CN107868047B - 一种催化氧化制备二氯喹啉酸的方法 - Google Patents
一种催化氧化制备二氯喹啉酸的方法 Download PDFInfo
- Publication number
- CN107868047B CN107868047B CN201610871748.8A CN201610871748A CN107868047B CN 107868047 B CN107868047 B CN 107868047B CN 201610871748 A CN201610871748 A CN 201610871748A CN 107868047 B CN107868047 B CN 107868047B
- Authority
- CN
- China
- Prior art keywords
- reaction
- quinclorac
- chloride
- methylquinoline
- chloro
- 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
- FFSSWMQPCJRCRV-UHFFFAOYSA-N quinclorac Chemical compound ClC1=CN=C2C(C(=O)O)=C(Cl)C=CC2=C1 FFSSWMQPCJRCRV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title abstract description 16
- 230000003197 catalytic effect Effects 0.000 title abstract description 14
- 230000003647 oxidation Effects 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 66
- RTSCXWFBJWJHNJ-UHFFFAOYSA-N CC1=C2N=CC=CC2=CC=C1Cl.Cl Chemical compound CC1=C2N=CC=CC2=CC=C1Cl.Cl RTSCXWFBJWJHNJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002808 molecular sieve Substances 0.000 claims abstract description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 25
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 23
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 238000007599 discharging Methods 0.000 claims description 10
- LPXYXBZAXFTFKH-UHFFFAOYSA-N ClC=1C(=C(C(=NC1)C(=O)O)C(=O)O)Cl Chemical compound ClC=1C(=C(C(=NC1)C(=O)O)C(=O)O)Cl LPXYXBZAXFTFKH-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 75
- 239000007800 oxidant agent Substances 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 230000001590 oxidative effect Effects 0.000 abstract description 14
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- -1 transition metal salt Chemical class 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical class [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical class [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000192043 Echinochloa Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical class BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- 239000011630 iodine Chemical class 0.000 description 2
- 229910052740 iodine Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- SQQMOCHTAKMTGJ-UHFFFAOYSA-N 3,7-dichloro-8-(chloromethyl)quinoline Chemical compound ClC1=CN=C2C(CCl)=C(Cl)C=CC2=C1 SQQMOCHTAKMTGJ-UHFFFAOYSA-N 0.000 description 1
- 229930192334 Auxin Natural products 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- ZBICJTQZVYWJPB-UHFFFAOYSA-N [Mn].[Co].[Br] Chemical compound [Mn].[Co].[Br] ZBICJTQZVYWJPB-UHFFFAOYSA-N 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005002 aryl methyl group Chemical group 0.000 description 1
- 239000002363 auxin Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- MWSPFHZPVVWJCO-UHFFFAOYSA-M hydron;methyl(trioctyl)azanium;sulfate Chemical compound OS([O-])(=O)=O.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC MWSPFHZPVVWJCO-UHFFFAOYSA-M 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7003—A-type
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域
本发明涉及一种芳香酸的制备的方法,具体地说,是涉及一种催化氧化7-氯-8-甲基喹啉氯化物制备二氯喹啉酸的方法。
背景技术
二氯喹啉酸(Quinclorac),又名3,7-二氯-8-喹啉羧酸,分子式为C10H5Cl2NO2,分子量为242.1。二氯喹啉酸是防除稻田稗草的特效选择性除草剂,属激素型喹啉羧酸类除草剂,杂草中毒症状与生长素类作用相似,主要用于防治稗草且适用期很长,1-7叶期均有效,水稻安全性好。近年来,二氯喹啉酸优异的除草性能,受到了市场的青睐,原药价格居高不下,因此,其均具有较大开发价值及良好的推广使用前景。
二氯喹啉酸的生产涉及到氧化合成芳香基羧酸化合物这一关键技术。其中,专利US4632696和4497651中公开了以二氯喹啉衍生物制备二氯喹啉酸,其中二氯喹啉酸中羧基的制备是在50~150℃条件下,以二氯化合物与浓硫酸或浓盐酸反应得到,产率为90%以上。专利CN 101851197A和102796042A中公开了以3,7-二氯-8-氯甲基喹啉氧化得到二氯喹啉酸,在氧化过程中采用了浓硫酸和硝酸,在氧化催化剂的催化下,使得二氯喹啉酸收率较高(≥65%),含量高(≥98%),操作简便,并且降低了生产成本。虽然该类方法二氯喹啉酸的产率较高,但是使用了大量的强酸,在生产中会对设备造成腐蚀,并且在反应完后产生大量的含酸废水,对环境造成严重污染。
为了克服浓硝酸作为氧化剂带来的危害,专利CN 101337929A中公开了以7-氯-8-甲基喹啉氯化物为原料,水和硫酸为溶剂,加入氧化剂氯、溴、碘的含氧酸及盐类与过氧化氢,制得二氯喹啉酸,含量为80%以上。该方法的氧化剂为氯、溴、碘的含氧酸及碱金属盐类与过氧化氢,优于浓硝酸作氧化剂,具有绿色、环保等特点,和以前的工艺相比,节省了生产成本,提高了产品质量。但在生产过程中用到了大量的浓硫酸为反应介质,依然会产生大量的含酸废水,对环境造成严重危害。
目前,二氯喹啉酸的生产工艺主要为7-氯-8-甲基喹啉氯化物的氧化过程,以浓硫酸为介质,浓硝酸为氧化剂,但存在着以下问题:
(1)以浓硝酸作为氧化剂,氧化反应剧烈,不易控制,副产物多,生产成本高,会产生大量废酸,对环境产生巨大危害。
(2)以浓硫酸为反应介质,生产中也会产生大量废酸,同时会对造成设备腐蚀。
(3)反应中使用大量的金属盐,会产生含金属离子废液,存在着严重环境污染。
综合考量当前的研究状况,可以看出在当今节能减排、“原子经济”的趋势下,产率低、“三废”排放多、环境不友好的传统工艺已不能够满足生产实践的发展需要。因此,开发高效、安全、绿色环保的先进氧化工艺势在必行。近年来,氧气、双氧水或叔丁基过氧化氢等绿色氧化剂,已经在许多氧化反应中得到一定应用,并成为研究热点。
专利CN 103420909A中公开了以氧气为氧化剂,钴-锰-溴三元复合催化剂存在下,脂肪族羧酸为溶剂的条件下,催化氧化7-氯-8-甲基喹啉氯化物制备二氯喹啉酸。该方法采用了绿色的氧气为氧化剂,改进了先前二氯喹啉酸制备工艺中产生大量废酸不易处理的问题,得到了高含量的二氯喹啉酸(≥97%)。但该方法存在着反应温度高,压力大等缺点。Shi等人(J.Org.Chem.2001,66,3235-3237)报道了以双氧水为氧化剂Na2WO4,Na2VO4,Na2MoO4作为催化剂,在三辛基甲基铵硫酸氢盐和分子筛存在下,催化氧化苄氯为苯甲酸,该方法使用的双氧水作为绿色的氧化剂,反应后对环境没有污染,并且反应条件温和,反应时间较短,苯甲酸收率达到了83%。Sudalai等人(Eur.J.Org.Chem.2008,4877-4880)报道了以叔丁基过氧化氢为氧化剂,氧化钨为催化剂,氧化脂肪族和芳香族类酮化合物为相应的羧酸产物。该方法收率高,并且反应过程无溶剂,氧化剂使用量少,对环境污染小。
发明内容
本发明提供了一种将7-氯-8-甲基喹啉氯化物催化氧化为二氯喹啉酸的新工艺,以水、乙腈或甲醇中的一种或两种组合为溶剂,通入氧气、滴加双氧水或叔丁基过氧化氢至反应体系中,选用一定量的过渡金属盐作为催化剂,与助催化剂分子筛和季铵盐构成复合催化体系,在35-90℃下,反应时间1-12h,经常规分离后,制得二氯喹啉酸,其收率范围在26-84%。
本发明方法与现有方法相比,具有以下优点:
(1)本方法以环境友好的氧气、双氧水或叔丁基过氧化氢为氧化剂代替成本高、污染严重的浓硝酸用于二氯喹啉酸的合成。其优点在于氧化剂对环境没有危害,成本低,有利于工业化生产。
(2)本方法使用的过渡金属盐为催化剂,用量极少,显著减少含金属离子废水的排放,降低了对环境的破坏。
(3)以水、甲醇或乙腈代替浓硫酸为反应介质,不仅大大降低了生产成本,减少对设备的腐蚀,而且还减少了废酸的排放,符合清洁化生产,同时也提高了生产过程中的安全性。
(4)本方法反应条件相对温和,操作简便,安全系数高。
具体实施方式
实施例1
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应5h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为68%。
实施例2
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为76%。
实施例3
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为78%。
实施例4
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应12h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为63%。
实施例5
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.012g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为61%。
实施例6
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.018g钨酸钠二水合物,四丁基溴化铵0.1g,分子筛0.1g,加入乙腈50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为69%。
实施例7
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.036g钒酸钠,四丁基溴化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为67%。
实施例8
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.01g,分子筛0.1g,加入乙腈50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为62%。
实施例9
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.10g,分子筛0.1g,加入乙腈50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为65%。
实施例10
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基氯化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为79%。
实施例11
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基硫酸氢铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,4.1mL 70%叔丁基过氧化氢滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为75%。
实施例12
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钼酸钠二水合物,四丁基溴化铵0.05g,分子筛0.05g,加入乙腈50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为64%。
实施例13
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.3g,加入乙腈50mL,搅拌,3.6mL叔丁基过氧化氢滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为75%。
实施例14
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,1mL 30%双氧水滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为78%。
实施例15
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,2.1mL 30%双氧水滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为52%。
实施例16
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,6.2mL 30%双氧水滴加至反应瓶中,在90℃下反应10h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为69%。
实施例17
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入甲醇50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应5h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为84%。
实施例18
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入水和乙腈50mL(V/V=1∶9),搅拌,4.1mL30%双氧水滴加至反应瓶中,在90℃下反应5h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为72%。
实施例19
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入水和甲醇50mL(V/V=1∶9),搅拌,4.1mL30%双氧水滴加至反应瓶中,在90℃下反应5h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为67%。
实施例20
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,氧气流速20mL/min,通入液面以下,在90℃下反应5h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为26%。
实施例21
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,氧气流速100mL/min,通入液面以下,在90℃下反应5h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为42%。
实施例22
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.1g,加入乙腈50mL,搅拌,氧气流速200mL/min,通入液面以下,在90℃下反应5h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为66%。
实施例23
在100mL三口圆底烧瓶中,依次加入2.5g 7-氯-8-甲基喹啉氯化物,0.024g钨酸钠二水合物,四丁基溴化铵0.05g,分子筛0.5g,加入乙腈50mL,搅拌,4.1mL 30%双氧水滴加至反应瓶中,在90℃下反应5h。反应结束后将反应液冷却至室温,出料,经HPLC分析,二氯喹啉酸收率为43%。
实施例24
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610871748.8A CN107868047B (zh) | 2016-09-27 | 2016-09-27 | 一种催化氧化制备二氯喹啉酸的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610871748.8A CN107868047B (zh) | 2016-09-27 | 2016-09-27 | 一种催化氧化制备二氯喹啉酸的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107868047A CN107868047A (zh) | 2018-04-03 |
CN107868047B true CN107868047B (zh) | 2023-03-21 |
Family
ID=61761157
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610871748.8A Active CN107868047B (zh) | 2016-09-27 | 2016-09-27 | 一种催化氧化制备二氯喹啉酸的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107868047B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112390753B (zh) * | 2019-08-15 | 2022-08-26 | 北京颖泰嘉和生物科技股份有限公司 | 二卤喹啉酸中间体及其制备方法 |
CN112174887B (zh) * | 2020-11-02 | 2022-08-23 | 江苏快达农化股份有限公司 | 一种制备8-喹啉羧酸及其衍生物的方法 |
CN115385855B (zh) * | 2022-10-11 | 2023-12-01 | 河北允升精细化工有限公司 | 两步氧化制备二氯喹啉酸的方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3202736A1 (de) * | 1982-01-28 | 1983-08-04 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von chinolinmonocarbonsaeuren |
CN103420909B (zh) * | 2012-05-16 | 2016-05-18 | 中国中化股份有限公司 | 一种液相催化氧化制备二氯喹啉酸的方法 |
CN102942524B (zh) * | 2012-11-21 | 2014-12-31 | 北京法盖银科技有限公司 | 一种喹啉衍生物的制备方法 |
-
2016
- 2016-09-27 CN CN201610871748.8A patent/CN107868047B/zh active Active
Non-Patent Citations (1)
Title |
---|
"二氯喹啉酸氧化工艺探讨";陈其商;《农药》;第35卷(第6期);第17-18页 * |
Also Published As
Publication number | Publication date |
---|---|
CN107868047A (zh) | 2018-04-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107868047B (zh) | 一种催化氧化制备二氯喹啉酸的方法 | |
CN103626691B (zh) | 啶氧菌酯的制备方法 | |
CN107983408B (zh) | 一种制备亚砜类催化剂及其选择性制备亚砜类化合物的方法 | |
CN111689844A (zh) | 一种2-甲基-1,4-萘醌新型生产工艺 | |
CN107626349B (zh) | 一种制备苯甲醇、苯甲醛和苯甲酸的催化剂及制备苯甲醇、苯甲醛和苯甲酸的方法 | |
CN106866326A (zh) | 一种伯醇制备腈的方法 | |
JP2016517846A (ja) | アセトフェノンの合成方法 | |
CN107935828A (zh) | 一种由甲苯类化合物高选择性制备芳香醛的方法 | |
CN116693453A (zh) | 一种催化氧化制备二氯喹啉酸的新工艺 | |
CN112961116B (zh) | 一种2-芳基甲酰基苯并恶唑化合物的合成方法 | |
CN104557640A (zh) | 一种分子氧催化氧化制备2-硝基-4-甲砜基苯甲酸的方法 | |
CN103012028B (zh) | 一种由甲苯类化合物催化氧化制备芳香醛的方法 | |
CN107129426B (zh) | 一种2,5-二氯苯酚制备方法 | |
CN101830783B (zh) | 一种希夫碱配合物催化氧气氧化醇制备醛的方法 | |
CN109574814A (zh) | 一种甲苯液相催化氧化制备苯甲醛和苯甲醇的方法 | |
CN107602393B (zh) | 一种苄位c-h键直接氧化成酮或酸的方法 | |
CN106565415A (zh) | 一种制备一氯化苯的方法 | |
WO2006131040A1 (fr) | Procede de preparation de l'acide glyoxalique par oxydation du glyoxal avec l'ozonide de l'acide maleique | |
CN102964230A (zh) | 一种甲苯液相催化氧化制苯甲醛的方法 | |
CN107337576B (zh) | 常温催化合成2-溴-5-氟三氟甲苯 | |
CN108059593B (zh) | 一种芳香仲醇氧化裂解制备有机酸的方法 | |
CN112979441B (zh) | 卤水为氯化剂的氯化饱和c-h的方法 | |
CN102941120A (zh) | 一种用于环己烷液相催化氧化制备环己醇和环己酮的催化体系及其使用方法 | |
CN113862703A (zh) | 一种苯唑草酮中间体的制备方法 | |
CN104311483A (zh) | 一种喹啉-2-羧酸的制备方法 |
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 |