CN108178768B - 一种二氯二(1-丁基咪唑)锌催化剂的制备方法及应用 - Google Patents
一种二氯二(1-丁基咪唑)锌催化剂的制备方法及应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 125000003963 dichloro group Chemical group Cl* 0.000 title claims abstract description 13
- AAEJPCNXKQDHTR-UHFFFAOYSA-N 1-butylimidazole zinc Chemical compound [Zn].CCCCN1C=CN=C1 AAEJPCNXKQDHTR-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims abstract description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004246 zinc acetate Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 11
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims abstract description 11
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- 239000007853 buffer solution Substances 0.000 claims abstract description 3
- 238000011049 filling Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 18
- 239000011701 zinc Substances 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 8
- 150000002460 imidazoles Chemical class 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- -1 zinc metal complex Chemical class 0.000 description 3
- 101100309315 Danio rerio rxrbb gene Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
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- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
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- 238000002447 crystallographic data Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
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- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- PEVXENGLERTHJE-UHFFFAOYSA-N methyl 3,5-dimethylbenzoate Chemical compound COC(=O)C1=CC(C)=CC(C)=C1 PEVXENGLERTHJE-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000003232 p-nitrobenzoyl group Chemical group [N+](=O)([O-])C1=CC=C(C(=O)*)C=C1 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- C07C201/06—Preparation of nitro compounds
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract
本发明公开了二氯二(1‑丁基咪唑)锌催化剂的制备方法,该种方法将1‑丁基咪唑、乙酰丙酮氧钒、乙酸锌加入到盛有NaOAc‑HOAc的缓冲溶液中,再加入适量的氯化钠,混合搅拌,加热,冷却、得到块状二氯二(1‑丁基咪唑)锌催化剂。本发明方法具有反应过程简单,后处理简单。在4‑硝基苯甲酸甲酯的乙酯化反应中,产率高达93%。
Description
技术领域
本发明属于催化剂材料制备技术领域,其中涉及到二氯二(1-丁基咪唑)锌催化剂的制备技术,为其催化应用奠定基础。
技术背景
锌是一种非常重要的生命过渡元素,以锌为中心金属有机化合物被广泛应用于人民生活的各个方面,同样此类化合物在催化领域也具有着重要应用。这类锌配合物可以用作多种反应体系的催化剂,这些催化剂催化活性高,且催化反应条件温和、催化产物选择性好及催化搓成成本较低。卢忠林课题组以3,5-二甲基苯甲酸甲酯衍生的配体设计合成了2个锌金属配合物,二者均能催化2-羟丙基对硝基苯基磷酸二酯的降解反应(高等学校化学学报,2011,32(9),2128-2132)。这也为我们研究其他新型锌配合物进行路易斯催化其他反应提供了依据。
酯类化合物在医药、化工等领域有着广泛的应用,酯交换反应一直是合成酯类化合物的主要途径。硫酸是酯化反应常用催化剂,但具有对设备腐蚀性强,难于从均相体系分离等缺点。因此,设计高效的催化剂体系,对于有机化学工业具有重大的科学意义。
基于以上文献的基础上,设计一个酯交换反应的催化体系是十分必要的。
通过检索,尚未发现与本发明申请相关的公开专利文献。
发明内容
本项发明的目的提供一种合成二氯二(1-丁基咪唑)锌催化剂的制备方法,希望实现4-硝基苯甲酸甲酯的乙基化反应合成苯甲酸乙酯的目标。
本发明的的技术方案是:新型二氯二(1-丁基咪唑)锌催化剂,结构式为:
前面所述的二氯二(1-丁基咪唑)锌催化剂的制备方法,步骤如下:
将1-丁基咪唑、乙酰丙酮氧钒、乙酸锌加入到盛有NaOAc-HOAc的缓冲溶液中,再加入适量的氯化钠,混合搅拌,装入反应釜中,加热,冷却、得到块状单晶,产率32-59%。
前面所述的制备方法,优选的方案是,原料物质的量之比1-丁基咪唑:乙酰丙酮氧钒:乙酸锌:氯化钠物质的量之比为10~15:0.5~1.2:0.3~0.8:0.2~0.7(优选的,1-丁基咪唑:乙酰丙酮氧钒:乙酸锌物质的量之比为12:0.8:0.5:0.4)。
前面所述的制备方法,优选的方案是,加热温度为120~180℃(优选的,加热温度为150℃)。
前面所述的制备方法,优选的方案是,加热反应时间为72~96h(优选的,加热反应时间为84h)。
前面所述的制备方法,优选的方案是,强烈搅拌30-120min(优选的,强烈搅拌120min)。
本发明还提供了二氯二(1-丁基咪唑)锌催化剂在催化4-硝基苯甲酸甲酯的乙基化。催化剂可以实现4-硝基苯甲酸甲酯的乙基化反应,产率高达93%。
上述催化反应溶剂选用乙醇等,产率通过气相色谱检测。
本发明的设计思路如下:将1-丁基咪唑与锌盐以及适量的无机盐在水热反应中构筑二氯二(1-丁基咪唑)锌金属配合物,将具有明确结构的二氯二(1-丁基咪唑)锌催化剂应用于4-硝基苯甲酸甲酯的乙基化,实现高产率的目标。
催化剂的结构信息通过以下方法获得的:在一个25mL的反应釜中依次加入1-丁基咪唑(10~15mmol),乙酰丙酮氧钒(0.5~1.2mmol),乙酸锌(0.3~0.8mmol),NaOAc-HOAc(15~20mL)以及氯化钠(0.2~0.5mmol),强烈搅拌30~120min,在120~180度下加热反应72~96h,冷却、过滤,得到块状单晶。产率约32~59%。
产品通过单晶X衍射,粉末X射线衍射进行表征,从图1、图2、以及晶体结构数据表1可以得到关于催化剂结构的信息。
从单晶X衍射结构分析(图1),催化剂的分子式为C14H24Cl2ZnN4。其中阳离子为Zn阳离子,氯离子为阴离子,二者通过共价键相互作用结合在一起。此化合物中含有一个锌原子,原子与两个N-丁基咪唑发生配位及两个氯原子配位,形成三角锥结构。正好与化合物的分子式吻合。
从粉末X射线衍射分析(图2),此化合物的物相能够与模拟数据进行较好地吻合,说明此化合物的物相较纯。
表1.化合物Zn[(1-bIM)4]2Cl2的晶体学数据
从表1可以看出,此化合物的晶体数据为正交晶体,空间群为Pbca,晶体学分子式与晶体结构能够较好地吻合。
附图说明
图1为化合物Zn[(1-bIM)4]2Cl2的晶体结构。
图2为本发明所得催化剂的RXRD表征,其中灰线为合成的样品,黑线为模拟的样品。
具体实施方式
下面结合实施例和附图详细说明本发明的技术方案,但保护范围不被此限制。
实施例1:化合物Zn[(1-bIM)4]2Cl2的制备:在一个25mL的反应釜中依次加入1-丁基咪唑(10mmol),乙酰丙酮氧钒(0.5mmol),乙酸锌(0.3mmol),NaOAc-HOAc(15mL)以及氯化钠(0.2mmol),强烈搅拌30min,在120度下加热反应72h,冷却、过滤,得到块状单晶。产率约34%。
实施例2:化合物Zn[(1-bIM)4]2Cl2的制备:在一个25mL的反应釜中依次加入1-丁基咪唑(12mmol),乙酰丙酮氧钒(0.5mmol),乙酸锌(0.4mmol),NaOAc-HOAc(15mL)以及氯化钠(0.2mmol),强烈搅拌30min,在120度下加热反应96h,冷却、过滤,得到块状单晶。产率约36%。
实施例3:化合物Zn[(1-bIM)4]2Cl2的制备:在一个25mL的反应釜中依次加入1-丁基咪唑(15mmol),乙酰丙酮氧钒(0.5mmol),乙酸锌(0.5mmol),NaOAc-HOAc(20mL)以及氯化钠(0.3mmol),强烈搅拌50min,在180度下加热反应72h,冷却、过滤,得到块状单晶。产率约41%。
实施例4:化合物Zn[(1-bIM)4]2Cl2的制备:在一个25mL的反应釜中依次加入1-丁基咪唑(13mmol),乙酰丙酮氧钒(0.8mmol),乙酸锌(0.5mmol),NaOAc-HOAc(20mL)以及氯化钠(0.5mmol),强烈搅拌60min,在120度下加热反应72h,冷却、过滤,得到块状单晶。产率约57%。
实施例5:化合物Zn[(1-bIM)4]2Cl2的制备:在一个25mL的反应釜中依次加入1-丁基咪唑(14mmol),乙酰丙酮氧钒(0.9mmol),乙酸锌(0.7mmol),NaOAc-HOAc(18mL)以及氯化钠(0.4mmol),强烈搅拌120min,在180度下加热反应96h,冷却、过滤,得到块状单晶。产率约54%。
实施例6:化合物Zn[(1-bIM)4]2Cl2的制备:在一个25mL的反应釜中依次加入1-丁基咪唑(15mmol),乙酰丙酮氧钒(1.2mmol),乙酸锌(0.8mmol),NaOAc-HOAc(20mL)以及氯化钠(0.5mmol),强烈搅拌120min,在180度下加热反应96h,冷却、过滤,得到块状单晶。产率约58%。
实施例7:化合物Zn[(1-bIM)4]2Cl2的制备:在一个25mL的反应釜中依次加入1-丁基咪唑(14mmol),乙酰丙酮氧钒(1.0mmol),乙酸锌(0.6mmol),NaOAc-HOAc(18mL)以及氯化钠(0.4mmol),强烈搅拌120min,在170度下加热反应89h,冷却、过滤,得到块状单晶。产率约56%。
本发明所得二氯二(1-丁基咪唑)锌催化剂,催化剂的分子式为Zn[(1-bIM)4]2Cl2。
图1为化合物Zn[(1-bIM)4]2Cl2的晶体结构。
图2为本发明所得催化剂的RXRD表征。由此可以看出合成的此化合物能与其单晶结构很好地吻合,说明利用此方法合成的催化剂是纯品。
试验例1:4-硝基苯甲酸甲酯的乙基化的催化应用:取0.25mmol 4-硝基苯甲酸甲酯溶于1mL乙醇中,并加入实施例1-6所得催化剂10~20mg,加热搅拌并维持温度在70~80摄氏度,反应24~36h后,用气相色谱检测,反应液中的4-硝基苯甲酸甲酯绝大部分全部转化为4-硝基苯甲酸乙酯,产率高达93%。
经过对比文献报道(Blumel,Marcus et al,Organic Letters,18(9),2208-2211;2016)4-硝基苯甲酸甲酯的乙酯化产率为86%,此催化剂能够较好地进行催化4-硝基苯甲酸甲酯的乙酯化反应,说明此催化剂在此反应中能够起到良好的催化作用。
Claims (5)
1.一种二氯二(1-丁基咪唑)锌催化剂的制备方法,其特征在于:步骤为:将1-丁基咪唑、乙酰丙酮氧钒、乙酸锌加入到盛有NaOAc-HOAc的缓冲溶液中,再加入适量的氯化钠,1-丁基咪唑:乙酰丙酮氧钒:乙酸锌:氯化钠物质的量之比为10~15:0 .5~1 .2:0 .3~0.8:0 .2~0 .7,混合并强烈搅拌30-120min,装入反应釜中,加热,加热温度为120~180℃,加热反应时间为72~96h,冷却、得到块状单晶。
2.根据权利要求1所述的制备方法,其特征在于:1-丁基咪唑:乙酰丙酮氧钒:乙酸锌:氯化钠物质的量之比为12:0 .8:0 .5:0 .4。
3.根据权利要求1所述的制备方法,其特征在于:加热温度为150℃。
4.根据权利要求1所述的制备方法,其特征在于:加热反应时间为84h。
5.根据权利要求1所述的制备方法,其特征在于:强烈搅拌120min。
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