CN102584905B - Method for preparing chloromethyl methyl ether ferrocene - Google Patents
Method for preparing chloromethyl methyl ether ferrocene Download PDFInfo
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- CN102584905B CN102584905B CN201110419571.5A CN201110419571A CN102584905B CN 102584905 B CN102584905 B CN 102584905B CN 201110419571 A CN201110419571 A CN 201110419571A CN 102584905 B CN102584905 B CN 102584905B
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- ferrocene
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- hydrogen chloride
- methyl ether
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 12
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 title abstract 4
- 229940061627 chloromethyl methyl ether Drugs 0.000 title abstract 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 14
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011592 zinc chloride Substances 0.000 claims abstract description 12
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 20
- GQXNQHQSPIQKFR-UHFFFAOYSA-N 5-(chloromethyl)cyclopenta-1,3-diene cyclopenta-1,3-diene iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.ClC[c-]1cccc1 GQXNQHQSPIQKFR-UHFFFAOYSA-N 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 238000004809 thin layer chromatography Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010464 Blanc reaction Methods 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- -1 chlorine halides Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005442 molecular electronic Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【技术领域】 【Technical field】
本发明属于化学合成领域，特别涉及一种制备氯甲基二茂铁的方法。The invention belongs to the field of chemical synthesis, in particular to a method for preparing chloromethyl ferrocene.
【背景技术】 【Background technique】
二茂铁的出现在近代化学发展史上具有划时代的意义。而我国对于二茂铁及其衍生物的开发利用研究起步较晚，随着科学技术的进步，二茂铁的特殊作用将逐渐被认识，对其研究将会有新的突破性的进展。可以预料，二茂铁及其衍生物将会在生物科学、染料、医药、分子电子学等领域存在巨大的应用前景，必将日益受到人们的重视。氯甲基二茂铁含活泼的氯的卤化物，可参与众多的化学反应，是一种合成二茂铁衍生物重要的中间体。The appearance of ferrocene has epoch-making significance in the history of modern chemical development. However, the research on the development and utilization of ferrocene and its derivatives started relatively late in China. With the advancement of science and technology, the special role of ferrocene will be gradually recognized, and new breakthroughs will be made in its research. It can be expected that ferrocene and its derivatives will have great application prospects in the fields of biological sciences, dyes, medicine, molecular electronics, etc., and will be increasingly valued by people. Chloromethyl ferrocene contains active chlorine halides, can participate in many chemical reactions, and is an important intermediate for the synthesis of ferrocene derivatives.
【发明内容】 【Content of invention】
本发明的目的是提供一种制备的氯甲基二茂铁方法。The object of this invention is to provide a kind of chloromethyl ferrocene method of preparation.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种制备氯甲基二茂铁的方法，其包括以下步骤：第一步，向反应器中，依次加a mol多聚甲醛，b mol无水氯化锌，d ml浓盐酸，搅拌溶解，加热至60℃并保温；A method for preparing chloromethyl ferrocene, which comprises the following steps: the first step, in the reactor, successively add a mol paraformaldehyde, b mol anhydrous zinc chloride, d ml concentrated hydrochloric acid, stirring and dissolving, Heating to 60°C and keeping warm;
第二步，向反应器中加用乙醇溶解的c mol二茂铁，并通入由浓硫酸和氯化钠产生的干燥氯化氢气体，反应6h后结束，待反应结束后，搅拌冷却至室温，减压蒸馏，干燥，过柱即得氯甲基二茂铁；In the second step, add c mol ferrocene dissolved in ethanol to the reactor, and pass into the dry hydrogen chloride gas produced by the vitriol oil and sodium chloride, finish after the reaction 6h, after the reaction finishes, stir and cool to room temperature, Distill under reduced pressure, dry, and pass through the column to obtain chloromethyl ferrocene;
其中a∶b∶c＝(1.0～1.15)∶(1.0～1.15)∶1，d≥600c。Wherein a:b:c=(1.0～1.15):(1.0～1.15):1, d≥600c.
本发明进一步的改进在于：所述浓盐酸的质量分数为36％。The further improvement of the present invention is that: the mass fraction of the concentrated hydrochloric acid is 36%.
本发明进一步的改进在于：二茂铁加入后进行恒温搅拌。The further improvement of the present invention lies in: constant temperature stirring is carried out after ferrocene is added.
本发明进一步的改进在于：所述a∶b∶c＝1.05∶1.05∶1。A further improvement of the present invention lies in: said a:b:c=1.05:1.05:1.
本发明进一步的改进在于：反应6h后反应结束。The further improvement of the present invention lies in: the reaction ends after 6 hours of reaction.
本发明进一步的改进在于：所述反应器为有回流冷凝管、滴液漏斗的三口烧瓶，所述回流冷凝管接有干燥管。The further improvement of the present invention is that: the reactor is a three-necked flask with a reflux condenser and a dropping funnel, and the reflux condenser is connected with a drying tube.
本发明进一步的改进在于：a∶b＝1∶1。A further improvement of the present invention lies in: a:b=1:1.
本发明进一步的改进在于：所述干燥氯化氢气体由浓硫酸和氯化钠反应制得。The further improvement of the present invention is that: the dry hydrogen chloride gas is produced by reacting concentrated sulfuric acid and sodium chloride.
相对于现有技术，本发明具有以下优点：本发明是一种全新的合成氯甲基二茂铁的方法；通过多聚甲醛，氯化氢和二茂铁在氯化锌的催化下发生blanc氯甲基化反应形成氯甲基二茂铁。Compared with the prior art, the present invention has the following advantages: the present invention is a brand-new method for synthesizing chloromethyl ferrocene; by paraformaldehyde, hydrogen chloride and ferrocene produce blanc chloroform under the catalysis of zinc chloride Sylation reaction to form chloromethylferrocene.
【具体实施方式】 【Detailed ways】
下面结合本发明较佳的具体实施例对本发明作进一步详细说明。The present invention will be further described in detail below in combination with preferred specific embodiments of the present invention.
本发明一种制备氯甲基二茂铁的方法，其化学反应方程式为：A kind of method for preparing chloromethyl ferrocene of the present invention, its chemical reaction equation is:
实施例1Example 1
在带有回流冷凝管(接有干燥管)、滴液漏斗的三口烧瓶中，依次加0.0105mol多聚甲醛、0.0105mol无水氯化锌、6ml浓盐酸，搅拌溶解，加热；当温度至60℃时，加入0.01mol用乙醇溶解的二茂铁，通入由浓硫酸和氯化钠反应产生的干燥氯化氢气体，通过浓硫酸的滴加控制通入气体的量，多余气体用水吸收，恒温搅拌，用薄层色谱检测反应。待反应结束后，搅拌冷却至室温，减压蒸馏，干燥，过柱，干燥制得产品。Add 0.0105mol of paraformaldehyde, 0.0105mol of anhydrous zinc chloride, and 6ml of concentrated hydrochloric acid in sequence in a three-necked flask with a reflux condenser (connected with a drying tube) and a dropping funnel, stir to dissolve, and heat; when the temperature reaches 60 At ℃, add 0.01mol of ferrocene dissolved in ethanol, pass in the dry hydrogen chloride gas produced by the reaction of concentrated sulfuric acid and sodium chloride, control the amount of gas introduced by dropping concentrated sulfuric acid, absorb the excess gas with water, and stir at constant temperature , and the reaction was detected by thin-layer chromatography. After the reaction is finished, stir and cool to room temperature, distill under reduced pressure, dry, pass through the column, and dry to obtain the product.
实施例2Example 2
在带有回流冷凝管(接有干燥管)、滴液漏斗的三口烧瓶中，依次加0.011mol多聚甲醛、0.011mol无水氯化锌、7ml浓盐酸，搅拌溶解，加热；当温度至60℃时，加入0.01mol用乙醇溶解的二茂铁，通入由浓硫酸和氯化钠反应产生的干燥氯化氢气体，通过浓硫酸的滴加控制通入气体的量，多余气体用水吸收，恒温搅拌，用薄层色谱检测反应。待反应结束后，搅拌冷却至室温，减压蒸馏，干燥，过柱，干燥制得产品。Add 0.011mol of paraformaldehyde, 0.011mol of anhydrous zinc chloride, and 7ml of concentrated hydrochloric acid in sequence in a three-neck flask with a reflux condenser (connected with a drying tube) and a dropping funnel, stir to dissolve, and heat; when the temperature reaches 60 At ℃, add 0.01mol of ferrocene dissolved in ethanol, pass in the dry hydrogen chloride gas produced by the reaction of concentrated sulfuric acid and sodium chloride, control the amount of gas introduced by dropping concentrated sulfuric acid, absorb the excess gas with water, and stir at constant temperature , and the reaction was detected by thin-layer chromatography. After the reaction is finished, stir and cool to room temperature, distill under reduced pressure, dry, pass through the column, and dry to obtain the product.
实施例3Example 3
在带有回流冷凝管(接有干燥管)、滴液漏斗的三口烧瓶中，依次加0.0115mol多聚甲醛、0.0115mol无水氯化锌、6ml浓盐酸，搅拌溶解，加热；当温度至60℃时，加入0.01mol用乙醇溶解的二茂铁，通入由浓硫酸和氯化钠反应产生的干燥氯化氢气体，通过浓硫酸的滴加控制通入气体的量，多余气体用水吸收，恒温搅拌，用薄层色谱检测反应。待反应结束后，搅拌冷却至室温，减压蒸馏，干燥，过柱，干燥制得产品。Add 0.0115mol of paraformaldehyde, 0.0115mol of anhydrous zinc chloride, and 6ml of concentrated hydrochloric acid in sequence in a three-neck flask with a reflux condenser (connected with a drying tube) and a dropping funnel, stir to dissolve, and heat; when the temperature reaches 60 At ℃, add 0.01mol of ferrocene dissolved in ethanol, pass in the dry hydrogen chloride gas produced by the reaction of concentrated sulfuric acid and sodium chloride, control the amount of gas introduced by dropping concentrated sulfuric acid, absorb the excess gas with water, and stir at constant temperature , and the reaction was detected by thin-layer chromatography. After the reaction is finished, stir and cool to room temperature, distill under reduced pressure, dry, pass through the column, and dry to obtain the product.
实施例4Example 4
在带有回流冷凝管(接有干燥管)、滴液漏斗的三口烧瓶中，依次加0.0105mol多聚甲醛、0.011mol无水氯化锌、10ml浓盐酸，搅拌溶解，加热；当温度至60℃时，加入0.01mol用乙醇溶解的二茂铁，通入由浓硫酸和氯化钠反应产生的干燥氯化氢气体，通过浓硫酸的滴加控制通入气体的量，多余气体用水吸收，恒温搅拌，用薄层色谱检测反应。待反应结束后，搅拌冷却至室温，减压蒸馏，干燥，过柱，干燥制得产品。Add 0.0105mol of paraformaldehyde, 0.011mol of anhydrous zinc chloride, and 10ml of concentrated hydrochloric acid in sequence in a three-necked flask with a reflux condenser (connected with a drying tube) and a dropping funnel, stir to dissolve, and heat; when the temperature reaches 60 At ℃, add 0.01mol of ferrocene dissolved in ethanol, pass in the dry hydrogen chloride gas produced by the reaction of concentrated sulfuric acid and sodium chloride, control the amount of gas introduced by dropping concentrated sulfuric acid, absorb the excess gas with water, and stir at constant temperature , and the reaction was detected by thin-layer chromatography. After the reaction is finished, stir and cool to room temperature, distill under reduced pressure, dry, pass through the column, and dry to obtain the product.
实施例5Example 5
在带有回流冷凝管(接有干燥管)、滴液漏斗的三口烧瓶中，依次加0.011mol多聚甲醛、0.0105mol无水氯化锌、8ml浓盐酸，搅拌溶解，加热；当温度至60℃时，加入0.01mol用乙醇溶解的二茂铁，通入由浓硫酸和氯化钠反应产生的干燥氯化氢气体，通过浓硫酸的滴加控制通入气体的量，多余气体用水吸收，恒温搅拌，用薄层色谱检测反应。待反应结束后，搅拌冷却至室温，减压蒸馏，干燥，过柱，干燥制得产品。In a three-necked flask with a reflux condenser (connected with a drying tube) and a dropping funnel, add 0.011mol of paraformaldehyde, 0.0105mol of anhydrous zinc chloride, and 8ml of concentrated hydrochloric acid in sequence, stir to dissolve, and heat; when the temperature reaches 60 At ℃, add 0.01mol of ferrocene dissolved in ethanol, pass in the dry hydrogen chloride gas produced by the reaction of concentrated sulfuric acid and sodium chloride, control the amount of gas introduced by dropping concentrated sulfuric acid, absorb the excess gas with water, and stir at constant temperature , and the reaction was detected by thin-layer chromatography. After the reaction is finished, stir and cool to room temperature, distill under reduced pressure, dry, pass through the column, and dry to obtain the product.
本发明一种制备氯甲基二茂铁的方法，通过多聚甲醛，氯化氢和二茂铁在氯化锌的催化下发生blanc氯甲基化反应形成氯甲基二茂铁。The invention discloses a method for preparing chloromethyl ferrocene. The chloromethyl ferrocene is formed through the blanc chloromethylation reaction of paraformaldehyde, hydrogen chloride and ferrocene under the catalysis of zinc chloride.
步骤一中加入浓盐酸和多聚甲醛在加热情况让多聚甲醛进行醛解，以形成blanc氯甲基化反应所需的甲醛；步骤二，加入二茂铁和氯化氢在氯化锌的催化下发生blanc氯甲基化反应，从而形成氯甲基二茂铁。In step one, add concentrated hydrochloric acid and paraformaldehyde and allow paraformaldehyde to carry out aldolysis under heating conditions, to form the required formaldehyde of blanc chloromethylation reaction; Step two, add ferrocene and hydrogen chloride under the catalysis of zinc chloride A blanc chloromethylation reaction occurs to form chloromethylferrocene.
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| CN1341232A (en) * | 1999-02-18 | 2002-03-20 | 日石三菱株式会社 | Electrochemical element |
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| Title |
|---|
| JP特开平11-130706A 1999.05.18 * |
| Tverdokhlebov, V. P.等,.Alkylation of ferrocene by halomethyl ethers. I. Reaction of ferrocene with methyl(chloromethyl)ether.《Zhurnal Organicheskoi Khimii》.1980,第16卷(第1期),第46-49页. * |
| 王涛.4,4’-双氯甲基-联苯的合成研究.《吉林大学硕士学位论文》.2009,第3页. * |
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