Method for preparing copper (ii) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) from production waste

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

 

The invention relates to chemical technology of organic compounds, in particular to a method for producing bis(1-hydroxyethane-1,1-di-phosphonate(1-)) copper(II). The product obtained in this way can be used to prepare complex electrolyte galvanic and chemical copper plating, for inhibiting corrosion of equipment in the oil and petrochemical industry, as a bactericidal drug, as a fungicide and copper micronutrients in agriculture as a micronutrient Supplement multivitamin preparations and animal feed, as a drug in veterinary medicine, for other complex compounds of copper.

Bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II) is a compound (chelate) copper(II) with 1-hydroxyethane-1,1-diphosphono acid CH3S(HE)(RHO3H2)2[C2H8O7P2] the composition Cu(C2H7O7P2)2·4H2O.

A method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II), comprising preparing an aqueous solution containing a chloride of copper(II) and 1-hydroxyethane-1,1-diphosphonic acid in a molar ratio of 1.0:3.0, addition of acetic acid, the crystallization of the desired product, separating the crystals from the solution and drying (And the onini Mrs x, Alexandrov GG, Sergienko, V.S. // Coordination chemistry, 1997, Volume 23, No. 11, S). The disadvantage of this method is the additional cost reagent chloride copper(II) and the solvent is acetic acid.

Closest to the claimed method is a method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II), comprising preparing an aqueous solution with a salt concentration of copper(II) from 0.5 to 2.0 mol/l and the concentration of 1-hydroxyethane-1,1-diphosphonic acid from 2.0 to 6.0 mol/l, the crystallization of the desired product, separating the crystals from the solution and drying (Afonin Mrs x, Lviv V.M., Barinov AV RF Patent №2224763 C2, CL. 7 07 F 9/38, publ. 27.02.2004,). As a salt of copper(II) in the prototype use sulpham, sulfate, chloride, perchlorate, nitrate, tetrafluoroborate, hexafluorosilicate and other salts of copper(II). The way the prototype allows to obtain single-phase bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II) with high yield. The disadvantage of this method is the need for the extra cost of the reagent salt of copper(II).

In the claimed invention, the aim was to reduce material costs to obtain bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II), to expand the range of materials used to obtain the target product, dispose of toxic waste.

Set for the ache is solved by what a way to obtain bis(1-guide-roxita-1,1-diphosphonate(1-)) copper(II) includes the preparation of an aqueous solution with a salt concentration of copper(II) from 0.5 to 2.0 mol/l and the concentration of 1-hydroxyethane-1,1-diphosphonic acid from 2.0 to 6.0 mol/l, the crystallization of the desired product, separating the crystals from the solution and drying. New in the claimed method is that as the source of the salts of copper(II) use liquid copper production waste and/or source 1-hydroxyethane-1,1-diphosphonic acid is used for the intermediate production of 1-hydroxyethane-1,1-diphosphonic acid. As liquid copper-containing waste production it is desirable to use the spent electrolyte galvanic copper plating or the spent solution in the etching of printed circuit boards or the ion exchange eluate wastewater from copper ion(II). If necessary, liquid copper production waste pre-concentrate or dilute with water, or pre-add in the oxide, hydroxide, gidroksicarbonat copper(II). Source 1-hydroxy-ethane-1,1-diphosphonic acid, it is desirable to use a technical 1-hydroxyethane-1,1-diphosphonic acid with a basic substance content above 85% or intermediate in the production of 1-hydroxyethane-1,1-diphosphonic acid, containing as the basic compound is 1-hydroxyethane-1,1-diphosphonic acid, water, acetic acid. It is desirable to prepare an aqueous solution containing a salt of copper(II) and 1-hydroxyethane-1,1-diphosphonic acid in a molar ratio equal to 1,0:(1,8-4,0).

The method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II) from waste production is the mixing of liquid copper-containing waste production and crystalline 1-hydroxyethane-1,1-diphosphonic acid (aqueous solution) or mixed salts of copper(II) (aqueous solution) and intermediate production 1-hydroxyethane-1,1-diphosphonic acid, crystallization of the desired product when standing solution for a certain period of time, the separation of crystals from solution one of the known methods, washing (if necessary) the precipitate on the filter with a solvent, drying of the crystals in the air.

Bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II) it is soluble in water. So it is received from aqueous solution with high yield it is necessary to prepare an aqueous solution with a salt concentration of copper(II) above 0.5 mol/l and 1-hydroxyethane-1,1-diphosphonic acid above 2.0 mol/l Upper limit of acceptable concentrations of salt of copper(II) 2.0 mol/l and 1-hydroxyethane-1,1-diphosphonic acid of 6.0 mol/l is limited by the solubility of substances in water, as well as the need to obtain a solution of moderate viscosity.

To obtain bis(1-hydroxyethane-1,1-diphosphono is a(1-)) copper(II) as a liquid copper-containing waste production, you can use waste solutions of different composition, containing salts of copper(II) (simple or complex) in high concentrations. It is desirable to use waste to produce copper coatings by electrochemical method is used, the electrolyte of the galvanic copper plating (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, Page 61, 65. Guskov SV, Kazakovtsev SCI, Bychkov V.F. // Currency production and technical experience, 1989, No. 5, P.14), which have the composition, for example:

Sulphate of copper(II)100-190 g/l
Sulfuric acid40-110 g/l

or

Sulphate of copper(II)65-130 g/l
Nitrate copper(II)80-120 g/l
Sulfuric acid40-110 g/l

waste electronic production - proven solutions etching of printed circuit boards (Fedulova A.A., YURI Ustinov, Cats, H.E., Shustov VP, AVIC E.R. multilayer printed circuit boards. - M.: Radio and communication, 1990, S. Dudko NICHOLAS, Nikolaev E.M., Solovieva YEAR // Currency production and technical experience, 1988, No. 8, P.29), which have the composition, for example:

Chloride copper(II) 180-240 g/l
Hydrogen chloride30-85 g/l

waste cleaning copper-containing wastewater production, electroplating, printed circuit boards - eluate formed during leaching (regeneration) of ion exchange resins solutions of mineral acids (Proskuryakov, VA, Schmidt LI wastewater treatment in the chemical industry. - L.: Chemistry, 1977, S. 169. Nadeau T., M. Dejak // Plating and Surface Finishing, 1986, No. 4, P.48. Flexible automated electroplating line. The Handbook. - M.: Mashinostroenie, 1989, S. Trunova V.I., bad, in SV, Matasova I.G., Mikhalenko MG // Ecology and industry of Russia, 1999, No. 5, P.35), which have the composition, for example:

Sulphate of copper(II)60-110 g/l
Sulfuric acid30-60 g/l

or

Chloride copper(II)25-40 g/l
Hydrogen chloride40-60 g/l

In addition to these liquid waste to obtain bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II) can be used directly and other waste solutions containing copper(II) in concentrations from 0.5 to 2.0 mol/l, for example the spent copper-ammonia solution is the production of butadiene (Trunin A.S., Chumanov A.N., Kosmynin A.S., Hontou VG, Eremin A RF patent №2166491 C2, CL. 7 05 D 9/02, 11/00, a 01 N 59/20, publ. 2001).

To obtain bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II) you can also use liquid copper production waste containing salt of copper(II) concentration below 0.5 mol/L. Such solutions pre-concentrated by known techniques (evaporation at atmospheric pressure, vacuum evaporation, freezing solvent and other) to the salt concentration of copper(II) from 0.5 to 2.0 mol/liter of Liquid copper-containing waste containing salt of copper(II) concentration below 0.5 mol/l) and mineral acids (sulfuric, salt, tetracarbonyl), to increase the salt concentration of copper(II) and, consequently, to increase the yield of the target product, it is desirable to pre-process the oxide, hydroxide or hydroxocobalamin copper(II).

To obtain bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II) you can use 1-hydroxyethane-1,1-diphosphonic acid brand "h"produced by the chemical industry, for example on THE 6-09-713-84, THE 6-09-5372-87, THE 6-09-20-174-90, or the monohydrate of 1-hydroxyethane-1,1-diphosphonic acid, which is obtained by recrystallization of reagent grade "h" from an aqueous solution of acetic acid (Afonin Mrs x, Mechurova N. // Journal of General chemistry, 1987, CH, No. 3, S). To reduce material costs for obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II) together is the trademark of the reagent can be used 1-hydroxyethane-1,1-diphosphonic acid technical grade, concentrated aqueous solution or aqueous suspension of 1-hydroxyethane-1,1-diphosphonic acid, and a mixture of 1-hydroxyethane-1,1-diphosphonic acid with acetic acid or a mixture of 1-hydroxyethane-1,1-diphosphonic acid with acetic acid and water formed at various stages of industrial production 1-hydroxyethane-1,1-diphosphonic acid (Panfilov VA, Efremov A.I., Sinitsyn PS, Abramov, I., Kasimov RG, Danilov S.D., E.A. Vinogradov, Hoskin N.P., Grads, VA, Nikitinsky E, Ed. mon. The USSR №1065418, CL. 07 F 9/38, publ. 1984; Knots A.V., F. W. Wise, Milgaten IM, Bolsova IV, the Rich man E.V., Kuznetsov A.A., ALEXANDER Badmaev, Komova, S.N., Kostryukov mathematical SCIENCES. RF patent №2173321 C1, CL. 07 F 9/38, publ. 2001; Badmaev V., F. W. Wise, Knots AV, Milgaten IM, Rich E.V., Kuznetsov A.A., Bolsova IV Patent RF № 2178793 C1, CL. 07 F 9/38, publ. 2002). The output and quality of the obtained target product remain high (see examples 7,8).

Since bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II) is formed in solution in the equilibrium process

CuX2+2C2H8O7P2↔Cu2H7O7P2)2+NH,

where X is the anion of a mineral acid, to shift the equilibrium of the reaction towards formation of the target product contribute not only to the high concentration of reagents in solution, but the creation process is e a molar excess of 1-hydroxyethane-1,1-diphosphonic acid. The lower boundary of the desired molar ratio of copper(II): 1-hydroxyethane-1,1-diphosphonic acid 1.0 to:1,8 determined by the need to obtain the target product with a yield not lower than 30% from solutions with high concentrations of copper(II). The upper boundary of the desired molar ratio of copper(II): 1-hydroxyethane-1,1-diphosphonic acid 1.0 to:4,0 determined by the need to obtain the target product with a yield not lower than 30% from solutions with low concentration of copper(II).

Example 1.

to 20.0 ml of the spent electrolyte galvanic copper plating with concentrations of copper sulfate(II) 141 g/l, sulfuric acid 50 g/l evaporated when heated up to a volume of 10.0 ml and added with stirring to 11.0 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h". Make a crystal seed Cu2H7O7P2)2·4H2O. the Solution is kept for crystallization at 4 days at a temperature of 18-20°C. the Precipitate is filtered off on a glass filter THEN 100 under reduced pressure, washed the precipitate on the filter first 50%aqueous solution of ethanol (three portions of 1 ml), then with ethanol (three portions of 1 ml). The precipitate is dried in air at room temperature to constant weight. The output of copper(II) 94%.

Found, %: C And 8.6; N - 3,9; P - 22,4; Cu - 11,6.

Calculated for Cu(C2H7O7P2)2·4H2O,%: C - 8,80; THERE - 4,06; P - 22,71; Cu - 11,65.

Example 2.

10.0 ml of the spent electrolyte galvanic copper plating with concentrations of copper sulfate(II) 128 g/l, sulfuric acid, 39 g/l evaporated when heated up to a volume of 5.0 ml) and added with stirring to 4.2 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h". After cooling to room temperature in solution contribute crystalline seed Cu2H7O7P2)2·4H2O. the Solution is left to crystallize for 1 day at a temperature (-4)-(-6)°C. the Precipitate is filtered off on a glass filter THEN 100 under reduced pressure, washed on the filter with ethanol (two servings 2 ml) and dried in air at room temperature to constant weight. The output of copper(II) 85%.

Found, %: C - 8,5; N - 3,8; P - 22,4; Cu - 11,3.

Example 3.

In 20,0 ml of spent electrolyte galvanic copper plating with concentrations of copper sulfate(II) 152 g/l, sulfuric acid 98 g/l dissolved under stirring to 1.59 g of copper oxide(II) GOST 16539-79 mark "h", the resulting solution was heated to a temperature of 60-70°With and dissolve in it to 20.6 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h". After cooling to room temperature in solution contribute crystalline seed Cu2H7O7P2)2·4H2O. the Solution is left to crystallize for 6 days in to matnog temperature. The precipitate is filtered off on a glass filter THEN 40 under reduced pressure, washed on the filter with 80%aqueous solution of ethanol (three portions 3 ml) and dried in air at room temperature to constant weight. The output of copper(II) 82%.

Found, %: C - 8,5; 4,1; P - 22, 0mm; Cu - 11,8.

Example 4.

In 20,0 ml of spent electrolyte galvanic copper plating with concentrations of copper sulfate(II) 148 g/l, sulfuric acid 51 g/l dissolved 0,83 g of copper oxide(II) GOST 16539-79 mark "h", then added 18.2 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h". Evaporated solution when heated up to a volume of 20.0 ml After cooling to room temperature in solution contribute crystalline seed Cu2H7O7P2)2·4H2O. the Solution is kept for crystallization at 4 days at room temperature. The precipitate is filtered off on a glass filter THEN 40 under reduced pressure, washed on the filter first with 60%aqueous solution of ethanol (three portions of 2 ml), then with ethanol (three portions 2 ml) and dried in air at room temperature to constant weight. The output of copper(II) 97%.

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

Example 5.

In 10.0 ml of the spent solution from the etching of printed circuit boards with chloride concentrations of copper(II) 136 g/l, chloride 82 g/l dissolved first 0.87 g of oxidised(II) GOST 16539-79 mark "h", then 18.0 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h". Contribute to the solution of the crystal seed Cu2H7O7P2)2·4H2O. the Solution is left to crystallize for 3 days at a temperature of 20-22°C. the Precipitate is filtered off on a glass filter THEN 40 under reduced pressure, washed on the filter with ethanol (four portions 2 ml) and dried in air at room temperature to constant weight. The output of copper(II) 85%.

Found, %: C And 8.6; N - 3,9; P - 22,4; Cu - 11,4.

Example 6.

10.0 ml of the eluate ion exchange wastewater from ions of copper(II) concentrations of copper sulfate(II) 80 g/l, sulfuric acid 59 g/l, heated to 70-80°C, add with stirring first 1.48 g of copper oxide(II) GOST 16539-79 mark "h", then 14.9 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h". After cooling to room temperature, make the crystal seed Cu2H7O7P2)2·4H2O and leave the solution for crystallization for 3 days at room temperature. The precipitate is filtered off on a glass filter THEN 16 under reduced pressure, washed on the filter with ethanol (three portions 3 ml) and dried in air at room temperature to constant weight. The output of copper(II) 96%.

Found, %: C - 8,7; 4,1; P - 22,8; Cu - 11,8.

Example 7.

10.0 m of the water when heated to a temperature of 60-80° With dissolve 5.0 g of the pentahydrate of copper sulfate(II) GOST 4165-78 mark "h" and 13.6 g technical 1-hydroxyethane-1,1-diphosphonic acid (content of 1-hydroxyethane-1,1-diphosphonic acid, 91%, phosphorous acid 2%, acetic acid 3%, water 4%). The solution is left to crystallize for 1 day at room temperature. The precipitate is filtered off on a glass filter THEN 40 under reduced pressure, washed on the filter first with 70%aqueous solution of ethanol (three portions of 1 ml), then with ethanol (two servings 2 ml) and dried in air at room temperature to constant weight. The output of copper(II) 91%.

Found, %: C - 8,5; N - 3,6; P - 22,3; Cu - 11,6.

Example 8.

To 10.0 ml of the spent electrolyte galvanic copper plating with concentrations of copper sulfate(II) 140 g/l, sulfuric acid 50 g/l with stirring is added first, 1.50 g of gidroksicarbonata copper(II), then 21,0 g of intermediate production 1-hydroxyethane-1,1-diphosphonic acid, containing 67 wt.% 1-hydroxyethane-1,1-diphosphonic acid, 16 wt.% water, 17 wt.% acetic acid and heated at a temperature of 40-50°to dissolve substances. The solution is left to crystallize for 1 day at room temperature. The precipitate is filtered off on a glass filter THEN 40 under reduced pressure, washed on the filter first with 70%aqueous solution of acetic acid (three portions p is 2 ml), then acetone (two servings 2 ml). The substance is dried in air at room temperature to constant weight. The output of copper(II) 95%.

Found, %: C And 8.6; N - 3,8; P - 22,5; Cu - 11,7.

Obtained in examples 1-8 bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II) is a crystalline substance is blue. The substance is soluble in water, alkalis, aqueous solutions of ammonia and mineral acids, slightly soluble in ethanol, acetic acid, acetone, chloroform, carbon tetrachloride, hexane, benzene. The substance is stable during storage in air at room temperature.

According to elemental analysis (see examples) and x-ray powder (see table) the claimed method allows to obtain well zakristallizovannykh single-phase bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II), Cu(C2H7O7P2)2·4H2O high yield. The reduction of material costs in obtaining the target product in the claimed method is achieved by using as the source of copper(II) liquid copper-containing waste, in particular waste electrolyte galvanic copper plating, the spent solution from the etching of printed circuit boards, ion exchange eluate wastewater from copper ion, instead of used in the method according to the prototype of the purchase of reagents, salts of copper(II), and t is the train due to use as source 1-hydroxyethane-1,1-diphosphonic acid 1 technical-hydroxyethane-1,1-diphosphonic acid or intermediates industrial production of this substance, in particular, mixtures of 1-hydroxyethane-1,1-diphosphonic acid, acetic acid, and other substances. Liquid copper-containing waste products pose a serious environmental problem because they contain high concentrations toxic to humans and animals copper(II) in the form of various simple and complex compounds. To neutralize them requires significant material costs. Disposal of liquid copper-containing waste in the process of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II) allows to reduce the costs of environmental protection. The use of copper-containing waste provides an opportunity to expand the range of materials and raw materials for obtaining bis(1-hydroxy-ethane-1,1-diphosphonate(1-)) copper(II) while maintaining a high yield of the target product and its high quality.

tr>
Table 1

Radiographic identification of bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II)
hk1The calculated valuesThe experimental values
d, EI, %Example 1Example 8
d, EI, %d, EI, %
1108,582108,5778,564
-1118,114818,11458,1240
2006,572100to 6.57100to 6.58100
1115,92823of 5.9222to 5.9317
-2025,811105,8010of 5.819
0205,666475,66355,6730
0025,507635,50505,5145
-1125,48036
-3114,553104,5594,559
-2214,50454,5044,513
220at 4,29154,2944,294
1124,089394.09 to304.09 to28
-2224,0575
-3133,66663,66843,6634
-1313,592213,591163,59617
2023,47863,47763,4854
3-113,37110 3,37393,37211
-1323,23453,23333,2345
-4223,105323,106273,10625
1133,048103,04873,0487
-3142,985232,985162,98415
-4042,90662,898202,89919
-5122,89719
1322,86262,86052,8675
4202,842182,841202,840 19
0402,83315
-1332,77172,77172,7725
0042,753122,750102,75212
0412,7446
-4242,585172,585122,58810
2232,438102,43892,4418
4022,36672,36472,3697
-5322,34752,34652,3485
-5312,29582,29572,297
3132,27182,27162,2718
-3162,05352,05242,0534
2242,04452,043102,0469
6202,0437
-5161,99881,99861,9985
Legend: d - interplanar distance, I is the relative intensity of reflections on the x-ray powder.

1. The method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II) from waste products, comprising preparing an aqueous solution with a salt concentration of copper(II) from 0.5 to 2.0 mol/l and the concentration of 1-hydroxyethane-1,1-diphosphonic acid from 2.0 to 6.0 mol/l, the crystallization of the desired product, separating the crystals from the solution and drying, characterized in that as the source of the salts of copper(II) COI is lsout liquid copper production waste and/or source 1-hydroxyethane-1,1-diphosphonic acid is used for the intermediate production of 1-hydroxyethane-1,1-diphosphonic acid.

2. The method according to claim 1, characterized in that as the liquid copper-containing waste production using spent electrolyte galvanic copper plating.

3. The method according to claim 1, characterized in that as the liquid copper-containing waste production use waste solution etching printed circuit boards.

4. The method according to claim 1, characterized in that as the liquid copper-containing waste production using ion-exchange eluate wastewater from copper ion(II).

5. The method according to claim 1, characterized in that the liquid copper-containing waste product of the pre-concentrate or dilute with water.

6. The method according to claim 1, characterized in that the liquid copper-containing waste pre-production add substance selected from the group consisting of oxide, hydroxide, gidroksicarbonata copper(II).

7. The method according to claim 1, characterized in that an intermediate in the production of 1-hydroxyethane-1,1-diphosphonic acid contains as main components 1-hydroxyethane-1,1-diphosphonic acid, water, or 1-hydroxyethane-1,1-diphosphonic acid, acetic acid or 1-hydroxyethane-1,1-diphosphonic acid, water, acetic acid.

8. The method according to claim 1, characterized in that the intermediate product manufacturing 1-hydroxyethane-1,1-diphosphonic acid use technical 1-hydroxyethane-1,1-diphosphonic is islote with a basic substance content above 85%.

9. The method according to claim 1, wherein preparing an aqueous solution containing a salt of copper(II) and 1-hydroxyethane-1,1-diphosphonic acid in a molar ratio 1,0:(1,8-4,0).



 

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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

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing metal complexes of tetra-(5,8-dihydroxy-6-sulfo)-anthraquinone porphyrazine. Method is carried out by interaction of 2,3-dicarboxy-5,8-dimethoxy-6-sulfoanthraquinone with urea and the corresponding metal salt in the presence of chloride and ammonium molybdate and the following hydrolysis of the synthesized metal complex - tetra-(5,8-dimethoxy-6-sulfo)-anthraquinone porphyrazine by its treatment with sodium hydroxide. Proposed metal complexes can be used as catalysts, dyes and in other fields of science and technique.

EFFECT: improved preparing method.

2 cl, 3 dwg, 4 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing metal complexes of tetra-(5,8-dihydroxy)-anthraquinone porphyrazine. Method involves interaction of 2,3-dicarboxy-5,8-dimethoxyantraquinone with urea, salt of corresponding metal in the presence of ammonium molybdate and chloride and the following hydrolysis of prepared metal complex of tetra-(5,8-dimethoxy)-anthraquinone porphyrazine. Prepared metal complexes can be used as catalysts, dyes and in another branches of science and technique. Method provides enhancing yield of the end product up to 24%.

EFFECT: improved preparing method.

2 cl, 3 dwg, 4 ex

FIELD: chemistry of chelated compounds.

SUBSTANCE: invention relates to copper porphyrazine chelates comprising linear anellated quinoline cycles, namely, to copper tetra-(6-tert.-butyl-2,3-quinolino)-porphyrazine of the formula (I): that can be used a dyeing substance of optical filters.

EFFECT: valuable properties of substance.

2 cl, 1 dwg, 1 ex

FIELD: chemistry of metalloorganic compounds.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazines of the general formula (I):

wherein M means Cu, Co. These compounds can be used as dyes, catalysts of different processes and material for sensitive members of gas pickups.

EFFECT: valuable properties of complexes.

4 fig, 1 dwg, 5 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazine of the general formula (I): wherein M means Cu, Co. These compounds can be used as dyes, catalysts in different processes and materials of sensitive members of gas sensor.

EFFECT: valuable properties of compounds.

2 cl, 6 sch, 1 dwg, 5 ex

The invention relates to new derivatives of metalloporphyrins that can primeneniia as pigments, catalysts, materials sensitive elements gases

The invention relates to a new derived metalloporphyrins, which may find application as dyes catalysts for various processes, materials sensitive elements (CHAD) gases, etc

The invention relates to a new method of obtaining metallizovannyh derived bacteriochlorophyll for use in the methods of photodynamic therapy (PDT) and in vivo diagnostics and photodynamic destruction of viruses and microorganisms in vitro, as well as some new metallosalen derived bacteriochlorophyll

The invention relates to coordination compounds of metals exhibiting cytotoxic activity and can be used in medicine and veterinary medicine for the purpose of chemotherapy

,,,-tetramethylcyclotetrasiloxane and methods for their production" target="_blank">

The invention relates to chemistry and chemical technology, and more specifically to the synthesis of a new breed of macroheterocyclic compounds, tetrasauropus chlorine, namely,,,-tetramethylcyclotetrasiloxane

FIELD: organic chemistry.

SUBSTANCE: invention relates to new derivatives of metalloporphyrazine of the general formula (I): wherein M means Cu, Co. These compounds can be used as dyes, catalysts in different processes and materials of sensitive members of gas sensor.

EFFECT: valuable properties of compounds.

2 cl, 6 sch, 1 dwg, 5 ex

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