The method of obtaining tetrathionate of tetraethylammonium
(57) Abstract:Usage: in inorganic chemistry and to obtain tocomplex elements of the seventh group, in particular to obtain tetrathionate of tetraethylammonium, which can find application in organic synthesis. The inventive method, including the dissolution of the original substances and their interaction in an alcohol solution, ammonium perrhenate dissolved in ammonia-ethanol solution, and then injected aqueous solutions of hydroxide tetraethylammonium and ammonium polysulfide and through the reaction mixture miss the sulphide precipitate is filtered off and the mother liquor is returned to the beginning of the process. Yield 96%. 1 C. p. F.-ly. The invention relates to inorganic chemistry, namely to receive tocomplex elements of the seventh group, in particular to a method for tetrathionate of tetraethylammonium.Tetrathionate can be used as starting compounds for various polynuclear Homo - and heterometallic serosoderjaschei complexes of rhenium and catalysts based on them.A method of obtaining tetrathionate tetrabutylammonium [(n-Bu4N)ReS4] consisting in shadowstrike potassium (KOH) and boil. The resulting mixture is filtered into a solution of tetrabutylammonium bromide deposited precipitate is filtered off. The yield of the target product 20% 
The disadvantages of the method are: low yield of the target product, a high consumption of reagents (up to 2 l of ammonia to 2 g Re2O7), the use of Re2O7expensive and unsustainable in the air due to the high hygroscopic substances.Closest to the present invention is a method of obtaining tetrathionate of tetraethylammonium. Tetraethylammonium bromide dissolved in the metal solution of ammonium polysulfide and enter Re2O7. The mixture is heated, then the precipitate is filtered off and the filtrate is left in a closed vessel under argon. After 1-2 days the precipitated crystals filtered off. The yield of the target product is 71% 
The disadvantages of the method are: the complexity of the method due to the use of unstable air Re2O7the need for process in an inert atmosphere, labor-intensive process, requiring a lot of time to prepare a methanol solution of ammonium polysulfide, so as to obtain the necessary carefully dried methanol and dry ammonia and hydrogen sulfide. In addition to the what is the difficulty in recycling, obtained by carrying out this method.The objective of the invention is to provide a simple, technologically advanced way to obtain a product with a practically quantitative yield, and to use available reagents that do not require pre-cleaning and resistant to air, to carry out the process with fewer reagents and reusing the mother liquor, which is very important for the environment and recycling.The task is solved in that tetratogenic of tetraethylammonium get interaction derived tetraethylammonium with ammonium polysulfide and registertask reagent in the environment of the solvent, followed by separation of the target product, as derived tetraethylammonium hydroxide use of tetraethylammonium, as registertimer reagent use ammonium perrhenate and the process is conducted in an aqueous-ammonia-alcohol medium by sequential processing of ammonium perrhenate in the ammonia-ethanol solution aqueous solutions of hydroxide tetraethylammonium and ammonium polysulfide, and the subsequent transmission of hydrogen sulfide in the reaction mass resulting from the reaction of the target product is filtered off, and match isawanya instead of Re2O7simple reagent of ammonium perrhenate, dissolution of ammonium perrhenate in aqueous ammonia-ethanol solution, the introduction of aqueous solutions of hydroxide tetraethylammonium and ammonium polysulfide, passing through the reaction mixture of hydrogen sulfide, reusing the mother liquor, i.e., returning the mother liquor to the process.This allows to simplify the method and to increase the yield of the target product to 95-96% which is especially important considering the high cost of rhenium.As a source of reagent is used, the ammonium perrhenate NH4ReO4since this salt is soluble in ammonia-ethanol mixture and readily available. Dissolving salt in ammonia-ethanol solution, on the one hand, allows one to quickly and completely without heating to dissolve the original salt, and ethanol environment allows to avoid the formation of oxocomplexes that would defile the obtained product.The use of ammonia solution contributes to the dissolution of ammonium perrhenate and serves the formation of ammonium sulfide by passing hydrogen sulfide (H2S.Introduction hydroxide tetraethylammonium [(C2H5)4NOH] the resulting product, affordable and stable during storage, which allows to carry out the reaction under normal conditions and gives the opportunity not to contaminate the reaction mixture extraneous ions, as in the substitution of NH4+on (C2H5)4N+there is only the additional number of NH4OH.The use of the mother liquor may due to the fact that during the reaction consumes NH4ReO4(solid), H2S (gas) and (C2H5)4NOH (aqueous solution). All other reagents serve as a medium for education (C2H5)4NReS4. Thus, in the mother solution is added an aqueous solution (C2H5)4NOH, however, the quantity (5 ml) practically does not change the volume of the mother liquor. The amount of ammonium perrhenate is determined by its solubility, and the introduction of a hydroxide of tetraethylammonium is abundant for a complete passage of the reaction.Pass hydrogen sulfide through the mother solution due to the formation of sulfide in the ammonia-ethanol solution and substitution of oxygen in ReO4-the sulfur in the formation of the target product.Thus, the use of the mother liquor allows the 95-96%
Industrial applicability is illustrated by examples.The method is as follows.To a solution of ammonium perrhenate in a mixture of ammonia-ethanol add the hydroxide of tetraethylammonium, ammonium polysulfide and within 5 min after the reaction mixture miss sulfide. After the reaction, the mixture is left for a day, the precipitation tetrathionate of tetraethylammonium separated by filtration, washed and dried. The resulting crystalline product precipitates dark purple color. The yield of the target product 95-96%
P R I m e R 1. 2 g of ammonium perrhenate dissolved in 30 ml of aqueous ammonia solution and 10 ml of 30% aqueous solution of hydroxide of tetraethylammonium. To the solution was added ethanol, a few milliliters of ammonium polysulfide and a saturated solution of hydrogen sulfide for 5 minutes at 24 h, the precipitation was filtered, washed with ethanol, ether and dried in vacuum. Received 3,15 g (C2H5)4NReS4. The output is 95.2%
Found, From 22.0; N 4,6; N 3,14; S 29,1; Re 41,0.For C8H20NReS4calculated From 21.6; H 4.5; N 3,15; S 28,9; Re 41,9.The IR spectrumRe-S482 cm-1.Data of x-ray phase analysis are in good agreement with literature data, Polak and 10 ml of 30% aqueous solution of hydroxide of tetraethylammonium. To the solution was added ethanol, a few milliliters of ammonium polysulfide and a saturated solution of hydrogen sulfide for 5 minutes at 24 h, the precipitation was filtered, washed with ethanol, ether and dried in vacuum. Received 2.85 g (C2H5)4NReS4. Output 95.6% of
To the stock solution was added 1 g of ammonium perrhenate. The resulting solution was saturated with hydrogen sulfide for 5 minutes at 24 h, the precipitation was filtered. Obtained 1.6 g of product. The output 96%
P R I m e R 3. To the stock solution obtained according to example 2, was added 2.2 g of ammonium perrhenate and 5 ml of hydroxide tetraethylammonium. The resulting solution was saturated with hydrogen sulfide 5 minutes After 24 hours the precipitate was filtered. Obtained 3.5 g of product. Output 95.9% of
The method allows to obtain tetratogenic of tetraethylammonium, which can be used to produce polynuclear tocomplex rhenium and catalysts based on them. 1. The METHOD of OBTAINING TETRATHIONATE of TETRAETHYLAMMONIUM interaction derived tetraethylammonium with ammonium polysulfide and registertask reagent in the environment of the solvent, followed by separation of the target product, characterized in that as a derivative of tetraethylammonium use Hydra the water-ammonia-alcohol medium by sequential processing of perinata of ammonia in the ammonia-ethanol solution aqueous solutions of hydroxide tetraethylammonium and ammonium polysulfide and subsequent transmission of hydrogen sulfide in the reaction mass.2. The method according to p. 1, characterized in that the resulting solid reaction, the target product is filtered off and the mother liquor is returned to the beginning of the process.
FIELD: organic chemistry, medicine, physiology.
SUBSTANCE: invention relates to agents for regulation (maintaining or suppression) of physical working ability and/or adaptation to different variants represented by solvated complex compounds of the general formula (I): Katm+[L1 qEL2]Ann- x p.Solv (I) wherein L1 means aminothiols of the formula: R1NHCH(R2)(CH2)1-2SR3 wherein R1 means hydrogen atom (H), (C1-C20)-alkyl or RCO; R means (C1-C19)-alkyl; R2 means H or carboxyl; R3 means H, (C1-C20)-alkyl, (C2-C20)-alkenyl or benzyl; q = 1, 2 or 3; L2 means halogen atom, water and/or organic ligand. For example, bis-(N-acetyl-L-cysteinato)aquozinc (II) diheptahydrate suppresses physical working ability and in the dose 50 mg/kg increases reviving time of mice by 6 times and cats - by 2.8fold under conditions of acute hypoxia with hypercapnia, and increases reviving time of mice by 4 times under conditions of acute hypobaric hypoxia. Under the same conditions the known antihypoxic agents amtizol, acizol or mexidol are inactive or less active significantly by their activity. Bis-(N-acetyl-L-cysteinato)-ferrous (II) pentahydrate is more active as compared with the known antihypoxic agents and protects experimental animals in 4 variants of hypoxia. Bis-(N-acetyl-L-cysteinato)zinc (II) sulfate octahydrate is similar to enumerated compounds by its antihypoxic activity.
EFFECT: valuable medicinal properties of compounds.
4 cl, 1 dwg, 11 tbl, 33 ex
FIELD: catalyst preparation methods.
SUBSTANCE: invention relates to preparation of manganese (III) acetylacetonate, which can be used as catalyst as well as vinyl monomer polymerization initiator. Method is implemented in aqueous medium with ammonium acetylacetonate freshly prepared by mixing acetylacetone with aqueous ammonia solution. Hydrogen peroxide is used as oxidant and sodium bicarbonate is additionally introduced into reaction mixture. Following consecutive operations are carried out: reaction of manganese (II) chloride tetrahydraye with sodium bicarbonate; separating thus formed manganese (II) bicarbonate in the form of paste; adding ammonia acetylacetonate and then hydrogen peroxide aqueous solution to the paste; and recovering manganese (III) acetylacetonate with yield 95%.
EFFECT: improved economical and environmental characteristics of process.
FIELD: chemical technology.
SUBSTANCE: invention relates to technology for synthesis of acetic acid inorganic salts. Method involves interaction of metallic manganese or its dioxide with acetic acid in the presence of oxidizing agent. Process is carried out in beaded mill of vertical type fitted with reflux cooling-condenser, high-speed blade mixer and glass beads as grinding agent loaded in the mass ratio to liquid phase = 1.5:1. Liquid phase represents glacial acid solution in ethylcellosolve, ethylene glycol, 1,4-dioxane, isoamyl alcohol and n-butyl alcohol as a solvent. The concentration of acid in liquid phase is 3.4-4 mole/kg. Then method involves loading iodine in the amount 0.025-0.070 mole/kg of liquid phase, metallic manganese and manganese dioxide in the mole ratio = 2:1 and taken in the amount 11.8% of liquid phase mass. The process starts at room temperature and carries out under self-heating condition to 30-38°C to practically complete consumption of manganese dioxide. Prepared salt suspension is separated from beads and unreacted manganese and filtered off. Filtrate is recovered to the repeated process and prepared precipitate is purified by recrystallization. Invention provides simplifying method using available raw and in low waste of the process.
EFFECT: improved method of synthesis.
3 cl, 9 ex
FIELD: chemical industry; methods of production of the bromine derivatives of fullerene С60.
SUBSTANCE: the invention is pertaining to the method of production of the bromine derivatives of fullerene С60. The process consists in the interaction of the bromoform and the tetra bromomethane with fullerene С60 at presence of the rhodium-containing catalyst - Wilkinson's complex [RhCl(PPh3)3] at the temperature of 100°С within 10-20 hours, at the molar ratio of [Rh]:[C60]:[CHBr3 or CBr4]= 1:100:100-500. The technical result of the invention is the increased output of the product, the reduced amount of the wastes, the insignificant consumption of the catalyst.
EFFECT: the invention ensures the increased output of the product, the reduced amount of the wastes, the insignificant consumption of the catalyst.
3 ex, 1 tbl
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to an improved solid-phase method for synthesis of radioisotope indicators, in particular, for synthesis of compounds labeled with 18F that can be used as radioactive indicators for positron- emission tomography (PET). In particular, invention relates to a method for synthesis of indicator labeled with 18F that involves treatment of a precursor fixed on resin if the formula (I): SOLID CARRIER-LINKER-X-INDICATOR wherein X means a group promoting to nucleophilic substitution by a definite center of a fixed INDICATOR with 18F- ion for preparing a labeled indicator of the formula (II): 18F-INDICATOR; to compound of the formula (Ib):
and compound of the formula (Ih): ;
to radiopharmaceutical set of reagents for preparing indicator labeled with 18F for using in PET; to a cartridge for radiopharmaceutical set of reagents for preparing indicator labeled with 18F for using in positron-emission tomography.
EFFECT: improved method of synthesis.
13 cl, 1 sch, 3 ex
FIELD: chemical industry; methods of production of the manganese salts with the organic acids.
SUBSTANCE: the invention is pertaining to production of the manganese salts with the organic acids in particular, to the salt of the divalent manganese and formic acid. The method is exercised by interaction of manganese, its oxides in the state of the highest valence with the formic acid solution in the organic solvent in the presence of iodine as the stimulating additive. The production process is conducted in the bead grinder of the vertical type having the revertive cooler-condenser, the high-speed paddle stirrer and the glass beads of in the capacity of the grinding agent loaded in the mass ratio to the loading of the liquid phase as (1÷2): 1. The liquid phase consists of the formic acid solution in the organic solvent. The concentration of the acid is taken within the range of 3.5÷10.8 mole/kg. In the loaded liquid phase they dissolve the stimulating additive of iodine in the amount of 0.025-0.100 mole/kg of the liquid phase. The ratio of the masses of the liquid phase and the total of the metallic manganese and the manganese oxide are as(4.9÷11):1. The molar ratio of the metal and the oxide in the loading is as (1.8÷2.,2):1. The metal and the oxide are loaded the last. It is preferable in the capacity of the dissolvent to use the butyl alcohol, ethyl acetate, ethylene glycol, 1.4-dioxane, dimethyl formamide. The production process is started and conducted at the indoor temperature up to practically complete(consumption of the whole loaded manganese oxide. Then the stirring is stopped, the suspension of the salt is separated from the beads and the nonreacted manganese and after that conduct filtration. The filtrate and the nonreacted manganese are returned into the repeated production process, and the filtered out settling of the manganese salt is exposed to purification by recrystallization. The technical result of the invention is - simplification of the method at usage of accessible reactants.
EFFECT: the invention ensures simplification of the method at usage of accessible reactants.
16 ex, 2 tbl
SUBSTANCE: invention is related to improved method for preparation of manganese oxalate (II) by means of direct interaction of metal with acid in bead mill in presence of liquid phase, in which manganese and oxalic acid are loaded into bead mill in stoichiometric ratio in amount of 0.75-2.4 mole/kg of load at mass ratio of load and glass beads of 1:1.2, liquid phase dissolvent used is water or organic substance, or mixture of organic substances; loading is carried out in the following sequence: liquid phase dissolvent, acid, then metal; process is started at room temperature and is carried out under conditions of forced cooling in the temperature range of 18-39°C with control over procedure by sampling method to practically complete spend of loaded reagents for product making, afterwards mixing and cooling are terminated, suspension of reaction mixture is separated from glass beads and filtered, salt deposit is sent for product cleaning from traces of non-reacted metal, and filtrate is returned into repeated process.
EFFECT: method makes it possible to produce target product in absence of manganese dioxide and stimulating additive at temperatures close to room temperature.
2 cl, 13 ex, 2 tbl
SUBSTANCE: invention refers to chelating agents and their technetium complexes to be used as radiopharmaceuticals and characterised by formula I where X is -NR-, -CO2-, -CO-, -NR(C=S)-, -NR(C=O)-, -CONR- or Q; Y represents amino acid, -CH2-, -CH2OCH2-, -OCH2CH2O- or X; Z is an aggregation from peptides, their analogues, substrata, antagonists or enzyme inhibitors, receptor-bonding compounds, oligonucleotides, oligo-DNA- or oligo-RNA-fragments; n is a number 1 to 8; m is a number 0 to 30; R represents H, C1-4alkyl, C2-4alkoxyalkyl, C1-4hydroxyalkyl or C1-4fluoroalkyl; Q represents remains of succinimide , A is a pharmaceutically acceptable anion.
EFFECT: production of new chelating agents applicable for making the technetium complexes.
22 cl, 12 ex, 3 dwg, 2 tbl
SUBSTANCE: invention relates to an improved method of producing manganese (II) fumarate from manganese metal and its oxide (III) through direct reaction of the metal and its oxide Mn2O3 with an acid in the presence of a liquid phase and a stimulating iodine additive in a vertical type bead mill with glass beads as grinding agent. The metal and its oxide are loaded in molar ratio (2±0.1):1 in total amount of 7.87 to 10.93% of the mass of the load. Acid is added with 15 to 25% excess of the calculated value, equal to the number of moles of metal and twice the number of moles of metal oxide in the load. The base of the liquid phase is isoamyl alcohol, in which the iodine stimulating additive is dissolved in amount of 0.02 to 0.05 mol/kg. Glass beads are loaded first, in mass ratio to the reaction mixture of 1.35:1, and then later the liquid phase solvent, acid and stimulating additive, and after brief stirring, metal oxide and metal, stirring all the while. Taking this moment as the beginning of the process, forced cooling is introduced right away. Operating temperature is stabilised in the range 33 to 45°C and in this mode, the process is carried out until virtually quantitative conversion of metal and its oxide to the target salt, after which stirring and forced cooling are stopped. The reaction mixture is separated from the glass beads, cooled to temperature 5 to 6°C and kept at that temperature for 1 to 2 hours. The solid phase of the target salt is filtered off and washed with isoamyl on a filter cooled to approximately the same temperature, after which it is taken for purification by recrystallisation. The filtrate and the cleaning solvent, containing excess acid, the bulk of the stimulating additive and a certain amount of dissolved target salt, are returned for loading in the repeated process. The process is carried out in light temperature conditions. The target substance can be easily separated.
EFFECT: design of a low-waste method, which allows for obtaining target product from available manganese oxide with an easy to implement process.
SUBSTANCE: method of synthesis of manganese (II) fumarate through direct reaction of metal with acid is presented. The process is carried out in a vertical type bead mill with mass ratio of beads to the reaction mixture equal to 1:1, and the liquid phase is a solution of fumaric acid in an organic solvent with content of acid of 0.70-1.80 mol/kg. Manganese is taken in stoichiometric amount with acid or in deficiency of up to 5%. The process is started by loading the liquid phase solvent and acid and preparation of the acid solution in a bead mill, after which metal is loaded and the process is carried out at temperature ranging from 25 to 35°C while preventing spontaneous increase of temperature through forced cooling and controlling through sample taking and determination of manganese salt in the samples and residual amount of acid until attaining values close to calculated values during quantitative conversion of the reagent in deficiency. After that stirring and cooling are stopped. The suspension of the reaction mixture is separated from the glass beads, cooled to temperature between 5.2 and 6.2°C and filtered. The filtering residue is washed with the liquid phase solvent, cooled to approximately the same temperature, and taken for purification by recrystallisation. The filtrate and the washing solvent are returned to the repeated process.
EFFECT: method is easy to implement, the end product can be easily separated and there are no auxiliary materials which contaminate the obtained product.
2 cl, 11 ex