The method of obtaining ligand complexes of rare earth elements with acetylacetone and cis - or trans-butandiol acid

 

The invention relates to coordination chemistry, more specifically to obtaining ligand complexes of rare earth elements (lanthanides) with acetylacetone and CIS - or TRANS-butandiol acid, namely complex compounds of General formula 1 or LnAA2L, where Ln is a rare earth element ion, AA - acetylacetone, L - anion CIS - or TRANS-butandiol acid

For the development of a secure one-step method of obtaining ligand complexes of rare earth elements with acetylacetone and CIS - or TRANS-butandiol acid, not containing solvate molecules of the solvent, it is proposed to carry out the electrolysis of a solution of acetylacetone, CIS - or TRANS-butandiol acid and lithium perchlorate in acetonitrile, taken in the ratio 2:1:1:500, with rare earth metal anode and an inert cathode at a potential of the anode in the range of 0,5-1, using a single semiconductor diode, connected in series with the cell to create an asymmetric alternating current. The resulting electrolysis precipitate was separated, washed with absolute alcohol and dried. The technical result consists in the fact that the compounds can b iational resistance, that allows to apply them to solve problems of space science. 1 Il.

The invention relates to coordination chemistry, more specifically to obtaining ligand complexes of rare earth elements (lanthanides) with acetylacetone and CIS - or TRANS-butandiol acid, widely used as raw material components for polymeric materials with enhanced radiation resistance, allowing you to apply them for solving problems of space science, namely complex compounds of General formula 1 or LnAA2L, where Ln is a rare earth element ion, AA - acetylacetone, L - anion CIS - or TRANS-butandiol acid

A method of obtaining ligand complexes of rare earth elements with-diketonates and unsaturated acids (such as Panyushkin, A. A. Mashtakov, N. N. Books/inch So 28. B. 11. 1.1983), which includes two stages. At first receive-diketonate of lanthanide, interaction-diketone with a slight excess of anhydrous lanthanide chloride and metallic sodium in dioxane at 60C. the second in distilled over nutrie the consistent solution is added dropwise a solution of unsaturated acid in dioxane. To highlight the product is added an excess of distilled hexane and decanted solution. The precipitate is washed with hexane and dried in air.

The closest analogue to the claimed method is (N.In.Akhrimenko, C. T. Panyushkin/Joh. So 64. Century 3. 1994. S. 515), including the dissolution in diethyl ether trihydrateclavulanate of lanthanide followed by filtration of the solution. To the filtered solution is added dropwise polutorakratnyj excess dissolved in ether CIS - or TRANS-butandiol acid. The obtained compound decanted hexane, and the solution is filtered. The precipitate is washed with hexane and air-dried. The complex compound has a composition LnAA2LH2O.

The disadvantages of the prototype include its complexity, which is caused by dvustadiinomu process to the final product, as well as the need to use hexane extraction, which is toxic and flammable substance. The disadvantages include the complexity of the process of obtaining complex compounds, which consists in the need for decanting for separation of compounds in solid form. In addition, the resulting compound contains solvate water molecules, removal is her invention is the development of the one safe method of obtaining ligand complex compounds of lanthanides with acetylacetone and CIS - or TRANS-butandiol acid, not containing solvate molecules of solvent.

To solve the technical task proposed receiving ligand complex compounds of rare earth elements with acetylacetone and fumaric or maleic acid of General formula 1 to carry out the electrolysis of a solution of acetylacetone, CIS - or TRANS-butandiol acid and lithium perchlorate in acetonitrile, taken in the ratio 2:1:1:500, with rare earth metal anode and an inert cathode at a potential of the anode in the range of 0,5-1, using a single semiconductor diode, connected in series with the cell to create an asymmetric alternating current. The resulting electrolysis precipitate was separated, washed with absolute alcohol and dried.

The proposed method of obtaining differs from the closest analogue that allows you to obtain the compounds described by General formula 1 by electrochemical method in one stage, then there is not need to get-diketonate of lanthanoid. Upon receipt of these coordination compounds were used anodes of rare-earth metals, acetylacetone, CIS - or TRANS-Buendia acid, and as a background electrolyte per the ale anode 0.5 to 1 C. The use of acetonitrile allows to avoid the formation of solvated complexes. Used the ratio of the initial reagents, allows to obtain a complex compound of a specified structure. Experimentally selected, the potential of the anode of 0.5-1 allows you to select mainly the products corresponding to formula 1. In the synthesis process is simple to manufacture and cheap equipment. A significant advantage is the use for electrolysis asymmetric alternating current generated by including in the circuit in series with the cell semiconductor rectifying diode. Because of this becomes possible continuous synthesis, which is formed on the anode, a dense film of complex compound and preventing further flow of current loses adhesion to the metal electrode and is easily removed as sludge. Drying the obtained product can be performed in vacuum or an inert atmosphere over the North or P2O5.

The drawing shows the circuit used to implement the proposed method of synthesis.

The electrosynthesis ligand complexes of rare earth elements with acetylacetone and CIS - and terasul as a current source adjustable step-down transformer 1 at 220 V, the cell 2 is connected in series to the rectifier diode 3 series KD 202, ammeter 4 100 mA, the voltmeter 5 on a 1-10 Century

The electrolyzer 2 composed of a glass vessel (thermostatted chemical glass (298 K)), in which are placed two electrodes: one of the rare earth metal, the other of platinum or graphite (in the drawing not shown), is filled with electrolyte consisting of a solution of acetylacetone, CIS - or TRANS-butandiol acid and lithium perchlorate in acetonitrile in the ratio 2:1:1:500.

The transformer 1 is set to the minimum output voltage, is included in the circuit of AC 220 V, 50 Hz and adjust so that the voltmeter 5 showed the voltage between the electrodes 1-5 In passing through the electrolytic cell 2 current should correspond to the anodic current density of 0.1-0.5 A/cm2. The resulting electrolysis product in the form of sediment on the bottom of the glass is separated, washed with absolute alcohol and dried under vacuum over P2O5.

Example 1. Bis(acetylacetonato)maleinate holmium.

The synthesis was performed at room temperature (298 K). The anode is made of metal holmium purity of 99.99%. The ratio of the components of the working solution containing acetylaceton the%. Drying was carried out in a vacuum desiccator over P2O5.

Calculated, %: But 35,10, 30,65, N 3,62, 30,78.

Found, %: But 35,12, 30,48, N 3,61, 30,75.

The compounds of formula C4H17O8Ho

IR spectrum (liquid paraffin): 1710, 1645, 1570, 1540 cm-1.

The nature of the IR spectra of the bis(acetylacetonato)maleinate holmium in absorptionascarboxyl groups can be explained by the fact that the terminal-COOH group CIS-butandiol acid is not involved in intermolecular interactions due to steric hindrance.

Example 2. Bis(acetylacetonato)fumarate holmium.

The synthesis was performed at room temperature (298 K). The anode is made of metal holmium purity of 99.99%. The ratio of the components of the working solution containing acetylacetone, fumaric acid, lithium perchlorate in acetonitrile, corresponds to a 2:1:1:500. The potential of the anode 0.5 V, the current efficiency of 82%. Drying was carried out in a vacuum desiccator over P2O5.

Calculated, %: But 35,10, 30,65, N 3,62, 30,78.

Found, %: But 35,05, 30,78, N 3,72, 30,45.

The compounds of formula C4H17O8Ho

IR spectrum (liquid paraffin): 1688, 1652, 1580, 1541 cm-1.

The nature of the IR spectra of the bis(acetylacetonato)fumarata holmium in the field of absorption is TRANS-butandiol acid can participate in intermolecular interactions.

Proposed one-step secure electrochemical method of synthesis of the ligand of the complex compounds of rare earth elements with acetylacetone and CIS - or TRANS-butandiol acid. The proposed method offers the possibility of obtaining compounds in a single phase, which significantly reduces the cost of the final product; security, which contributes to a further method to obtain the desired product in the industry, in addition, allows to obtain compounds not containing solvate molecules of the solvent.

Claims

The method of obtaining ligand complexes of rare earth elements with acetylacetone and CIS - or TRANS-butandiol acid of General formula 1

where Ln is a rare earth element ion,

characterized in that conduct the electrolysis of a solution containing acetylacetone, CIS - or TRANS-butandiol acid and lithium perchlorate in acetonitrile in the ratio 2:1:1:500, with rare earth metal anode and an inert cathode at a potential of the anode in the range of 0,5-1, using an asymmetric alternating current generated by including in the circuit a single semiconductor the mouth and dried.

 

Same patents:

The invention relates to a method of chemical purification of exhaust gases from sulfur and can be used in power system for treatment and disposal of flue gases of thermal power plants, as well as in the petrochemical industry during the combustion of hydrogen sulfide in Claus furnaces, ferrous and nonferrous metallurgy, coal and chemical industry

The invention relates to a method of chemical purification of exhaust gases from sulfur and can be used in power system for treatment and disposal of flue gases of thermal power plants, as well as in the petrochemical industry during the combustion of hydrogen sulfide in Claus furnaces, ferrous and nonferrous metallurgy, coal and chemical industry
The invention relates to the production of chlorine dioxide, used in particular for disinfection in the purification of drinking and waste water

The invention relates to an improved process for the preparation of cyclohexanol by electrochemical

The invention relates to Sol-gel technologies for Staropromyslovsky of ion exchangers and sorbents on the basis of hydroxide and zirconium oxide, as well as catalysts and powders for plasma spraying and high temperature ceramics based on zirconium dioxide

The invention relates to a method of producing hydrogen, in particular orthovalerate and prevodioca, and device for its implementation

The invention relates to physico-chemical technologies for producing hydrogen and oxygen

The invention relates to physico-chemical technologies, techniques for the production of hydrogen and oxygen, as well as to the field of nuclear energy and can be used for energy released in the fusion reaction occurring in the reactor

The invention relates to metallogenica derivative containing four nitrogen atom of the macrocycle, fused with the pyridine cycle, methods for their preparation and their use in medicine to obtain an image

The invention relates to a method of obtaining new alyuminiiorganicheskikh compounds which may find application as components of catalytic systems in the processes of oligomerization and polymerization of olefin and diene hydrocarbons, and fine organic and ORGANOMETALLIC syntheses
The invention relates to a method for producing salts consisting of a bulky organic cation and bulk organic anion, specifically salts triarylmethyl cations with organoboron anion

The invention relates to the chemistry of organophosphorus compounds with s-R connection, namely to obtain alkyl(phenyl)phosphine-Baranovka complex of the General formula R2PHBH3(1), where R is alkyl or phenyl, which are used as starting substances for the synthesis of water-soluble catalysts used in the production of polymers
The invention relates to a method for producing tert-butylaniline that can be used as a selective reducing agent in aqueous and organic media

The invention relates to a method of obtaining a new alyuminiiorganicheskikh connection, which can be applied in thin organic synthesis, and as acetalization in oligo - and polymerization of Alifanov and conjugated dienes

The invention relates to a method of obtaining new alyuminiiorganicheskikh compounds of General formula

< / BR>
where R is CH3or n-C3H7; R1-n-C6H13or n-C8H17that may find application in thin organic and ORGANOMETALLIC synthesis, as well as socialization in the processes of oligo - and polymerization of olefins and conjugated dienes

The invention relates to methods of producing new aluminum-organic compounds, which can find application in organic and ORGANOMETALLIC synthesis

The invention relates to methods of producing new aluminum-organic compounds, which can find application in organic and ORGANOMETALLIC synthesis
The invention relates to the stabilization of halogenated polymers
Up!