SU690018A1 - Method of preparing methoxocomplexes of copper/11/ - Google Patents

Description

one

The present invention relates to an improved process for the preparation of copper (II) methoxo complexes of the general formula Cu (OCH) L where neither is acetylacetone, acetoacetic ester, salicylic aldehyde, 2-hydroxy acetopheon, propionic acid or 2,4,6-trichlorophenol, which is used in as catalysts for the oxidative polymerization of 2,6-xylenol, the initiation of the polymerization of vinyl monomers, the curing of epoxy compositions in k, as selective catalysts for the hydrolysis and transesterification of complex ethers,

. A method of producing copper (II) methoxo complexes, for example, methox) copper ocarbosilates, provides for two options for their preparation: A — producing copper methoxo-carboxy acids by direct contact of anhydrous copper carboxylate with an equimolar amount of 1 potassium methylate in absolute methanol solution and B - production of methoxo-carboxylates by copper exchange reaction between the preliminarily obtained ethoxo-carboxylate in a solution of absolute ethyl alcohol and an excess amount of absolute methanol 1.

The disadvantage of this method is its multi-stage, since it is first necessary to obtain anhydrous copper carboxylates, and relatively low yields of the target product.

The closest to the described invention to the technical essence and the achieved result is a method of obtaining methoxo-complexes

0 copper, as follows.

Initially, a suitable copper salt (chloride, sulfate or nitrate) and an HL ligand such as (i-diketone, 2-hydroxyacetic phenone or salicylic aldehyde) synthesize the CuL2 complex and dry it. Then, the anhydrous CuLjpacTBO compound is dissolved in absolute methyl alcohol. And is treated with an equimolar amount of potassium hydroxide 2. The yield of the methoxo-complex, depending on the ligand, is 10-70% based on the initial simple copper salt.

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A significant disadvantage of this method is its multi-stage nature, the need for an expansion and dehydration of intermediate compounds of the composition CuLj- and the use of absolute methyl alcohol. In addition. This method is not universal for obtaining copper (II) methoxo-complexes with a wide range of anionic ligands L, and is only suitable for preparing copper-methoxo-complexes (11) on the basis of p-diketones, salicylic aldehyde and 2-oxyacetophenone. The aim of the invention is to simplify the process and increase the yield of the target product. This goal is achieved by the described method of obtaining copper methoxocomplexes (II) of the general formula Cu (OCHg) L, where HL is acetylacetone, acetic ester, salicylic aldehyde, 2-hydroxyacetophenone, propionic acid or 2,4,6-trichlorophenol, by the interaction of the copper salt with a corresponding ligand in a methanol-based medium, characterized in that the methanolic solution of nitrate or perchlorate copper, in the presence of a dehydrating agent, orthoformate, is reacted with a methanol solution of the corresponding ligand containing piperidine as base, with a ratio of copper nitrate or perchlorate and piperidine ligand = 1: 1: 2. The yield of the target product is 70-90%. . A distinctive feature of the method is that a methanol solution of copper nitrate or perchlorate, in the presence of a dehydrating agent, ort formic ether, is subjected to a reaction with a methanol solution with a response ligand containing piperidine as the base, with a ratio of nitrate or copper perchlorate to ligand and piperidine is 1: 1: 2. - Technological methods are as follows. Easily available copper nitrate Cu (NO3) 2 or copper perchlorate Cu {Ceo) 2 eHjO is dehydrated by dissolving in methyl alcohol containing a 1C% molar excess of orthracetate ester based on the amount of water of crystallization, and keeping at room temperature for 24 hours To the resulting solution, a methanol solution is gradually added, containing an equimolar amount of ligand and a double molar volume of piperidon per copper salt. When e; h, the formation of the desired methoxo complex Cu (HCH3) b occurs immediately. The one-step process described can be represented as: С uXz 4-СНз OHi БЫ-2 CjHnTf- - С (ОНз) Ь4 zCsHj uV, where X Се04 or NO. The piperidinium salt which forms is well dissolved in the methyl spin can easily be separated by filtering and washing the precipitate of the methoxo complex with a small amount of methanol. Example 1. Copper (II) metoxo-acetylacetonate. 1.21 g of copper copper nitrate (CICLO), dissolved in 50 ml of methyl alcohol containing 2.8 ml of orthoformate. The solution is kept for 24 hours at room temperature and a solution of 0.51 ml of acetylacetone and 1 ml of piperidine in 20 ml of methanol is gradually added with stirring. A finely crystalline violet precipitate immediately forms, which is filtered off, washed on the filter with methanol 1 and dried in a vacuum desiccator. Obtain 0.8 g (83%) of the product. Found,%: C 37.17; H 5.42; C 32.49. CfiH.oOjCu Calculated: С 37.21; H 5.20; C 32.80. 0.83 mb IR spectrum: ff.-o 556 cm-, 1) s-about 1068 cm. Example 2. Copper (II) methoxalusalicyl aldehyde. 1.85 g of copper Cu perchlorate (Ceo), 6 is dissolved in 50 ml of methyl alcohol containing 5.8 ml of ortoformate ether. The solution is kept for 24 hours at room temperature and a solution of 0.52 ml of salicylic aldehyde and 1 ml of piperidine in 20 ml of methyl alcohol is added to it. A crystalline precipitate of a bright green color is formed immediately, which is filtered and washed on the filter with methanol. Get 0.9 g (85%) of the product. Found,%: C 44.78; H 3.94; C 29.41. CgHeOjCu Calculated,%: C 44.55; H 3.74; C 29.46 .XI elsr 1.46 mb IR spectrum: L), 543 cm--; с-о1051 cm: Example 3. Copper (II) methoxo-propionate. 1.85 g of copper perchlorate CttUCEO) 6H.gO is dissolved in 50 ml of methyl alcohol containing 5.8 ml of orthoformate ether. The solution is kept for 24 hours at room temperature and a solution of 0.37 ml of propionic acid and 1 ml of piperidine in 20 ml of methyl alcohol is added to it. From the resulting bright green solution, 0.7 g (72%) of a blue-green crystalline substance is recovered every other day, which is filtered off, washed with methyl alcohol and dried in a vacuum desiccator. Found,%: C 28.18; H 4.66; C 38.19. C HeOjCu Calculated,%: C 28.66; H 4.81; C 37.91.