CN114950554A - 一种用于含氧气体氧化制备2-烷基蒽醌的催化剂及其应用 - Google Patents
一种用于含氧气体氧化制备2-烷基蒽醌的催化剂及其应用 Download PDFInfo
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- CN114950554A CN114950554A CN202210424803.4A CN202210424803A CN114950554A CN 114950554 A CN114950554 A CN 114950554A CN 202210424803 A CN202210424803 A CN 202210424803A CN 114950554 A CN114950554 A CN 114950554A
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- alkyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 25
- 239000001301 oxygen Substances 0.000 title claims abstract description 25
- 239000007789 gas Substances 0.000 title claims abstract description 24
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 13
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 128
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 116
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 239000013110 organic ligand Substances 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002262 Schiff base Substances 0.000 claims abstract description 5
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 47
- -1 dimethyl-substituted benzene Chemical class 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- 150000000703 Cerium Chemical class 0.000 claims description 3
- 150000001844 chromium Chemical class 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 150000002940 palladium Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000003283 rhodium Chemical class 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003681 vanadium Chemical class 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 claims 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 41
- 239000000758 substrate Substances 0.000 abstract description 22
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- LUACOWBTSAPURU-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)anthracene Chemical compound C1=CC=CC2=CC3=CC(C(C)(C)CC)=CC=C3C=C21 LUACOWBTSAPURU-UHFFFAOYSA-N 0.000 description 46
- 230000008569 process Effects 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- WUKWGUZTPMOXOW-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)CC)=CC=C3C(=O)C2=C1 WUKWGUZTPMOXOW-UHFFFAOYSA-N 0.000 description 22
- 238000004817 gas chromatography Methods 0.000 description 19
- 239000000543 intermediate Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 239000013589 supplement Substances 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- ZXAGXLDEMUNQSH-UHFFFAOYSA-N 2-ethylanthracene Chemical compound C1=CC=CC2=CC3=CC(CC)=CC=C3C=C21 ZXAGXLDEMUNQSH-UHFFFAOYSA-N 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000009423 ventilation Methods 0.000 description 5
- GPOMKCKAJSZACG-UHFFFAOYSA-N 2-phenylanthracene Chemical compound C1=CC=CC=C1C1=CC=C(C=C2C(C=CC=C2)=C2)C2=C1 GPOMKCKAJSZACG-UHFFFAOYSA-N 0.000 description 4
- FCCAUIVKYBOVPW-UHFFFAOYSA-N 2-propan-2-ylanthracene Chemical compound C1=CC=CC2=CC3=CC(C(C)C)=CC=C3C=C21 FCCAUIVKYBOVPW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- WYBPLXLPOLAWTE-UHFFFAOYSA-N 2-pentylanthracene Chemical compound C1=CC=CC2=CC3=CC(CCCCC)=CC=C3C=C21 WYBPLXLPOLAWTE-UHFFFAOYSA-N 0.000 description 2
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 2
- NCNWINUHAGZMKB-UHFFFAOYSA-N C(CCCC)C1=CC=2C(C3=CC=CC=C3CC2C=C1)=O Chemical compound C(CCCC)C1=CC=2C(C3=CC=CC=C3CC2C=C1)=O NCNWINUHAGZMKB-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229940052810 complex b Drugs 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- DJWVKJAGMVZYFP-UHFFFAOYSA-N 1,1,3,3-tetrachloropropan-2-one Chemical class ClC(Cl)C(=O)C(Cl)Cl DJWVKJAGMVZYFP-UHFFFAOYSA-N 0.000 description 1
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 1
- YLEGOJOHDJQACZ-UHFFFAOYSA-N 2-pentylanthracen-1-ol Chemical compound C1=CC=CC2=CC3=C(O)C(CCCCC)=CC=C3C=C21 YLEGOJOHDJQACZ-UHFFFAOYSA-N 0.000 description 1
- NTZCFGZBDDCNHI-UHFFFAOYSA-N 2-phenylanthracene-9,10-dione Chemical compound C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 NTZCFGZBDDCNHI-UHFFFAOYSA-N 0.000 description 1
- BQUNPXRABCSKJZ-UHFFFAOYSA-N 2-propan-2-ylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3C(=O)C2=C1 BQUNPXRABCSKJZ-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 102000005720 Glutathione transferase Human genes 0.000 description 1
- 108010070675 Glutathione transferase Proteins 0.000 description 1
- 229910004373 HOAc Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- ICIFYHOILPYQKB-UHFFFAOYSA-N manganese(ii) phthalocyanine Chemical compound [Mn+2].[N-]1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)[N-]3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 ICIFYHOILPYQKB-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HCIIFBHDBOCSAF-UHFFFAOYSA-N octaethylporphyrin Chemical compound N1C(C=C2C(=C(CC)C(C=C3C(=C(CC)C(=C4)N3)CC)=N2)CC)=C(CC)C(CC)=C1C=C1C(CC)=C(CC)C4=N1 HCIIFBHDBOCSAF-UHFFFAOYSA-N 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CRNIHJHMEQZAAS-UHFFFAOYSA-N tert-amyl chloride Chemical compound CCC(C)(C)Cl CRNIHJHMEQZAAS-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
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Abstract
本发明涉及化学工程的技术领域,公开了一种用于含氧气体氧化制备2‑烷基蒽醌的催化剂及其应用,所述催化剂为金属盐与有机配体形成的配合物;所述有机配体为卟啉类、酞菁类、Salen型席夫碱类、联吡啶类和乙酰丙酮类中的一种或多种。本发明以金属盐和有机配体形成的配合物作为催化剂,反应流程短,2‑烷基蒽的转化率和2‑烷基蒽醌的选择性、收率均较高;以含氧气体为氧化剂,2‑烷基蒽为底物氧化制备2‑烷基蒽醌,反应污染少,原子利用率高,基本不产生“三废”,操作安全方便,适用于工业化生产。
Description
技术领域
本发明涉及化学工程的技术领域,尤其是涉及一种用于含氧气体氧化制备2-烷基蒽醌的催化剂。
背景技术
2-烷基蒽醌是一种兼具研究和应用价值的精细化学品,其应用场景涉及化工、医药等多个领域,与其相关的实验室和工业应用探索都已经成为了热点。一方面,使用2-烷基蒽醌作为工作液载体的蒽醌法生产了全球95%产量和国内98%产量的双氧水,2025年全球双氧水市场规模预计将达到36.8亿美元,而国内双氧水的需求量将达到2379万吨。另一方面,2-烷基蒽醌也是一种重要的医药中间体和高级染料中间体,如2-甲基蒽醌可以用作抗肿瘤药物的中间体,2-叔丁基蒽醌可以用作树脂合成过程中的阻聚剂和催化剂等。综上所述,开发绿色廉价的生产2-烷基蒽醌的新方法其重要性不言而喻。
目前商品化的2-烷基蒽醌的主要生产工艺为苯酐法,例如,公开号为CN113683497A的中国发明专利公开了一种烷基蒽醌的制备方法,以2-叔戊基蒽醌的制备为例,该方法分三步进行:1)第一步采用苯与2-氯-2-甲基丁烷为原料,在催化剂的作用下,通过烷基化反应得到2-叔戊基苯;2)第二步反应中加入苯酐,在路易斯酸AlCl3的催化下,通过酰基化反应得到中间体I酮酸;3)第三步反应中加入五氧化二磷和发烟硫酸作为催化剂,将中间体I酮酸最终转化为2-叔戊基蒽醌。通过苯酐法制备2-烷基蒽醌的工艺较为成熟,但是有以下几个问题:1)“三废”问题严重,增加后处理成本;2)原料成本较高;3)流程长,总收率低;4)浓硫酸对设备腐蚀严重,固定投资高等。
而烷基蒽氧化法是一种研究较为广泛但是还未实现工业化的方法,该方法由蒽的烷基化反应与2-烷基蒽的氧化反应的共两步反应组成。第二步氧化反应中,相关研究较多采用远远大于当量的双氧水作为氧化剂,但成本较高且安全性较差。采用氧气(空气)代替双氧水实现2-烷基蒽醌的生产无疑具有更好的应用前景,但是该方法仍处于研究探讨阶段,催化氧化效率和收率较低,因而,为了更适用于工业化生产,开发一种高效催化剂是十分有必要的。
发明内容
为了解决含氧气体氧化制备2-烷基蒽醌过程中催化氧化效果差、收率低等不足,本发明提供了一种用于含氧气体氧化制备2-烷基蒽醌的催化剂及其应用,具有反应流程短、收率高、三废少、原子利用率高等优点,能够以2-烷基蒽为底物绿色高效制备2-烷基蒽醌,操作安全方便,适用于工业化生产。
本发明的目的通过以下技术方案予以实现:
第一方面,本发明提供了一种用于含氧气体氧化制备2-烷基蒽醌的催化剂,所述催化剂为金属盐与有机配体形成的配合物;所述有机配体为卟啉类、酞菁类、Salen型席夫碱类、联吡啶类和乙酰丙酮类中的一种或多种;所述有机配体的结构如下:
其中,R3、R4、R5、R6、R7、R8独立地选自H、芳基、C1-C10的直链或支链烷基、芳基取代的C1-C10的直链或支链烷基、C3-C6的环烷基、C3-C6的取代环烷基、杂环、羧基、烯基、酯基、羟基、烷氧基、氨基、卤素和硝基等中的一种或多种。
本发明的反应机理可以阐释如下:在反应过程开始时,金属配合物A首先失去一个轴向配体,同时中心金属的价态由三价变为二价(该过程也可以通过具有一定还原能力的底物给出一个电子来驱动完成);二价的中心金属极容易与分子氧结合形成超氧阴离子络合物中间体C,超氧阴离子络合物中间体C再与第二分子的二价配合物B结合形成μ-过氧络合物D;由于双金属对于氧氧键极大的削弱作用,该μ-过氧络合物可以进一步断裂形成四价的金属单氧络合物中间体E,该高价中间体E具有很强的氧化能力。在本发明中,金属单氧络合物中间体E可以从2-烷基蒽底物上攫取一个电子,将底物S变为自由基中间体S·,进一步地,将该自由基中间体进行羟基化反应得到SO氧化产物,而有机配体则被还原恢复为二价配合物B。另外,金属单氧络合物中间体E同样也可以将羟基化的中间体进一步氧化从而得到最终的氧化产物。在2-戊基蒽氧化示意中,2-戊基蒽到2-戊基蒽醌氧化所经历的中间体分别为:2-戊基蒽酚I、2-戊基蒽酮II和2-戊基蒽酮酚III,氧化所得氧化产物为2-戊基蒽醌。
金属配合物催化剂的催化氧化能力是由电子效应与空间效应综合决定的,进一步的也就是中心金属的变价能力(氧化还原电势)及空间环境与底物或中间体是否匹配的问题。电子效应一方面是受中心金属自身的性质影响,另一方面则是受有机配体的π-电子共轭体系的性质影响。前者受自身d轨道的性质决定,后者则决定于配体结构以及配体上的不同取代基基团,另外轴向配体对中心金属的轨道能级和对称性也会造成显著的影响。
有机配体更优选为卟啉类与联吡啶类有机配体,因为对于2-烷基蒽的氧化,其决速步往往是底物自由基或自由基阳离子的形成过程,卟啉类与联吡啶类有机配体形成的配合物由于其较强的得电子能力,可以加速蒽自由基阳离子的形成,因而是更有潜力的催化剂。
作为优选,所述金属盐为铜盐、钴盐、铁盐、锰盐、镍盐、铬盐、钒盐、锌盐、钠盐、钯盐、银盐、铈盐和铑盐等中的一种或多种。
根据上述机理可知,催化剂的催化效果与金属活性中心紧密相关,金属盐的选择影响着中心金属自身的性质。
第二方面,本发明还提供了上述催化剂用于含氧气体氧化制备2-烷基蒽醌中的应用,包括如下步骤:在催化剂存在条件下,2-烷基蒽于水或有机溶剂中,经含氧气体氧化得到2-烷基蒽醌。
本发明的反应方程式如下:
其中,R选自C1-C10的直链或支链烷基、芳基或者芳基取代的C1-C10的直链或支链烷基。
烷基作为弱给电子基团,可以使底物更容易被活化,另一方面若取代基过大会导致较大的空间位阻,使底物难以接近催化中心;芳基则是一种富电子的取代基,从电子效应角度有利于氧化反应,但是从空间位阻的角度则不如烷基更合适。综上,有必要限定合适的取代基以达到最好的催化氧化效果。
作为优选,所述含氧气体包括纯氧、空气或氧气与惰性气体的混合气体;更优选为纯氧、空气。
作为优选,所述含氧气体的压力为1~8Mpa;更优选为4~6MPa。
作为优选,所述应用的反应温度为65~120℃,反应时间为1~24h;更优选为反应温度80℃~110℃,反应时间6~12h。由于反应需要一定的活化能,当温度过低时会导致反应停留在中间体阶段或底物不能完全转化为产物,而温度过高则会导致反应中同时出现较多的自由基中间体,往往会导致分子量较大的黑色聚合副产物的出现,另外温度过高也会导致产物的深度氧化,同样不利于保证反应的收率。
作为优选,所述有机溶剂为乙酸、乙腈、N,N-二甲基甲酰胺、苯、甲苯、二甲基取代苯、氯苯、乙二醇甲醚、戊醇、乙酸乙酯、乙酸正丁酯、1,4-二氧六环、吡啶、二氯甲烷酮和二甲基亚砜中的一种或多种。
作为优选,所述水或有机溶剂、2-烷基蒽和催化剂的质量比为1~100:1:0.01~1;更优选为2~3:1:0.05~0.1。对于催化反应,溶剂、底物、催化剂的比例对反应的结果往往有非常显著的影响,这一方面是由于反应体系中的微环境所致,特别是反应的过渡态对其有非常精确的要求,另一方面根据反应热力学与动力学计算,催化剂的配位结构变化也会受三者的比例影响,最终反映在能否高选择性的得到反应产物。
作为优选,所述2-烷基蒽的投料方式为一次性投料或分批投料;所述分批投料的投料间隔时间为0.5~24h;更优选为分批投料,投料间隔时间为6~12h。投料方式会影响底物浓度,对于自由基机理反应而言,底物浓度经常会影响反应的选择性与收率,由于自由基中间体是一种高度活泼的中间体,浓度过高会导致自由基之间发生不必要的副反应,因此通过控制底物浓度控制自由基中间体的生成速率,进而提高反应收率。
作为优选,所述2-烷基蒽醌的分离方式包括萃取分离、结晶分离或减压精馏分离;更优选为萃取分离。
与现有技术相比,本发明具有以下有益效果:
(1)以金属盐和有机配体形成的配合物作为催化剂,催化氧化效率高,反应流程短,2-烷基蒽醌的收率高;
(2)以含氧气体为氧化剂,2-烷基蒽为底物氧化制备2-烷基蒽醌,反应污染少,原子利用率高,基本不产生“三废”,操作安全方便,适用于工业化生产
具体实施方式
以下用具体实施例来说明本发明的技术方案,但本发明的保护范围不限于此:
总实施例
1.催化剂的制备
催化剂为金属盐与有机配体形成的配合物,有机配体为卟啉类、酞菁类、Salen型席夫碱类、联吡啶类和乙酰丙酮类中的一种或多种,金属盐为铜盐、钴盐、铁盐、锰盐、镍盐、铬盐、钒盐、锌盐、钠盐、钯盐、银盐、铈盐和铑盐等中的一种或多种。
(1)卟啉类催化剂的合成(以间-四羟乙基(4-甲氧苯基)卟啉钴(II)为例)
参照文献(Tabushi,I.,Kugimiya,S.,Sasaki,T.,J.Am.Chem.Soc.,1985,107(18),5159-5163.)与(Pizzotti,M.,Ugo,R.,Annoni,E.,Quici,S.,Inorg.Chim.Acta,2002,340,70-80.)。
具体步骤如下:将20mmol(2.73g)对甲氧基苯甲醛、20mmol(1.34g)吡咯、2mmol(0.38g,10mol%)对甲基苯磺酸、5mL 30wt%的双氧水和50mL醋酸混合,使用氮气换气三次后将反应体系密闭,然后置于120℃的油浴中加热搅拌3h;反应结束将反应液冷却至室温后倒入100mL甲醇中,过滤并将滤饼置于30mL甲醇中在室温下进行悬浮洗涤30min,过滤可得到有机配体1.3g。将有机配体和2.64mmol(0.47g)乙酸钴混合,并加入40mL N,N-二甲基甲酰胺,使用氮气换气三次后将反应体系密闭,然后置于140℃的油浴中加热搅拌10h,反应结束后加入40mL乙醚将配合物析出并进行过滤。使用柱色谱的方法对配合物进行提纯,其中流动相为石油醚:二氯甲烷=3:1(体积比),最后可得催化剂1.09g。
(2)Salen型席夫碱类配合物的合成(以N,N′-二水杨醛乙二胺钴(II)为例)
参照文献(Kapturkiewicz,A.,Behr,B.,Inorg.Chim.Acta,1983,69,247-251.)与(Shen,D.,Martell,A.E.,Sun,U.,Inorg.Chem.,1989,28,2647-2662.)
具体步骤如下:将150mL甲醇、20mmol(1.2g)乙二胺和5mmol(0.3g)LiOH·H2O混合,加热至65℃回流并搅拌溶解,溶解完全后开始向反应液中滴加20mL含有44mmol(5.37g)水杨醛的乙醇溶液,滴加时间约为1h,滴加结束后继续回流反应2h。反应结束后减压蒸馏去除大部分溶剂,然后加入20mL异丙醇,过滤洗涤后可得到有机配体3.57g。将有机配体和50mL乙醇混合,在室温下搅拌溶解后逐滴加入10mL含有15mmol(1.95g)氯化钴的乙醇溶液,滴加时间约为30min,滴加结束后继续搅拌1h,此时会有明显的沉淀形成。反应结束后减压蒸馏去除大部分溶剂,过滤洗涤后得到的滤饼在60℃下真空干燥。通过重结晶提纯,使用乙醇作为溶剂,最终得到催化剂2.09g。
(3)联吡啶类催化剂的合成(以2,2′-联吡啶氯化铜为例)
具体步骤如下:将5mmol(0.78g)2,2′-联吡啶(外购获得)和50mL乙醇混合,在室温下搅拌溶解后逐滴加入10mL含有5mmol(0.67g)氯化铜的乙醇溶液,滴加时间约为1h,滴加结束后继续搅拌3h。反应结束后将反应液倒入40mL乙醚中将配合物析出并进行过滤。使用柱色谱的方法进行提纯,其中流动相为石油醚:二氯甲烷=4:1(体积比),最后可得催化剂1.14g。
(4)酞菁类催化剂的合成:与卟啉类催化剂或联吡啶类催化剂相同,均为两步法合成。
(5)乙酰丙酮类催化剂的合成:与联吡啶类催化剂相同,均为一步法合成。
2.应用
在上述催化剂存在条件下,将2-烷基蒽一次性或分批投料于水或有机溶剂中,水或有机溶剂、2-烷基蒽和催化剂的质量比为1~100:1:0.01~1,更优选的质量比为3:1:0.1;使用含氧气体氧化并在65~120℃下反应1~24h,得到2-烷基蒽醌,产物分离方式包括萃取分离、结晶分离或减压精馏分离。
其中,含氧气体包括纯氧、空气或氧气与惰性气体的混合气体,更优选为纯氧、空气,其压力为1~8Mpa,更优选为4~6MPa。有机溶剂为乙酸、乙腈、N,N-二甲基甲酰胺、苯、甲苯、二甲基取代苯、氯苯、乙二醇甲醚、戊醇、乙酸乙酯、乙酸正丁酯、1,4-二氧六环、吡啶、二氯甲烷酮和二甲基亚砜中的一种或多种。2-烷基蒽分批投料时,投料间隔时间为0.5~24h,更优选的投料间隔时间为6~12h。
实施例1
在100mL反应釜中加入二氯甲烷(CH2Cl2,60mL)、间-四羟乙基(4-甲氧苯基)卟啉钴(II)(C48H36CoN4O4,1.15g,1.5mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h;然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例2
在100mL反应釜中加入二氯甲烷(CH2Cl2,60mL)、钒基八乙基卟啉(C36H44N4OV,0.87g,1.5mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h,然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例3
在100mL反应釜中加入N,N-二甲基甲酰胺(DMF,60mL)、2,2′-联吡啶氯化铜(C10H8N2CuCl2,1.4g,5mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h,然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例4
在100mL反应釜中加入吡啶(pyridine,60mL)、N,N′-二水杨醛乙二胺钴(II)(C16H14CoN2O2,0.94g,3mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h,然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例5
在100mL反应釜中加入吡啶(pyridine,60mL)、(S,S)-(-)-N,N′-双(3,5-二-叔丁基亚水杨基)-1,2-环己二胺氯化锰(III)(C36H52ClMnN2O2,1.84g,3mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h,然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例6
在100mL反应釜中加入吡啶(pyridine,60mL)、N,N'-双(3,5-二叔丁基亚水杨基)-1,1,2,2-四甲基乙二胺氯化锰(III)(C36H54ClMnN2O2,1.85g,3mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h,然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例7
在100mL反应釜中加入乙腈(CH3CN,60mL)、酞菁化锰(II)(C32H16MnN8,0.83g,1.5mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h,然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例8
在100mL反应釜中加入二甲基亚砜(DMSO,60mL)、氧化二乙酰丙酮合钒(C10H14O5V,1.28g,5mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h,然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例9
与实施例1的区别在于:2-叔戊基蒽为一次性投料。
在100mL反应釜中加入二氯甲烷(CH2Cl2,60mL)、间-四羟乙基(4-甲氧苯基)卟啉钴(II)(C48H36CoN4O4,1.15g,1.5mol%)、2-叔戊基蒽(AAN,一次性投入24g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h;然后将反应釜冷却至室温后放出釜内气体并重新补充5MPa标准空气,继续反应6h,该补充过程重复三次。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例10
与实施例1的区别在于:反应温度为70℃。
在100mL反应釜中加入二氯甲烷(CH2Cl2,60mL)、间-四羟乙基(4-甲氧苯基)卟啉钴(II)(C48H36CoN4O4,1.15g,1.5mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),70℃下搅拌反应6h;然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例11
与实施例1的区别在于:反应温度为95℃。
在100mL反应釜中加入二氯甲烷(CH2Cl2,60mL)、间-四羟乙基(4-甲氧苯基)卟啉钴(II)(C48H36CoN4O4,1.15g,1.5mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),95℃下搅拌反应6h;然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例12
与实施例1的区别在于:反应温度为120℃。
在100mL反应釜中加入二氯甲烷(CH2Cl2,60mL)、间-四羟乙基(4-甲氧苯基)卟啉钴(II)(C48H36CoN4O4,1.15g,1.5mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),120℃下搅拌反应6h;然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例13
与实施例1的区别在于:空气压力为4MPa。
在100mL反应釜中加入二氯甲烷(CH2Cl2,60mL)、间-四羟乙基(4-甲氧苯基)卟啉钴(II)(C48H36CoN4O4,1.15g,1.5mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(4MPa,换气三次),85℃下搅拌反应6h;然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例14
与实施例1的区别在于:空气压力为6MPa。
在100mL反应釜中加入二氯甲烷(CH2Cl2,60mL)、间-四羟乙基(4-甲氧苯基)卟啉钴(II)(C48H36CoN4O4,1.15g,1.5mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(6MPa,换气三次),85℃下搅拌反应6h;然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
实施例15
与实施例1的区别在于:使用的反应底物为2-乙基蒽。
在100mL反应釜中加入二氯甲烷(CH2Cl2,60mL)、间-四羟乙基(4-甲氧苯基)卟啉钴(II)(C48H36CoN4O4,1.15g,1.5mol%)、2-乙基蒽(EAN,5g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h;然后打开反应釜补充进料2-乙基蒽(EAN,5g),继续反应6h,该补充进料过程重复三次,最终2-乙基蒽(EAN)进料合计20g。反应结束后,将反应液经过萃取分离得到2-乙基蒽醌(EAQ),进行气相色谱分析。
实施例16
与实施例1的区别在于:使用的反应底物为2-异丙基蒽。
在100mL反应釜中加入二氯甲烷(CH2Cl2,60mL)、间-四羟乙基(4-甲氧苯基)卟啉钴(II)(C48H36CoN4O4,1.15g,1.5mol%)、2-异丙基蒽(iPAN,5.3g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h;然后打开反应釜补充进料2-异丙基蒽(iPAN,5.3g),继续反应6h,该补充进料过程重复三次,最终2-异丙基蒽(iPAN)进料合计21.2g。反应结束后,将反应液经过萃取分离得到2-异丙基蒽醌(iPAQ),进行气相色谱分析。
实施例17
与实施例1的区别在于:使用的反应底物为2-苯基蒽。
在100mL反应釜中加入二氯甲烷(CH2Cl2,60mL)、间-四羟乙基(4-甲氧苯基)卟啉钴(II)(C48H36CoN4O4,1.15g,1.5mol%)、2-苯基蒽(BzAN,6.1g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h;然后打开反应釜补充进料2-苯基蒽(BzAN,6.1g),继续反应6h,该补充进料过程重复三次,最终2-苯基蒽(BzAN)进料合计24.4g。反应结束后,将反应液经过萃取分离得到2-苯基蒽醌(BzAQ),进行气相色谱分析。
对比例1
与实施例1的区别在于:不使用催化剂。
在100mL反应釜中加入二氯甲烷(CH2Cl2,60mL)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h;然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
对比例2
与实施例1的区别在于:使用的催化剂为硝酸钴。
在100mL反应釜中加入乙酸(HOAc,60mL)、纯水(H2O,6mL)、硝酸钴(Co(NO3)2·6H2O,1.41g,5mol%)、2-叔戊基蒽(AAN,6g),充入标准空气(5MPa,换气三次),85℃下搅拌反应6h;然后打开反应釜补充进料2-叔戊基蒽(AAN,6g),继续反应6h,该补充进料过程重复三次,最终2-叔戊基蒽(AAN)进料合计24g。反应结束后,将反应液经过萃取分离得到2-叔戊基蒽醌(AAQ),进行气相色谱分析。
表1.不同催化剂催化空气氧化制备2-叔戊基蒽醌
表2.不同反应条件下空气氧化制备2-叔戊基蒽醌
表3.催化剂催化空气氧化制备2-烷基蒽醌
由表1所示,结合实施例1-9和对比例1-2,相对于不加催化剂或者常规催化剂,本发明中催化剂催化空气氧化制备2-叔戊基蒽醌的催化效果更佳,可获得高的转化率、选择性和收率。不同有机配体和金属活性中心的配合会对催化性能产生影响,有机配体更优选为卟啉类与联吡啶类有机配体,因为对于2-烷基蒽的氧化,其决速步往往是底物自由基或自由基阳离子的形成过程,卟啉类与联吡啶类有机配体形成的配合物由于其较强的得电子能力,可以加速蒽自由基阳离子的形成。并且,反应底物2-烷基蒽的不同投料方式会对催化效果产生影响,分批投料更有利于提高反应转化率、选择性和收率。
由表2所示,不同反应条件下空气氧化制备2-叔戊基蒽醌,结合实施例1和实施例10-12,反应温度对于催化剂催化氧化反应会有影响,反应温度更优选为80~110℃,在该范围内具有更好的催化效果和更高的收率。由表3所示,不同反应底物进行催化剂催化空气氧化制备2-烷基蒽醌,均具有较高的转化率、选择性和收率。
以上仅为本发明的优选实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (10)
2.如权利要求1所述用于含氧气体氧化制备2-烷基蒽醌的催化剂,其特征在于,所述金属盐为铜盐、钴盐、铁盐、锰盐、镍盐、铬盐、钒盐、锌盐、钠盐、钯盐、银盐、铈盐和铑盐等中的一种或多种。
3.如权利要求1-2任一所述催化剂用于含氧气体氧化制备2-烷基蒽醌中的应用,其特征在于,包括如下步骤:在催化剂存在条件下,2-烷基蒽于水或有机溶剂中,经含氧气体氧化得到2-烷基蒽醌。
5.如权利要求3所述应用,其特征在于,所述含氧气体包括纯氧、空气或氧气与惰性气体的混合气体;所述含氧气体的压力为1~8MPa。
6.如权利要求3~5之一所述应用,其特征在于,所述应用的反应温度为65~120℃,反应时间为1~24h。
7.如权利要求3所述应用,其特征在于,所述有机溶剂为乙酸、乙腈、N,N-二甲基甲酰胺、苯、甲苯、二甲基取代苯、氯苯、乙二醇甲醚、戊醇、乙酸乙酯、乙酸正丁酯、1,4-二氧六环、吡啶、二氯甲烷酮和二甲基亚砜中的一种或多种。
8.如权利要求3或7所述应用,其特征在于,所述水或有机溶剂、2-烷基蒽和催化剂的质量比为1~100:1:0.01~1。
9.如权利要求3所述应用,其特征在于,所述2-烷基蒽的投料方式为一次性投料或分批投料;所述分批投料的投料间隔时间为0.5~24h。
10.如权利要求3所述应用,其特征在于,所述2-烷基蒽醌的分离方式包括萃取分离、结晶分离或减压精馏分离。
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