CN102993206B - Method for synthesising tetraphenylporphyrin metal complex via one-step process - Google Patents
Method for synthesising tetraphenylporphyrin metal complex via one-step process Download PDFInfo
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Abstract
本发明公开了一种一步法合成四苯基卟啉金属配合物的方法,包括以下步骤:(1)将金属醋酸盐溶于DMF中,金属醋酸盐:DMF=1g:8~16ml;(2)将反应容器中加入溶剂丙酸,然后按先后顺序依次加入苯甲醛、溶有金属醋酸盐的DMF溶液和用丙酸稀释的吡咯溶液,在120-150℃范围内回流30-120min;其中苯甲醛、吡咯和金属醋酸盐的摩尔比为1:1:0.25~2.5,溶剂丙酸与DMF的体积比为1:1~1:1.5;(3)反应结束后,冷却,除去溶剂,分离,得到产物。该工艺具有使用原料成本低、反应条件温和、操作简单、污染小、环境友好的特点,改变了以往用两步合成金属卟啉的方法,节省了时间,可以制备出更多的四苯基卟啉金属配合物,从而为各种金属卟啉染料应用到染料敏化太阳能电池中提供了更多的可能性。
The invention discloses a method for synthesizing tetraphenylporphyrin metal complexes in one step, comprising the following steps: (1) dissolving metal acetate in DMF, metal acetate: DMF=1g:8~16ml; (2) Add solvent propionic acid to the reaction vessel, then add benzaldehyde, DMF solution dissolved in metal acetate and pyrrole solution diluted with propionic acid in sequence, and reflux at 120-150°C for 30-120min ; Wherein the mol ratio of benzaldehyde, pyrrole and metal acetate is 1:1:0.25~2.5, the volume ratio of solvent propionic acid and DMF is 1:1~1:1.5; (3) After the reaction finishes, cool, remove Solvent, separated to give the product. The process has the characteristics of low cost of raw materials, mild reaction conditions, simple operation, less pollution, and environmental friendliness. It changes the previous method of synthesizing metalloporphyrins in two steps, saves time, and can prepare more tetraphenylporphyrins. Porphyrin metal complexes, thus providing more possibilities for the application of various metal porphyrin dyes in dye-sensitized solar cells.
Description
技术领域technical field
本发明属于合成化学领域,具体涉及一种四苯基卟啉金属配合物的合成方法。The invention belongs to the field of synthetic chemistry, and in particular relates to a synthesis method of a tetraphenylporphyrin metal complex.
背景技术Background technique
卟啉是一种重要的有机化合物,被用来合成各种农药、医药、高级染料以及各种功能材料。卟啉类化合物具有刚性为主兼有柔性的大环共轭结构,具有一定的芳香性,稳定性好,光谱响应宽,因而有广泛的用途。金属卟啉化合物在医学、生物学、催化、材料等方面发挥着重要的作用,引起了人们的广泛兴趣,并存在巨大的应用潜力。四苯基卟啉金属配合物是卟啉类太阳能电池敏化剂的中间体,可用来合成更多结构的卟啉类染料敏化剂,从而为其应用到染料敏化太阳能电池中提供了更多的可能性。Porphyrin is an important organic compound, which is used to synthesize various pesticides, medicines, advanced dyes and various functional materials. Porphyrins have a macrocyclic conjugated structure with both rigidity and flexibility, certain aromaticity, good stability, and wide spectral response, so they have a wide range of uses. Metalloporphyrin compounds play an important role in medicine, biology, catalysis, materials, etc., which have aroused widespread interest and have great application potential. Tetraphenylporphyrin metal complexes are intermediates of porphyrin-based solar cell sensitizers, which can be used to synthesize porphyrin-based dye sensitizers with more structures, thus providing more opportunities for their application in dye-sensitized solar cells. many possibilities.
四苯基卟啉金属配合物的结构如下:The structure of the tetraphenylporphyrin metal complex is as follows:
Adler(J.Am.Chem.Soc.,1964,84(15):3145—3149)报道了一种四苯基卟啉金属配合物的合成方法,第一步用吡咯和苯甲醛在丙酸作溶剂的条件下反应首先生成四苯基卟啉,第二步在氯仿作溶剂的条件下再与金属盐反应生成金属四苯基卟啉。这种方法产率很低,第一步只有15%左右,第二步在80%左右,两步反应总产率只有12%左右;而且该方法反应过程复杂,反应时间较长,不易操作。Adler (J.Am.Chem.Soc., 1964,84(15):3145-3149) reported a synthetic method of tetraphenylporphyrin metal complexes, the first step using pyrrole and benzaldehyde in propionic acid Under the condition of solvent, the reaction first generates tetraphenylporphyrin, and in the second step, under the condition of chloroform as solvent, it reacts with metal salt to generate metal tetraphenylporphyrin. This method yield is very low, the first step has only about 15%, the second step is about 80%, and the total yield of the two-step reaction has only about 12%; and the method has complicated reaction process, long reaction time, and is difficult to operate.
发明内容Contents of the invention
本发明的目的是为克服上述现有技术的不足,提供一种一步法合成四苯基卟啉金属配合物的方法,使得两步合成金属卟啉的方法变成一步合成,节省了时间,提高了产率,更易于操作。The purpose of the present invention is to overcome above-mentioned deficiencies in the prior art, provide a kind of method for synthesizing tetraphenylporphyrin metal complex in one step, make the method for synthesizing metalloporphyrin in two steps become one-step synthesis, save time, improve Improved productivity and easier operation.
为实现上述目的,本发明采用下述技术方案:To achieve the above object, the present invention adopts the following technical solutions:
一种一步法合成四苯基卟啉金属配合物的方法,包括以下步骤:A method for synthesizing tetraphenylporphyrin metal complexes in one step, comprising the following steps:
(1)将金属醋酸盐溶于DMF(N,N-二甲基甲酰胺)中,金属醋酸盐:DMF=1g:8~16ml;(1) Dissolve metal acetate in DMF (N,N-dimethylformamide), metal acetate: DMF=1g: 8~16ml;
(2)首先将反应容器中加入溶剂丙酸,然后按先后顺序依次加入苯甲醛、溶有金属醋酸盐的DMF溶液和用丙酸稀释的吡咯溶液,在120-150℃范围内回流30-120min;其中苯甲醛、吡咯和金属醋酸盐的摩尔比为1:1:0.25~2.5,溶剂丙酸与DMF的体积比为1:1~1:1.5;(2) First add solvent propionic acid into the reaction vessel, then add benzaldehyde, DMF solution dissolved in metal acetate and pyrrole solution diluted with propionic acid in sequence, and reflux at 120-150°C for 30- 120min; wherein the molar ratio of benzaldehyde, pyrrole and metal acetate is 1:1:0.25~2.5, and the volume ratio of solvent propionic acid to DMF is 1:1~1:1.5;
(3)反应结束后,冷却,除去溶剂,用硅胶柱进行层板分离,得到产物。(3) After the reaction is completed, cool down, remove the solvent, and perform layer separation with a silica gel column to obtain the product.
所述用于稀释吡咯的丙酸与吡咯的体积比为:3:1~10:1。The volume ratio of the propionic acid used to dilute the pyrrole to the pyrrole is: 3:1-10:1.
所述金属醋酸盐为醋酸锌、醋酸铜或醋酸镍。The metal acetate is zinc acetate, copper acetate or nickel acetate.
所述步骤(3)中除去溶剂的步骤为:将冷却后的反应液倒入水中,产生沉淀后再进行抽滤,取滤渣。The step of removing the solvent in the step (3) is as follows: pour the cooled reaction liquid into water, after precipitation occurs, perform suction filtration, and take the filter residue.
所述步骤(3)中层板分离的步骤为:将除去溶剂后的物质经真空干燥后溶于氯仿,采用硅胶为固定相、氯仿为洗脱剂进行干法过柱,收集第二层紫红色带,浓缩,干燥,得到紫红固体粉末即为产物。The step of separating the middle plate in the step (3) is as follows: the substance after removing the solvent is vacuum-dried and then dissolved in chloroform, using silica gel as the stationary phase and chloroform as the eluent to carry out dry-passing through the column, and collecting the second layer of purple-red strip, concentrated and dried to obtain a purple solid powder as the product.
在步骤(2)反应前还包括以下步骤:在115℃下回流吡咯,得到无色的溶液,避光保存。The following step is also included before the step (2) reaction: reflux pyrrole at 115° C. to obtain a colorless solution, and store it away from light.
所述步骤(2)的具体步骤是:在反应容器中加入溶剂丙酸,然后加入苯甲醛,搅拌,在120-150℃下回流,待温度稳定后,用恒压滴液漏斗滴入溶有金属醋酸盐的DMF溶液,再用胶头滴管缓慢加入溶有吡咯的丙酸溶液,反应物全部加完后,反应30-120min。The specific steps of the step (2) are as follows: add solvent propionic acid into the reaction vessel, then add benzaldehyde, stir, and reflux at 120-150°C. After the temperature is stable, use a constant pressure dropping funnel to drop the dissolved DMF solution of metal acetate, then slowly add pyrrole-dissolved propionic acid solution with a rubber dropper, after all the reactants are added, react for 30-120min.
所述回流温度为140℃。The reflux temperature is 140°C.
所述反应时间为90min。The reaction time is 90min.
本发明的反应式为:Reaction formula of the present invention is:
其中M可以为锌、铜、镍等金属元素。Wherein M can be metal elements such as zinc, copper, nickel, etc.
本发明中,(1)由于金属醋酸盐不溶于原有溶剂丙酸,将金属盐溶于与丙酸沸点相近的DMF溶液中。(2)由于将溶有金属盐的DMF溶液加入丙酸时,加到一定量后金属盐会析出,实验后发现丙酸与DMF的比例范围大约为1:1~1:1.5时较合适。(3)在反应过程中,各种反应物加入的先后顺序依次为苯甲醛、溶有金属盐的DMF溶液,丙酸稀释的吡咯溶液,这样的加入顺序可以有效地防止吡咯与苯甲醛合成其他形式的多聚物,减少目标产物的产量损失。(4)由于黑色固体在氯仿中溶解所需的溶剂较多,不适于湿法过柱,故本发明使用干法上柱,能更有效地减少产物的损失。In the present invention, (1) since metal acetate is insoluble in the original solvent propionic acid, the metal salt is dissolved in a DMF solution with a boiling point close to that of propionic acid. (2) Since when the DMF solution dissolved with metal salt is added to propionic acid, the metal salt will precipitate after adding a certain amount. After the experiment, it is found that the ratio of propionic acid to DMF is about 1:1~1:1.5. (3) During the reaction process, the order of adding various reactants is benzaldehyde, DMF solution dissolved in metal salt, and pyrrole solution diluted with propionic acid. This order of addition can effectively prevent pyrrole and benzaldehyde from synthesizing other form of polymers, reducing the yield loss of the target product. (4) Since the black solid needs more solvents to dissolve in chloroform, it is not suitable for wet column loading, so the present invention uses dry column loading, which can more effectively reduce the loss of products.
本发明在制备的过程中将金属盐溶于DMF中后直接加入反应体系,一步反应直接获得四苯基卟啉金属配合物。该工艺具有(1)使用原料廉价易得,可以降低成本,原料毒性小,对人体伤害较小;(2)反应条件温和、操作简单、节省时间;(3)生产污染小、对环境友。本发明改变了以往用两步合成金属卟啉的方法,节省了时间,可以制备出更多的四苯基卟啉金属配合物,从而为各种金属卟啉染料应用到染料敏化太阳能电池中提供了更多的可能性。In the preparation process of the present invention, the metal salt is dissolved in DMF and then directly added to the reaction system, and the tetraphenylporphyrin metal complex is directly obtained through one-step reaction. The process has (1) the use of cheap and easy-to-obtain raw materials, which can reduce costs, and the raw materials are less toxic and less harmful to the human body; (2) the reaction conditions are mild, the operation is simple, and time is saved; (3) the production pollution is small and friendly to the environment. The present invention changes the previous two-step method for synthesizing metalloporphyrins, saves time, and can prepare more tetraphenylporphyrin metal complexes, so that various metalloporphyrin dyes can be applied to dye-sensitized solar cells Provides more possibilities.
附图说明Description of drawings
图1是实施例1中的合成的四苯基卟啉锌的核磁共振图。Fig. 1 is the nuclear magnetic resonance figure of the synthetic zinc tetraphenylporphyrin in embodiment 1.
图2是实施例1中合成的四苯基卟啉锌的局部谱图。Fig. 2 is the partial spectrogram of the zinc tetraphenylporphyrin synthesized in embodiment 1.
具体实施方式Detailed ways
下面通过具体实例对本发明进行进一步的阐述,应该说明的是,下述说明仅是为了解释本发明,并不对其内容进行限定。The present invention will be further elaborated below through specific examples. It should be noted that the following descriptions are only for explaining the present invention, and do not limit its content.
实施例1:Example 1:
第一步:由于吡咯长期放置在在空气中易被氧化,故首先在115℃下回流吡咯,得到无色的溶液,避光保存,量取0.68ml的吡咯倒入3.5ml的丙酸中,摇匀,以待使用。Step 1: Since pyrrole is easily oxidized when placed in the air for a long time, first reflux pyrrole at 115°C to obtain a colorless solution and store it in the dark. Measure 0.68ml of pyrrole and pour it into 3.5ml of propionic acid. Shake well and ready to use.
第二步:称取2.9g醋酸锌,溶于35ml的DMF溶液中,搅拌使其完全溶解,并将其倒入恒压滴液漏斗中,以待使用。Step 2: Weigh 2.9g of zinc acetate, dissolve it in 35ml of DMF solution, stir to dissolve it completely, and pour it into a constant pressure dropping funnel for use.
第三步:在100ml的三颈烧瓶中加入35ml的丙酸,1ml的苯甲醛,搅拌,在140℃下回流,待温度稳定后,用恒压滴液漏斗滴入溶有2.9g醋酸锌的DMF的溶液35ml,再用胶头滴管缓慢加入溶有0.65ml吡咯的丙酸溶液,反应物全部加完后,反应90min。Step 3: Add 35ml of propionic acid and 1ml of benzaldehyde into a 100ml three-necked flask, stir, and reflux at 140°C. After the temperature is stable, drop in 2.9g of zinc acetate dissolved in 35ml of DMF solution, then slowly add propionic acid solution dissolved in 0.65ml of pyrrole with a rubber dropper, and react for 90min after all the reactants have been added.
第四步:反应结束后,冷却,将产品倒入大约500ml水中,出现大量黑色固体,抽滤,将滤渣真空干燥。Step 4: After the reaction, cool down, pour the product into about 500ml of water, a large amount of black solid appears, filter with suction, and dry the filter residue in vacuum.
第五步:将产品溶于氯仿,然后加入硅胶,采用干法过柱,用硅胶为固定相,氯仿作为洗脱剂,收集第二层紫红色带,浓缩,干燥,得到紫色固体粉末0.36g,产率25%。Step 5: Dissolve the product in chloroform, then add silica gel, pass through the column by dry method, use silica gel as the stationary phase, and chloroform as the eluent, collect the second layer of purple-red band, concentrate, and dry to obtain 0.36g of purple solid powder , yield 25%.
实施例2:Example 2:
与实施例1相同,但是第二步中的醋酸锌改为醋酸铜,并且丙酸与溶有醋酸铜的DMF溶液的体积比为1:1.2,每克醋酸铜溶于15mlDMF溶液中,反应得到紫色固体粉末0.22g,产率为15%。Same as Example 1, but the zinc acetate in the second step changes copper acetate into, and the volume ratio of propionic acid and the DMF solution that is dissolved with copper acetate is 1:1.2, and every gram of copper acetate is dissolved in 15mlDMF solution, and reaction obtains Purple solid powder 0.22g, yield 15%.
实施例3:Example 3:
与实施例1相同,但是第二步中的醋酸锌改为醋酸镍,并且丙酸与溶有醋酸镍的DMF的溶液的体积比为1:1.5,每克醋酸镍溶于16mlDMF溶液中,反应得到紫色固体粉末0.18g,产率为12%。Same as Example 1, but the zinc acetate in the second step changes nickel acetate into, and the volume ratio of propionic acid and the solution of the DMF that is dissolved with nickel acetate is 1:1.5, every gram of nickel acetate is dissolved in 16mlDMF solution, reaction Obtained 0.18 g of purple solid powder with a yield of 12%.
注意:醋酸铜和醋酸镍在DMF中的溶解度不是很大,要将金属盐研磨成粉末,利于溶解。Note: The solubility of copper acetate and nickel acetate in DMF is not very high, and the metal salt should be ground into powder to facilitate dissolution.
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