CN106694045A - 3:1型Mg/Li双金属催化剂及其制备方法和应用 - Google Patents
3:1型Mg/Li双金属催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN106694045A CN106694045A CN201611059463.0A CN201611059463A CN106694045A CN 106694045 A CN106694045 A CN 106694045A CN 201611059463 A CN201611059463 A CN 201611059463A CN 106694045 A CN106694045 A CN 106694045A
- Authority
- CN
- China
- Prior art keywords
- type
- catalyst
- preparation
- reaction
- bimetallic catalyst
- 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 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 239000005457 ice water Substances 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- -1 ketone compounds Chemical class 0.000 claims abstract description 4
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 239000011777 magnesium Substances 0.000 abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 21
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000003612 Meerwein-Ponndorf-Verley reduction reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002641 lithium Chemical group 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 229910006715 Li—O Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910014276 N-Li Inorganic materials 0.000 description 1
- 229910014326 N—Li Inorganic materials 0.000 description 1
- 150000001257 actinium Chemical class 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
-
- 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
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/11—Lithium
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/22—Magnesium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明提供了一种3:1型Li/Mg双金属催化剂及其制备方法和应用。催化剂制备方法:1)制备N,N,O‑三齿的胺基醇配体;2)在惰性气体保护和冰水浴下,将1.5倍量的正丁基锂逐滴滴加到胺基醇的乙醚溶液中,所得反应液中滴加0.5倍量的二丁基镁,然后滴入0.5倍量水的乙醚溶液,待反应完毕后过滤,真空浓缩滤液,析出无色透明晶体即可。该催化剂制备方法简便,条件要求低,使用廉价、低毒性的非过渡金属锂、镁为催化活性金属,对不同类型的醛、酮化合物还原制备相应的一级和二级醇类化合物的Meerwein‑Ponndorf‑Verley(MPV)反应具有较高选择性和催化活性,该催化反应时间短,产率高,有很好的工业应用前景。
Description
技术领域
本发明涉及双金属催化剂,具体涉及一种3:1型N,N,O-三齿Mg/Li双金属及其制备方法和应用。
背景技术
一级和二级醇的选择性合成是有机合成、制药和食物香料工业等领域的一个重要转化过程。Meerwein-Ponndorf-Verley(MPV)反应被认为是由醛、酮制备一级和二级醇的重要反应之一,通常使用一个氢供体与强碱和催化剂的系统,而最主要的部分还是高效的催化剂。因此,开发新的和有效的催化反应系统仍然是科研工作者努力的重点。MPV反应通常使用主族金属、过渡金属、镧系和锕系等金属化合物作为催化剂,主要是单金属的醇盐,氧化物及其配合物等,而且催化剂存在结构复杂,不易制备,催化剂活性不够高,用量大,反应时间长等不足。双金属化合物因其含有两种金属原子显示出不同于其中任一单金属前体的催化性能,被认为是潜在的高效催化剂。金属锂和镁通常作为低毒的金属中心原子被广泛用于催化剂的合成与应用,而含Li/Mg的双金属化合物用于催化MPV反应有望成为具有高活性、低毒性和可再生利用的新型催化剂,旨在为今后的工业应用开发新技术。
发明内容
本发明的目的是提供一种3:1型Mg/Li双金属催化剂及其制备方法,该催化剂合成简便,反应条件温和,对选择性合成一级和二级醇具有较高的催化活性。
本发明提供的一种3:1型Mg/Li双金属催化剂,其结构式为:
式中:镁原子与两个氧原子和丁基的碳原子形成三配位模式,锂原子存在三配位和四配位两种成键模式,四配位的锂原子与配体中的氧原子和氮原子形成四配位结构,而且形成两个共用N-Li键的五元环;三配位的锂原子处于分子结构中心,并以Li-O配位键形成二聚体构型的分子结构。
本发明提供的一种3:1型Mg/Li双金属催化剂的制备方法,包括如下步骤:
(1)N,N,N′,N′-四甲基乙二胺(TMEDA)经正丁基锂锂化后与环己酮加成,在酸性条件下水解后,水相用氢氧化钠水溶液中和至弱碱性,再用无水乙醚萃取2-3次,有机相干燥后减压蒸馏,收集中间无色馏分得到N,N,O-三齿的胺基醇配体;反应式:
(2)在惰性气体保护下,首先将等1.5倍量的正丁基锂逐滴滴加到N,N,O-三齿胺基醇配体的乙醚溶液中,搅拌1-2小时,然后在冰水浴中缓慢滴入0.5倍当量的二丁基镁试剂,恢复室温搅拌2-4小时,然后滴入0.5倍量水的乙醚溶液,反应完毕后真空浓缩滤液,析出无色透明晶体,即为3:1型N,N,O-三齿Mg/Li双金属催化剂,产率84-86%。反应式:
该催化剂可在醛、酮化合物还原制备相应的一级、二级醇类化合物中的应用。
与现有技术相比本发明的优点和效果:本发明合成的催化剂制备过程简单,原料易得,使用廉价、无毒的非过渡金属镁和锂为催化活性金属,反应条件温和,对醛、酮类化合物的MPV反应有较高选择性,能高效地合成相应的醇类化合物,该催化反应时间短,产率高,有很好的应用前景。
附图说明
图1本发明3:1型N,N,O-三齿Mg/Li双金属催化剂的单晶X射线结构图
具体实施方式:
以下仅仅为详细说明本发明而给出的具体实施例,这些实施例并非用于限制本发明的保护范围。
实施例1 3:1型N,N,O-三齿Mg/Li双金属催化剂的制备
将正丁基锂(29.20mL,2.5M,正己烷溶液)在0℃缓慢滴入TMEDA(11.02g,73mmol)的乙醚溶液中,恢复室温后反应2小时,再将环己酮(7.54mL,73mmol)滴入上述反应液中继续反应2小时,然后在酸性条件下水解,分液后所得水相用5%的氢氧化钠水溶液中和至弱碱性,再用无水乙醚萃取三次,有机相用无水硫酸镁干燥后减压蒸馏,收集78℃无色馏分得N,N,O-三齿的胺基醇配体,产率84%;
在惰性气体保护下,将N,N,O-三齿胺基醇配体(2.0mmol,0.43g)溶解在10mL乙醚溶剂中,然后逐滴滴加正丁基锂(1.20mL,2.5M,正己烷溶液)到搅拌上述溶液中,搅拌1小时,然后在冰水浴中缓慢滴入等当量的二丁基镁(1.0mL,1.0M,正戊烷溶液),恢复室温搅拌2小时,然后滴入经脱气后的水(1.0mL,1.0M,乙醚溶液),反应完毕后真空浓缩滤液,析出无色透明晶体,即为3:1型N,N,O-三齿Mg/Li双金属催化剂,产率86%,熔点为121-124℃。
晶体参数:化学式:C56H118Li6Mg2N8O6,单斜晶系(Monoclinic),空间群P 21/c,晶胞参数α=90.000°,β=98.3980(10)°,γ=90.000°,V=3257.84(17),Z=2。单晶结构图见图1。部分键长Li(1)-O(1)1.934(5),Li(1)-O(2)1.925(5),Li(1)-N(1)2.191(5),Li(1)-N(2)2.076(5),Li(2)-O(1)1.927(5),Li(2)-O(2)1.976(5),Li(2)-N(3)2.188(5),Li(2)-N(4)2.032(5),Li(3)-O(1)1.867(5),Li(3)-O(3)1.947(5),Li(3)-O(3)′1.943(5),Mg(1)-O(2)2.008(2),Mg(1)-O(3)2.084(2);键角(°):O(3)-Li(3)-O(3)′98.9(2),Li(3)-O(3)-Li(3)′81.1(2),O(1)-Li(1)-O(2)98.0(2),O(1)-Li(1)-N(1)87.0(2),O(1)-Li(1)-N(2)129.8(3),O(2)-Li(1)-N(1)155.1(3),O(2)-Li(1)-N(2)106.8(2),N(1)-Li(1)-N(2)87.78(19),O(2)-Li(1)-O(3)80.97(18),O(1)-Li(1)-O(3)83.54(17),O(1)-Li(2)-O(2)96.6(2),O(1)-Li(2)-N(3)149.2(3),O(1)-Li(2)-N(4)118.2(3),O(2)-Li(2)-N(3)83.6(2),O(2)-Li(2)-N(4)114.9(2),N(3)-Li(2)-N(4)88.8(2),O(1)-Li(3)-O(3)109.8(2),O(1)-Li(3)-O(3)′148.4(3),O(3)-Li(3)-O(3)′98.9(2),O(2)-Mg(1)-O(3)96.04(8)。
实施例2
(1)催化剂的制备同实施例1
催化苯甲醛还原为苄醇(MPV):常温氮气保护下,将苯甲醛(0.42g,4.0mmol)和异丙醇(0.37mL,4.8mmol)加入到氮气保护的3:1型N,N,O-三齿Mg/Li双金属催化剂(1.06g,0.2mmol)中,回流搅拌反应1小时后,然后用水终止反应,用乙醚萃取,干燥,旋蒸后,用柱层析法分离(流动相为7:3的正己烷和乙酸乙酯混合溶剂),浓缩后即为苯甲醇。产率94%。1HNMR(300MHz,CDCl3):δ(ppm)3.62(s,1H,OH),4.55(s,2H,CH2),6.86-7.39(m,5H,C6H5)。
实施例3
(1)催化剂的制备同实施例1
(2)催化苯乙酮还原为1-苯乙醇(MPV):常温氮气保护下,将苯乙酮(0.48g,4.0mmol)和异丙醇(0.37mL,4.8mmol)加入到氮气保护的3:1型N,N,O-三齿Mg/Li双金属催化剂(1.06g,0.2mmol)中,回流搅拌反应1小时后,然后用水终止反应,用乙醚萃取,干燥,旋蒸后,用柱层析法分离(流动相为7:3的正己烷和乙酸乙酯混合溶剂),浓缩后即为1-苯乙醇,产率91%。1H NMR(300MHz,CDCl3):δ(ppm)1.48(d,3H,CH3),3.62(s,1H,OH),4.65(s,H,CH),7.13-7.45(m,5H,C6H5)。
Claims (3)
1.一种3:1型Li/Mg双金属催化剂,其特征在于,结构式为:
2.如权利要求1所述的一种3:1型Li/Mg双金属催化剂的制备方法,其特征在于,包括如下步骤:
1)N,N,N′,N′-四甲基乙二胺(TMEDA)经正丁基锂锂化后与环己酮加成,在酸性条件下水解后,水相用氢氧化钠水溶液中和至弱碱性,再用无水乙醚萃取2-3次,有机相干燥后减压蒸馏,收集中间无色馏分得到N,N,O-三齿的胺基醇配体;
2)在惰性气体保护下,首先将等1.5倍量的正丁基锂逐滴滴加到N,N,O-三齿胺基醇配体的乙醚溶液中,搅拌1-2小时,然后在冰水浴中缓慢滴入0.5倍当量的二丁基镁试剂,恢复室温搅拌2-4小时,然后滴入0.5倍量水的乙醚溶液,反应完毕后真空浓缩滤液,析出无色透明晶体即可。
3.如权利要求1所述的3:1型Mg/Li双金属催化剂在催化醛、酮类化合物的MPV反应中应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611059463.0A CN106694045B (zh) | 2016-11-25 | 2016-11-25 | 3:1型Mg/Li双金属催化剂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611059463.0A CN106694045B (zh) | 2016-11-25 | 2016-11-25 | 3:1型Mg/Li双金属催化剂及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106694045A true CN106694045A (zh) | 2017-05-24 |
CN106694045B CN106694045B (zh) | 2019-05-17 |
Family
ID=58934853
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611059463.0A Expired - Fee Related CN106694045B (zh) | 2016-11-25 | 2016-11-25 | 3:1型Mg/Li双金属催化剂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106694045B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109092363A (zh) * | 2018-08-23 | 2018-12-28 | 鄂尔多斯应用技术学院 | 含氮氧离子型锂镁双金属催化剂及其制备方法和应用 |
CN110903327A (zh) * | 2019-12-10 | 2020-03-24 | 鄂尔多斯应用技术学院 | 一种磁性五配位单核钴配合物及合成方法和应用 |
CN113173938A (zh) * | 2021-04-08 | 2021-07-27 | 鄂尔多斯应用技术学院 | 一种磁性车轮六核铽簇合物催化剂及其制备方法和应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104211726A (zh) * | 2014-08-11 | 2014-12-17 | 中南民族大学 | 非茂类三齿双核钛配合物、制备方法及用途 |
-
2016
- 2016-11-25 CN CN201611059463.0A patent/CN106694045B/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104211726A (zh) * | 2014-08-11 | 2014-12-17 | 中南民族大学 | 非茂类三齿双核钛配合物、制备方法及用途 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109092363A (zh) * | 2018-08-23 | 2018-12-28 | 鄂尔多斯应用技术学院 | 含氮氧离子型锂镁双金属催化剂及其制备方法和应用 |
CN109092363B (zh) * | 2018-08-23 | 2021-03-23 | 鄂尔多斯应用技术学院 | 含氮氧离子型锂镁双金属催化剂及其制备方法和应用 |
CN110903327A (zh) * | 2019-12-10 | 2020-03-24 | 鄂尔多斯应用技术学院 | 一种磁性五配位单核钴配合物及合成方法和应用 |
CN110903327B (zh) * | 2019-12-10 | 2022-04-22 | 鄂尔多斯应用技术学院 | 一种磁性五配位单核钴配合物及合成方法和应用 |
CN113173938A (zh) * | 2021-04-08 | 2021-07-27 | 鄂尔多斯应用技术学院 | 一种磁性车轮六核铽簇合物催化剂及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
CN106694045B (zh) | 2019-05-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Choi et al. | [RuCl2 (p-cymene)] 2 on carbon: An efficient, selective, reusable, and environmentally versatile heterogeneous catalyst | |
Tomás-Mendivil et al. | Water-soluble gold (I) and gold (III) complexes with sulfonated N-heterocyclic carbene ligands: Synthesis, characterization, and application in the catalytic cycloisomerization of γ-alkynoic acids into enol-lactones | |
Song et al. | Bis-paracyclophane N-heterocyclic carbene–ruthenium catalyzed asymmetric ketone hydrosilylation | |
Zhang et al. | Air-stable hypervalent organobismuth (III) tetrafluoroborate as effective and reusable catalyst for the allylation of aldehyde with tetraallyltin | |
Horváth et al. | Water-soluble (η6-arene) ruthenium (II)-phosphine complexes and their catalytic activity in the hydrogenation of bicarbonate in aqueous solution | |
Denmark et al. | Synthesis, structure, and reactivity of an organogermanium Lewis acid | |
CN106694045B (zh) | 3:1型Mg/Li双金属催化剂及其制备方法和应用 | |
CN110404587A (zh) | 一种负载型团簇催化剂及其制备和应用 | |
Webber et al. | Fast CO2 hydrogenation to formic acid catalyzed by an Ir (PSiP) pincer hydride in a DMSO/water/ionic liquid solvent system | |
CN103864549B (zh) | 一种制备二苯甲酮类化合物的方法 | |
CN104098607B (zh) | 含三环己基膦的单膦单氮杂环卡宾镍(ii)配合物及其应用 | |
CN105618143B (zh) | 一种七元氮杂镁金属催化剂及其制备方法和应用 | |
Naskar et al. | Ruthenium cationic species for transfer hydrogenation of aldehydes: Synthesis and catalytic properties of [(PPh3) 2Ru (CH3CN) 3Cl]+[A]−{A= BPh4 or ClO4} and structure of [(PPh3) 2Ru (CH3CN) 3Cl]+[BPh4]− | |
CN104788480B (zh) | 一种合成氨基苯硼酸频那醇酯的方法 | |
Van der Drift et al. | Ruthenium‐Catalyzed Isomerization of Allylic Alcohols: Oxidation State Determines Resistance Against Diene Inhibition | |
CN106749430B (zh) | N,N,O-三齿Mg/Li双金属催化剂及其制备方法和应用 | |
CN103172479B (zh) | 一种钯催化的联芳烃制备方法 | |
CN109810125A (zh) | 手性铜复合物及其制备方法、手性不饱和β-硝基α-羟基酯的制备方法 | |
CN104496929B (zh) | 一种含氯仿结晶的手性锌配合物晶体及用途 | |
CN106699575B (zh) | 一种含氮氧三齿化合物及其制备方法和应用 | |
Oe et al. | Addition reaction of 2-phenylbenzoic acid onto unactivated olefins catalyzed by Ru (II)–xantphos catalysis | |
CN105175364A (zh) | 一种制备抗艾滋病药物安普那韦中间体的方法 | |
CN109092363A (zh) | 含氮氧离子型锂镁双金属催化剂及其制备方法和应用 | |
CN110903327B (zh) | 一种磁性五配位单核钴配合物及合成方法和应用 | |
Liu et al. | Heterogeneous gold-catalyzed oxidative cross-coupling of propargylic acetates with arylboronic acids leading to (E)-α-arylenones |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190517 Termination date: 20211125 |
|
CF01 | Termination of patent right due to non-payment of annual fee |