CN1068811A - 一步法低热固相反应合成金属盐及配合物的方法 - Google Patents
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种一步法低热固相反应合成金属盐及配合物
方法,该方法不需用溶剂,使两种固态反应直接在低
热温度下进行反应制备纯净的过渡金属或过渡后金
属的有机酸盐或配合物的方法。如将80-100目的
醋酸铜(或氢氧化铜)与甘氯酸按1∶2摩尔比在室温
下充分碾磨混合均匀,静置1小时,用乙醇和***各
淋洗一次,干燥后得反式(或顺式)甘氨酸铜,产率
90%(或92%)。
Description
本发明是一种在低热温度用固-固相反应制备过渡金属或过渡后金属的盐或配合物的方法。
本发明前制取过渡金属或过渡后金属的盐或配合物的方法都是在液相或固-液相中起化学反应,并且认为在室温或低热条件下固-固相反应不能进行或只在表面进行反应,因此得不到纯净化合物。
液相反应制备上述化合物需要大量的溶剂,因而回收溶剂要消耗大量的能量,生产步骤多,设备利用率低,生产周期长,还会造成对环境污染。
本发明的目的在于提供一种不需要溶剂,在低热温度下,使固相反应物直接反应制备纯净的过渡金属或过渡后金属的有机酸盐或配合物的方法。
本发明的技术方案是:将两种固相反应物以化学计量混合,在室温至100℃,碾磨均匀,静置数小时使反应完全,即得纯净的所需的过渡金属或过渡后金属的盐或配合物。
本发明的具体技术方案是:将过渡金属或过渡后金属(如Mn、Fe、Co、Ni、Cu、Zn、Pb等)的醋酸盐、或氢氧化物与有机羧酸(如草酸、丙二酸、丁二酸、水杨酸、苯甲酸、柠檬酸、酒石酸、氨基酸等)以化学计量的比例混合,在室温至100℃,碾磨均匀,静置,待反应完全后,即得纯净的有机羧酸盐,若有需要,也可用少量溶剂淋洗或真空干燥除去醋酸,以保证得到纯净的化合物。
或者将过渡金属离子或过渡后金属离子的无机盐与含有N、O、S、P等原子的配体(如席夫碱、醛酮肟、有机胺、有机硫化物等)以化学计量的比例混合,在室温至100℃,碾磨均匀,静置,待反应完全后,根据需要,用少量有机溶剂淋洗,干燥后即得纯净的所需的过渡金属或过渡后金属配合物。
本发明是在分析比较了配位化合物、无机和有机化合物的结构和化学键的性质后提出的,考虑到配位化合物容易形成各种类型的晶体点缺陷,这为固相反应创造了条件,当生成的产物有更大的热力学稳定性,或生成的产物中含有挥发性物质能使反应进行到底时,用固-固相反应就有其很大的优越性。
本发明的特点在于使两个固态的反应物在室温或低热温度(100℃以下)直接进行固相反应,得到高产率的纯净反应产物。本发明方法与液相反应方法相比,有着明显的优越性。它不仅产品纯度好,得率高,而且生产步骤少,生产设备简单,设备利用率高,生产周期短,节约了大量溶剂,大大降低能量消耗,也减少了对环境的污染。
以下为本发明的实施例。
一、醋酸盐与有机羧酸的反应
将80-100目的醋酸锌与草酸按1∶1摩尔比在室温下混合均匀,碾磨10分钟,静置反应1小时,产物用少量乙醇淋洗一次,再用***淋洗一次,即得到纯净的草酸锌(ZnC2O4·2H2O)得率为66.0%,其元素分析数据如下:
元素 | C% | H% | Zn% | |
2nC2O4·2H2O | 计算值实验值 | 12.6713.22 | 2.112.08 | 34.5934.87 |
用相同的方法制备了其他的羧酸锌,其结果见表1。
用相同的方法制备了柠檬酸盐,其结果见表1。
二、氢氧化铜与氨基酸的反应
1、将80-100目的新制备的Cu(OH)2与甘氨酸按1∶2摩尔比在室温下充分碾磨混合均匀,固相反应很快进行。静置1小时,使反应完全,用乙醇和***各淋洗一次,干燥后得顺式甘氨酸铜,产率92%其元素分析数据如下:
元素 | C% | H% | N% | Cu% | |
Cu(NH2CH2CO2)2·H2O | 计算值实验值 | 20.9820.91 | 4.304.39 | 12.3212.20 | 27.5127.62 |
2、将80-100目的醋酸铜与甘氨酸按1∶2摩尔比在室温下充分碾磨混合均匀,静置1小时,用乙醇和***各淋洗一次,干燥后得反式甘氨酸铜,产率90%。
用相同的方法制备了其它反式氨基酸铜,其结果见表2。
三、过渡金属或过渡后金属醋酸盐与配体的反应:
1、将80-100目的醋酸铜与8-羟基喹啉(Oxine)按1∶2摩尔比,在室温下混合均匀,碾磨约10分钟,静置1小时,混合物由蓝色转变成绿色,最后变为黄色,产物用少量乙醇、丙酮各淋洗一次,干燥后,得产物Cu(C9H6NO)2,产率为84.5%。
用相同的方法制备了其他金属的8-羟基喹啉配合物,其结果见表3。
2、将80-100目的醋酸铜与席夫碱均匀混合,在室温下碾磨10分钟,静置1小时,产物用少量乙醇和丙酮各淋洗一次,干燥后得产物,结果见表4。
3、将80-100目的醋酸镍与水杨醛肟按1∶2摩尔比均匀混合,碾磨10分钟,静置1小时,产物用少量乙醇淋洗一次,得二水杨醛肟合镍〔Ni(C7H6NO2)2〕,产率99%。
4、将80-100目的醋酸铜与2,4-二羟基苯甲醛以1∶1摩尔比均匀混合,碾磨10分钟,静置1小时后,产物用少量乙醇和丙酮各淋洗一次,得2,4-二羟基苯甲醛铜,产率80%。
四、过渡金属或过渡后金属无机盐与配体的反应:
1、将80-100目的NiCl2与菲萝啉按1∶3摩尔比碾磨混合均匀,在40℃温度下静置3小时,反应体系由淡绿色变为银灰色,再逐渐变为粉红色,得氯化三菲萝啉合镍〔Ni(Phen)3Cl2〕产率85%。
用相同方法制备了氯化三菲萝啉合铜和铁。
2、将80-100目的氯化银与三苯基膦以1∶1摩尔比混合,碾磨均匀,在100℃下反应10小时,产物用乙醇洗涤,得簇状化合物〔AgClPPh3〕4,转化率为80%。
3、将80-100目氯化铜(CuCl2·2H2O)与铁***〔K4〔Fe(CN)6〕2H2O〕以2∶1摩尔比混合,碾磨均匀,产物由淡绿转变为红褐色,用少量水淋洗,转化率为85%。
Claims (5)
1、一种在低热温度用固-固相反应制备过渡金属或过渡后金属有机酸盐或配合物的方法,其特征是将固态的过渡金属或过渡后金属的氢氧化物或盐与固态的有机酸或配体以化学计量混合,在低热温度。碾磨均匀,静置使反应完全,即得所需的过渡金属或过渡后金属有机酸盐或配合物。
2、根据权利要求1所述的制备方法,其特征是作为原料的过渡金属或过渡后金属的盐可以是有机酸盐或无机酸盐。
3、根据权利要求1所述的制备方法,其特征是作为原料的有机酸可以是脂肪族羧酸,芳香族羧酸或氨基酸。
4、根据权利要求1所述的制备方法,其特征是作为原料的配体可以是含氮、氧、硫、磷等原子的配体化合物,如席夫碱、醛酮肟、有机胺、有机硫化合物、有机膦等。
5、根据权利要求1所述的制备方法,其特征是反应在室温至100℃进行。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101139299B (zh) * | 2007-09-06 | 2010-07-14 | 广州天科生物科技有限公司 | 球磨固相制备铜、锌甘氨酸配合物的方法 |
CN101811919A (zh) * | 2010-04-27 | 2010-08-25 | 哈尔滨理工大学 | 一种无溶剂法制备氨基酸席夫碱金属络合物的方法 |
DE102011011924A1 (de) | 2011-02-17 | 2012-08-23 | Isf Gmbh | Verfahren zur Herstellung von Aminosäure-Chelat-Verbindungen, Aminosäure-Chelat-Verbindungen und Verwendung von Aminosäure-Chelat-Verbindungen |
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1992
- 1992-01-27 CN CN92107282.1A patent/CN1068811A/zh active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101139299B (zh) * | 2007-09-06 | 2010-07-14 | 广州天科生物科技有限公司 | 球磨固相制备铜、锌甘氨酸配合物的方法 |
CN101811919A (zh) * | 2010-04-27 | 2010-08-25 | 哈尔滨理工大学 | 一种无溶剂法制备氨基酸席夫碱金属络合物的方法 |
CN101811919B (zh) * | 2010-04-27 | 2012-07-25 | 哈尔滨理工大学 | 一种无溶剂法制备氨基酸席夫碱金属络合物的方法 |
DE102011011924A1 (de) | 2011-02-17 | 2012-08-23 | Isf Gmbh | Verfahren zur Herstellung von Aminosäure-Chelat-Verbindungen, Aminosäure-Chelat-Verbindungen und Verwendung von Aminosäure-Chelat-Verbindungen |
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