CN114588929A - 一种负载型铜纳米团簇催化剂及其在aha偶联反应中的应用 - Google Patents
一种负载型铜纳米团簇催化剂及其在aha偶联反应中的应用 Download PDFInfo
- Publication number
- CN114588929A CN114588929A CN202210258123.XA CN202210258123A CN114588929A CN 114588929 A CN114588929 A CN 114588929A CN 202210258123 A CN202210258123 A CN 202210258123A CN 114588929 A CN114588929 A CN 114588929A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- sba
- supported copper
- copper nanocluster
- 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
- 239000010949 copper Substances 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 238000001354 calcination Methods 0.000 claims abstract description 8
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 claims abstract description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 56
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 50
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 24
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 24
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 5
- 239000002114 nanocomposite Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- LFZJRTMTKGYJRS-UHFFFAOYSA-N 1-chloro-4-ethynylbenzene Chemical group ClC1=CC=C(C#C)C=C1 LFZJRTMTKGYJRS-UHFFFAOYSA-N 0.000 claims description 3
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 claims description 3
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical group CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- QXSWHQGIEKUBAS-UHFFFAOYSA-N 1-ethynyl-4-fluorobenzene Chemical group FC1=CC=C(C#C)C=C1 QXSWHQGIEKUBAS-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 44
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- 239000011541 reaction mixture Substances 0.000 description 30
- 238000005119 centrifugation Methods 0.000 description 24
- 239000012300 argon atmosphere Substances 0.000 description 22
- 238000004440 column chromatography Methods 0.000 description 21
- 235000019439 ethyl acetate Nutrition 0.000 description 21
- 238000004817 gas chromatography Methods 0.000 description 21
- 239000011949 solid catalyst Substances 0.000 description 21
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 150000001345 alkine derivatives Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 229910017392 Au—Co Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 206010012289 Dementia Diseases 0.000 description 1
- 241001599881 Euphorbia maculata Species 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- CRFJRGSTIQFTQW-UHFFFAOYSA-N acetylene fluorobenzene Chemical group C#C.FC1=CC=CC=C1 CRFJRGSTIQFTQW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006452 multicomponent reaction Methods 0.000 description 1
- 230000004770 neurodegeneration Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- RUOKEQAAGRXIBM-GFCCVEGCSA-N rasagiline Chemical compound C1=CC=C2[C@H](NCC#C)CCC2=C1 RUOKEQAAGRXIBM-GFCCVEGCSA-N 0.000 description 1
- 229960000245 rasagiline Drugs 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- MEZLKOACVSPNER-GFCCVEGCSA-N selegiline Chemical compound C#CCN(C)[C@H](C)CC1=CC=CC=C1 MEZLKOACVSPNER-GFCCVEGCSA-N 0.000 description 1
- 229960003946 selegiline Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940126585 therapeutic drug Drugs 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- 150000003952 β-lactams Chemical class 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/06—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals
- C07D295/073—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals with the ring nitrogen atoms and the substituents separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/096—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种负载型铜纳米团簇催化剂及其在AHA偶联反应中的应用,其中负载型铜纳米团簇催化剂的分子式为Cu3I2H(Dppm)3/SBA‑15‑X,简记为Cu3/SBA‑15‑X,其中X指催化剂的煅烧温度。本发明负载型铜纳米团簇催化剂可在较温和反应条件下,高效的催化AHA偶联反应,此外还具有良好的催化活性和稳定性,能够循环多次使用,活性没有发生较明显的降低,并且对底物普适较广。
Description
技术领域
本发明涉及一种负载型铜纳米团簇催化剂及其在AHA偶联反应中的应用。
背景技术
炔丙胺一般用作固体燃料推进剂,同时也在合成医药中发挥着重要作用,如它是β-内酰胺等治疗药物的关键中间体。此外,已知的某些炔丙胺能够作为一种保护基团来抑制神经变性。例如像帕金森病这类的痴呆疾病经常使用雷沙吉兰和丙炔苯丙胺来对患者进行有效地治疗。尽管不同种类的催化剂被设计用来催化合成炔丙胺,但仍然存在着较大的催化剂金属用量,较高的反应温度以及环境污染大等问题。近年来,炔丙胺通常通过炔烃、胺和活性亚甲基来源的三组分偶联反应合成。当醛用作亚甲基源时,这种反应称为的A3多组分反应。比如, 2019年,MahmoudNasrollahzadeh组等人以斑大戟提取物为还原剂和稳定剂,制备了纳米尺度Fe3O4上负载高活性镍基催化剂。该催化剂在95℃的反应温度下用于催化醛、仲胺和炔烃的三组分A3偶联反应(Appl.Organomet.Chem.,2020,34,e5473)。2021年,Alhomaid组等人采用后功能化方法合成了双胍修饰介孔二氧化硅KIT-5修饰的Ag纳米颗粒,即 (KIT-5-bigua-Ag),在80℃的反应温度下进行醛、胺和炔的三元反应(Arab.J.Chem.,2022, 15,103548)。而相较于A3偶联反应,对合成炔丙胺的另一种策略:激活炔烃的C-H键和二卤甲烷的C-X键,即AHA偶联反应研究较少。其中,Shuang-Feng Yin组以5mol%AgOAc 为催化剂,在120℃,12小时的反应条件下成功制备了炔丙胺(Org.Biomol.Chem.,2014,12, 247-250)。2015年NoureddineChoukchou-Braham组报道了一种以纳米Au/CeO2为非均相催化剂、1,4-二氮杂双环[2.2.2]辛烷为碱、乙腈为溶剂,在65℃的反应温度下通过胺、二氯甲烷和末端炔烃的偶联反应合成炔丙胺(TetrahedronLett.,2015,56,1302-1306)。之后在2019年, K.Belkacemi组研究了负载在CeO2载体上的双金属纳米粒子,即Au-Co/CeO2催化剂对AHA 偶联的反应活性。该催化剂在65℃,24小时的反应条件下得到60-85%的炔丙胺产物(Res. Chem.Intermed.,2019,45,3481-3495)。
到目前为止,三组分偶联反应制备炔丙胺的催化剂体系依然面临着诸多挑战,如使用贵金属催化剂、反应温度高、催化剂用量大等弊端。所以,如何制备高活性的催化剂体系就成为一种迫切需要解决的问题。
发明内容
本发明针对上述现有技术所存在的问题,提供了一种负载型铜纳米团簇催化剂及其在 AHA偶联反应中的应用。本发明负载型铜纳米团簇催化剂可在较温和反应条件下,高效的催化AHA偶联反应,此外还具有良好的催化活性和稳定性,能够循环多次使用,活性没有发生较明显的降低,并且对底物普适较广。
本发明负载型铜纳米团簇催化剂,其分子式为Cu3/SBA-15-X,其中X指催化剂的煅烧温度,X=120-500℃。
所述负载型铜纳米团簇催化剂是通过包括如下步骤的方法制备获得:
步骤1:首先合成Cu3纳米团簇,纳米团簇的分子式为Cu3I2H(Dppm)3,简写为Cu3纳米团簇。
步骤2:将SBA-15通过超声处理使其均匀分散在二氯甲烷溶液中,得到悬浊液A;
步骤3:向步骤2获得的悬浊液A中滴加含有Cu3纳米团簇的二氯甲烷溶液,搅拌4小时,分离、洗涤并干燥,得到Cu3/SBA-15纳米复合材料;
步骤4:将步骤3获得的Cu3/SBA-15纳米复合材料在管式炉中以5℃/min的升温速度升温至120-500℃煅烧2小时,最终得到Cu3/SBA-15-X催化剂。
步骤4中,煅烧温度优选为400-500℃。
本发明Cu3/SBA-15-X纳米复合材料中Cu的实际含量为(0.15-0.35)wt%。
本发明负载型铜纳米团簇催化剂的应用,是在AHA偶联反应中作为催化剂使用。
进一步地,偶联反应中,反应原料为苯乙炔或取代苯乙炔,六氢吡啶,二溴甲烷,以及催化剂;反应温度为40℃-80℃。
所述取代苯乙炔为4-氟苯乙炔、4-氯苯乙炔、4-甲基苯乙炔或4-甲氧基苯乙炔,同样具有较好的催化活性。
所述反应原料还包括碱,所述碱为DBU或Cs2CO3,碱的添加量为0.25mmol-1.0mmol(苯乙炔或取代苯乙炔的添加量为0.5mmol)。
催化剂的添加量为40mg-80mg范围内均对AHA偶联反应具有反应活性,并且该催化剂对含不同取代基的苯乙炔同样具有较好的催化活性。
本发明的有益效果体现在:
1、材料合成制备简单,催化材料性能好。
2、本发明的材料作为催化剂催化AHA偶联反应,能够在一定反应条件范围内实现催化反应,并且在至少三次循环使用后催化活性基本上没有明显的变化,且底物普适较广。
附图说明
图1为Cu3纳米团簇的MS和XPS图。
图2为Cu3纳米团簇的晶体结构。
图3为Cu3/SBA-15-400℃的TEM图。
具体实施方式
下面结合具体的实施例对本发明的技术方案作进一步阐述。
实施例1:Cu3纳米团簇的制备
将含有碘化亚铜(190mg,1.0mmol)放入圆底烧瓶中,然后,烧瓶中加入15mL甲苯溶剂,搅拌5分钟后,往烧瓶中加入1,3-双二苯基膦甲烷(475mg,1.2mmol),形成白色浑浊液。继续搅拌15min,向上述溶液中加入含有二苯基硅烷(115ul,0.62mmol),持续搅拌 12小时,停止搅拌。反应停止后,离心去除上清液,将得到的白色固体用少量CH2Cl2溶液溶解,将其存储于单晶瓶中,单晶瓶上层铺正己烷溶液(与二氯甲烷体积比为1:3),中间铺一层乙醇试剂,静置3到5天后单晶瓶中出现白色的Cu3I2H(Dppm)3纳米团簇,简称Cu3纳米团簇。附图1分别为Cu3纳米团簇的MS和XPS图。
实施例2:Cu3/SBA-15-X℃(X=120,150,300,400℃,500)催化剂的制备
将SBA-15(100mg)超声分散于15mL二氯甲烷溶液中,然后用二氯甲烷(1mL)溶解Cu3纳米团簇(2mg),将其逐滴滴到上述SBA-15溶液中。搅拌4小时后,停止搅拌。通过离心(10000 rpm)收集产物并用二氯甲烷清洗二次。接着,将固体在真空烘箱中于50℃下干燥过夜,收集固体得到Cu3/SBA-15。最后,将得到的Cu3/SBA-15固体在管式炉中以5℃/min的升温速率煅烧 120℃,150℃,300℃,400℃及500℃,保温时常为2小时,分别得到Cu3/SBA-15-120℃, Cu3/SBA-15-150℃,Cu3/SBA-15-300℃,Cu3/SBA-15-400℃及Cu3/SBA-15-500℃催化剂。附图 3为Cu3/SBA-15-400℃的TEM图,通过图片可以看出Cu3/SBA-15-400℃表面无金属颗粒的存在。
实施例3:SBA-15催化AHA偶联反应
向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg SBA-15催化剂,0.6mmol 六氢吡啶,0.5mmol碳酸铯和1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)分离固液,反应液通过GC分析,产率为2.1%。
实施例4:Cu3/SBA-15-X℃(X=120,150,300,400,500)催化AHA偶联反应(催化剂煅烧温度不同)
(1)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg Cu3/SBA-15-120℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为43.3%。
(2)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg Cu3/SBA-15-150℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为57.1%。
(3)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg Cu3/SBA-15-300℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为68.7%。
(4)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg Cu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为85.7%。
(5)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg Cu3/SBA-15-500℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为84.7%。
1H NMR(400MHz,CDCl3)δ7.49-7.46(m,2H),7.33-7.30(m,3H),3.51(s,2H),2.62(s,4H), 1.71-1.66(m,4H),1.49-1.45(m,2H);13C NMR(101MHz,CDCl3)δ131.58,128.21,127.95, 123.29,85.06,85.00,52.94,48.42,25.79,24.00ppm.
实施例5:Cu3/SBA-15-400℃催化AHA偶联反应(反应温度不同)
(1)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg Cu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于40℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为15.8%。
(2)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg Cu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于60℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为88.7%。
(3)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg Cu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于80℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为90.3%。
实施例6:Cu3/SBA-15-400℃催化AHA偶联反应(反应碱的种类不同)
(1)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg Cu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.5mmol1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)和1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE =1:10)纯化粗产物,得到主要产物,产率为34.6%。
(2)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg Cu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,1mL二溴甲烷,在不加任何碱的条件下,于氩气气氛中以50℃搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为38.6%。
实施例7:Cu3/SBA-15-400℃催化AHA偶联反应(碱用量不同)
(1)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg Cu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.25mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为62.7%。
(2)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mg Cu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,1.0mmol碳酸铯和1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为87.9%。
实施例8:Cu3/SBA-15-400℃催化AHA偶联反应(催化剂用量不同)
(1)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、40mg Cu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为40.6%。
(2)向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、60mg Cu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为67.8%。
基于上述实施案例,我们选取反应条件(0.5mmol苯乙炔、80mgCu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,氩气气氛中,反应温度为50℃,反应时间12h),来测试Cu3/SBA-15-400℃催化剂对AHA偶联反应的稳定性能,反应效果见下列实施案例。
实施例9:Cu3/SBA-15-400℃催化AHA偶联反应的一次循环
向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mgCu3/SBA-15-400℃催化剂, 0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为85.5%.
回收的Cu3/SBA-15-400℃催化剂用甲醇清洗三次,在真空烘箱中50℃干燥2小时,以备下次循环使用。
实施例10:Cu3/SBA-15-400℃催化AHA偶联反应的二次循环
向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mgCu3/SBA-15-400℃催化剂, 0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为82.3%。
实施例11:Cu3/SBA-15-400℃催化AHA偶联反应的三次循环
向10mL的Schlenk反应瓶中依次加入0.5mmol苯乙炔、80mgCu3/SBA-15-400℃催化剂, 0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为80.1%。
以下实施案例为Cu3/SBA-15-400℃催化剂进行AHA偶联反应对炔类的底物拓展。
实施例12:Cu3/SBA-15-400℃催化4-氟苯乙炔的AHA偶联反应
向10mL的Schlenk反应瓶中依次加入0.5mmol 4-氟苯乙炔、80mgCu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为89.2%。
1H NMR(400MHz,CDCl3)δ7.41-7.26(m,2H),6.99-6.95(m,2H),3.45(s,2H),2.56(s,4H), 1.66-1.64(m,4H),1.44(s,2H);13C NMR(101MHz,CDCl3)δ163.50,160.65,133.55,133.46, 119.32,119.29,115.54,115.28,84.63,83.90,52.96,48.36,25.82,23.85ppm.
实施例13:Cu3/SBA-15-400℃催化4-氯苯乙炔的AHA偶联反应
向10mL的Schlenk反应瓶中依次加入0.5mmol 4-氯苯乙炔、80mgCu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为87.3%。
1H NMR(400MHz,CDCl3)δ7.35(d,2H),7.26(d,2H),3.45(s,2H),2.55(s,4H),1.66-1.61 (m,4H),1.45-1.44(m,2H);13C NMR(101MHz,CDCl3)δ134.16,133.13,128.74,121.99,86.37, 84.12,53.75,48.65,26.12,24.11ppm.
实施例14:Cu3/SBA-15-400℃催化4-甲基苯乙炔的AHA偶联反应
向10mL的Schlenk反应瓶中依次加入0.5mmol 4-甲基苯乙炔、80mgCu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为86.9%。
1H NMR(400MHz,CDCl3)δ7.33(d,2H),7.09(d,2H),3.47(s,2H),2.58(s,4H),2.33(s, 3H),1.66-1.63(m,4H),1.45(s,2H);13C NMR(101MHz,CDCl3)δ138.04,131.60,128.97,120.12,85.20,84.03,53.37,48.46,25.84,23.86,21.40ppm.
实施例15:Cu3/SBA-15-400℃催化4-甲氧基苯乙炔的AHA偶联反应
向10mL的Schlenk反应瓶中依次加入0.5mmol 4-甲氧基苯乙炔、80mgCu3/SBA-15-400℃催化剂,0.6mmol六氢吡啶,0.5mmol碳酸铯,1mL二溴甲烷,在氩气气氛中于50℃下搅拌反应12h,反应结束后,待反应液温度冷却至室温,通过离心(10000rpm)除去固体催化剂后得到产物,反应液通过GC分析和柱色谱法(EtOAc/PE=1:10)纯化粗产物,得到主要产物,产率为84.8%。
1H NMR(400MHz,CDCl3)δ7.36(d,2H),6.81(d,2H),3.79(s,3H),3.45(s,2H),2.56(s, 4H),1.69-1.57(m,4H),1.53-1.44(m,2H);13C NMR(101MHz,CDCl3)δ159.29,133.05,115.37, 113.76,84.78,83.34,55.20,53.37,48.43,25.84,23.84ppm。
Claims (9)
1.一种负载型铜纳米团簇催化剂,其特征在于:
所述负载型铜纳米团簇催化剂的分子式为Cu3/SBA-15-X,其中X指催化剂的煅烧温度。
2.根据权利要求1所述的负载型铜纳米团簇催化剂,其特征在于是通过包括如下步骤的方法制备获得:
步骤1:首先合成Cu3纳米团簇,纳米团簇的分子式为Cu3I2H(Dppm)3,简写为Cu3纳米团簇;
步骤2:将SBA-15通过超声处理使其均匀分散在二氯甲烷溶液中,得到悬浊液A;
步骤3:向步骤2获得的悬浊液A中滴加含有Cu3纳米团簇的二氯甲烷溶液,搅拌4小时,分离、洗涤并干燥,得到Cu3/SBA-15纳米复合材料;
步骤4:将步骤3获得的Cu3/SBA-15纳米复合材料在管式炉中升温至120-500℃煅烧2小时,最终得到Cu3/SBA-15-X催化剂。
3.根据权利要求2所述的负载型铜纳米团簇催化剂,其特征在于:
步骤4中,煅烧时的升温速率为5℃/min。
4.根据权利要求2所述的负载型铜纳米团簇催化剂,其特征在于:
步骤4中,煅烧温度为400-500℃。
5.根据权利要求1或2所述的负载型铜纳米团簇催化剂,其特征在于:
Cu3/SBA-15-X催化剂中Cu的实际含量为(0.15-0.35)wt%。
6.根据权利要求1或2所述的负载型铜纳米团簇催化剂的应用,其特征在于:在AHA偶联反应中作为催化剂使用。
7.根据权利要求6所述的应用,其特征在于:
偶联反应中,反应原料为苯乙炔或取代苯乙炔,六氢吡啶,二溴甲烷,以及催化剂;反应温度为40℃-80℃。
8.根据权利要求7所述的应用,其特征在于:
所述取代苯乙炔为4-氟苯乙炔、4-氯苯乙炔、4-甲基苯乙炔或4-甲氧基苯乙炔。
9.根据权利要求7或8所述的应用,其特征在于:
所述反应原料还包括碱,所述碱为DBU或Cs2CO3。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210258123.XA CN114588929B (zh) | 2022-03-16 | 2022-03-16 | 一种负载型铜纳米团簇催化剂及其在aha偶联反应中的应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210258123.XA CN114588929B (zh) | 2022-03-16 | 2022-03-16 | 一种负载型铜纳米团簇催化剂及其在aha偶联反应中的应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114588929A true CN114588929A (zh) | 2022-06-07 |
CN114588929B CN114588929B (zh) | 2023-10-03 |
Family
ID=81809489
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210258123.XA Active CN114588929B (zh) | 2022-03-16 | 2022-03-16 | 一种负载型铜纳米团簇催化剂及其在aha偶联反应中的应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114588929B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115041236A (zh) * | 2022-07-25 | 2022-09-13 | 安徽大学 | 一种负载型Au-Ag纳米团簇催化剂及其在酮炔基化反应中的应用 |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004352988A (ja) * | 2003-05-02 | 2004-12-16 | Rikogaku Shinkokai | 触媒、およびポリマーの製造方法 |
WO2012005692A1 (en) * | 2010-07-07 | 2012-01-12 | Agency For Science, Technology And Research | Propargylamine synthesis using a copper (i) catalysed three component coupling reaction |
CN104447805A (zh) * | 2014-11-13 | 2015-03-25 | 郑州轻工业学院 | 一种含双二苯基膦的硼氢酸铜配合物及其制备方法和应用 |
KR20170011773A (ko) * | 2015-07-24 | 2017-02-02 | 서울대학교산학협력단 | 알카인을 이용한 아마이드 화합물의 제조방법 및 이를 이용한 펩타이드 제조 방법 |
CN107335454A (zh) * | 2017-08-28 | 2017-11-10 | 安徽大学 | 一种负载型Pd3Cl团簇催化剂的制备及其应用 |
KR20180068417A (ko) * | 2016-12-14 | 2018-06-22 | 인천대학교 산학협력단 | 불균일 구리 촉매를 이용한 삼성분 짝지음 반응을 통한 n-술폰아미딘의 합성법 |
CN110404587A (zh) * | 2019-08-22 | 2019-11-05 | 安徽大学 | 一种负载型团簇催化剂及其制备和应用 |
CN110420669A (zh) * | 2019-06-18 | 2019-11-08 | 南京大学 | 铜原子簇制备方法以及催化co2反应用途 |
CN111871466A (zh) * | 2020-08-24 | 2020-11-03 | 国家纳米科学中心 | 一种金属有机框架结构中节点负载金属团簇催化剂及其制备方法和应用 |
CN112337466A (zh) * | 2020-11-27 | 2021-02-09 | 辽宁大学 | 一种纳米碳负载团簇态铜纳米酶及其制备方法和应用 |
CN112892597A (zh) * | 2021-01-22 | 2021-06-04 | 安徽大学 | 一种负载型团簇催化剂及其制备和应用 |
CN113117724A (zh) * | 2021-04-26 | 2021-07-16 | 安徽大学 | 一种可回收负载型Au52Cu72(SR)55团簇催化剂及其应用 |
CN113717397A (zh) * | 2021-09-02 | 2021-11-30 | 暨南大学 | 一种金属团簇基晶态多孔材料的制备方法 |
-
2022
- 2022-03-16 CN CN202210258123.XA patent/CN114588929B/zh active Active
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004352988A (ja) * | 2003-05-02 | 2004-12-16 | Rikogaku Shinkokai | 触媒、およびポリマーの製造方法 |
WO2012005692A1 (en) * | 2010-07-07 | 2012-01-12 | Agency For Science, Technology And Research | Propargylamine synthesis using a copper (i) catalysed three component coupling reaction |
CN104447805A (zh) * | 2014-11-13 | 2015-03-25 | 郑州轻工业学院 | 一种含双二苯基膦的硼氢酸铜配合物及其制备方法和应用 |
KR20170011773A (ko) * | 2015-07-24 | 2017-02-02 | 서울대학교산학협력단 | 알카인을 이용한 아마이드 화합물의 제조방법 및 이를 이용한 펩타이드 제조 방법 |
KR20180068417A (ko) * | 2016-12-14 | 2018-06-22 | 인천대학교 산학협력단 | 불균일 구리 촉매를 이용한 삼성분 짝지음 반응을 통한 n-술폰아미딘의 합성법 |
CN107335454A (zh) * | 2017-08-28 | 2017-11-10 | 安徽大学 | 一种负载型Pd3Cl团簇催化剂的制备及其应用 |
CN110420669A (zh) * | 2019-06-18 | 2019-11-08 | 南京大学 | 铜原子簇制备方法以及催化co2反应用途 |
CN110404587A (zh) * | 2019-08-22 | 2019-11-05 | 安徽大学 | 一种负载型团簇催化剂及其制备和应用 |
CN111871466A (zh) * | 2020-08-24 | 2020-11-03 | 国家纳米科学中心 | 一种金属有机框架结构中节点负载金属团簇催化剂及其制备方法和应用 |
CN112337466A (zh) * | 2020-11-27 | 2021-02-09 | 辽宁大学 | 一种纳米碳负载团簇态铜纳米酶及其制备方法和应用 |
CN112892597A (zh) * | 2021-01-22 | 2021-06-04 | 安徽大学 | 一种负载型团簇催化剂及其制备和应用 |
CN113117724A (zh) * | 2021-04-26 | 2021-07-16 | 安徽大学 | 一种可回收负载型Au52Cu72(SR)55团簇催化剂及其应用 |
CN113717397A (zh) * | 2021-09-02 | 2021-11-30 | 暨南大学 | 一种金属团簇基晶态多孔材料的制备方法 |
Non-Patent Citations (1)
Title |
---|
蒋凯, 赵东, 郭利兵, 张传建, 杨瑞娜: "Synthesis and Characterization of an Unexpected Asymmetric Binuclear Copper(I) Complex Containing 4-Vinyl-pyridine", CHINESE JOURNAL OF CHEMISTRY, no. 11, pages 1297 - 1302 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115041236A (zh) * | 2022-07-25 | 2022-09-13 | 安徽大学 | 一种负载型Au-Ag纳米团簇催化剂及其在酮炔基化反应中的应用 |
CN115041236B (zh) * | 2022-07-25 | 2024-02-13 | 安徽大学 | 一种负载型Au-Ag纳米团簇催化剂及其在酮炔基化反应中的应用 |
Also Published As
Publication number | Publication date |
---|---|
CN114588929B (zh) | 2023-10-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8586757B2 (en) | Ruthenium-based catalytic complexes and the use of such complexes for olefin metathesis | |
US8097738B2 (en) | Ruthenium (II) catalysts for use in stereoselective cyclopropanations | |
EP2228377B1 (en) | Novel organometallic complex and process for preparing amine compound | |
JP2014501719A (ja) | キラルスピロ−ピリジルアミドフォスフィン配位子化合物、その合成方法及びその利用 | |
JP5847386B2 (ja) | アミン化合物の製造方法 | |
JP6246202B2 (ja) | 3座アミノジカルベン配位子を有する金属錯体及びそれを用いた水素化還元方法 | |
Lagasi et al. | Anchoring of Pd on silica functionalized with nitrogen containing chelating groups and applications in catalysis | |
CN114588929A (zh) | 一种负载型铜纳米团簇催化剂及其在aha偶联反应中的应用 | |
CN113877630B (zh) | 一种制备双[(3-二甲基氨基)丙基]胺的催化剂及其应用 | |
JP6879523B2 (ja) | 遷移金属−イソシアニド錯体の製造方法 | |
JP2010037332A (ja) | キラルなイリジウムアクア錯体およびそれを用いた光学活性ヒドロキシ化合物の製造方法 | |
CN102976879A (zh) | 负载型PtAu催化剂及其催化还原烯键或炔键的方法 | |
CN113173859B (zh) | 一种合成手性α-胺基醇化合物的方法 | |
CN113117724B (zh) | 一种可回收负载型Au52Cu72(SR)55团簇催化剂及其应用 | |
JP5152895B2 (ja) | 環状アルキレンイミンの製造方法 | |
US20040167018A1 (en) | Palladium catalysts | |
JP2022022755A (ja) | 脱水素反応用錯体触媒及び固体触媒、並びにそれらを用いたアルコール類の脱水素化方法及び水素の製造方法 | |
KR101667223B1 (ko) | 카보닐화 반응에 의한 초산 제조용 Rh/WxC 불균일 촉매 | |
CN115710199B (zh) | 光氧化还原催化方法 | |
CN110292948B (zh) | 含单亚胺功能化的咪唑氯盐作为催化剂在制备芳香杂环甲酸酯类化合物中的应用 | |
JP2018197218A (ja) | 不均一系パラジウム触媒を用いたシクロアルカジエンまたはシクロアルケン構造を有する化合物の脱水素反応による芳香族化合物の製造方法 | |
CN115041236A (zh) | 一种负载型Au-Ag纳米团簇催化剂及其在酮炔基化反应中的应用 | |
RU2544101C1 (ru) | Катализатор для гидроаминирования ацетиленовых углеводородов и способ гидроаминирования ацетиленовых углеводородов с использованием этого катализатора | |
CN115925555A (zh) | 一种α,β-不饱和亚胺的选择性氢化还原方法 | |
KR101509646B1 (ko) | 미티글리나이드의 중간체 합성 방법 |
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 |