CN108659056A - 一种以含氧羧酸为配体的茂钛配合物及其制备方法和应用 - Google Patents

一种以含氧羧酸为配体的茂钛配合物及其制备方法和应用 Download PDF

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CN108659056A
CN108659056A CN201810814510.0A CN201810814510A CN108659056A CN 108659056 A CN108659056 A CN 108659056A CN 201810814510 A CN201810814510 A CN 201810814510A CN 108659056 A CN108659056 A CN 108659056A
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titanium complex
complex
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cyclopentadienyl titanium
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高子伟
王芸芸
杨明明
张伟强
孙华明
简亚军
张国防
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Ningxia Normal University
Shaanxi Normal University
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    • C07F17/00—Metallocenes
    • 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
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • 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
    • B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
    • 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
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium

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Abstract

本发明公开了一种以含氧羧酸为配体的茂钛配合物及其制备方法和应用，该配合物的结构式为其是以含氧羧酸作为配体，二氯二茂钛作为路易斯酸，5‑磺基水杨酸作为过渡性配体，制备成茂钛配合物。本发明配合物对空气稳定，其合成方法所用原料成本低廉易得，合成步骤简便易行，产品后处理简单，条件温和，目标产物产率高。本发明配合物用于催化2‑氨基苯乙酮和芳香醛反应合成2‑芳基‑2,3‑二氢化喹啉酮取得了较好的收率。

Description

一种以含氧羧酸为配体的茂钛配合物及其制备方法和应用
技术领域
本发明涉及一种以含氧羧酸为配体的茂钛配合物，以及该配合物的制备方法和应用。
背景技术
金属有机配合物一般在严格无水的有机相中合成，然而，近年来，研究有水条件下二茂钛衍生物的合成与反应日益引起人们的兴趣。因其广泛地用于催化、材料、药物等领域，尤其是茂钛配合物，对空气和水稳定，在有机催化反应中表现出良好的活性，但是通常情况下其制备过程复杂，原料昂贵，对水敏感，因此发展一种条件温和、对空气水稳定、操作步骤简单的制备方法尤为必要。
发明内容
本发明所要解决的技术问题在于克服现有茂钛配合物制备方法存在的缺陷，提供一种对空气和水稳定、制备原料廉价易得、制备条件温和，合成步骤简单的茂钛配合物，以及该配合物的制备方法，并为其提供一种新的应用。
解决上述技术问题所采用的茂钛配合物的结构式如下所示：
式中R1和R2代表H、NO2、COOH、F、OH中任意一种，且R1和R2中有且仅有一个代表H。
本发明茂钛配合物优选结构式如下的化合物：
其属于单斜晶系，晶胞参数a＝28.8740(11)，b＝10.2722(4)，c＝16.4969(6)，α＝90°，β＝97.1350(10)°，γ＝90°，Z＝8。
本发明茂钛配合物的制备方法为：将5-磺基水杨酸溶于去离子水中，然后加入二氯二茂钛，搅拌至二氯二茂钛溶解完全，再加入完全溶解于有机溶剂的含氧羧酸溶液，充分搅拌2～3小时，萃取、干燥、重结晶，得到茂钛配合物，具体反应方程式如下：
上述制备方法中，所述二氯二茂钛、5-磺基水杨酸、含氧羧酸的摩尔比为1:1.0～1.3:2.0～2.5。
上述制备方法中，所述有机溶剂为乙醇或甲醇。
上述有机溶剂与蒸馏水的加入量只要保证所有物质都能溶解即可。
本发明茂钛配合物在催化2-氨基苯乙酮和芳香醛反应合成2-芳基-2,3-二氢化喹啉酮中的用途，具体方法为：以甲醇为溶剂，将2-氨基苯乙酮和芳香醛按摩尔比为1:1，在室温条件下反应，即得到2-芳基-2,3-二氢化喹啉酮，反应方程式如下所示：
上述的芳香醛为苯甲醛、卤代苯甲醛、C1～C4烷基取代苯甲醛、C1～C4烷氧基取代苯甲醛、硝基取代苯甲醛、吡啶-2-甲醛、呋喃-2-甲醛、2-羟基苯甲醛、1-萘醛中任意一种。
本发明以含氧羧酸为模板催化剂，通过水/有机两相反应，分液，干燥，结晶，即制得目标茂钛配合物，该配合物对空气和水稳定，制备原料廉价易得，合成步骤简便易行，产品后处理容易，产率高。本发明配合物可以同时满足反应催化条件的路易斯性要求，也可以满足布朗斯特酸性要求，在催化有机反应中具有广发的应用前景，应用于2-氨基苯乙酮和芳香醛反应合成2-芳基-2,3-二氢化喹啉酮，取得了较好的收率。
附图说明
图1是实施例1中茂钛配合物的X射线单晶结构图。
图2是实施例1中茂钛配合物的晶胞结构图。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明，但本发明所要保护的范围不仅限于这些实施例。
实施例1
制备结构式如下的茂钛配合物：
将0.51g(2.0mmol)5-磺基水杨酸溶于15mL蒸馏水中，然后分三次加入0.5g(2.0mmol)二氯二茂钛，搅拌至二氯二茂钛完全溶解；将0.844g(4.0mmol)3-硝基邻苯二甲酸溶于30mL乙醇中，然后将两种溶液混合，室温搅拌4小时，减压浓缩，用无水硫酸镁干燥15min，旋蒸浓缩，用乙醇/正己烷重结晶，得到橘红色茂钛配合物0.801g，其产率为67％，X射线单晶结构图如图1所示。该配合物属于单斜晶系，晶胞参数a＝28.8740(11)，b＝10.2722(4)，c＝16.4969(6)，α＝90°，β＝97.1350(10)°，γ＝90°，Z＝8，O002-Ti-O00B＝85.4(2)°。
实施例2
制备结构式如下的茂钛配合物：
本实施例中，用等摩尔4-硝基邻苯二甲酸替换实施例1中的3-硝基邻苯二甲酸，其他步骤与实施例1相同，得到目标茂钛配合物。
实施例3
制备结构式如下的茂钛配合物：
本实施例中，用等摩尔4-氟邻苯二甲酸替换实施例1中的3-硝基邻苯二甲酸，其他步骤与实施例1相同，得到目标茂钛配合物。
实施例4
制备结构式如下的茂钛配合物：
本实施例中，用等摩尔偏苯三甲酸替换实施例1中的3-硝基邻苯二甲酸，其他步骤与实施例1相同，得到目标茂钛配合物。
实施例1的茂钛配合物在催化2-氨基苯乙酮和芳香醛反应合成2-芳基-2,3-二氢化喹啉酮中的应用，具体方法如下：
将1.2mmol 2-氨基苯乙酮和1.0mmol芳香醛加入2mL甲醇中，室温反应26小时，反应结果见表1。
表1
Ar 2-氯苯基 3-溴苯基 2-溴苯基 4-溴苯基 4-氟苯基 2-甲氧基苯基
产率 92％ 84％ 79％ 92％ 92％ 91％
Ar 2-硝基苯基 苯基 4-硝基苯基 4-甲基苯基 3-甲氧基苯基 3,4-二甲氧基苯基
产率 46％ 84％ 57％ 78％ 88％ 69％
Ar 2-吡啶基 2-萘基 2-呋喃基 2-羟基苯基 4-叔丁基苯基 4-异丙基苯基
产率 63％ 62％ 67％ 72％ 97％ 91％

Claims (7)

1.一种以含氧羧酸为配体的茂钛配合物，其特征在于该配合物的结构式如下所示：
式中R1和R2代表H、NO2、COOH、F、OH中任意一种，且R1和R2中有且仅有一个代表H。
2.根据权利要求1所述的茂钛配合物，其特征在于该配合物的结构式如下所示：
其属于单斜晶系，晶胞参数a＝28.8740(11)，b＝10.2722(4)，c＝16.4969(6)，α＝90°，β＝97.1350(10)°，γ＝90°，Z＝8。
3.一种权利要求1所述的茂钛配合物的制备方法，其特征在于：将5-磺基水杨酸溶于去离子水中，然后加入二氯二茂钛，搅拌至二氯二茂钛溶解完全，再加入完全溶解于有机溶剂的含氧羧酸溶液，充分搅拌2～3小时，萃取、干燥、重结晶，得到茂钛配合物；
上述的含氧羧酸的结构式为：
4.根据权利要求3所述的茂钛配合物的制备方法，其特征在于：所述二氯二茂钛、5-磺基水杨酸、含氧羧酸的摩尔比为1:1.0～1.3:2.0～2.5。
5.根据权利要求3所述的茂钛配合物的制备方法，其特征在于：所述有机溶剂为乙醇或甲醇。
6.权利要求1所述的茂钛配合物在催化2-氨基苯乙酮和芳香醛反应合成2-芳基-2,3-二氢化喹啉酮中的用途。
7.根据权利要求6所述的茂钛配合物在催化2-氨基苯乙酮和芳香醛反应合成2-芳基-2,3-二氢化喹啉酮中的用途，其特征在于：所述的芳香醛为苯甲醛、卤代苯甲醛、C1～C4烷基取代苯甲醛、C1～C4烷氧基取代苯甲醛、硝基取代苯甲醛、吡啶-2-甲醛、呋喃-2-甲醛、2-羟基苯甲醛、1-萘醛中任意一种。
CN201810814510.0A 2018-07-23 2018-07-23 一种以含氧羧酸为配体的茂钛配合物及其制备方法和应用 Pending CN108659056A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110052244A (zh) * 2019-03-21 2019-07-26 天津科技大学 一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法
CN113173884A (zh) * 2021-05-06 2021-07-27 陕西师范大学 二氯二茂钛催化汉斯酯1,4-二氢吡啶类化合物合成吡啶及其衍生物的方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110052244A (zh) * 2019-03-21 2019-07-26 天津科技大学 一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法
CN110052244B (zh) * 2019-03-21 2022-04-01 天津科技大学 一种用于孔雀石绿富集和传感的金属有机配合物材料的制备方法
CN113173884A (zh) * 2021-05-06 2021-07-27 陕西师范大学 二氯二茂钛催化汉斯酯1,4-二氢吡啶类化合物合成吡啶及其衍生物的方法
CN113173884B (zh) * 2021-05-06 2023-08-15 陕西师范大学 二氯二茂钛催化汉斯酯1,4-二氢吡啶类化合物合成吡啶及其衍生物的方法

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