CN110590671A - Copper complex catalyst, preparation method thereof and application thereof in synthesis of 4, 4' -diamino diphenyl sulfone - Google Patents
Copper complex catalyst, preparation method thereof and application thereof in synthesis of 4, 4' -diamino diphenyl sulfone Download PDFInfo
- Publication number
- CN110590671A CN110590671A CN201910828333.6A CN201910828333A CN110590671A CN 110590671 A CN110590671 A CN 110590671A CN 201910828333 A CN201910828333 A CN 201910828333A CN 110590671 A CN110590671 A CN 110590671A
- Authority
- CN
- China
- Prior art keywords
- complex catalyst
- copper complex
- copper
- solution
- synthesis
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 150000004699 copper complex Chemical class 0.000 title claims abstract description 46
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title abstract description 8
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 22
- FERCTUUKKXAWIL-UHFFFAOYSA-N 5-oxo-1,2-dihydropyrazole-3-carboxylic acid Chemical compound OC(=O)C=1C=C(O)NN=1 FERCTUUKKXAWIL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000007036 catalytic synthesis reaction Methods 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 125000003047 N-acetyl group Chemical group 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000010924 continuous production Methods 0.000 abstract description 3
- 150000001879 copper Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 15
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001844 chromium Chemical class 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- -1 lithium aluminum hydride Chemical compound 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 235000012736 patent blue V Nutrition 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KRPUDHQXDFRBGF-UHFFFAOYSA-N 1-azido-4-(4-azidophenyl)sulfonylbenzene Chemical compound C1=CC(N=[N+]=[N-])=CC=C1S(=O)(=O)C1=CC=C(N=[N+]=[N-])C=C1 KRPUDHQXDFRBGF-UHFFFAOYSA-N 0.000 description 1
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 description 1
- BVHNGWRPAFKGFP-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenyl)sulfonylbenzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 BVHNGWRPAFKGFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 241001048891 Jatropha curcas Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 229960000860 dapsone Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010189 synthetic method Methods 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
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- 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
- C07D231/14—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 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
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a copper complex catalyst, a preparation method thereof and application thereof in catalytic synthesis of 4, 4' -diamino diphenyl sulfone. The structural formula of the copper complex catalyst is as follows:the preparation method comprises the following steps: dissolving 5-hydroxy-3-pyrazolecarboxylic acid in ethanol waterAnd adding an aqueous solution of copper chloride into the solution, uniformly mixing to obtain a mixed solution, standing and reacting for 2-4 days at the temperature of 5 ℃ to obtain blue crystals, namely the copper complex catalyst. The invention also provides application of the copper complex catalyst in catalytic synthesis of 4, 4' -diaminodiphenyl sulfone. The copper complex catalyst disclosed by the invention is simple in synthesis step, the copper salt is cheap and easy to obtain, the catalyst is less in dosage and higher in yield in the application of catalytic synthesis of 4, 4' -diaminodiphenyl sulfone, the yield of two-step continuous production is 84-92%, and the catalyst is safe, pollution-free and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a copper complex catalyst, a preparation method thereof and application thereof in catalytic synthesis of 4, 4' -diamino diphenyl sulfone.
Background
4, 4' -diamino diphenyl sulfone is called dapsone (abbreviated as DDS), has a plurality of excellent chemical properties, is a chemical industrial product with multiple purposes, can be used for synthesizing a curing agent in an epoxy resin adhesive, can also be used as a synthetic monomer of a high polymer material, and is used for synthesizing high-temperature resistant high polymer materials such as polysulfonamide resin and the like and chromatographic stationary liquid; in addition, it can be used as antibiotic medicine for treating bacterial infection of human or animal, such as Jatropha curcas, etc.
Therefore, the demand of 4, 4' -diaminodiphenyl sulfone is also increasing on the market, and there are currently reported various synthetic methods for DDS, such as: 1) dichlorodiphenyl sulfone or dibromodiphenyl sulfone is used as a raw material, and the halogen ammonolysis reaction is carried out to prepare (chemical product handbook, rubber additive, Zhanglian edition, P310; CN 201310060592.1; 2) preparing 4,4 '-di (N-acetyl) diphenyl sulfoxide by Friedel-crafts reaction with acetanilide and other starting raw materials, oxidizing the sulfoxide by hydrogen peroxide or chromium salt to obtain 4, 4' -di (N-acetyl) diphenyl sulfone, and finally hydrolyzing to obtain a target product (Macromolecules (Washington, DC, United States),2015,48(6),1748 and 1758; acta Ciencia Indica, Chemistry,2009,35(1), 11-18; J.am.chem.Soc.,1939,61, 2763-; yakugaku Zasshi,1940,60,22-4, Abstracts 1-3; ) (ii) a 3) 4,4 '-dinitro diphenyl sulfone or 4, 4' -diazido diphenyl sulfone is first prepared, and then the nitro or azido group is converted into an amino group (CN 201410734026.9; phosphorous, Sulfur and Silicon and the related Elements,2004,179(9), 1813-1817; ranliao Yu Ranse,2005,42(3), 43-46).
The preparation method has the defects of high cost, complex steps, low safety, easy environmental pollution and the like: the method 1) needs ammonia water which is a chemical reagent which is not friendly to the environment, is easy to explode and not easy to store, and has high requirements on equipment and high environmental protection cost because of the reaction at high temperature and high pressure; method 3) converting functional groups of nitro or azide into amino, wherein the azide is easy to explode and is not easy to industrialize, and reducing nitro requires reducing agents such as lithium aluminum hydride and the like, so that the post-treatment is complex and the cost is high; the raw materials of the method 2) are cheap and easy to obtain, but hydrogen peroxide or heavy metal chromium salt is used during oxidation, the hydrogen peroxide is also easy to explode, and the heavy metal chromium salt is a heavy metal reagent with very heavy environmental pollution.
In view of this, the invention is particularly proposed.
Disclosure of Invention
In order to overcome the defects of complex preparation steps and easy pollution to the environment in the prior art, the invention provides a copper complex catalyst, a preparation method thereof and application thereof in catalytic synthesis of 4, 4' -diamino diphenyl sulfone. The copper complex catalyst is utilized to perform catalytic oxidation reaction under mild conditions, 4 ' -di (N-acetyl) diphenyl sulfoxide is oxidized to obtain 4,4 ' -di (N-acetyl) diphenyl sulfone, and finally, the target product, namely 4,4 ' -diamino diphenyl sulfone is obtained through hydrolysis.
The specific technical scheme is as follows:
a copper complex catalyst having the formula:
further, the copper complex catalyst is monoclinic system, P21/c space group, unit cell parameters are as follows:α＝90°，β＝98.476(3)°，γ＝90°。
another object of the present invention is to provide a method for preparing the copper complex catalyst, comprising the steps of:
dissolving 5-hydroxy-3-pyrazolecarboxylic acid in an ethanol aqueous solution, adding a copper chloride aqueous solution, uniformly mixing to obtain a mixed solution, standing at 5 ℃ for reaction for 2-4 days to obtain blue crystals, filtering, and drying to obtain the copper complex catalyst.
Preferably, after the 5-hydroxy-3-pyrazolecarboxylic acid is dissolved in an aqueous ethanol solution, the concentration of the 5-hydroxy-3-pyrazolecarboxylic acid is (0.05-0.5) mol/L.
Preferably, the volume ratio of the ethanol to the water in the ethanol aqueous solution is (1-3) to 1; the concentration of the copper chloride in the aqueous solution of the copper chloride is (0.2-2.0) mol/L.
Preferably, the molar ratio of the 5-hydroxy-3-pyrazolecarboxylic acid to the copper chloride in the mixed solution is (2-6): 1.
The invention further aims to provide the application of the copper complex catalyst in catalytic synthesis of 4, 4' -diaminodiphenyl sulfone.
Further, 4 '-di (N-acetyl) diphenyl sulfoxide is used as a raw material, and the 4, 4' -diamino diphenyl sulfone is obtained through catalytic oxidation and hydrolysis reaction under the condition of the copper complex catalyst.
The chemical reaction equation is as follows:
the catalytic oxidation and hydrolysis reaction steps are as follows:
catalytic oxidation: dissolving 4, 4' -di (N-acetyl) diphenyl sulfoxide (compound 1) in an alcohol solvent, and adding a copper complex catalyst (denoted as CuL)2-Cat.), and continuously introducing oxygen, and carrying out catalytic oxidation reaction at the temperature of 50-100 ℃. Stirring for 12-48 hours, and filtering and separating CuL after the reaction is finished2Concentrating the filtrate under reduced pressure to remove the solvent to obtain intermediate 4, 4' -di (N-acetyl) diphenylThe sulfone (compound 2), the intermediate, was used directly in the next hydrolysis reaction without purification.
The alcohol solvent is preferably one or more of ethanol, isopropanol and tert-butanol; the concentration of 4, 4' -di (N-acetyl) diphenyl sulfoxide (compound 1) dissolved in the alcohol solvent is 0.1-5 mol/L; the copper complex catalyst (CuL)2-Cat.) in a molar amount of 1% to 3% of 4, 4' -bis (N-acetyl) diphenylsulfoxide (Compound 1).
And (3) hydrolysis reaction: suspending the intermediate 4,4 '-bis (N-acetyl) diphenyl sulfone (compound 2) in hydrochloric acid solution with the concentration of 1.0-6.0mol/L, heating to 40-100 ℃, stirring for 4-48 hours at the reaction temperature until hydrolysis is completed, cooling to room temperature, adjusting the pH to 10-14 by using sodium hydroxide solution with the mass fraction of 5-20 wt% to generate a large amount of solid, filtering, washing with water, and recrystallizing the solid crude product to obtain a pure product of 4, 4' -diamino diphenyl sulfone (compound 3);
the concentration of the 4, 4' -di (N-acetyl) diphenyl sulfone (compound 2) in the hydrochloric acid solution is preferably 0.1-10 mol/L; the solvent used for recrystallization is preferably acetone.
The invention has the beneficial effects that:
(1) the copper complex catalyst of the invention is metal ion Cu2+The coordination compound is used as the center of the coordination compound, and is coordinated with two nitrogen atoms and two oxygen atoms in two 5-hydroxy-3-pyrazole carboxylic acids and two oxygen atoms in two water molecules, compared with an inorganic metal catalyst, the coordination compound can improve the utilization rate of metal, the dosage of the catalyst is small, the catalytic effect is good, and the coordination compound has higher yield in the application of catalytic synthesis of 4, 4' -diamino diphenyl sulfone, wherein the yield of two-step continuous preparation is 84-92%.
(2) The copper complex catalyst disclosed by the invention is simple in synthesis step, the copper salt is cheap and easy to obtain, and in the application of catalytic synthesis of 4, 4' -diamino diphenyl sulfone, the catalyst is low in dosage, safe and pollution-free, and environment-friendly, and has good popularization and application values and industrialization potential.
Drawings
FIG. 1 is a crystal structure diagram (hydrogen atom is omitted in the drawing) of a copper complex catalyst prepared by the present invention;
FIG. 2 is a PXRD pattern of a copper complex catalyst prepared in accordance with the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples, but the present invention is not limited thereto.
Example 1: preparation of copper complex catalyst
Weighing CuCl2·2H2O (20mmol,3.40g) was dissolved in 100mL of distilled water to give CuCl2An aqueous solution; 5-hydroxy-3-pyrazolecarboxylic acid (100mmol,1.28g) was dissolved in a mixed solution of 200mL of ethanol and 100mL of distilled water to prepare a ligand solution. Adding CuCl2Adding the water solution into the ligand solution, mixing to obtain transparent sky blue solution, standing at 5 deg.C for 3 days to precipitate blue cluster crystal, filtering, and drying to obtain copper complex catalyst (CuL)2-Cat.) the product mass was 3.74 g, yield was 53%. The product was characterized by infrared, with the results: IR (KBr, cm)-1)：3527(m)，3419(m)，2892(w)，1552(s)，1452(s)，1411(m)，1346(m)，1213(m)，1031(w)，904(w)，842(m)，765(m)，597(w)，480(w)。
The copper complex catalyst of the resulting product has the chemical formula [ Cu (H)2pzc)2(H2O)2]In the formula H3pzc is 5-hydroxy-3-pyrazolecarboxylic acid; the structural formula is as follows:
example 2: preparation of copper complex catalyst
Weighing CuCl2·2H2O (50mmol,8.50g) was dissolved in 100mL of distilled water to give CuCl2An aqueous solution; 5-hydroxy-3-pyrazolecarboxylic acid (200mmol,2.56g) was dissolved in a mixed solution of 300mL of ethanol and 100mL of distilled water to prepare a ligand solution. Adding CuCl2Adding the aqueous solution into the ligand solution, mixing uniformly to obtain a transparent sky blue solution, standing at the temperature of 5 ℃ for 4 days, and separating out 11.8 g of blue cluster crystal, wherein the yield is 67%. The product was characterized by infrared, with the results: IR (KBr,cm-1)：3528(m)，3419(m)，2891(w)，1550(s)，1451(s)，1415(m)，1342(m)，1213(m)，1034(w)，906(w)，843(m)，767(m)，591(w)，483(w)。
The infrared test results showed that the product prepared in this example was the same as the product of example 1, and was a copper complex catalyst [ Cu (H)2pzc)2(H2O)2]。
FIG. 1 shows a copper complex catalyst [ Cu (H) prepared in example 12pzc)2(H2O)2]The crystal structure of (2) (hydrogen atom is omitted in the figure), it can be seen that the central metal Cu1 of the complex catalyst is in { N }2O4In the octahedral coordination environment with two H2Nitrogen atom (N1, N1A), two H on pyrazole ring of pzc ligand2The carboxyl groups of the pzc ligand are coordinated with oxygen atoms O1 and O1A and two water molecules O4 and O4A.
FIG. 2 shows a copper complex catalyst [ Cu (H) prepared in example 12pzc)2(H2O)2](denoted as CuL2Cat.) as seen by the simulated diffraction peak position.
Table 1 shows the copper complex catalyst [ Cu (H) prepared in example 12pzc)2(H2O)2]Crystallographic data of (a):
TABLE 1
Table 2 shows the copper complex catalyst [ Cu (H) ] prepared in example 12pzc)2(H2O)2]Crystal bond length ofData:
TABLE 2
| Cu1-N1 | 1.953(3) | Cu1-O1A | 1.977(3) |
| Cu1-N1A | 1.953(3) | Cu1-O4 | 2.561(24) |
| Cu1-O1 | 1.977(3) | Cu1-O4A | 2.561(24) |
Table 3 shows the copper complex catalyst [ Cu (H) ] prepared in example 12pzc)2(H2O)2]Crystal bond angle (°) data:
TABLE 3
It can be seen that the bond lengths of Cu1-N1 and Cu1-N1A are allThe bond lengths of Cu1-O1 and Cu1-O1A are allThe bond lengths of Cu1-O4 and Cu1-O4A are allThe bond angles N1-Cu1-N1A, O1-Cu1-O1A and O4-Cu1-O4A are all 180 degrees.
Copper complex catalyst [ Cu (H)2pzc)2(H2O)2]The application of the catalyst in the catalytic synthesis of 4, 4' -diamino diphenyl sulfone is as shown in examples 3-4:
example 3: synthesis of 4, 4' -diaminodiphenyl sulfone
Catalytic oxidation: in a 1000 ml three-necked flask, 4' -bis (N-acetyl) diphenylsulfoxide (compound 1, 31.6 g, 100mmol) was dissolved in 500 ml of isopropanol, and then copper complex catalyst (CuL) was added2-Cat.) (0.374 g, 1.0mmol) as catalyst, and under stirring, oxygen was continuously introduced to conduct catalytic oxidation reaction at 75 ℃. After stirring for 24 hours, the reaction was terminated, the reaction was cooled to room temperature, and CuL was separated by filtration2-cat, the filtrate was concentrated under reduced pressure to remove the isopropanol solvent and dried under vacuum to give 4, 4' -bis (N-acetyl) diphenylsulfone (compound 2) as a white solid, all solids were used directly in the next hydrolysis reaction.
And (3) hydrolysis reaction: suspending the solid in 200ml of hydrochloric acid solution with the concentration of 3.0mol/L, heating the reaction solution to reflux to 50 ℃, stirring for 4 hours, cooling to room temperature after complete hydrolysis, adjusting the pH of the solution to 14 by using 10 mass percent of sodium hydroxide solution, precipitating a large amount of solid, filtering and washing the product to obtain a crude product of 4,4 ' -diaminodiphenyl sulfone, recrystallizing the crude product of 4,4 ' -diaminodiphenyl sulfone by using acetone to obtain 20.8 g of white solid, namely a pure product of 4,4 ' -diaminodiphenyl sulfone (compound 3), wherein the yield of the two-step continuous process is 84%.
Identification data: melting point: 175-177 ℃; and (3) infrared characterization results: IR (KBr, cm)-1): 3480, 3300, 3275, 1630, 1570, 1275, 1214, 1135. Nuclear magnetic results: NMR1H(DMSO-d6)δ＝7.44(d,J＝8.4Hz,4H),6.58(d,J＝8.4Hz,4H),5.97(br s,4H)ppm；NMR13C(DMSO-d6)δ＝153.4,129.3,128.8,113.5.
Example 4: synthesis of 4, 4' -diaminodiphenyl sulfone
Catalytic oxidation: 4, 4' -bis (N-acetyl) diphenylsulfoxide (compound 1, 158 g, 500mmol) was dissolved in 2000 mL of isopropanol in a 5L three-necked flask with mechanical stirring, followed by addition of copper complex catalyst (CuL)2-Cat.) (2.8 g, 7.5mmol) as catalyst, and under the condition of stirring, continuously introducing oxygen, and carrying out catalytic oxidation reaction at 80 ℃. After stirring for 24 hours, the reaction was terminated, the reaction was cooled to room temperature, and CuL was separated by filtration2-Cat, concentrating the filtrate under reduced pressure to remove the isopropanol solvent, and drying under vacuum to obtain 4, 4' -bis (N-acetyl) diphenyl sulfone (compound 2) as a white solid, all solids being used directly in the next hydrolysis reaction.
And (3) hydrolysis reaction: suspending the solid obtained by the reaction in 1000 ml of hydrochloric acid solution with the concentration of 2.0mol/L, heating the reaction solution to reflux to 100 ℃, stirring for 6 hours, cooling to room temperature after complete hydrolysis, adjusting the pH of the solution to 12 by using 10 mass percent of sodium hydroxide solution, precipitating a large amount of solid, filtering and washing the product to obtain a crude product of 4,4 ' -diaminodiphenyl sulfone, recrystallizing the crude product of 4,4 ' -diaminodiphenyl sulfone by using acetone to obtain 114 g of white solid, namely a pure product of 4,4 ' -diaminodiphenyl sulfone (compound 3), wherein the yield of the two-step continuous production is 92%.
Identification data: melting point: 176 ℃ and 178 ℃; and (3) infrared characterization results: IR (KBr, cm)-1): 3481, 3301, 3274, 1632, 1570, 1276, 1213, 1135. Nuclear magnetic results: NMR1H(DMSO-d6)δ＝7.45(d,J＝8.4Hz,4H),6.58(d,J＝8.4Hz,4H),5.96(br s,4H)ppm；NMR13C(DMSO-d6)δ＝153.4,129.3,128.8,113.5.
Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (8)
1. A copper complex catalyst, characterized in that the copper complex catalyst has the following structural formula:
2. the copper complex catalyst according to claim 1, wherein the copper complex catalyst is monoclinic, P21/c space group, and has unit cell parameters of: α＝90°，β＝98.476(3)°，γ＝90°。
3. a method for preparing the copper complex catalyst according to claim 1 or 2, comprising the steps of:
dissolving 5-hydroxy-3-pyrazolecarboxylic acid in an ethanol aqueous solution, adding a copper chloride aqueous solution, uniformly mixing to obtain a mixed solution, standing at 5 ℃ for reaction for 2-4 days to obtain blue crystals, filtering, and drying to obtain the copper complex catalyst.
4. The method for producing a copper complex catalyst according to claim 3, wherein the concentration of 5-hydroxy-3-pyrazolecarboxylic acid is (0.05 to 0.5) mol/L after dissolving 5-hydroxy-3-pyrazolecarboxylic acid in an aqueous ethanol solution.
5. The method for producing a copper complex catalyst according to claim 3, wherein the volume ratio of ethanol to water in the aqueous ethanol solution is (1-3): 1; the concentration of the copper chloride in the aqueous solution of the copper chloride is (0.2-2.0) mol/L.
6. The method for producing a copper complex catalyst according to claim 3, wherein the molar ratio of 5-hydroxy-3-pyrazolecarboxylic acid to copper chloride in the mixed solution is (2-6): 1.
7. Use of a copper complex catalyst according to claim 1 or 2 in the catalytic synthesis of 4, 4' -diaminodiphenyl sulfone.
8. The use of claim 7, wherein 4,4 '-di (N-acetyl) diphenyl sulfoxide is used as a raw material, and 4, 4' -diamino diphenyl sulfone is obtained through catalytic oxidation and hydrolysis reaction under the condition of the copper complex catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910828333.6A CN110590671B (en) | 2019-09-03 | 2019-09-03 | Copper complex catalyst, preparation method thereof and application thereof in synthesis of 4,4' -diamino diphenyl sulfone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910828333.6A CN110590671B (en) | 2019-09-03 | 2019-09-03 | Copper complex catalyst, preparation method thereof and application thereof in synthesis of 4,4' -diamino diphenyl sulfone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110590671A true CN110590671A (en) | 2019-12-20 |
| CN110590671B CN110590671B (en) | 2022-12-23 |
Family
ID=68857150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910828333.6A Active CN110590671B (en) | 2019-09-03 | 2019-09-03 | Copper complex catalyst, preparation method thereof and application thereof in synthesis of 4,4' -diamino diphenyl sulfone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110590671B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112094236A (en) * | 2020-09-14 | 2020-12-18 | 江苏理工学院 | Indazole zinc dicarboxylate complex with photocatalytic degradation function and preparation method and application thereof |
| CN115555051A (en) * | 2022-10-08 | 2023-01-03 | 江苏快达农化股份有限公司 | Pd/CuMOF-x composite material catalyst, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012442A (en) * | 2012-12-25 | 2013-04-03 | 常州大学 | Cuprum (II) coordination compound catalyst of selective catalytic oxidation thioether and preparation method of cuprum (II) coordination compound catalyst |
| CN105348304A (en) * | 2015-10-18 | 2016-02-24 | 桂林理工大学 | Mononuclear copper pyrazole-3-formic acid complex and preparation method thereof |
| CN109020889A (en) * | 2018-06-07 | 2018-12-18 | 江苏理工学院 | A kind of pyrazole carboxylic acid copper complex and its preparation method and application |
-
2019
- 2019-09-03 CN CN201910828333.6A patent/CN110590671B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012442A (en) * | 2012-12-25 | 2013-04-03 | 常州大学 | Cuprum (II) coordination compound catalyst of selective catalytic oxidation thioether and preparation method of cuprum (II) coordination compound catalyst |
| CN105348304A (en) * | 2015-10-18 | 2016-02-24 | 桂林理工大学 | Mononuclear copper pyrazole-3-formic acid complex and preparation method thereof |
| CN109020889A (en) * | 2018-06-07 | 2018-12-18 | 江苏理工学院 | A kind of pyrazole carboxylic acid copper complex and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| HONG-BING JI，等: "ONE-POT OXIDATION OF SULFIDES TO SULFONES BY REUSABLE HETEROGENEOUS RUTHENIUM CATALYST IN THE PRESENC OF MOLECULAR OXYGEN", 《REACT.KINET.CATAL.LETT.》 * |
| 张秀清，等: "吡唑羧酸类金属配合物的合成、晶体结构及其与牛血清白蛋白的相互作用", 《化学试剂》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112094236A (en) * | 2020-09-14 | 2020-12-18 | 江苏理工学院 | Indazole zinc dicarboxylate complex with photocatalytic degradation function and preparation method and application thereof |
| CN115555051A (en) * | 2022-10-08 | 2023-01-03 | 江苏快达农化股份有限公司 | Pd/CuMOF-x composite material catalyst, preparation method and application thereof |
| CN115555051B (en) * | 2022-10-08 | 2023-09-15 | 江苏快达农化股份有限公司 | Pd/CuMOF-x composite material catalyst, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110590671B (en) | 2022-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ahmad et al. | Synthesis of 2D MOF having potential for efficient dye adsorption and catalytic applications | |
| CN103265492B (en) | Chlorinated 1-vinyl-3-carboxymethyl imidazole polymerizable acidic ionic liquid and synthetic method thereof | |
| CN1834092B (en) | Preparation of pramipexole | |
| CN110590671B (en) | Copper complex catalyst, preparation method thereof and application thereof in synthesis of 4,4' -diamino diphenyl sulfone | |
| CN108912009B (en) | Asymmetric diimine nickel catalyst and ligand, preparation method and application thereof | |
| CN110563678A (en) | Preparation method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride | |
| WO2021000429A1 (en) | Catalyst for preparing high purity taurine and use thereof | |
| CN108384017B (en) | Chiral Ni (II) amino acid Schiff base coordination polymer and preparation method thereof | |
| US8680329B2 (en) | Process for preparation of α-ketoglutaric acid | |
| CN108148029B (en) | Preparation method of bisphenol A diether dianhydride | |
| CN114644582B (en) | Preparation method of phenyl dithiourea compound | |
| CN102363607B (en) | Method for synthesizing maleimide by using strongly acidic room-temperature ionic liquid as medium | |
| CN112479937B (en) | Preparation method of 2- [ [ tri (hydroxymethyl) methyl ] amino ] ethanesulfonic acid | |
| CN102584636A (en) | Synthetic method of kreatine | |
| CN102391170B (en) | A kind of preparation method of N, N-diallyl-5-methoxytryptamine hydrochlorides | |
| CN109096205B (en) | Synthesis method of benzimidazole compound | |
| CN106496582A (en) | 3 formic acid copper polymer of pyrazoles and preparation method thereof | |
| CN111040064A (en) | Preparation method of modified macroporous styrene divinylbenzene chelating ion exchange resin | |
| CN111499533B (en) | Method for preparing acetamino dimethyl phthalate | |
| CN111499530B (en) | Method for preparing amino methyl phthalate by one step | |
| CN114920670B (en) | Preparation method of 5-chloro-2-aminobenzenesulfonamide | |
| CN110938015B (en) | Preparation method of azido-substituted salicylic acid derivative | |
| CN115160110B (en) | Method for synthesizing bisphenol Z | |
| CN113429558B (en) | Preparation method of high-purity polyethylene glycol bisacrylamide | |
| CN110551158B (en) | Preparation method of chloro [ (tricyclohexylphosphine) -2- (2-aminobiphenyl) ] palladium (II) |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231122 Address after: 226400 Yangkou Second Road, Yangkou Chemical Industry Park, Rudong County, Nantong City, Jiangsu Province Patentee after: NANTONG VOLANT-CHEM Corp. Patentee after: JIANGSU University OF TECHNOLOGY Address before: 213001 No. 1801 Wu Cheng Road, Changzhou, Jiangsu Patentee before: JIANGSU University OF TECHNOLOGY |