CN106749430B - N,N,O-三齿Mg/Li双金属催化剂及其制备方法和应用 - Google Patents
N,N,O-三齿Mg/Li双金属催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- -1 amido alcohol Chemical compound 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims abstract description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 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
- 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 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 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
- 239000011777 magnesium Substances 0.000 abstract description 31
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 4
- 238000003612 Meerwein-Ponndorf-Verley reduction reaction Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000006722 reduction reaction Methods 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
- 230000035484 reaction time Effects 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
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- 125000004429 atom Chemical group 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DUUYSQCTBVHCOI-UHFFFAOYSA-N CCN(CCN(C)C)CC1(C2C1CCC2)OC Chemical compound CCN(CCN(C)C)CC1(C2C1CCC2)OC DUUYSQCTBVHCOI-UHFFFAOYSA-N 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
- 229910019092 Mg-O Inorganic materials 0.000 description 1
- 229910019395 Mg—O Inorganic materials 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
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006664 bond formation reaction Methods 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
- 230000007812 deficiency Effects 0.000 description 1
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- 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
- 230000003301 hydrolyzing effect Effects 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
- 150000002641 lithium Chemical group 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000003863 metallic catalyst Substances 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
- 239000002904 solvent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
本发明提供了一种N,N,O‑三齿Mg/Li双金属催化剂及其制备方法和应用。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,将等当量的正丁基锂逐滴滴加到胺基醇的乙醚溶液中,所得反应液中滴加等当量的二丁基镁,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和镁为催化活性金属,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N,N,O-三齿Mg/Li双金属催化剂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N,N,O-三齿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N,N,O-三齿Mg/Li双金属催化剂,其结构式为:
式中:锂原子与配体中的氧原子和两个氮原子形成三配位结构,而且形成两个共用N-Li键的五元环;镁原子分别与两个配体中的氧原子和两个丁基的碳原子形成四配位模式,并以Mg-O配位键形成二聚体构型的分子结构。
本发明提供的一种N,N,O-三齿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,首先将等当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等当量的二丁基镁试剂,恢复室温搅拌2-4小时,反应完毕后真空浓缩滤液,析出无色透明晶体,即为N,N,O-三齿Mg/Li双金属催化剂,产率86-90%。反应式:
该催化剂可在在醛、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1N,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(0.96mL,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(2.0mL,1.0M,正戊烷溶液),恢复室温搅拌2小时,反应完毕后真空浓缩滤液,析出无色透明晶体,即为N,N,O-三齿Mg/Li双金属催化剂,产率90%,熔点为128-130℃。
晶体参数:化学式:C40H85Li2Mg2N4O2,单斜晶系(Monoclinic),空间群Pc,晶胞参数α=90.000°,β=98.5750(10)°,γ=90.000°,V=4604.0(2),Z=4。单晶结构图见图1。
部分键长:Mg(1)-O(1)2.032(3),Mg(1)-O(2)2.045(4),Mg(2)-O(1)2.063(4),Mg(2)-O(2)2.039(3),Li(1)-O(1)1.955(9),Li(1)-N(1)2.095(10),Li(1)-N(2)2.235(10),Li(2)-O(2)1.978(10),Li(2)-N(3)2.103(9),Li(2)-N(4)2.192(10);键角(°):O(1)-Mg(1)-O(2)85.99(14),O(1)-Mg(2)-O(2)85.35(14),Mg(1)-O(1)-Mg(2)93.69(14),Mg(1)-O(2)-Mg(2)94.00(14),Li(1)-O(1)-Mg(1)105.9(3),Li(1)-O(1)-Mg(2)84.7(3),Li(2)-O(2)-Mg(1)84.4(3),Li(2)-O(2)-Mg(2)108.0(3),O(1)-Li(1)-N(1)86.3(4),O(1)-Li(1)-N(2)137.4(5),O(2)-Li(2)-N(3)86.2(4),O(2)-Li(2)-N(4)138.7(5)。
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96%。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93%。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N,N,O-三齿Mg/Li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N,N,O-三齿Mg/Li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,首先将等当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等当量的二丁基镁试剂,恢复室温搅拌2-4小时,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N,N,O-三齿Mg/Li双金属催化剂在催化醛、酮类化合物的MPV反应中应用。
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