Method for preparing nickel (ii) bis-(1-hydroxyethane-1,1-diphosphonate (1-))

FIELD: chemical technology of organophosphorus compounds.

SUBSTANCE: method involves preparing nickel (II) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) by addition 1-hydroxyethane-1,1-diphosphonic acid in the concentration 0.2-4.5 mole/l to an aqueous solution containing nickel (II) in the concentration 0.1-2.0 mole/l and organic solvent mixing with water followed by crystallization of the end substance from the solution. Method provides preparing the pure homogeneous end product with high yield, and utilization of depleted electrolyte in nickel plating representing a toxic waste in galvanic manufacture.

EFFECT: improved preparing method.

11 cl, 1 tbl, 12 ex

 

The invention relates to chemical technology of organic compounds, in particular to a method for producing bis(1-hydroxyethane-1,1-di-phosphonate(1-)) Nickel(II), which is a complex of Nickel(II) with 1-hydroxyethane-1,1-diphosphonic acid CH3S(HE)(RHO3H2)2[C2H8O7P2] the composition of the Ni(C2H7O7P2)2·4H2O. Compound obtained in this way can be used to prepare electrolyte galvanic and chemical Nickel plating, to obtain other compounds of Nickel(II) with 1-hydroxyethane-1,1-diphosphonic acid.

A method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II), Ni(C2H7O7P2)2·2H2O as a result of interaction of Nickel acetate(II) and aqueous solution of disodium salt of 1-hydroxyethane-1,1-di-phosphonic acid (Kogan, VA, masuk A.A., Seifullina SM, Zhakov IV, L. Shkolnikov Complexes 1-hydroxyethylidenediphosphonic acid with Cu2+, Mn2+, Ni2+, Fe3+// Russian journal of inorganic chemistry, 1987, 32, No. 8, s). The disadvantage of this method is that specific conditions for obtaining the target product in the source information is not disclosed.

Closest to the claimed method is a method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel is(II), Ni(C 2H7O7P2)2·4H2O, comprising preparing an aqueous solution containing Nickel(II) and anion 1-hydroxyethane-1,1-diphosphonic acid, the interaction of salts of Nickel(II) and 1-hydroxyethane-1,1-diphosphonic acid in the aquatic environment, the crystallization of the desired product, separating the precipitate from the solution and drying the precipitate (Keshikbaeva KAPYSHEV, Mitrofanova N, Martynenko LI Solid complexions Nickel with oxoethylidene-diphosphonic acid. The collection of articles "the Chemistry of chelating agents and their application". - Kalinin: KGU, 1986, p.85. Keshikbaeva KAPYSHEV Synthesis, properties and structure of complexions of some transition metals (Cu, Ni, Co, Mn, Zn) with oksietilidendifosfonovaya and ethylenediphosphonic acids. Diss.... Kida. chem. Sciences. - M.: Moscow state University, 1988). As a salt of Nickel(II) in the method according to prototype use gidroksicarbonat Nickel(II). The method is based on the following reaction:

Ni(OH)2·NiCO3+4C2H8O7P2→2Ni(C2H7O7P2)2+3H2O+CO2.

The above reaction is carried out by interaction of the primary carbonate Nickel(II) and aqueous solution of 1-hydroxyethane-1,1-diphosphonic acid, taken in a molar ratio of Nickel(II): 1-hydroxyethane-1,1-diphosphonic acid is 1:2, when heated and when the pH value is equal to 1.0. The disadvantage of this method on the prototype of which is the low yield of the target product, due to its high solubility in water, low purity and homogeneity of the target product, due to the peculiarities of the way of its receipt.

In the claimed invention, the aim was to increase the output of bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II), to improve the purity and homogeneity of the target product, to expand the range of materials used to obtain the target product.

The problem is solved in that a method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) includes the preparation of an aqueous solution containing Nickel(II) and anion 1-hydroxyethane-1,1-diphosphonic acid, the interaction of salts of Nickel(II) and 1-hydroxyethane-1,1-diphosphonic acid in the aquatic environment, the crystallization of the desired product, separating the precipitate from the solution and drying the precipitate. New this method is that preparing an aqueous solution with the concentration of Nickel(II) 0.1 to 2.0 mol/l and 1-hydroxyethane-1,1-diphosphonic acid 0.2-4.5 mol/l and to aqueous solution optionally add miscible with water, an organic solvent. As a salt of Nickel(II) it is desirable to use a salt selected from the group consisting of gidroksicarbonata, formate, acetate, chloride, bromide, iodide, sulfate, sulpham, methansulfonate, bansilalpet, chlorate, perchlorate, nitrate, thiocyanate, tetrafluoroborate, hexaf is borosilicate Nickel(II). It is desirable to prepare an aqueous solution containing Nickel(II) and anion 1-hydroxyethane-1,1-diphosphonic acid in a molar ratio, preferably equal to 1.0:(from 1.8 to 4.5). For the preparation of an aqueous solution containing Nickel(II) and anion 1-hydroxyethane-1,1-diphosphonic acid, as the source of Nickel(II) it is desirable to use waste galvanic production - proven Nickel plating electrolyte containing as main components, Nickel chloride, boric acid, or exhaust Nickel plating electrolyte containing as main components, Nickel sulfate, Nickel chloride, boric acid, or exhaust Nickel plating electrolyte containing as main components, Nickel chloride, Nickel acetate, or exhaust Nickel plating electrolyte containing as main components sulpham Nickel, boric acid, or exhaust Nickel plating electrolyte containing as main components sulpham Nickel, Nickel chloride, boric acid, or exhaust Nickel plating electrolyte containing as a main component tetrafluoroborate Nickel, tetrafluoroboric acid, boric acid. As miscible with water, an organic solvent, it is desirable to use a solvent selected from the group consisting of formic acid, acetic acid is you, acetone, acetonitrile, methanol, ethanol, propanol-1, propanol-2,2-methylpropanol-2, dimethyl sulfoxide.

The method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) consists in the preparation of an aqueous solution containing Nickel(II) and anion 1-hydroxyethane-1,1-diphosphonic acid, by dissolving in water soluble salts of Nickel(II), for example chloride, nitrate, sulfate, acetate, and 1-hydroxyethane-1,1-diphosphonic acid or by the reaction of gidroksicarbonata Nickel(II) with 1-hydroxyethane-1,1-diphosphonic acid in the aqueous medium followed by addition to the specified aqueous solution, miscible with water, an organic solvent, crystallization of the desired product from the resulting aqueous-organic solution, separating the precipitate from the solution by the known methods of washing (if necessary) the precipitate with a solvent and drying the precipitate.

The method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) based on the reactions, for example:

NiCl2+2C2H8O7P2+4H2O→Ni(C2H7O7P2)2·4H2O+2HCl

With NISO4+2C2H8O7P2+4H2O→Ni(C2H7O7P2)2·4H2O+H2SO4

Ni(H2NSO3)2+2C2H8O7P2+4H2O→Ni(C2H7 7P2)2·4H2O+2H2NSO3N

Ni(NO3)2+2C2H8O7P2+4H2O→Ni(C2H7O7P2)2·4H2O+2N3

Ni(OH)2·NiCO3+4C2H8O7P2+5H2O→2Ni(C2H7O7P2)2·4H2O+CO2

As a salt of Nickel(II) to obtain an aqueous solution of bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) it is desirable to use a salt having a high solubility in water: formate Ni(HCOO)2·2H2O, acetate Ni(CH3Soo)2·4H2O, chloride NiCl2·6H2O, bromide NiBr2·3H2O, iodide NiI2, sulfates with NISO4·7H2O, with NISO4·6H2O, sulpham Ni(H2NSO3)2·4H2O, methanesulfonate Ni(CH3SO3)2, bansilalpet Ni(C6H5SO3)2the chlorate Ni(ClO3)2·6H2O, perchlorate Ni(ClO4)2·6H2O, nitrate Ni(NO3)2·6N2O, thiocyanate Ni(SCN)2tetrafluoroborate Ni(BF4)2·6H2O, hexafluorosilicate NiSiF6·6H2O and some other salts, which react with 1-hydroxyethane-1,1-diphosphonic acid in aqueous solution in accordance with the scheme:

NiX2+2C2H8O7P2 ↔Ni(C2H7O7P2)2+2HX,

and insoluble in water gidroksicarbonat Nickel Ni(OH)2·NiCO3that reacts with 1-hydroxyethane-1,1-diphosphonic acid in the aquatic environment in accordance with the reaction equation:

Ni(OH)2·NiCO3+4C2H8O7P2→2Ni(C2H7O7P2)2+CO2+3H2O.

For a homogeneous bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) with high output Nickel(II) and 1-hydroxyethane-1,1-diphosphonic acid, it is desirable to prepare an aqueous solution containing Nickel(II) and anion 1-hydroxyethane-1,1-diphosphonic acid in a molar ratio of 1.0:(from 1.8 to 4.5). From solutions in which 1.0 mol of Nickel(II) is less than 1.8 mol 1-hydroxyethane-1,1-diphosphonic acid, adding an organic solvent can fall compounds of Nickel(II) with 1-hydroxyethane-1,1-diphosphonic acid composition different from the composition of the target product. From solutions in which 1.0 mol of Nickel(II) accounts for more than 4.5 mol 1-hydroxyethane-1,1-diphosphonic acid, the target product stands out with high output Nickel(II), but its output to 1 hydroxyethane-1,1-diphosphonic acid is reduced, which leads to unproductive expenditure of this reagent.

Spent electrolytes Nickel steel, cast iron, titanium alloy which is a toxic waste galvanic production (USSR GOST 9.305-84. Coating of metallic and non-metallic inorganic. Operation of the technological processes of obtaining coatings. - M: in state standard, 1988, p.67. Kudryavtsev N.T. Electrolytic coating of metals. - M.: Chemistry, 1979, s. Sudakov GA electroplating. - M.: Mashinostroenie, 1987, p.77) and subject reduction (Smirnov, D.N., Genkin VE wastewater treatment in the processing of metals. - M.: metallurgy, 1989, p.9), which requires significant material costs. To obtain bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) as a source of salt is Nickel(II) it is possible to use waste solutions galvanic Nickel plating containing high concentrations of soluble salts of Nickel(II), having the composition, for example:

With NISO4·7H2O 200-330 g/l

NiCl2·6H2O 40-180 g/l

H3IN325-40 g/l,

or

NiCl2·6H2O 280-320 g/l

H3IN330-40 g/l,

or

NiCl2·6H2O 120-140 g/l

Ni(CH3Soo)2·4H2O 100-110 g/l,

or

Ni(H2NSO3)2·4H2O 300-450 g/l

H3IN325-40 g/l,

or

Ni(BF4)2·6H2O 420-460 g/l

HBF43-30 g/l

H3IN320-40 g/l

Use as one of the two reagents necessary for obtaining the target product, waste Electrol is the galvanic Nickel-plating extends the range of materials used to acquire it allows not only to obtain high yield of uniform bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II), but also to obtain additional technical result is to reduce the cost of production of the product and dispose of toxic waste production.

To obtain bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) high yield it is necessary to prepare an aqueous solution with concentrations of Nickel(II) 0.1 to 2.0 mol/l and 1-hydroxyethane-1,1-diphosphonic acid 0.2-4.5 mol/L. From solutions in which the concentration of the reagents indicated below, the target product is highlighted with output less than 50%. The upper limit of the concentration of reagents is limited by the solubility of substances in water, as well as the need to obtain a solution which does not separate when adding organic solvent.

Bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) very soluble in water but poorly soluble in many organic solvents: aliphatic hydrocarbons and aromatic series, chlorinated hydrocarbons, monocarboxylic acids, NITRILES of carboxylic acids, amido carboxylic acids, monohydroxy alcohols, ethers, esters, ketones and other experimental data when added to aqueous solution containing Nickel(II) and 1-hydroxyethane-1,1-diphosphonic acid, some organises the x solvents the solubility of bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) significantly reduced due to the effect of vysalivaniya, which improves the yield of the target product. The organic solvent suitable for the production of bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II), but the ability to mix with water, must have the following properties: does not dissolve or destroy bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) in solution and in the solid phase, to be acidic or neutral nature, dissolve 1-hydroxyethane-1,1-diphosphonic acid, does not cause the formation of micro-crystals or colloidal particles bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II). The experimental data these properties are some of monocarboxylic aliphatic acid series, monohydroxy alcohols, NITRILES of carboxylic acids, ketones with small alkyl radicals and a number of other substances, including: formic acid, acetic acid, acetone, acetonitrile, methanol, ethanol, propanol-1, propanol-2,2-methylpropanol-2, dimethylsulfoxide. In the proposed method, the crystallization of bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) comes from dilute aqueous-organic solution, resulting in increased purity of the target product, as the admixture of foreign substances remain in solution and do not pass into the sediment. At the same time, in the way the prototype crystallization of bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) goes only kontsentrirovannej the aqueous solution with a high viscosity, the resulting target product captures from solution a foreign substance and is less pure than the product obtained by the claimed method. In the proposed method the selection of the target product comes from dilute aqueous-organic solution, therefore, the crystallization of bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) with a low speed, thereby increasing the homogeneity and crystallinity of the target product.

Example 1 (the prototype).

11.5g 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h" is dissolved in 50 ml of water, heat the solution to a temperature of 70-80°and add 3,44 g gidroksicarbonata Nickel(II) GOST 4466-78 mark "h" (with a mass fraction of Nickel(II) 47,0%) portions of 0.5 g (new portion added after dissolution of the previous servings). The resulting solution is kept for crystallization at room temperature. Within 6 days of crystallization does not occur. Contribute to the solution of the crystal seed bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) and leave the solution in a closed vessel for crystallization for 8 days at room temperature. The precipitate is filtered off on a glass filter THEN 40 under reduced pressure and dried in air at room temperature to constant weight. Yield 80%.

Found, %: C - 8,4; N - 4,0; P - 22, 0mm; Ni - 11,2.

Calculated for Ni(C2H7O 7P2)2·4H2O, %: C - 8,88; N - 4,10; P - 22,91; Ni - 10,85.

Example 2.

of 12.6 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h" is dissolved in 35 ml of water at room temperature, was added 2.6 g of gidroksicarbonata Nickel(II) GOST 4466-78 mark "h" and is stirred until complete dissolution of the reagent. To the resulting solution was added 70 ml of acetic acid GOST 61-75 marks "h". The solution is kept in a closed vessel for crystallization for 8 days at a temperature of 18-20°C. After the precipitation is filtered off on a glass filter THEN 40 under reduced pressure. The precipitate is washed on the filter first with 5 ml of 80%aqueous solution of acetic acid, then with two portions of acetone and 5 ml of the Precipitate is dried in air at room temperature to constant weight. The output of Nickel(II) 85%.

Found, %: C - 9,1; N - 4,0; R - 23,3; Ni - 10,9.

Calculated for Ni(C2H7O7P2)2·4H2O, %: C - 8,88; N - 4,10; P - 22,91; Ni - 10,85.

IR spectrum, cm-1: 3570, 3415, 3200, 1635, 1415, 1150, 1090, 1070, 1025, 940, 820, 655, 568, 480, 465, 435.

Example 3.

of 13.4 g of the monohydrate of 1-hydroxyethane-1,1-diphosphonic acid and 4.7 g of uranyl chloride Nickel GOST 4038-79 brand "chemically pure" dissolved in 20 ml of water by heating to a temperature of 50-60°and add 40 ml of acetic acid GOST 61-75 marks "chemically pure". The solution is kept in a closed vessel for crystallization at 25 su is OK at a temperature of 22-24° C. the Solution is poured with loose sediment, the sediment was washed with two portions of 50%aqueous solution of acetic acid (10 ml), press the precipitate on filter paper and dried precipitate at room temperature to constant weight. Yield 87%.

Found, %: C - 8,8; N - 4,2; P - 22,6; Ni - 10,7.

IR spectrum, cm-1: 3575, 3420, 3205, 1635, 1410, 1150, 1090, 1070, 1030, 945, 825, 655, 565, 485, 465, 440.

Example 4.

to 10.1 g of the monohydrate of 1-hydroxyethane-1,1-diphosphonic acid are dissolved in 10.0 ml of an aqueous solution of Nickel nitrate with a concentration of 1.5 mol/l when heated to a temperature of 60-70°and add 25 ml of acetic acid GOST 61-75 marks "chemically pure". The solution is kept in a closed vessel for crystallization to 5 days at a temperature of 16-18°C. After the precipitation is filtered off on a glass filter THEN 16 under reduced pressure, washed the precipitate on the filter first two portions 70%aqueous solution of acetic acid 3 ml, then with two portions of ethanol and 5 ml of the Precipitate is dried in air at room temperature to constant weight. The yield of 98.5%.

Found, %: C - 8,9; N - 4,0; R Is 22.6; Ni - 11,1.

Example 5.

of 12.6 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h" and 5.0 g of the acetate tetrahydrate Nickel(II) THAT 6-09-3848-75 mark "h" is dissolved in 15 ml of water by heating to a temperature of 70-80°and add 25 ml of acetic acid GOST 61-75 marks "h". The solution ostable the t in a closed vessel for crystallization for 4 days at a temperature of 23-25° C. the precipitation is filtered off on a glass filter THEN 40 under reduced pressure, washed the precipitate on the filter with three portions of ethanol and 5 ml of the Precipitate is dried in air at room temperature to constant weight. Yield 79%.

Found, %: C - 9,2; N - 4,0; R Is 22.6; Ni - 11,2.

Example 6.

6.3 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h" is dissolved in 6.0 ml of water and added with stirring, 2.8 g of sulfate heptahydrate Nickel GOST 4465-74 brand "analytical grade". After the dissolution of the substance to the solution was added 12.0 ml of formic acid GOST 5848-73 mark "h" and leave the solution in a closed vessel for crystallization for 4 days at a temperature of 20-25°C. the precipitation is filtered off on a glass filter THEN 100 under reduced pressure, washed precipitate on the filter with two portions of 50%aqueous formic acid (5 ml) and dried precipitate in air at room temperature to constant weight. Yield 88%.

Found, %: C - 8,8; N - 4,0; R 22,5; Ni - 10,9.

Example 7.

In 10.0 ml of spent electrolyte galvanic Nickel-plating with the concentration of Nickel sulfate 182 g/l of Nickel chloride 25 g/l, boric acid 25 g/l dissolved 8.6 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h" and add 40 ml of acetic acid mark "h". Contribute to the solution of the crystal seed bis(1-hydroxy-ethane-1,1-diphospho is the(1-)) Nickel(II). The solution is kept in a closed vessel for crystallization for 6 days at a temperature of 20-25°C. After the precipitation is filtered off on a glass filter THEN 40 under reduced pressure, washed the precipitate on the filter first two portions 70%aqueous solution of acetic acid 3 ml, then with three portions of propanol-2 to 3 ml of the Precipitate is dried in air at room temperature to constant weight. Yield 97%.

Found, %: C And 8.6; N - 3,9; P - 22,9; Ni - 11,0.

Example 8.

In 10.0 ml of spent electrolyte galvanic Nickel-plating with the concentration of Nickel sulfate 179 g/l of Nickel chloride 26 g/l, boric acid 24 g/l dissolve 8.8 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h" and add 10.0 ml of acetone GOST 2603-79 mark "h". The solution is kept in a closed vessel for crystallization to 9 days at a temperature of 18-20°C. the Solution is drained from the precipitate, the precipitate is washed with two portions of 50%aqueous solution of acetone and 5 ml.

Sludge press on filter paper and dried in air at room temperature to constant weight. A yield of 75%.

Found, %: C - 8,7; N - 4,0; R Is 22.6; Ni - 11,2.

Example 9.

In 10.0 ml of spent electrolyte galvanic Nickel-plating with a concentration of Nickel chloride 73 g/l of Nickel acetate (75 g/l dissolve 6.2 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h" and probabl the Ute with stirring, 40 ml of acetic acid GOST 61-75 marks "h". Contribute to the solution of the crystal seed bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II). The solution is kept in a closed vessel for crystallization to 11 days at a temperature of 19-22°C. the precipitation is filtered off on a glass filter THEN 16 under reduced pressure, washed on the filter with three portions 70%aqueous solution of acetic acid in 3 ml of the Precipitate is dried in air at room temperature to constant weight. Exit 98%.

Found, %: C - 8,5; N - 3,9; P - 22,7; Ni - 11,0.

IR spectrum, cm-1: 3570, 3420, 3205, 1635, 1410, 1150, 1095, 1070, 1025, 945, 820, 655, 567, 480, 460, 435.

Example 10.

In 10.0 ml of spent electrolyte galvanic Nickel-plating with a concentration of sulpham Nickel(II) 351 g/l, boric acid 15 g/l dissolved 10.3 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-5372-87 mark "h" and add 50 ml of ethanol GOST 18300-87. After 2 hours the solution is filtered, and the filtrate make a crystal seed bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II). The solution is kept in a closed vessel for crystallization for 7 days at a temperature of 23-26°C. the precipitation is filtered off on a glass filter THEN 40 under reduced pressure, washed on the filter with two portions of ethanol (5 ml) and dried in air at room temperature to constant weight. Yield 95%.

Found, %: C - 9,3; N - 3,0; P - 23,2; Ni - 11,6.

Example 11.

In 10.0 ml load, is that up to a temperature of 80-90° With spent electrolyte galvanic Nickel-plating with a concentration of sulpham Nickel(II) 326 g/l of Nickel chloride 13 g/l boric acid 30 g/l, sodium lauryl sulphate 0.1 g/l dissolve 8.8 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-5372-87 mark "h". The slurry for 2 hours at a temperature of 0-2°and filtered through a glass filter under reduced pressure. To the filtrate add 2 ml of water and 45 ml of acetic acid GOST 61-75 marks "h". Contribute to the solution of the crystal seed bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II). The solution is kept in a closed vessel for crystallization for 2 days at a temperature of 22-25°C. the precipitation is filtered off on a glass filter THEN 40 under reduced pressure, washed on the filter with three portions of a 60%aqueous solution of acetic acid in 3 ml of the Precipitate is dried in air at room temperature to constant weight. Exit 98%.

Found, %: C - 9,9; N - 3,8; P - 23,2; Ni - 11,5.

Example 12.

In 10.0 ml of spent electrolyte galvanic Nickel-plating with a concentration of tetrafluoroborate Nickel(II) 298 g/l, tetrafluoroboric acid 4.5 g/l, boric acid 25 g/l dissolved at a temperature of 60-70°From 8.1 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-5372-87 mark "h". To the obtained solution under stirring was added 45 ml of 80%aqueous solution of acetic acid THAT 6-09-07-1716-5. The solution is kept in a closed vessel for crystallization to 10 days at a temperature of 5-7°C. the precipitation is filtered off on a glass filter THEN 40 under reduced pressure, washed the precipitate on the filter with three portions 70%aqueous solution of acetic acid (5 ml) and dried precipitate in air at room temperature to constant weight. Yield 93%.

Found, %: C - 8,9; N - 4,0; R - 23,1; Ni - 11,3.

Obtained in examples 2-12 bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) is a crystalline substance green-yellow color. This compound is well soluble in water, aqueous solutions of ammonia and mineral acids, slightly soluble in formic acid, glycerin, dimethyl sulfoxide, slightly soluble in acetic acid, ethyl, propyl, butyl alcohols, dimethylformamide, dioxane, tetrahydrofuran, chloroform, carbon tetrachloride, hexane, benzene. Bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) stable when stored in air at room temperature, while heating gradually loses water of crystallization.

Examples 1-12 show that the method according to the invention allows to obtain pure bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II), Ni(C2H7O7P2)2·4H2O with a higher yield than the prototype. Showpad is the results of elemental analysis, IR spectra (examples) and powder x-ray (table) products obtained in different conditions in examples 2, 3, 9, indicating the homogeneity of the obtained target product. The x-ray powder drugs bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II) (table) there are a large number of reflexes, which indicates the high zakristallizovannykh obtained target product. In the process according to the invention as an additional technical result can be disposed of toxic waste galvanic production - exhaust electrolyte Nickel - and thereby reduce the costs of environmental protection and to reduce the cost of the target product.

3.18
Table 1.

X-ray powder bis(1-hydroxyethane-1,1-diphosphonates(1-)) Nickel(II) Ni(C2H7O7P2)2·4H2O obtained in different conditions (diffractometer DRON-3M, radiation Juiceα, Fe-filter)
Conditions of receiving
Example 2Example 3Example 9
d,I, %d,I, %d, I, %
10.6510010.6510010.65100
7.86957.85857.8585
7.10407.13257.1025
5.75155.7385.7410
5.3265.3135.325
5.04205.0385.0412
4.94184.9784.9511
4.20104.1954.208
4.0194.0124.005
3.92503.91253.9130
3.5753.5623.574
3.28153.2983.288
3.25303.24153.2422
3.19253.18815
3.00403.00252.9925
2.881102.87782.8809
2.76832.76622.7662
2.695302.692152.69315
2.650252.649142.64815
2.598122.602102.6009
2.52762.52622.5273
2.376202.373112.37415
2.30832.30722.3052
2.24732.2452
2.16642.16532.1633
2.10132.09922.0962
2.01342.01222.0103
1.96071.960 61.9586
1.91351.91041.9084
1.86931.86921.8672
1.82331.82021.8182
1.75331.75321.7522
1.70051.70041.6994
1.6664Done with 1,6673
1.64041.64021.6393
1.58451.58341.5794
Legend: d - interplanar distance, I is the relative intensity of the reflections.

1. The method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) Nickel(II), comprising preparing an aqueous solution containing Nickel(II) and anion 1-hydroxyethane-1,1-diphosphonic acid, the interaction of salts of Nickel(II) and 1-hydroxyethane-1,1-diphosphonic acid in the aquatic environment, the crystallization of the desired product, separating the precipitate from the solution and drying the precipitate, which distinguishes the I, they are preparing an aqueous solution with the concentration of Nickel(II) 0.1 to 2.0 mol/l and 1-hydroxyethane-1,1-diphosphonic acid 0.2-4.5 mol/l and to aqueous solution optionally add miscible with water, an organic solvent.

2. The method according to claim 1, characterized in that salts of Nickel(II) using salt selected from the group consisting of gidroksicarbonata, formate, acetate, chloride, bromide, iodide, sulfate, sulpham, methansulfonate, bansilalpet, chlorate, perchlorate, nitrate, thiocyanate, tetrafluoroborate, hexafluorosilicate Nickel(II).

3. The method according to claim 1, wherein preparing an aqueous solution containing Nickel(II) and anion 1-hydroxyethane-1,1-diphosphonic acid in a molar ratio of 1.0:(1,8÷4,5).

4. The method according to claim 1,characterized in that for the preparation of a solution containing Nickel(II) and anion 1-hydroxyethane-1,1-diphosphonic acid, as the source of the salts of Nickel(II) use waste galvanic production - exhaust electrolyte Nickel plating.

5. The method according to claim 4, characterized in that use exhaust Nickel plating electrolyte containing as main components, Nickel chloride, boric acid.

6. The method according to claim 4, characterized in that use exhaust Nickel plating electrolyte containing as the main components of Nickel sulfate, chloride nick who I am, boric acid.

7. The method according to claim 4, characterized in that use exhaust Nickel plating electrolyte containing as main components, Nickel chloride, Nickel acetate.

8. The method according to claim 4, characterized in that use exhaust Nickel plating electrolyte containing as main components sulpham Nickel, boric acid.

9. The method according to claim 4, characterized in that use exhaust Nickel plating electrolyte containing as main components sulpham Nickel, Nickel chloride, boric acid.

10. The method according to claim 4, characterized in that use exhaust Nickel plating electrolyte containing as a main component tetrafluoroborate Nickel, tetrafluoroboric acid, boric acid.

11. The method according to claim 1, characterized in that as miscible with water, the organic solvent used, the solvent is selected from the group consisting of formic acid, acetic acid, acetone, acetonitrile, methanol, ethanol, propanol-1, propanol-2, 2-methylpropanol-2, dimethyl sulfoxide.



 

Same patents:

FIELD: organic chemistry, chemical technology, medicine.

SUBSTANCE: invention relates to acyclic nucleoside phosphonate derivatives of the formula (1): wherein means a simple or double bond; R1 means hydrogen atom; R2 and R3 mean hydrogen atom or (C1-C7)-alkyl; R7 and R8 mean hydrogen atom or (C1-C4)-alkyl; R4 and R5 mean hydrogen atom or (C1-C4)-alkyl possibly substituted with one or more halogen atoms, or -(CH2)m-OC(=O)-R6 wherein m means a whole number from 1 to 5; R6 means (C1-C7)-alkyl or 3-6-membered heterocycle comprising 1 or 2 heteroatoms taken among the group consisting of nitrogen (N) and oxygen (O) atoms; Y means -O-, -CH(Z)-, =C(Z)-, -N(Z)- wherein Z means hydrogen atom, hydroxy-group or halogen atom, or (C1-C7)-alkyl; Q (see the claim invention); its pharmaceutically acceptable salts or stereoisomers. Also, invention proposes methods for preparing compounds of the formula (1) and their using in treatment of hepatitis B or preparing a medicinal agent designated for this aim.

EFFECT: improved preparing method, valuable medicinal properties of compounds and agent.

16 cl, 10 tbl, 87 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a selective method for removing chloride as NaCl from waste in method for preparing N-phosphonomethyliminodiacetic acid. The waste flow is neutralized with NaOH to pH value about 7, water is evaporated from flow of neutralized waste under atmospheric or lower pressure at temperature from 40°C to 130°C until to precipitation of NaCl. The precipitate is filtered off at temperature from 35°C to 110°C to isolate NaCl from filtrate and NaCl is washed out with saturated saline solution. Invention provides effective removal of NaCl from waste in a method for manufacturing N-phoaphonomethyliminodiacetic acid.

EFFECT: improved treatment method.

7 cl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing N-phosphonomethylglycine. Method involves interaction of derivative of hexahydrotriazine of the formula (II):

wherein X represents CN, COOZ, CH2OY and others; Z and Y represent hydrogen atom and others with triacylphosphite of the formula: P(OCOR3)3 (III) wherein R3 means (C1-C18)-alkyl or aryl that can be substituted. The prepared product is hydrolyzed and (if X represents CH2OY) oxidized. The proposed method is a simple in realization, economy and provides high degree of the end product purity.

EFFECT: improved preparing method.

19 cl, 11 ex

FIELD: organophosphorus compounds, medicine.

SUBSTANCE: invention relates to new biologically active phosphonate compounds. Invention describes phosphonate compound of the formula:

wherein R1 and R'1 represent independently hydrogen atom (-H) substituted possibly with -O-(C1-C24)-alkyl, -O-(C1-C24)-alkenyl, -O-(C1-C24)-acyl, -S-(C1-C24)-alkyl, -S-(C1-C24)-alkenyl or -S-(C1-C24)-acyl wherein at least one among R and R'1 doesn't represent -H and wherein indicated alkenyl or acyl comprise from 1 to 6 double bonds; R2 and R'2 represent independently -H substituted possibly with -O-(C1-C7)-alkyl, -O-(C1-C7)-alkenyl, -S-(C1-C7)-alkyl, -S-(C1-C7)-alkenyl, -O-(C1-C7)-acyl, -S-(C1-C7)-acyl, -N-(C1-C7)-acyl, -NH-(C1-C7)-alkyl, -N-((C1-C7)alkyl)2, oxo-group, halogen atom, -NH2, -OH or -SH; R3 represents phosphonate derivative of nucleoside or biphosphonate; X represents compound of the formula:

L represents a valence bond or a bifunctional binding molecule of the formula: -J-(CR2)t-G- wherein t is a whole number from 1 to 24; J and G represent independently -O-, -S-, -C(O)O- or -NH-; R represents -H, unsubstituted or substituted alkyl or alkenyl; m means a whole number from 0 to 6; n = 0 or 1. Also, invention describes pharmaceutical compositions comprising phosphonate compounds, method for treatment of osteoporosis in mammal, method for increasing mineral osseous density, method for prophylaxis of apoptosis of osteoblasts and osteocytes in mammal, method for treatment of viral infection in mammal, method for treatment of growing neoplasm in mammal and method for proliferation of cells. Invention provides preparing new compounds eliciting useful biological properties.

EFFECT: valuable medicinal properties of phosphonate compounds.

17 cl, 2 dwg, 7 tbl, 21 ex

The invention relates to new and nitrate salts of compounds of formulas (I) to(VI), which can be used in medicine for the treatment of bone disorders such as abnormalities in bone and joints

New drug substances // 2237657
The invention relates to organic chemistry and can find application in medicine

New drugs // 2237057
The invention relates to organic chemistry and can find application in medicine

The invention relates to a method for dihydrate bis(1-hydroxyethane-1,1-diphosphonate(2-))cuprate(II) ammonium, which is as follows: dehydrate bis(1-hydroxyethane-1,1-diphosphonate(2-))cuprate(II) ammonium is produced by crystallization from a solution prepared by mixing the spent solution from the etching of printed circuit boards containing copper(II) and ammonia or ammonium salts, and 1-hydroxyethane-1,1-diphosphonic acid in an amount to provide a molar ratio of copper(II):1-hydroxyethane-1,1-diphosphonic acid 1.0:(2,0-4,0), and having a pH value preferably of 2.0 to 3.5

The invention relates to chemical technology of organophosphorus substances that can be used to prepare electrolyte galvanic and chemical abaltimore, as well as receive other organophosphorus substances, used as fertilizers in agriculture

The invention relates to the field of chemistry of organophosphorus compounds, in particular to an improved method for producing trinational the salt postemergency acid uranyl, which is carried out by reaction of sililirovanie phosphorous acid hexamethyldisiloxane taken at 1.5 to 2.5-fold excess of the stoichiometric required to monochloramine, subsequent similarobama and alkylation of intermediate reaction products undergo simultaneous introduction into the reaction mass hexamethyldisilazane in number, comprising 75-95% of the stoichiometric required, and alkylphosphonate, and saponification of Trevira postemergency acid is carried out in two stages, with the first stage using 20-70% stoichiometric alkali necessary, and the remaining amount of alkali - second stage

FIELD: organophosphorus compounds, medicine.

SUBSTANCE: invention relates to new biologically active phosphonate compounds. Invention describes phosphonate compound of the formula:

wherein R1 and R'1 represent independently hydrogen atom (-H) substituted possibly with -O-(C1-C24)-alkyl, -O-(C1-C24)-alkenyl, -O-(C1-C24)-acyl, -S-(C1-C24)-alkyl, -S-(C1-C24)-alkenyl or -S-(C1-C24)-acyl wherein at least one among R and R'1 doesn't represent -H and wherein indicated alkenyl or acyl comprise from 1 to 6 double bonds; R2 and R'2 represent independently -H substituted possibly with -O-(C1-C7)-alkyl, -O-(C1-C7)-alkenyl, -S-(C1-C7)-alkyl, -S-(C1-C7)-alkenyl, -O-(C1-C7)-acyl, -S-(C1-C7)-acyl, -N-(C1-C7)-acyl, -NH-(C1-C7)-alkyl, -N-((C1-C7)alkyl)2, oxo-group, halogen atom, -NH2, -OH or -SH; R3 represents phosphonate derivative of nucleoside or biphosphonate; X represents compound of the formula:

L represents a valence bond or a bifunctional binding molecule of the formula: -J-(CR2)t-G- wherein t is a whole number from 1 to 24; J and G represent independently -O-, -S-, -C(O)O- or -NH-; R represents -H, unsubstituted or substituted alkyl or alkenyl; m means a whole number from 0 to 6; n = 0 or 1. Also, invention describes pharmaceutical compositions comprising phosphonate compounds, method for treatment of osteoporosis in mammal, method for increasing mineral osseous density, method for prophylaxis of apoptosis of osteoblasts and osteocytes in mammal, method for treatment of viral infection in mammal, method for treatment of growing neoplasm in mammal and method for proliferation of cells. Invention provides preparing new compounds eliciting useful biological properties.

EFFECT: valuable medicinal properties of phosphonate compounds.

17 cl, 2 dwg, 7 tbl, 21 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing N-phosphonomethylglycine. Method involves interaction of derivative of hexahydrotriazine of the formula (II):

wherein X represents CN, COOZ, CH2OY and others; Z and Y represent hydrogen atom and others with triacylphosphite of the formula: P(OCOR3)3 (III) wherein R3 means (C1-C18)-alkyl or aryl that can be substituted. The prepared product is hydrolyzed and (if X represents CH2OY) oxidized. The proposed method is a simple in realization, economy and provides high degree of the end product purity.

EFFECT: improved preparing method.

19 cl, 11 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a selective method for removing chloride as NaCl from waste in method for preparing N-phosphonomethyliminodiacetic acid. The waste flow is neutralized with NaOH to pH value about 7, water is evaporated from flow of neutralized waste under atmospheric or lower pressure at temperature from 40°C to 130°C until to precipitation of NaCl. The precipitate is filtered off at temperature from 35°C to 110°C to isolate NaCl from filtrate and NaCl is washed out with saturated saline solution. Invention provides effective removal of NaCl from waste in a method for manufacturing N-phoaphonomethyliminodiacetic acid.

EFFECT: improved treatment method.

7 cl, 2 ex

FIELD: organic chemistry, chemical technology, medicine.

SUBSTANCE: invention relates to acyclic nucleoside phosphonate derivatives of the formula (1): wherein means a simple or double bond; R1 means hydrogen atom; R2 and R3 mean hydrogen atom or (C1-C7)-alkyl; R7 and R8 mean hydrogen atom or (C1-C4)-alkyl; R4 and R5 mean hydrogen atom or (C1-C4)-alkyl possibly substituted with one or more halogen atoms, or -(CH2)m-OC(=O)-R6 wherein m means a whole number from 1 to 5; R6 means (C1-C7)-alkyl or 3-6-membered heterocycle comprising 1 or 2 heteroatoms taken among the group consisting of nitrogen (N) and oxygen (O) atoms; Y means -O-, -CH(Z)-, =C(Z)-, -N(Z)- wherein Z means hydrogen atom, hydroxy-group or halogen atom, or (C1-C7)-alkyl; Q (see the claim invention); its pharmaceutically acceptable salts or stereoisomers. Also, invention proposes methods for preparing compounds of the formula (1) and their using in treatment of hepatitis B or preparing a medicinal agent designated for this aim.

EFFECT: improved preparing method, valuable medicinal properties of compounds and agent.

16 cl, 10 tbl, 87 ex

FIELD: chemical technology of organophosphorus compounds.

SUBSTANCE: method involves preparing nickel (II) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) by addition 1-hydroxyethane-1,1-diphosphonic acid in the concentration 0.2-4.5 mole/l to an aqueous solution containing nickel (II) in the concentration 0.1-2.0 mole/l and organic solvent mixing with water followed by crystallization of the end substance from the solution. Method provides preparing the pure homogeneous end product with high yield, and utilization of depleted electrolyte in nickel plating representing a toxic waste in galvanic manufacture.

EFFECT: improved preparing method.

11 cl, 1 tbl, 12 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing N-phosphonomethylglycine. Invention describes a method for preparing N-phosphonomethylglycine from an aqueous mixture containing dissolved N-phosphonomethylglycine, ammonium halides, alkali or earth-alkali metal halides and, optionally, organic impurities. Method involves (a) using a mixture with pH value from 2 to 8; (b) separation of mixture is carried out on a selective nanofiltration membrane, and retentate enriched with N-phosphonomethylglycine and depleted with halides and permeate depleted with N-phosphonomethylglycine are obtained, and (c) N-phosphonomethylglycine is isolated from retentate. Method provides preparing N-phosphonomethylglycine in simultaneous separation of halide salts.

EFFECT: improved preparing method.

13 cl, 5 dwg, 2 tbl, 2 ex

FIELD: organophosphorus compounds, chemical technology.

SUBSTANCE: invention relates to technology of organic substances, in particular, to the improved method for preparing copper (II) bis-(1-hydroxyethane-1,1-diphosphonate (1-)). The final copper (II) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) is prepared by crystallization from aqueous solution with concentrations of copper salt (II) from 0.5 to 2.0 mole/l and 1-hydroxyethane-1,1-diphosphonic acid with concentration from 2.0 to 6.0 mole/l prepared by using copper-containing waste in galvanic and electronic engineering manufacture, or by using a semi-finished product from production of 1-hydroxyethane-1,1-diphosphonic acid. Invention provides reducing cost in production of copper (I) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) in combination with retaining purity, expanded raw base for preparing the end product and utilization of manufacture waste.

EFFECT: improved preparing method.

9 cl, 1 tbl, 8 ex

FIELD: chemistry of organophosphorus compounds, agriculture, pesticides.

SUBSTANCE: invention describes bis-(diethylammonium)-dihydrogen-1-hydroxyethyl-1,1diphosphonate monohydrate of the formula (I) showing properties of stimulator of growth o agricultural root crop plants. Invention provides enhancing productivity of root crops beet and carrot and expanding assortment of agents for this designation.

EFFECT: valuable agricultural properties of agent.

1 tbl, 2 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to the improved method for preparing bis-(1-hydroxyethane-1,1-diphosphonate(1-)) zinc (II). Method involves interaction of zinc-containing reagent and 1-hydroxyethane-1,1-diphosphonic acid in a solvent medium, crystallization of the end product from solution, separation of deposit from solution and drying the deposit. Method involves using water-soluble zinc (II) salt with anion of strong acid as a zinc-containing reagent and preparing the solution with the concentration of zinc (II) salt from 0.2 to 2.2 mole/l and the concentration of 1-hydroxyethane-1,1-diphosphonic acid from 0.4 to 5.0 mole/l. The end product prepared by proposed method can be used in preparing phosphonate electrolytes for galvanic zinc-plating, for preparing zinc-phosphate inhibitors of steel corrosion, as trace supplement to vitamin preparations and fodders for animals, as a zinc microfertilizer in agriculture and for preparing other compounds of zinc (II). Invention provides enhancing purity and uniformity of the end product, increasing its yield, improved technological effectiveness of process, utilizing toxic waste in galvanic manufacturing.

EFFECT: improved preparing method.

8 cl, 1 tbl, 6 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to technology for synthesis of crystalline nitrilotrimethylphosphonic acid sodium salts. For synthesis of nitrilotrimethylphosphonic acid disodium salt monohydrate the method involves preliminary synthesis of nitrilotrimethylphosphonic acid by interaction of phosphorus trichloride, formaldehyde and ammonia or its derivative followed by neutralization with sodium hydroxide in the content in the reaction mass 46-54 wt.-% of nitrilotrimethylphosphonic acid and 6.0-16.0 wt.-% of hydrogen chloride up to pH value 2.5-4.5, and isolation of the end compound by crystallization. The mass part of the main substance in synthesized product is 88-95%, the content of chloride ions is 1.2-2.0%, yield is 50-60% as measured for PCl3. Synthesized compound is recommended for using as chelate compounds as a component of detergents, anti-rheological additive in drilling solutions, plasticizing agents for building concretes, in wine-making industry, as inhibitors of salt depositions in heat and power engineering and others fields.

EFFECT: improved method of synthesis.

2 tbl, 12 ex

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