CN110003109B - 一种适用于吡唑啉光催化氧化的系统 - Google Patents
一种适用于吡唑啉光催化氧化的系统 Download PDFInfo
- Publication number
- CN110003109B CN110003109B CN201910262169.7A CN201910262169A CN110003109B CN 110003109 B CN110003109 B CN 110003109B CN 201910262169 A CN201910262169 A CN 201910262169A CN 110003109 B CN110003109 B CN 110003109B
- Authority
- CN
- China
- Prior art keywords
- temperature
- silica gel
- weight
- residue
- roasting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 16
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 title abstract description 18
- 238000007254 oxidation reaction Methods 0.000 title abstract description 17
- 230000003647 oxidation Effects 0.000 title abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000741 silica gel Substances 0.000 claims abstract description 27
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 17
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- -1 3-chloro-2-pyridyl Chemical group 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000008247 solid mixture Substances 0.000 claims description 10
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 229910052805 deuterium Inorganic materials 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- YQDSXDPQYUXRDP-UHFFFAOYSA-N 1,3,5-triphenylpyrazole Chemical compound C=1C(C=2C=CC=CC=2)=NN(C=2C=CC=CC=2)C=1C1=CC=CC=C1 YQDSXDPQYUXRDP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- FBNAYEYTRHHEOB-UHFFFAOYSA-N 2,3,5-triphenyl-1,3-dihydropyrazole Chemical compound N1N(C=2C=CC=CC=2)C(C=2C=CC=CC=2)C=C1C1=CC=CC=C1 FBNAYEYTRHHEOB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims 4
- 238000010189 synthetic method Methods 0.000 claims 4
- 239000012467 final product Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 16
- 239000007800 oxidant agent Substances 0.000 abstract description 9
- 230000001590 oxidative effect Effects 0.000 abstract description 9
- 150000007524 organic acids Chemical class 0.000 abstract description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- 235000005985 organic acids Nutrition 0.000 abstract description 3
- 230000003100 immobilizing effect Effects 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- FQMUOIZSRNYHTL-UHFFFAOYSA-N ethyl 5-bromo-2-(3-chloropyridin-2-yl)pyrazole-3-carboxylate Chemical compound CCOC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl FQMUOIZSRNYHTL-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 150000003217 pyrazoles Chemical class 0.000 description 3
- 241000238876 Acari Species 0.000 description 2
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000000895 acaricidal effect Effects 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000005513 chalcones Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 2
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000005899 Fipronil Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 239000005869 Pyraclostrobin Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960004365 benzoic acid Drugs 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229940013764 fipronil Drugs 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明公布了一种适用于吡唑啉光催化氧化的系统,所述系统由光敏型催化剂、氧化剂和各种有机酸组成。在本发明中,利用硅胶固载TiO2粉末,制备获取光敏型催化剂,直接采用纯氧气或者空气作为氧化剂来源,由各种有机酸混合组成一种高效的适用于有机化合物光催化氧化应用系统,该系统特别适用于对吡唑啉氧化的反应。本发明具有反应效率高,产品分离简单和无污染等特点。
Description
技术领域
本发明属于吡唑啉氧化领域,具体涉及一种适用于吡唑啉光催化氧化的系统。
背景技术
吡唑啉和吡唑是两类具有良好的生理活性和药用价值的同系衍生杂环化合物,二者在医药和农药领域都有着巨大的应用价值和前景。在医药方面,吡唑啉是一类具有生物活性和很强的药用价值的五元杂环化合物,其在抗病毒、抑制免疫等方面有着良好的活性。同样吡唑啉可以发生脱氢芳构化生成相应的吡唑类衍生物,此类化合物也具有良好的医用前景,在抗菌、消炎、治疗糖尿病等药物研究当中应用广泛。因此,吡唑啉的合成也引起了人们的广泛关注。在农药方面,他被广泛应用在杀虫剂和杀螨剂方面。研究结果表明,该类型的药物具有独特的作用机理,选择性好,对各个生长阶段的螨类及各种类型的害螨均表现出很高的杀虫、杀螨活性,对环戊二烯类、有机磷、有机氯、氨基甲酸酯、拟除虫菊酯等有抗性的或敏感的害虫均有效,与传统杀虫剂不存在交互抗性,并且对哺乳动物及非靶标生物安全,对环境相容性好。吡唑类化合物以其高效、低毒和对环境友好的特性而成为农药界追捧的热门品种,而吡唑环上取代位点和取代基的多样性变化使市场化的吡唑类化合物日益丰富,并涌现出多个重量级产品,其中氟虫腈和吡唑醚菌酯更是荣登全球十大顶级品种之列。
吡唑啉的合成通常是由芳香醛与酮在碱性条件下,先生成查耳酮,然后查耳酮与肼发生反应,来制备吡唑啉类化合物。查耳酮的合成是在碱性条件下进行的,反应温度与醛的活性有关,一般在室温进行,必要的时候也可用冰水进行冷却;碱的浓度受芳香醛上羰基的活性及酮上α氢的影响,一般为20%-50%的NaOH溶液;吡唑啉的合成,溶剂多为极性较大的羧酸,常用的有乙酸和丙酸,也有在吡啶中回流进行。而对于吡唑的直接合成一般采用炔类化合物与肼的衍生物,在该类型贵金属化合物作催化剂,如三苯基磷氯化钯或六氟锑酸银。当然也可以采用酮和酸的氯化物在锂的催化下生成1,3-二酮,然后直接滴加肼,一步合成吡唑。在药物研究中,人们经常采用先合成吡唑啉类化合物,然后在经过氧化得到吡唑类化合物,研究其系列衍生物的生物活性和应用价值。目前,用于二氢吡啶芳构化的试剂主要采用一些重金属氧化剂,如高锰酸钾、二氧化锰、PCC、DDQ、FeCl3·6H2O、硝酸铁、四丁基锡重铬酸盐(TBPDC)和硝酸铋等。其反应摩尔比至少按照氧化的一比一进行,金属氧化剂使用量大,后处理难度大,环境污染性强。而采用硝酸类试剂作为氧化剂,必须在强酸性环境下进行,对很多的物质不适用,并且后处理时的废酸污染无法处理,给分离提纯带来了困难。
发明内容
针对上述难题,本发明旨在提供一种适用于吡唑啉光催化氧化的系统,所述系统由光敏型催化剂、氧化剂和有机酸组成,所述光敏型催化剂为硅胶固载TiO2粉末,所述氧化剂为纯氧气或者空气。
优选的,所述有机酸包括冰乙酸、苯甲酸、草酸和苯乙酸。
优选的,所述吡唑啉光催化氧化,包括如下步骤:将吡唑啉溶解在有机溶剂中,然后再加入光敏型催化剂和有机酸,并超声使光敏型催化剂和有机酸均匀分散在有机溶剂中,得到混合溶液,接着向混合溶液中持续通入氧化剂,通入5-20min后,在100-500W的氙灯下,磁力搅拌,进行反应,反应结束后蒸干溶剂,再洗涤过滤,重结晶得到吡唑类化合物;
所述通入氧化剂的流量为10-50mL/min;
所述反应温度为40-60℃。
优选的,所述有机溶剂包括:乙酸乙酯,乙腈,二氯甲烷,氯仿、丙酮和叔丁醇溶剂体系。
优选的,所述有机溶剂为氯仿、丙酮和叔丁醇溶剂体系时,向溶解了吡唑啉的有机溶剂中,加入光敏型催化剂即可,不需要加入有机酸。
优选的,所述加入光敏催化剂的物质的量,占吡唑啉物质的量的1%-10%。
优选的,所述光敏型催化剂的制备,包括如下步骤:
1)在惰性气体流量为0.2-0.35L/min的条件下,将硅胶在120-300℃下焙烧1-12h,再升温至300-500℃焙烧0.5-2h,焙烧结束后冷却;
2)将步骤1)中焙烧后的硅胶与钛酸四丁酯加入无水乙醇中,制备得到乙醇溶液;
3)将步骤2)得到的乙醇溶液,20-80℃条件下,磁力搅拌,浸渍4-5h,然后再向里滴加去离子水,浸渍1-6h,浸渍结束后蒸干液体,得到固体混合物;
4)将步骤3)得到的固体混合物,300-600℃条件下焙烧4-5h,得到硅胶固载TiO2粉末;
所述硅胶、钛酸四丁酯、无水乙醇和去离子水,按重量份计,分别为硅胶1份,钛酸四丁酯0.4-0.7份,无水乙醇2.6-5.9份,去离子水0.1-1.3份。
寻找一种氧化性温和,氧化效率高,毒性小的芳构化试剂已经成为人类对吡唑啉类化合物研究的热点之一。1972年日本Fujishima和Honda发现TiO2单晶电极光分解水产生强氧化活性,通过多年的大量研究,目前,在多相光催化反应所使用的半导体催化剂中,TiO2以其无毒、催化活性高、氧化能力强、稳定性好最为常用。它在废水处理中的应用潜力,已有许多文献报道。大量研究证实,染料、表面活性剂、有机卤化物、农药、油类、氰化物等都能有效地进行光催化反应,脱色、去毒,矿化为无机小分子物质,从而消除对环境的污染。而对于TiO2直接应用在有机合成氧化方面应用却很少,运用在吡唑啉氧化中更是没有。本发明中,利用硅胶固载TiO2粉末悬浊液,制备获取光敏型催化剂,直接采用纯氧气或者空气作为氧化剂来源,由各种有机酸混合组成一种高效的适用于有机化合物光催化氧化应用系统,该系统特别适用于对吡唑啉氧化的反应,该反应具有反应效率高,产品分离简单和无污染等特点。
本发明的有益效果:
本发明反应效率高,产品分离简单,对环境无污染,氧化性温和,氧化效率高,毒性小。
附图说明
图1实施例4合成的3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸乙酯的核磁共振氢谱图;
图2实施例3合成的1,3,5-三苯基吡唑的核磁共振氢谱图。
具体实施方式
为了进一步说明本发明的技术效果,下面通过实施例对本发明进行具体描述,
实施例1
1,3,5-三苯基吡唑的合成:
先将约5.0g的1,3,5-三苯基吡唑啉溶解在约60mL的乙腈溶液中,将溶解完全的溶液加入光催化反应器,然后加入约0.2g的催化剂,滴入约0.5mL的冰乙酸溶液,超声混合均匀,搅拌控制搅拌速度在150转/S以上,持续以30mL/min通入空气,通入20min后;开启氘灯,控制分液温度在40℃时,持续反应24h,TLC分析反应完全(P/E=7:3,Rf=0.45)。关闭光源,冷却到室温,旋转蒸干回收乙腈溶剂,残留物用将反应物用约100mL的乙酸乙酯溶解完全,加入150mL的水洗涤一次,饱和食盐水洗一次,无水硫酸钠干燥,过滤,滤液蒸馏除去溶剂,得到浅黄色固体,用石油醚重结晶,得到浅黄色晶体4.4g,产率88.6%。
实施例2
3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸乙酯的合成
先将约2.0g的3-溴-1-(3-氯-2-吡啶基)-4,5-二氢-1H-吡唑啉-5-甲酸乙酯溶解在约40mL的乙腈溶液中,将溶解完全的溶液加入光催化反应器,然后加入约0.1g的催化剂,滴入约0.2mL的冰乙酸溶液,超声混合均匀,搅拌控制搅拌速度在150转/S以上,持续以30mL/min通入空气,通入20min后;开启氘灯,控制分液温度在40℃时,持续反应16h,TLC分析反应完全(P/E=1:0,Rf=0.80)。关闭光源,冷却到室温,旋转蒸干回收乙腈溶剂,残留物用将反应物用约50mL的乙酸乙酯溶解完全,加入50mL的水洗涤一次,饱和食盐水洗一次,无水硫酸钠干燥,过滤,滤液蒸馏除去溶剂,得到浅黄色固体,用石油醚重结晶,得到浅黄色晶体1.5g,产率75%。
实施例3
1,3,5-三苯基吡唑的合成
先将约5.0g的1,3,5-三苯基吡唑啉溶解在约60mL的叔丁醇溶液中,将溶解完全的溶液加入光催化反应器,然后加入约0.2g的催化剂,超声混合均匀,搅拌控制搅拌速度在150转/S以上,持续以30mL/min通入空气,通入20min后;开启氘灯,控制分液温度在40℃时,持续反应24h,TLC分析反应完全(P/E=7:3,Rf=0.45)。关闭光源,冷却到室温,旋转蒸干回收乙腈溶剂,残留物用将反应物用约100mL的乙酸乙酯溶解完全,加入150mL的水洗涤一次,饱和食盐水洗一次,无水硫酸钠干燥,过滤,滤液蒸馏除去溶剂,得到浅黄色固体,用石油醚重结晶,得到浅黄色晶体4.6g,产率92.6%。
实施例4
3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸乙酯的合成
先将约2.0g的3-溴-1-(3-氯-2-吡啶基)-4,5-二氢-1H-吡唑啉-5-甲酸乙酯溶解在约40mL的叔丁醇溶液中,将溶解完全的溶液加入光催化反应器,然后加入约0.1g的催化剂,超声混合均匀,搅拌控制搅拌速度在150转/S以上,持续以30mL/min通入空气,通入20min后;开启氘灯,控制分液温度在40℃时,持续反应16h,TLC分析反应完全(P/E=1:0,Rf=0.80)。关闭光源,冷却到室温,旋转蒸干回收乙腈溶剂,残留物用将反应物用约50mL的乙酸乙酯溶解完全,加入50mL的水洗涤一次,饱和食盐水洗一次,无水硫酸钠干燥,过滤,滤液蒸馏除去溶剂,得到浅黄色固体,用石油醚重结晶,得到浅黄色晶体1.65g,产率83%。
最后需要说明的是,以上实施例仅用于说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明的技术方案进行了详细说明,本领域技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明的宗旨和范围,其均应涵盖在本发明的保护范围当中。
Claims (4)
1.一种1,3,5-三苯基吡唑的合成方法,其特征在于,合成路线为:
所述方法包括以下步骤:
先将5.0g的1,3,5-三苯基吡唑啉溶解在60mL的乙腈溶液中,将溶解完全的溶液加入光催化反应器,然后加入0.2g的硅胶固载TiO2粉末,滴入0.5mL的冰乙酸溶液,超声混合均匀,搅拌控制搅拌速度在150转/S以上,持续以30mL/min通入空气,通入20min后;开启氘灯,控制分液温度在40℃时,持续反应24h,TLC分析反应完全,展开剂为石油醚:乙酸乙酯=7:3,Rf=0.45;关闭光源,冷却到室温,旋转蒸干回收乙腈溶剂,残留物用100mL的乙酸乙酯溶解完全,加入150mL的水洗涤一次,饱和食盐水洗一次,无水硫酸钠干燥,过滤,滤液蒸馏除去溶剂,得到浅黄色固体,用石油醚重结晶,得到浅黄色晶体4.4g,产率88.6%;
其中,所述硅胶固载TiO2粉末的制备,包括如下步骤:
1)在惰性气体流量为0.2-0.35L/min的条件下,将硅胶在120-300℃下焙烧1-12h,再升温至300-500℃焙烧0.5-2h,焙烧结束后冷却;
2)将步骤1)中焙烧后的硅胶与钛酸四丁酯加入无水乙醇中,制备得到乙醇溶液;
3)将步骤2)得到的乙醇溶液,20-80℃条件下,磁力搅拌,浸渍4-5h,然后再向里滴加去离子水,浸渍1-6h,浸渍结束后蒸干液体,得到固体混合物;
4)将步骤3)得到的固体混合物,300-600℃条件下焙烧4-5h,得到硅胶固载TiO2粉末;
所述硅胶、钛酸四丁酯、无水乙醇和去离子水,按重量份计,分别为硅胶1份,钛酸四丁酯0.4-0.7份,无水乙醇2.6-5.9份,去离子水0.1-1.3份。
2.一种1,3,5-三苯基吡唑的合成方法,其特征在于,合成路线为:
所述方法包括以下步骤:
先将5.0g的1,3,5-三苯基吡唑啉溶解在60mL的叔丁醇溶液中,将溶解完全的溶液加入光催化反应器,然后加入0.2g的硅胶固载TiO2粉末,超声混合均匀,搅拌控制搅拌速度在150转/S以上,持续以30mL/min通入空气,通入20min后;开启氘灯,控制分液温度在40℃时,持续反应24h,TLC分析反应完全,展开剂为石油醚:乙酸乙酯=7:3,Rf=0.45;关闭光源,冷却到室温,旋转蒸干回收叔丁醇,残留物用100mL的乙酸乙酯溶解完全,加入150mL的水洗涤一次,饱和食盐水洗一次,无水硫酸钠干燥,过滤,滤液蒸馏除去溶剂,得到浅黄色固体,用石油醚重结晶,得到浅黄色晶体4.6g,产率92.6%;
其中,所述硅胶固载TiO2粉末的制备,包括如下步骤:
1)在惰性气体流量为0.2-0.35L/min的条件下,将硅胶在120-300℃下焙烧1-12h,再升温至300-500℃焙烧0.5-2h,焙烧结束后冷却;
2)将步骤1)中焙烧后的硅胶与钛酸四丁酯加入无水乙醇中,制备得到乙醇溶液;
3)将步骤2)得到的乙醇溶液,20-80℃条件下,磁力搅拌,浸渍4-5h,然后再向里滴加去离子水,浸渍1-6h,浸渍结束后蒸干液体,得到固体混合物;
4)将步骤3)得到的固体混合物,300-600℃条件下焙烧4-5h,得到硅胶固载TiO2粉末;
所述硅胶、钛酸四丁酯、无水乙醇和去离子水,按重量份计,分别为硅胶1份,钛酸四丁酯0.4-0.7份,无水乙醇2.6-5.9份,去离子水0.1-1.3份。
3.一种3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸乙酯的合成方法,其特征在于,合成路线为:
包括以下步骤:
先将2.0g的3-溴-1-(3-氯-2-吡啶基)-4,5-二氢-1H-吡唑啉-5-甲酸乙酯溶解在40mL的乙腈溶液中,将溶解完全的溶液加入光催化反应器,然后加入0.1g的硅胶固载TiO2粉末,滴入0.2mL的冰乙酸溶液,超声混合均匀,搅拌控制搅拌速度在150转/S以上,持续以30mL/min通入空气,通入20min后;开启氘灯,控制分液温度在40℃时,持续反应16h,TLC分析反应完全,展开剂为石油醚:乙酸乙酯=1:0,Rf=0.80;关闭光源,冷却到室温,旋转蒸干回收乙腈溶剂,残留物用50mL的乙酸乙酯溶解完全,加入50mL的水洗涤一次,饱和食盐水洗一次,无水硫酸钠干燥,过滤,滤液蒸馏除去溶剂,得到浅黄色固体,用石油醚重结晶,得到浅黄色晶体1.5g,产率75%;
其中,所述硅胶固载TiO2粉末的制备,包括如下步骤:
1)在惰性气体流量为0.2-0.35L/min的条件下,将硅胶在120-300℃下焙烧1-12h,再升温至300-500℃焙烧0.5-2h,焙烧结束后冷却;
2)将步骤1)中焙烧后的硅胶与钛酸四丁酯加入无水乙醇中,制备得到乙醇溶液;
3)将步骤2)得到的乙醇溶液,20-80℃条件下,磁力搅拌,浸渍4-5h,然后再向里滴加去离子水,浸渍1-6h,浸渍结束后蒸干液体,得到固体混合物;
4)将步骤3)得到的固体混合物,300-600℃条件下焙烧4-5h,得到硅胶固载TiO2粉末;
所述硅胶、钛酸四丁酯、无水乙醇和去离子水,按重量份计,分别为硅胶1份,钛酸四丁酯0.4-0.7份,无水乙醇2.6-5.9份,去离子水0.1-1.3份。
4.一种3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸乙酯的合成方法,其特征在于,合成路线为:
包括以下步骤:
先将2.0g的3-溴-1-(3-氯-2-吡啶基)-4,5-二氢-1H-吡唑啉-5-甲酸乙酯溶解在40mL的叔丁醇溶液中,将溶解完全的溶液加入光催化反应器,然后加入0.1g的硅胶固载TiO2粉末,超声混合均匀,搅拌控制搅拌速度在150转/S以上,持续以30mL/min通入空气,通入20min后;开启氘灯,控制分液温度在40℃时,持续反应16h,TLC分析反应完全,展开剂为石油醚:乙酸乙酯=1:0,Rf=0.80;关闭光源,冷却到室温,旋转蒸干回收叔丁醇,残留物用50mL的乙酸乙酯溶解完全,加入50mL的水洗涤一次,饱和食盐水洗一次,无水硫酸钠干燥,过滤,滤液蒸馏除去溶剂,得到浅黄色固体,用石油醚重结晶,得到浅黄色晶体1.65g,产率83%;
其中,所述硅胶固载TiO2粉末的制备,包括如下步骤:
1)在惰性气体流量为0.2-0.35L/min的条件下,将硅胶在120-300℃下焙烧1-12h,再升温至300-500℃焙烧0.5-2h,焙烧结束后冷却;
2)将步骤1)中焙烧后的硅胶与钛酸四丁酯加入无水乙醇中,制备得到乙醇溶液;
3)将步骤2)得到的乙醇溶液,20-80℃条件下,磁力搅拌,浸渍4-5h,然后再向里滴加去离子水,浸渍1-6h,浸渍结束后蒸干液体,得到固体混合物;
4)将步骤3)得到的固体混合物,300-600℃条件下焙烧4-5h,得到硅胶固载TiO2粉末;
所述硅胶、钛酸四丁酯、无水乙醇和去离子水,按重量份计,分别为硅胶1份,钛酸四丁酯0.4-0.7份,无水乙醇2.6-5.9份,去离子水0.1-1.3份。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910262169.7A CN110003109B (zh) | 2019-04-02 | 2019-04-02 | 一种适用于吡唑啉光催化氧化的系统 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910262169.7A CN110003109B (zh) | 2019-04-02 | 2019-04-02 | 一种适用于吡唑啉光催化氧化的系统 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110003109A CN110003109A (zh) | 2019-07-12 |
CN110003109B true CN110003109B (zh) | 2020-08-04 |
Family
ID=67169474
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910262169.7A Active CN110003109B (zh) | 2019-04-02 | 2019-04-02 | 一种适用于吡唑啉光催化氧化的系统 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110003109B (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114787141B (zh) * | 2019-11-11 | 2024-07-09 | Fmc公司 | 用于制备3-溴-1-(3-氯吡啶-2-基)-1h-吡唑-5-甲酸乙酯的方法 |
TW202140436A (zh) * | 2020-01-08 | 2021-11-01 | 美商富曼西公司 | 用於製備3-溴-1-(3-氯吡啶-2-基)-1h-吡唑-5-羧酸乙酯的方法 |
CN113735823A (zh) * | 2020-05-27 | 2021-12-03 | 江苏七洲绿色化工股份有限公司 | 一种氯虫苯甲酰胺中间体的制备方法 |
CN117865936A (zh) * | 2024-01-10 | 2024-04-12 | 山东金特安全科技有限公司 | 一种吡唑酸关键中间体的制备方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101497585B (zh) * | 2008-01-31 | 2011-01-12 | 中国科学院理化技术研究所 | 光催化合成1,3,5-三取代-2-吡唑衍生物的方法 |
CN106268904B (zh) * | 2016-08-05 | 2019-02-15 | 陕西科技大学 | 一种氮、硫共掺杂硅胶固载TiO2光催化剂及其制备方法 |
-
2019
- 2019-04-02 CN CN201910262169.7A patent/CN110003109B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN110003109A (zh) | 2019-07-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110003109B (zh) | 一种适用于吡唑啉光催化氧化的系统 | |
CN104610250A (zh) | 含三个氮杂环的1,2,3-噻二唑-5-甲脒类化合物及合成 | |
CN103626691B (zh) | 啶氧菌酯的制备方法 | |
CN108440345B (zh) | 一种磺酰胺类化合物的制备方法 | |
CN114380741B (zh) | 一种2-甲基喹啉类化合物的4号位烷基化衍生物的制备方法 | |
Azizi et al. | Deep eutectic solvent mediated rapid and selective one-pot synthesis of 5-alkylidene-Thiazolones | |
FERRIS | α-Oximino Ketones. III. A New Synthesis of α-Amino Acids1 | |
CN111875514A (zh) | 一种制备正壬酸香草酰胺的方法 | |
Hendrickson et al. | A NEW HETEROCYCLE SYNTHESIS: PYRROLES AND QUINOLINES | |
CN109824667A (zh) | 一种合成吲哚并吲哚嗪酮类化合物的方法 | |
CN110183453B (zh) | 一种无金属催化制备3-苯基-[1,2,4]三唑[4,3-a]吡啶类化合物的方法 | |
CN110963937B (zh) | 秋水仙碱和别秋水仙碱的不对称合成方法 | |
Strunz et al. | Fittig bislactones in cyclopentenone synthesis: short synthesis of methylenomycin B | |
CN103709175A (zh) | 6-氯-3H-恶唑并[4,5-b]吡啶-2-酮的一步合成法 | |
CN110317172A (zh) | 一种氮杂芴酮类衍生物及其制备方法和应用 | |
CN112939800B (zh) | 一种香草酰胺的合成方法 | |
CN109369587A (zh) | 一种高纯度高收率螺螨酯的生产工艺 | |
CN104910033A (zh) | 一种制备5-氨基酮戊酸盐酸盐的方法 | |
DE2351217C2 (de) | Verfahren zur Herstellung von 3,5-disubstituierten Phenylessigsäurederivaten | |
CN105348139B (zh) | O‑3‑氯‑2‑丙烯基羟胺的合成工艺 | |
CN115557855B (zh) | 多取代2-羟基二苯甲酮类化合物及其制备方法与应用 | |
CN114702364B (zh) | 一种多氟烷基芳香烃的制备方法 | |
Javani et al. | Green sonochemical synthesis of technical fenitrothion using protic ionic liquid | |
CN108101764A (zh) | 二羟基间苯二甲酸的合成 | |
JP4310391B2 (ja) | トロポロン化合物の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |