胍基金属（Li和Al）化合物的合成、结构和反应性研究
发布时间：2018-07-15 15:22
【摘要】：胍基配体具有良好的空间可协调性能,可以通过桥连和螯合两种模式同元素周期表中很多金属形成胍基金属有机化合物,它们在配位化学、合成化学、催化领域及稳定低价氧化态的金属等方面有着不可替代的重要作用。由于对胍基铝化合物的研究起步较晚,在合成它们时使用的碳化二亚胺种类单一,合成数量有限,其性质远远没有达到完全掌握的程度,因此目前这类化合物的应用范围也受到限制。本论文的主要内容分为三部分:第一部分选择不同种类的碳化二亚胺,采用传统的方法合成了一系列不同种类的胍基铝化合物;第二部分对单胍基铝化合物和氧气、碳化二亚胺及水的反应性做了初步的研究,并尝试使用各类胍基铝化合物作为前催化剂在Meerwein-Ponndorf-Verley(MPV)反应中进行了应用;第三部分合成了一种新的双胍基配体,对这种配体和烷基金属的反应性进行了研究,生成了三种胍基金属化合物,包括一种双核的含双负离子的双胍基锂化合物。另外,我们通过伯胺的锂盐和碳二亚胺反应也得到了一系列含双负离子的胍基锂化合物,为下一步制备多核的双胍基铝化合物提供了支撑。具体工作内容如下:1.通过制备胍基铝的常用方法制得了七个新的单核铝化合物,[{(Et_2N)C-(NCy)(NPh}_2AlMe](2c),[{(Et_2N)C(NPh)(NAr)}_2AlMe](2d),[{(C_5H_(10)N)C(NPh)-(NAr)}_2AlMe](2e),[{(Et_2N)C(NPh)(NAr)}_2AlCl](2f,Ar=2,6-Me_2C_6H_3),[{(Et_2N)C(NCy)(NPh)}AlMe_2](2g),[{(C_5H_(10)N)C(NCy)_2}AlMe_2](2h)和[{(Bz(Me)N)-C(NCy)_2}AlMe_2](2i)。化合物2c-2f属于双胍基铝化合物,2g-2i属于单胍基铝化合物,它们均获得了单晶结构,且经过NMR和元素分析的测定。研究表明,起始原料碳化二亚胺的种类决定胍基铝产物的类型-反应的主要产物为双胍基铝化合物还是单胍基铝化合物。当我们选择的起始原料碳化二亚胺为CyN=C=NPh时,可以从反应溶液中同时分离出了两种胍基铝化合物2c和2g,选择起始原料碳化二亚胺为CyN=C=NCy或者PhN=C=NAr时,仅能得到其中一种胍基铝化合物。2.选择不同的单胍基铝化合物分别和氧气、碳化二亚胺及水进行了反应性的初步研究。单胍基铝化合物和氧气反应合成了五个二聚的氧桥连的胍基铝化合物[LAlMe(μ-OMe)]_2(3a-3e,L代表胍基配体);单胍基铝化合物和碳化二亚胺反应合成了两个双胍基铝化合物,[{N(Ph)C(NR)N(Ph)C(NEt_2)N(R)}AlMe_2](R=Cy,3f;R=2,6-Me_2C_6H_3,3g);在制备单胍基铝的反应溶液中通入脱气的含水溶剂后分离得到一个四核的胍基铝化合物,(?)(验证了课题组前期得到的意外产物的形成原因),和同上述四核化合物主体结构相似的一个脒基铝化合物,(?)(Ar=2,6-Me_2C_6H_3),且以上化合物的结构均得到验证。另外,尝试不同种类的胍基铝化合物在催化Meerwein-Ponndorf-Verley反应中的应用,其中2g和3e的催化活性最高。当催化剂的加载量为10 mol%,在甲苯溶液中回流2 h后,不同种类的醛、酮化合物可以高产率地转化为相应的醇,最高产率大于99%。3.提供了简单、有效的制备含单阴离子的双胍化合物和含双阴离子双胍配体的方法和思路,为制备胍基双金属化合物提供了支撑。3g化合物的完全水解可以制备一种新的含一个活泼氢的双胍化合物4a,产率可以达到80%以上。对该双胍化合物4a同烷基金属(AlMe、ZnEt_2和n-BuLi)的反应性进行了简单的研究。有意义的是,当TMEDA存在时4a和n-BuLi反应生成了一种含双阴离子的双胍基锂化合物4d,4d也可以通过苯胺锂化和相应的碳化二亚胺加成得到。另外,我们也对苯胺的锂盐同不同碳化二亚胺加成反应进行了研究,生成了胍基锂化合物4e-4g,其中化合物4e和4f的结构类似于4d,而4g的结构属于普通的二聚单胍基锂化合物。研究表明,胍基锂化合物的种类和反应原料碳化二亚胺中N原子上连接的基团有关。
[Abstract]:Guanidine ligands have good spatial coordination properties and can form guanidine organometallic compounds by bridging and chelating two modes with many metals in the element periodic table. They have an irreplaceable role in the coordination of coordination chemistry, synthetic chemistry, catalysis and stable low oxidation states. The study of the compound started late. The carbonated two imines used in the synthesis of them were single and the synthetic quantity was limited. The properties of these compounds were far from fully mastered. Therefore, the application scope of these compounds was limited. The main content of this kind of compounds is divided into three parts: the first part chooses different kinds of carbonated two imines. A series of different kinds of guanidine aluminum compounds were synthesized by traditional methods; the second part made a preliminary study on the reactivity of single guanidine aluminum compound and oxygen, carbonated two imide and water, and tried to use various guanidine aluminum compounds as the former catalyst in the Meerwein-Ponndorf-Verley (MPV) reaction; third parts. A new kind of guanidine ligands was synthesized, and the reactivity of this ligand and alkyl metals was studied. Three guanidine metal compounds were formed, including a double nucleate lithium compound containing double negative ions. In addition, a series of guanidine lithium containing double negative ions was obtained by the reaction of lithium salt and carbon two imide in primary amine. The compound provides support for the preparation of multi nucleated guanidine aluminum compounds in the next step. The specific contents are as follows: 1. seven new mononuclear aluminum compounds are prepared by the common methods of preparing guanidine aluminum, [(Et_2N) C- (NCy) (NPh}_2AlMe] (2C), [Et_2N) C (NPh) (NAr)}_2AlMe] (2D) Ar)}_2AlCl] (2f, Ar=2,6-Me_2C_6H_3), [Et_2N C (NCy) (NPh)}AlMe_2] (2G), [[C_5H_ (C_5H_ (10) N] belong to the guanidine aluminum compound, which are single guanidine aluminum compounds, both of which have obtained single crystal structure and are determined by elemental analysis. The type of the carbonized two imide determines the type of guanidine aluminum products - the main product of the reaction is the guanidine aluminum compound or the single guanidine aluminum compound. When we choose the starting material to carbonate the two imide to CyN=C=NPh, we can separate two kinds of guanidine aluminum compounds 2C and 2G from the reaction solution, and choose the starting material to carbonization two sub. When amine is CyN=C=NCy or PhN=C=NAr, only one of the guanidine aluminum compound,.2., can choose different single guanidine aluminum compounds and oxygen, carbonized two imide and water. The reaction of guanidine aluminum compound and oxygen reaction synthesized five two poly (two oxygen bridge) guanidine aluminum compound [LAlMe (3a-3e)]_2 (3a-3e). L is on behalf of guanidine ligands; the single guanidine aluminum compound and carbonized two imide have synthesized two double guanidine aluminum compounds, [{N (Ph) C (NR) N (Ph) C (NEt_2) N (R)}AlMe_2] (R), and a four core guanidine aluminum compound was separated into the degassed aqueous solution in the reaction solution of the preparation of single guanidine aluminum (?) The formation cause of the unexpected products obtained by the project group, and a amidamidine aluminum compound, similar to the main structure of the four core compounds, (?) (Ar=2,6-Me_2C_6H_3), and the structure of the above compounds are all verified. In addition, the application of different kinds of guanidine aluminum compounds in the catalytic Meerwein-Ponndorf-Verley reaction, of which 2G And 3E has the highest catalytic activity. When the loading amount of the catalyst is 10 mol%, after the reflux of 2 h in the toluene solution, the different kinds of aldehydes and ketones can be converted to the corresponding alcohols with high yield. The highest yield is more than 99%.3. and provides a simple, effective method and thought for the preparation of monoguanidine compounds containing mono anion and the double anion metformin ligand. The complete hydrolysis of the supporting.3g compound for the preparation of guanidine bimetallic compounds can prepare a new type of metformin compound containing a active hydrogen, 4a, with a yield of more than 80%. The reactivity of the metformin compound 4a to the alkyl metal (AlMe, ZnEt_2 and n-BuLi) is simply studied. It is meaningful when TMEDA exists. 4A and n-BuLi react to the formation of a double guanidine lithium compound containing double anion 4D, and 4D can also be obtained by adding aniline lithium and corresponding carbonated two imide. In addition, we have also studied the addition reaction of different carbonated two imides with the lithium salt of aniline, and formed the guanidine lithium compound 4e-4g, the structure class of compound 4E and 4f. It is similar to 4D, and the structure of 4G belongs to the ordinary two polyguanidine lithium compound. The study shows that the types of guanidine lithium compounds and the reaction materials are related to the group of N atoms connected in the two imide.
【学位授予单位】：山西大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4
[Abstract]:Guanidine ligands have good spatial coordination properties and can form guanidine organometallic compounds by bridging and chelating two modes with many metals in the element periodic table. They have an irreplaceable role in the coordination of coordination chemistry, synthetic chemistry, catalysis and stable low oxidation states. The study of the compound started late. The carbonated two imines used in the synthesis of them were single and the synthetic quantity was limited. The properties of these compounds were far from fully mastered. Therefore, the application scope of these compounds was limited. The main content of this kind of compounds is divided into three parts: the first part chooses different kinds of carbonated two imines. A series of different kinds of guanidine aluminum compounds were synthesized by traditional methods; the second part made a preliminary study on the reactivity of single guanidine aluminum compound and oxygen, carbonated two imide and water, and tried to use various guanidine aluminum compounds as the former catalyst in the Meerwein-Ponndorf-Verley (MPV) reaction; third parts. A new kind of guanidine ligands was synthesized, and the reactivity of this ligand and alkyl metals was studied. Three guanidine metal compounds were formed, including a double nucleate lithium compound containing double negative ions. In addition, a series of guanidine lithium containing double negative ions was obtained by the reaction of lithium salt and carbon two imide in primary amine. The compound provides support for the preparation of multi nucleated guanidine aluminum compounds in the next step. The specific contents are as follows: 1. seven new mononuclear aluminum compounds are prepared by the common methods of preparing guanidine aluminum, [(Et_2N) C- (NCy) (NPh}_2AlMe] (2C), [Et_2N) C (NPh) (NAr)}_2AlMe] (2D) Ar)}_2AlCl] (2f, Ar=2,6-Me_2C_6H_3), [Et_2N C (NCy) (NPh)}AlMe_2] (2G), [[C_5H_ (C_5H_ (10) N] belong to the guanidine aluminum compound, which are single guanidine aluminum compounds, both of which have obtained single crystal structure and are determined by elemental analysis. The type of the carbonized two imide determines the type of guanidine aluminum products - the main product of the reaction is the guanidine aluminum compound or the single guanidine aluminum compound. When we choose the starting material to carbonate the two imide to CyN=C=NPh, we can separate two kinds of guanidine aluminum compounds 2C and 2G from the reaction solution, and choose the starting material to carbonization two sub. When amine is CyN=C=NCy or PhN=C=NAr, only one of the guanidine aluminum compound,.2., can choose different single guanidine aluminum compounds and oxygen, carbonized two imide and water. The reaction of guanidine aluminum compound and oxygen reaction synthesized five two poly (two oxygen bridge) guanidine aluminum compound [LAlMe (3a-3e)]_2 (3a-3e). L is on behalf of guanidine ligands; the single guanidine aluminum compound and carbonized two imide have synthesized two double guanidine aluminum compounds, [{N (Ph) C (NR) N (Ph) C (NEt_2) N (R)}AlMe_2] (R), and a four core guanidine aluminum compound was separated into the degassed aqueous solution in the reaction solution of the preparation of single guanidine aluminum (?) The formation cause of the unexpected products obtained by the project group, and a amidamidine aluminum compound, similar to the main structure of the four core compounds, (?) (Ar=2,6-Me_2C_6H_3), and the structure of the above compounds are all verified. In addition, the application of different kinds of guanidine aluminum compounds in the catalytic Meerwein-Ponndorf-Verley reaction, of which 2G And 3E has the highest catalytic activity. When the loading amount of the catalyst is 10 mol%, after the reflux of 2 h in the toluene solution, the different kinds of aldehydes and ketones can be converted to the corresponding alcohols with high yield. The highest yield is more than 99%.3. and provides a simple, effective method and thought for the preparation of monoguanidine compounds containing mono anion and the double anion metformin ligand. The complete hydrolysis of the supporting.3g compound for the preparation of guanidine bimetallic compounds can prepare a new type of metformin compound containing a active hydrogen, 4a, with a yield of more than 80%. The reactivity of the metformin compound 4a to the alkyl metal (AlMe, ZnEt_2 and n-BuLi) is simply studied. It is meaningful when TMEDA exists. 4A and n-BuLi react to the formation of a double guanidine lithium compound containing double anion 4D, and 4D can also be obtained by adding aniline lithium and corresponding carbonated two imide. In addition, we have also studied the addition reaction of different carbonated two imides with the lithium salt of aniline, and formed the guanidine lithium compound 4e-4g, the structure class of compound 4E and 4f. It is similar to 4D, and the structure of 4G belongs to the ordinary two polyguanidine lithium compound. The study shows that the types of guanidine lithium compounds and the reaction materials are related to the group of N atoms connected in the two imide.
【学位授予单位】：山西大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4
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