胍基金屬（Li和Al）化合物的合成、結(jié)構(gòu)和反應(yīng)性研究
發(fā)布時間：2018-07-15 15:22
【摘要】：胍基配體具有良好的空間可協(xié)調(diào)性能,可以通過橋連和螯合兩種模式同元素周期表中很多金屬形成胍基金屬有機化合物,它們在配位化學(xué)、合成化學(xué)、催化領(lǐng)域及穩(wěn)定低價氧化態(tài)的金屬等方面有著不可替代的重要作用。由于對胍基鋁化合物的研究起步較晚,在合成它們時使用的碳化二亞胺種類單一,合成數(shù)量有限,其性質(zhì)遠(yuǎn)遠(yuǎn)沒有達(dá)到完全掌握的程度,因此目前這類化合物的應(yīng)用范圍也受到限制。本論文的主要內(nèi)容分為三部分:第一部分選擇不同種類的碳化二亞胺,采用傳統(tǒng)的方法合成了一系列不同種類的胍基鋁化合物;第二部分對單胍基鋁化合物和氧氣、碳化二亞胺及水的反應(yīng)性做了初步的研究,并嘗試使用各類胍基鋁化合物作為前催化劑在Meerwein-Ponndorf-Verley(MPV)反應(yīng)中進(jìn)行了應(yīng)用;第三部分合成了一種新的雙胍基配體,對這種配體和烷基金屬的反應(yīng)性進(jìn)行了研究,生成了三種胍基金屬化合物,包括一種雙核的含雙負(fù)離子的雙胍基鋰化合物。另外,我們通過伯胺的鋰鹽和碳二亞胺反應(yīng)也得到了一系列含雙負(fù)離子的胍基鋰化合物,為下一步制備多核的雙胍基鋁化合物提供了支撐。具體工作內(nèi)容如下:1.通過制備胍基鋁的常用方法制得了七個新的單核鋁化合物,[{(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屬于雙胍基鋁化合物,2g-2i屬于單胍基鋁化合物,它們均獲得了單晶結(jié)構(gòu),且經(jīng)過NMR和元素分析的測定。研究表明,起始原料碳化二亞胺的種類決定胍基鋁產(chǎn)物的類型-反應(yīng)的主要產(chǎn)物為雙胍基鋁化合物還是單胍基鋁化合物。當(dāng)我們選擇的起始原料碳化二亞胺為CyN=C=NPh時,可以從反應(yīng)溶液中同時分離出了兩種胍基鋁化合物2c和2g,選擇起始原料碳化二亞胺為CyN=C=NCy或者PhN=C=NAr時,僅能得到其中一種胍基鋁化合物。2.選擇不同的單胍基鋁化合物分別和氧氣、碳化二亞胺及水進(jìn)行了反應(yīng)性的初步研究。單胍基鋁化合物和氧氣反應(yīng)合成了五個二聚的氧橋連的胍基鋁化合物[LAlMe(μ-OMe)]_2(3a-3e,L代表胍基配體);單胍基鋁化合物和碳化二亞胺反應(yīng)合成了兩個雙胍基鋁化合物,[{N(Ph)C(NR)N(Ph)C(NEt_2)N(R)}AlMe_2](R=Cy,3f;R=2,6-Me_2C_6H_3,3g);在制備單胍基鋁的反應(yīng)溶液中通入脫氣的含水溶劑后分離得到一個四核的胍基鋁化合物,(?)(驗證了課題組前期得到的意外產(chǎn)物的形成原因),和同上述四核化合物主體結(jié)構(gòu)相似的一個脒基鋁化合物,(?)(Ar=2,6-Me_2C_6H_3),且以上化合物的結(jié)構(gòu)均得到驗證。另外,嘗試不同種類的胍基鋁化合物在催化Meerwein-Ponndorf-Verley反應(yīng)中的應(yīng)用,其中2g和3e的催化活性最高。當(dāng)催化劑的加載量為10 mol%,在甲苯溶液中回流2 h后,不同種類的醛、酮化合物可以高產(chǎn)率地轉(zhuǎn)化為相應(yīng)的醇,最高產(chǎn)率大于99%。3.提供了簡單、有效的制備含單陰離子的雙胍化合物和含雙陰離子雙胍配體的方法和思路,為制備胍基雙金屬化合物提供了支撐。3g化合物的完全水解可以制備一種新的含一個活潑氫的雙胍化合物4a,產(chǎn)率可以達(dá)到80%以上。對該雙胍化合物4a同烷基金屬(AlMe、ZnEt_2和n-BuLi)的反應(yīng)性進(jìn)行了簡單的研究。有意義的是,當(dāng)TMEDA存在時4a和n-BuLi反應(yīng)生成了一種含雙陰離子的雙胍基鋰化合物4d,4d也可以通過苯胺鋰化和相應(yīng)的碳化二亞胺加成得到。另外,我們也對苯胺的鋰鹽同不同碳化二亞胺加成反應(yīng)進(jìn)行了研究,生成了胍基鋰化合物4e-4g,其中化合物4e和4f的結(jié)構(gòu)類似于4d,而4g的結(jié)構(gòu)屬于普通的二聚單胍基鋰化合物。研究表明,胍基鋰化合物的種類和反應(yīng)原料碳化二亞胺中N原子上連接的基團(tuán)有關(guān)。
[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.
【學(xué)位授予單位】：山西大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：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.
【學(xué)位授予單位】：山西大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O641.4
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