPa.
In some embodiments, the nitrobenzyl ethers are mixed with the catalyst in a solvent selected from one or more of alcohols, ethers, alkanes and water, such as ethanol, tetrahydrofuran, cyclohexane, and the like, followed by a hydrogenation reduction reaction.
The nanocomposite of the present invention is a composite material composed of a "graphitized carbon layer containing an alkaline earth metal, nitrogen and oxygen", nickel nanoparticles tightly coated (not in contact with the outside) with the graphitized carbon layer ", and" nickel nanoparticles in contact with the outside and confined regions ". The surface of the graphitized carbon layer doped with nitrogen and oxygen of the nano composite material has rich defect sites, the carbon material has catalytic activity, and the nickel coated in the graphitized carbon layer has a penetration effect, so that the electronic state of alkaline earth metal loaded on the surface of the graphitized carbon layer is influenced, and a synergistic effect is exerted, so that the nano composite material has better catalytic performance.
In some embodiments, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak. That is, the nano composite material has at least one mesoporous distribution peak on a pore distribution curve obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method. As known to those skilled in the art, mesoporous materials generally have large specific surface areas and relatively regular channel structures, so that the mesoporous materials can play better roles in separation, adsorption and catalytic reactions of macromolecules and can be used as microreactors for limited-domain catalysis. The nano composite material has rich mesoporous structure, so that the nano composite material has higher mass transfer efficiency and more excellent catalytic performance.
In some embodiments, the batch-produced composite has two distribution peaks in the mesoporous range; if a plurality of batches of the composite material are mixed, more distribution peaks can be obtained in the mesoporous range. When the nano composite material has the multilevel mesoporous structure with different aperture ranges, the nano composite material can show more unique performance, and the applicable application range of the multilevel mesoporous structure is wider.
According to the nanocomposite of the present invention, in some embodiments, the mesoporous structure has one mesoporous distribution peak in a pore size range of 2nm to 7nm and a pore size range of 8nm to 20nm, respectively.
In some embodiments, the proportion of mesopore volume in the composite material to the total pore volume is greater than 50%, preferably greater than 80%, according to the nanocomposite material of the present invention. In some embodiments, the proportion of mesopore volume to the total pore volume is greater than 90%, and even 100%.
According to the nanocomposite material of the present invention, in some embodiments, the mesoporous volume thereof may be 0.05cm3/g～1.25cm3Per g, also may be 0.30cm3/g～0.50cm3/g。
The nanocomposites according to the invention, in some embodiments, have specific surface areas generally greater than 140m2/g, may be greater than 200m2/g。
The nanocomposites according to the invention, which are not pyrophoric in air, can be stored in air.
According to an embodiment of the present invention, wherein the alkaline earth metal content is 0.1 at% to 3 at%, preferably 0.2 at% to 2 at%, in terms of atomic percentage; the carbon content is 65 at% to 95 at%, preferably 74 at% to 91 at%; the nickel content is 0.1 at% to 10 at%, preferably 1 at% to 8 at%; the oxygen content is 1 at% to 20 at%, preferably 4 at% to 15 at%; the nitrogen content is 1 at% to 10 at%, preferably 1 at% to 5 at%.
According to the invention, the sum of the contents of the individual components in the nanocomposite material is 100 at%.
According to one embodiment of the present invention, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm.
According to an embodiment of the present invention, the particle size of the core-shell structure is 1nm to 200nm, preferably 3nm to 100nm, more preferably 4nm to 50 nm.
According to an embodiment of the invention, wherein the alkaline earth metal is selected from one or more of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra).
The invention also provides a preparation method of the nano composite material, which comprises the following steps:
putting nickel salt, polybasic organic carboxylic acid and nitrogen-containing compound into a solvent to be mixed to form a homogeneous solution;
removing the solvent in the homogeneous solution to obtain a precursor;
carrying out primary pyrolysis on the precursor in an inert atmosphere or a reducing atmosphere;
contacting the product after the primary pyrolysis with a solution containing the alkaline earth metal, and then carrying out drying treatment; and the contact mode comprises the step of immersing the product after the primary pyrolysis in the alkaline earth metal solution, or the step of placing the product after the primary pyrolysis in the alkaline earth metal solution for stirring. The time for dipping or stirring is not suitable to be too long or too short, preferably between 10min and 300min, the temperature is preferably between 0 ℃ and 100 ℃, and the contact reaction is preferably carried out under the condition of stirring. According to the invention, the product of the primary pyrolysis may or may not be filtered after being contacted with the alkaline earth metal-containing solution, and the obtained product is dried.
And putting the dried product in an inert atmosphere for secondary pyrolysis to obtain the carbon-coated nickel nanocomposite containing the alkaline earth metal.
Specifically, the precursor is a water-soluble mixture, which means that nickel salt, polybasic organic carboxylic acid and nitrogen-containing compound are dissolved into a homogeneous solution in water and/or ethanol and other solvents, and then the solvent is directly removed to obtain the nickel-containing precursor. The solvent may be removed by evaporation, and the temperature and process of evaporation of the solvent may be by any available art, for example, spray drying at 80 ℃ to 120 ℃ or drying in an oven.
It should be noted that the polyvalent organic carboxylic acid may be a nitrogen-containing polyvalent organic carboxylic acid or a nitrogen-free polyvalent organic carboxylic acid, and when the polyvalent organic carboxylic acid is a nitrogen-containing polyvalent organic carboxylic acid, the mass of the nitrogen-containing compound may be zero, that is, the nitrogen-containing compound may not be added, and the mass ratio of the mass of the nitrogen element to the mass of the nickel salt and the polyvalent organic carboxylic acid may be within a certain range. In some embodiments, the mass ratio of the nickel salt, the organic polycarboxylic acid and the nitrogen-containing compound is 1: 0.1-100: 0-100, preferably 1: 0.5-5, and more preferably 1: 0.8-2: 1-2.
In some embodiments, the method further comprises mixing the nickel salt, the polybasic organic carboxylic acid, the nitrogen-containing compound and other organic compounds except the nickel salt, the polybasic organic carboxylic acid, the nitrogen-containing compound and other organic compounds in a solvent such as water, ethanol and the like to form a homogeneous solution, and then removing the solvent to obtain the water-soluble mixture containing nickel. Such other organic compounds include, but are not limited to, organic polyols. In some embodiments, the mass ratio of the nickel salt, the polybasic organic carboxylic acid, the nitrogen-containing compound and the other organic compound is preferably 1: 0.5-10: 0-10, more preferably 1: 1-3: 0-3, that is, the other organic compound may not be added at all.
In some embodiments, the nickel salt is selected from one or more of organic acid salts, carbonates, and basic carbonates of nickel, preferably organic acid salts of nickel without heteroatoms, more preferably acetates of the nickel without heteroatoms, wherein the heteroatoms refer to metal atoms other than the nickel.
In some embodiments, the poly-organic carboxylic acid includes, but is not limited to, one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, ethylenediaminetetraacetic acid (EDTA), and dipicolinic acid.
In some embodiments, wherein the primary pyrolysis comprises: heating the precursor to a constant temperature section in an inert atmosphere or a reducing atmosphere, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-30 ℃/min, preferably 1-10 ℃/min; the temperature of the constant temperature section is 400-800 ℃, and preferably 500-800 ℃; the constant temperature time is 20min to 600min, preferably 60min to 480 min; the inert atmosphere is nitrogen or argon, and the reducing atmosphere is a mixed gas of an inert gas and hydrogen, for example, a small amount of hydrogen is doped in the inert atmosphere.
In some embodiments, the alkaline earth metal-containing solution is an alkaline earth metal-containing salt and/or base solution, e.g., magnesium chloride (MgCl)2) Solution, magnesium nitrate (Mg (NO)3)2) Solution, calcium chloride (CaCl)2) Solution, calcium nitrate (Ca (NO)3)2) Solution, barium chloride (BaCl)2) Solutions, and the like. The mass ratio of the alkaline earth metal salt and/or alkali to the product after primary pyrolysis is 1: 1-100. Preferably 1: 1.5 to 50, preferably 1: 1.5 to 20. When the amount of the alkaline earth metal-containing salt or base is too large, the catalytic performance of the finally formed nanocomposite is affected, and the activity is lowered.
In some embodiments, wherein the secondary pyrolysis comprises: under the inert atmosphere, heating the dried product to a constant temperature section, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-10 ℃/min, preferably 2.5-10 ℃/min; the temperature of the constant temperature section is 80-800 ℃, and preferably 300-600 ℃; the constant temperature time is 20 min-600 min; the inert atmosphere is nitrogen or argon.
The carbon-coated nickel nanocomposite is prepared by the method, a method of pyrolyzing a metal-organic framework compound (MOF) serving as a precursor is not adopted, the method needs to prepare a crystalline solid Material (MOF) with a periodic structure in a solvent at high temperature and high pressure, the condition for preparing MOFs is strict, the needed ligand is expensive, and the mass production is difficult; in addition, the composite material prepared by the method has imprecise cladding on the metal particles, and is remarkably different from the nano composite material in structure. The method for preparing the carbon-coated nickel composite material is convenient for adjusting the nitrogen content and the oxygen content in the graphitized carbon layer in the preparation process, thereby conveniently adjusting the electronic characteristics of the nano composite material so as to be suitable for catalyzing different reactions.
The present invention is described in further detail below by way of specific embodiments in conjunction with the attached drawings, it being understood that the specific embodiments described herein are merely illustrative and explanatory of the invention and do not limit the invention in any way.
Preparation example 1
(1) Weighing 10g of nickel acetate, 10g of citric acid and 20g of hexamethylenetetramine, adding the nickel acetate, the citric acid and the hexamethylenetetramine into a beaker filled with 30m L deionized water, stirring at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating to dryness to obtain a solid precursor.
(2) And (2) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 100m L/min, heating to 650 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel material.
(3) Weighing 2g of the carbon-coated nickel material obtained in the step (2), adding 4m of L aqueous solution containing 0.5128g of magnesium nitrate, soaking for 24h, and drying the product at 120 ℃.
(4) And (3) placing the dried material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 50m L/min, heating to 350 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 3h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the magnesium-containing carbon-coated nickel nanocomposite.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: 88.68 at% carbon, 1.27 at% nickel, 5.67 at% oxygen, 3.56 at% nitrogen, and 0.82 at% magnesium.
As shown in fig. 1, the nanocomposite was placed in water as a suspension, a magnet was placed on the outside of the container, and after a period of time the nanocomposite was attracted to one side of the magnet, which was seen to be magnetic. The TEM image of the nanocomposite is shown in fig. 2, and it can be seen that a graphitized carbon layer is wrapped on the outer layer of the nickel nanoparticle to form a complete core-shell structure. As shown in fig. 3, the diffraction pattern of this material includes diffraction peaks (2 θ angle 25.9 °) of graphitic carbon and diffraction peaks (2 θ angles 44.37 °, 51.8 ° and 76.4 °) of face-centered cubic (fcc) Ni. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 6.8nm by the scherrer equation.
The BET test showed that the specific surface area of the composite material was 173.4m2Per g, pore volume 0.296cm3Per g, wherein>The mesoporous volume of 2nm is 0.296cm3(ii) in terms of/g, representing 100% of the total pore volume. FIG. 4a is N of the nanocomposite2An adsorption-desorption isotherm is shown in fig. 4b, which is a BJH pore size distribution curve of the nanocomposite, and it can be seen that the composite has two mesopore distribution peaks at 3.90nm and 15.03 nm.
Preparation example 2
(1) Weighing 10g of nickel acetate, 20g of citric acid and 20g of hexamethylenetetramine, adding the nickel acetate, the citric acid and the hexamethylenetetramine into a beaker containing 100m L deionized water, stirring at 80 ℃ to obtain a homogeneous solution, and continuously heating and evaporating to dryness to obtain a solid precursor.
(2) And (2) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 150m L/min, heating to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel material.
(3) Weighing 2g of the carbon-coated nickel material obtained in the step (2), adding 4m of magnesium nitrate L containing 0.8589 into the carbon-coated nickel material, soaking the mixture for 24 hours, and then drying the mixture at 120 ℃.
(4) And (3) placing the dried material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 70m L/min, heating to 500 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the magnesium-containing carbon-coated nickel nanocomposite.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: the carbon content was 82.4 at%, the nickel content was 2.68 at%, the oxygen content was 9.26 at%, the nitrogen content was 4.09 at%, and the magnesium content was 1.57 at%.
From the TEM image (fig. 5) of this material it can be seen that: the outer layer of the nickel nano-particles is wrapped with a graphitized carbon layer to form a complete core-shell structure. Fig. 6 shows an X-ray diffraction pattern of the nanocomposite material in which diffraction peaks corresponding to carbon (25.9 ° 2 θ angle) and fcc Ni (44.5 °, 51.7 ° and 76.4 ° 2 θ angle) and nickel (hcp-Ni) of close-packed cubic structure (41.9 °, 44.4 °, 47.3 ° and 62.4 ° 2 θ angle) exist. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 13.4nm by the scherrer equation.
The BET test shows that the specific surface area of the material is 142m2Per g, pore volume 0.221cm3Per g, wherein>Pore volume of 0.213cm at 2nm3In terms of/g, 96.3% of the total pore volume. Fig. 7 is a BJH pore size distribution curve of the nanocomposite, which has two mesopore distribution peaks at 3.65nm and 9.91 nm.
Comparative preparation example
(1) Weighing 10g of nickel acetate, 10g of citric acid and 20g of hexamethylenetetramine, adding the nickel acetate, the citric acid and the hexamethylenetetramine into a beaker filled with 30m L deionized water, stirring at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating to dryness to obtain a solid precursor.
(2) And (2) placing the precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 100m L/min, heating to 650 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite material, wherein the atomic percentage content of elements in the nanocomposite material is respectively 90.47at percent of carbon, 1.38at percent of nickel, 3.97at percent of oxygen and 4.18at percent of nitrogen, which are determined by X-ray photoelectron spectroscopy (XPS).
Example 1
The composite material obtained in preparation example 1 is used as a catalyst for a reaction of hydrogenation of a nitrobenzyl ether compound to prepare a target product, namely an amino phenyl ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 1.99g of p-nitroanisole and 100m of L ethanol into a reaction kettle, introducing H2Replacement reaction kettleAfter 3 times, H is introduced2And (3) controlling the pressure in the reaction kettle to be 2MPa, stirring and heating, heating to the preset reaction temperature of 50 ℃, stopping heating after reacting for 3 hours, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product, namely, p-anisidine to perform chromatographic analysis. The reactant conversion and the target product selectivity were calculated by the following formulas:
conversion-amount of reacted reaction mass/amount of added reaction × 100%
The selectivity is × 100% based on the mass of the target product/mass of the reaction product
After analysis, the conversion rate of the p-nitroanisole is 100 percent, and the selectivity of the p-anisidine is 99.2 percent.
When the reaction proceeded for 300s, a sample was taken and subjected to chromatography to calculate the conversion of the reactant, and TOF of the catalyst was 9.71 × 10, which was obtained by the formula TOF (amount of reacted reactant substance)/(amount of catalytically active metal substance 300s)-3s-1。
Example 2
The nano composite material prepared in preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.49g of p-nitroanisole and 50m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 0.5MPa, stirring and heating, heating to a preset reaction temperature of 120 deg.C, continuously reacting for 0.5 hr, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle and taking out the product to make chromatographic analysis of amino methyl ether, and respectively calculating reactant conversion rate, product selectivity and TOF by using the formula shown in example 1 to obtain p-nitroanisole conversion rate of 100%, p-aminophenylmethylether selectivity of 99.5% and TOF of 10.1 × 10-3s-1。
Example 3
The nano composite material prepared in preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
mixing 0.1g of nano composite material, 0.49g of p-nitroanisole and 30m ofL adding cyclohexane into the reaction kettle, charging H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 80 ℃, the heating is stopped after the reaction is continued for 1 hour, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product is taken out, the chromatographic analysis is carried out on the amino methyl ether, the conversion rate of the reactant, the selectivity of the product and the TOF are respectively calculated by the formula shown in the example 1, the conversion rate of the p-nitroanisole is 100 percent, the selectivity of the p-aminophenylmethylether is 99.3 percent-3s-1。
Example 4
The nano composite material prepared in preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.34g of p-nitroanisole and 30m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 100 ℃, the heating is stopped after the reaction lasts for 2 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product is taken out, the chromatographic analysis is carried out on the amino methyl ether, the conversion rate of the reactant, the selectivity of the product and the TOF are respectively calculated by the formula shown in the example 1, the conversion rate of the p-nitroanisole is 100 percent, the selectivity of the p-aminophenylmethylether is 99.1 percent-3s-1。
Example 5
The nano composite material prepared in preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.34g of o-nitroanisole and 30m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2And (3) controlling the pressure in the reaction kettle to be 1MPa, stirring and heating, heating to the preset reaction temperature of 100 ℃, stopping heating after continuously reacting for 2 hours, reducing the temperature to room temperature, discharging pressure, opening the reaction kettle, and taking out the product of the o-aminoanisole for chromatographic analysis. The reactant conversion, the product selectivity and the TOF were respectively calculated by the formulas shown in example 1,the conversion rate of the obtained o-nitroanisole is 100 percent, the selectivity of the o-aminoanisole is 99.5 percent, and the TOF is 10.5 × 10-3s-1。
Example 6
The nano composite material prepared in preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.34g of m-nitroanisole and 30m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 1MPa, stirring and heating, heating to preset reaction temperature of 100 deg.C, continuously making reaction for 2 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out product metaanisidine to make chromatographic analysis, and respectively calculating reactant conversion rate, product selectivity and TOF by using the formula shown in example 1 to obtain metanitroanisole conversion rate of 100%, metaanisidine selectivity of 99.2% and TOF of 9.45 × 10-3s-1。
Example 7
The nano composite material prepared in preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.33g of 3-methyl-4-nitrobenzyl ether and 30m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 100 ℃, the heating is stopped after the reaction is continued for 2 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product 3-methyl-4-aminobenzyl ether is taken out for chromatographic analysis, the conversion rate of the reactant, the product selectivity and TOF are respectively calculated by the formula shown in example 1, the conversion rate of the 3-methyl-4-nitrobenzyl ether is 100 percent, the selectivity of the 3-methyl-4-aminobenzyl ether is 99.4 percent, and the TOF is 9.49 × 10-3s-1。
Example 8
The nano composite material prepared in preparation example 2 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.2g of nano composite material, 0.69g of p-nitroanisole and 50m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1.5MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 80 ℃, the heating is stopped after the reaction is continued for 2 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product para-anisidine is taken out for chromatographic analysis, the conversion rate of the reactant, the product selectivity and TOF are respectively calculated by the formula shown in the example 1, the conversion rate of the para-anisidine is 100 percent, the selectivity of the para-anisidine is 99.1 percent, and the TOF is 8.72 × 10-3s-1。
Comparative example
The nano composite material prepared by the comparative preparation example is used for hydrogenation reduction reaction of nitrobenzophenone ether compounds as a catalyst, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 1.99g of p-nitroanisole and 100m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 2MPa, stirring and heating, heating to 50 deg.C, continuously making reaction for 3 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out product p-anisidine and making chromatographic analysis, and respectively calculating reactant conversion rate, product selectivity and TOF by using the formula shown in example 1 to obtain p-nitroanisole conversion rate of 100%, p-anisidine selectivity of 99.0% and TOF of 5.64 × 10-3s-1。
It can be seen from the above examples and comparative examples that the nanocomposite of the present invention has a good catalytic effect when used as a catalyst for catalyzing a catalytic hydrogenation reaction of nitroanisole compounds, and compared with a catalyst containing no alkaline earth metal, the nanocomposite containing carbon-coated nickel containing an alkaline earth metal not only enables the catalytic reaction to have a high conversion rate and product selectivity, but also has a higher catalytic reaction rate and better catalytic performance.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (12)
1. A synthetic method of an amino anisole compound comprises the following steps:
the carbon-coated nickel nano composite material containing alkaline earth metal is used as a catalyst to catalyze the nitrobenzyl ether compounds to carry out hydrogenation reduction reaction in the hydrogen atmosphere;
the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, and the inner core is nickel nano particles.
2. The synthesis method according to claim 1, wherein the phenyl ring of the nitrobenzyl ether compound further comprises a substituent selected from C1-20One or more of alkyl, cycloalkyl and aryl.
3. The synthesis method according to claim 1, wherein the nitroanisole compound is selected from one or more of o-nitroanisole, p-nitroanisole, m-nitroanisole and 3-methyl-4-nitroanisole.
4. The synthesis process according to claim 1, wherein the catalyst accounts for 1-50%, preferably 5-30% of the weight of the nitrobenzethers.
5. The synthesis process of claim 1, wherein the temperature of the hydrogenation reduction reaction is from 50 ℃ to 120 ℃.
6. The synthesis process according to claim 1, wherein the pressure of the hydrogen is between 0.5MPa and 2 MPa.
7. The synthesis method according to claim 1, wherein the nitrobenzyl ethers are mixed with the catalyst in a solvent and then subjected to a hydrogenation reduction reaction, wherein the solvent is selected from one or more of alcohols, ethers, alkanes and water.
8. The synthesis method according to any one of claims 1 to 7, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak.
9. The method of synthesizing as defined in claim 8 wherein the nanocomposite is a mesoporous material having two or more mesopore distribution peaks.
10. The method of synthesis according to claim 8, wherein the mesoporous material has a proportion of mesopore volume of more than 50%, preferably more than 80%, of the total pore volume.
11. The method of claim 1, wherein the alkaline earth metal is present at 0.1 at% to 3 at%, the carbon is present at 65 at% to 95 at%, the nickel is present at 0.1 at% to 10 at%, the oxygen is present at 1 at% to 20 at%, and the nitrogen is present at 1 at% to 10 at%, in atomic percentage.
12. The method of synthesis according to any one of claims 1 to 11, the alkaline earth metal being selected from one or more of beryllium, magnesium, calcium, strontium, barium and radium.
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| CN1439456A (en) * | 2003-04-08 | 2003-09-03 | 天津大学 | Catalyst for producing melaphenylene from m-dinitrobenze by liquid phase hydrogenation and preparation thereof |
| CN105032424A (en) * | 2015-06-05 | 2015-11-11 | 中国科学院化学研究所 | Catalyst for selective hydrogenation reaction of aromatic nitrocompound and preparation method of catalyst |
| CN106732733A (en) * | 2017-01-11 | 2017-05-31 | 北京化工大学 | A kind of application of preparation and its catalysis o-chloronitrobenzene hydrogenation reaction of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst |
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| CN1439456A (en) * | 2003-04-08 | 2003-09-03 | 天津大学 | Catalyst for producing melaphenylene from m-dinitrobenze by liquid phase hydrogenation and preparation thereof |
| CN105032424A (en) * | 2015-06-05 | 2015-11-11 | 中国科学院化学研究所 | Catalyst for selective hydrogenation reaction of aromatic nitrocompound and preparation method of catalyst |
| CN106732733A (en) * | 2017-01-11 | 2017-05-31 | 北京化工大学 | A kind of application of preparation and its catalysis o-chloronitrobenzene hydrogenation reaction of nitrogen-doped carbon coated core-shell structure dilval nanocatalyst |
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