CN105817264A - 一种铜配合物的用途 - Google Patents

一种铜配合物的用途 Download PDF

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CN105817264A
CN105817264A CN201610235071.9A CN201610235071A CN105817264A CN 105817264 A CN105817264 A CN 105817264A CN 201610235071 A CN201610235071 A CN 201610235071A CN 105817264 A CN105817264 A CN 105817264A
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罗梅
张志军
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Hefei Xiangchen Chemical Co ltd
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    • 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
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
    • C07C205/14—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to acyclic carbon atoms
    • C07C205/16—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to acyclic carbon atoms of a carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
    • C07C205/19—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
    • C07C205/26—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups and being further substituted by halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/32—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups bound to acyclic carbon atoms and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • 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
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
    • 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

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Abstract

一种 L‑缬氨酸铜配合物的用途，该配合物在芳醛与硝基甲烷制备目标产物时作为催化剂，所取的芳醛包括苯甲醛或取代苯甲醛，如4‑甲氧基苯甲醛、4‑氟苯甲醛，4‑溴苯甲醛、4‑硝基苯甲醛、4‑溴苯甲醛和1‑萘苯甲醛。

Description

一种铜配合物的用途
一、技术领域
本发明涉及一种金属有机配位化合物（配合物）的用途，特别涉及含氮的金属有机配合物的用途，确切地说是一种 L-缬氨酸铜配合物的用途。
二、背景技术
铜作为微量生命元素，在生命过程中起着非常重要的作用。铜配合物有着复杂的配位结构，在生命体的新陈代谢等生命活动过程中起着重要的作用。所以，研究铜金属有机配合物的合成及应用有着重要的理论和实际意义。
手性一水合二[L-缬氨酸]铜配合物在医药及生物领域有重要的用途，类似该化合物的结构已有文献报道[1-2]:
1.Synthesis, antimicrobial activity and cyclic voltammogram of Cu(II)complex , Li, Qiu-tong; Bo, Ying-ying; Xu, Xing-you; Duanmu, Chuan-song;Chen, Zhi-dong , Changzhou Daxue Xuebao, Ziran Kexueban (2012), 24(3), 75-79.
2.Synthesis, characterization and superoxide-dismutase-like activity ofCu(II) complex of L-
isoleucinate, Liao, Shengrong; Lin, Qingbin; Le, Xueyi; Feng, XiaolongHuaxue
Yanjiu (2006), 17(1), 9-12.
二、发明内容
本发明旨在为芳醛与硝基甲烷的加成反应制备目标产物，所要解决的技术问题是提供高效催化剂。
本发明所称的一水合二[L-缬氨酸]铜配合物的制备是由L-缬氨酸与二水合氯化铜作用，由以下化学式所示的化合物：
（I）。
化学名称：一水合二[L-缬氨酸]铜配合物,简称配合物(I)。
本合成方法包括合成和分离，所述的合成是称取称取1.7259g（0.015mol）L-缬氨酸放入100mL圆底烧瓶中，加入40mL无水甲醇并搅拌使其溶解；将0.9051g（0.05mol）二水合氯化铜加入上述溶液，加热回流48h；反应结束后趁热过滤反应溶液，将滤渣用20mL无水甲醇和20mL蒸馏水溶解，自然挥发，几天后有蓝色晶体析出；将蓝色晶体用石油醚和正己烷冲洗3次，真空干燥30min，得目标产物。
合成反应如下：
本合成方法一步得到目标产物，工艺简单，操作方便。
Henry反应是经典的有机人名反应之一。该反应是指羰基化合物通常是芳醛和有α-氢的硝基化合物之间的缩合反应,反应的结果是硝基的α-碳原子加成到羰基上,形成具有羟基、硝基的双官能团的化合物。Henry反应的产物可以方便地转化为各式各样有重要用途的化合物,如β-氨基醇、硝基烯烃、硝基酮、硝基烯酮或进行Nef反应。因此Henry反应在有机合成中是非常实用的反应之一。扩展这一反应的应用范围,合成具有更多官能团、结构上更为复杂的化合物,是一项有意义的工作。
本发明所称的一水合二[L-缬氨酸]铜配合物的用途是在邻、对位取代的芳香族醛类亨利反应中的用途，所述的芳醛包括苯甲醛或取代苯甲醛，如4-甲基苯甲醛、4-甲氧基苯甲醛、4-氟苯甲醛，4-溴苯甲醛，2-甲基苯甲醛、2-甲氧基苯甲醛、2-氟苯甲醛，1-萘醛。
三、附图说明
图1是配合物（Ⅰ）的单晶衍射图。
四、具体实施方式
1.称取1.7259g(0.015mol)L-缬氨酸放入100mL圆底烧瓶中，加入40mL无水甲醇并搅拌使其溶解；将0.9051g(0.05mol)二水合氯化铜加入上述溶液，加热回流48h；反应结束后趁热过滤反应溶液，将滤渣用20mL无水甲醇和20mL蒸馏水溶解，自然挥发，几天后有蓝色晶体析出。产率为31％，m.p.:>200℃,[α]20 D＝-271.0°(c＝0.0644，CH3OH)。元素分析数据Cu[C10H22N2O5]，理论值(％)：C：38.27％；H：7.07％；N：8.93％；实测值(％)：C：37.89％；H：7.01％；N：8.87％；红外光谱数据(KBr,cm-1)：588，645，794，923，1128，1382，1491，1621，2955，3289；
称取1.7259g(0.015mol)L-缬氨酸放入100mL圆底烧瓶中，加入40mL无水甲醇并搅拌使其溶解；将0.9051g(0.05mol)二水合氯化铜加入上述溶液，加热回流48h；反应结束后趁热过滤反应溶液，将滤渣用20mL无水甲醇和20mL蒸馏水溶解，自然挥发，几天后有蓝色晶体析出。产率为31％，m.p.:>200℃,[α]20 D＝-271.0°(c＝0.0644，CH3OH)。元素分析数据Cu[C10H22N2O5]，理论值(％)：C：38.27％；H：7.07％；N：8.93％；实测值(％)：C：37.89％；H：7.01％；N：8.87％；红外光谱数据(KBr,cm-1)：588，645，794，923，1128，1382，1491，1621，2955，3289；
2.亨利反应应用
(1)2-硝基-1-苯基乙醇
催化剂I(0.148mmol),苯甲醛0.10mL(0.986mmol)及硝基甲烷(0.50mL,9.255mmol)在室温下搅拌6h，用核磁监测，转化率：74％
(2)2-硝基-1-(4-甲氧基苯基)乙醇
反应步骤同(1)，转化率：69％
(3)2-硝基-1-(4-氟苯基)乙醇
反应步骤同(1)，转化率：68％
(4)2-硝基-1-(4-硝基苯基)乙醇
反应步骤同(1)，转化率：76％
(5)2-硝基-1-(4-溴苯基)乙醇
反应步骤同(1)，转化率：82％
(6)1-2-硝基-1-(1-萘基)乙醇
反应步骤同(1)，转化率：84％

Claims (6)

1.一种 L-缬氨酸铜配合物的用途，其特征是在芳醛的亨利反应制备目标产物时作为催化剂。
2.根据权利要求1所述的用途，其特征是在4-甲氧基苯甲醛的亨利反应制备目标产物时作为催化剂。
3.根据权利要求1所述的用途，其特征是在4-氟苯甲醛的亨利反应制备目标产物时作为手性催化剂。
4.根据权利要求1所述的用途，其特征是在4-硝基苯甲醛的亨利反应制备目标产物时作为手性催化剂。
5.根据权利要求1所述的用途，其特征是在4-溴苯甲醛的亨利反应制备目标产物时作为手性催化剂。
6.根据权利要求1所述的用途，其特征是在1-萘苯甲醛的亨利反应制备目标产物时作为催化剂。
CN201610235071.9A 2016-04-18 2016-04-18 一种铜配合物的用途 Pending CN105817264A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106902887A (zh) * 2017-03-14 2017-06-30 山东管理学院 一种可磁力回收的铜配合物催化剂及其制备方法与应用

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CN103285924A (zh) * 2013-07-03 2013-09-11 罗梅 一种手性铜配合物的用途
CN103450229A (zh) * 2013-07-29 2013-12-18 罗梅 一种手性铜配合物的用途

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103285924A (zh) * 2013-07-03 2013-09-11 罗梅 一种手性铜配合物的用途
CN103450229A (zh) * 2013-07-29 2013-12-18 罗梅 一种手性铜配合物的用途

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Title
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106902887A (zh) * 2017-03-14 2017-06-30 山东管理学院 一种可磁力回收的铜配合物催化剂及其制备方法与应用
CN106902887B (zh) * 2017-03-14 2019-06-14 山东管理学院 一种可磁力回收的铜配合物催化剂及其制备方法与应用

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