The method of obtaining dimethylzinc
(57) Abstract:The invention relates to the production of Organoelement compounds, in particular dimethylzinc. The method is carried out by reacting iodotope bromide with alloy zinc-copper-silver. This is achieved by reducing the duration of the synthesis process dimethylzinc and increasing the yield of the target product. The invention relates to the production of Organoelement compounds, in particular dimethylzinc.A method of obtaining dimethylzinc by interaction iodotope bromide with zinc-copper alloy . The alloy contains 8 - 10 wt.% copper and 90 - 92 wt. % zinc and is prepared by heating a mixture of powdered metals to a temperature of 420oC in an inert atmosphere. Air alloy rapidly loses its activity due to oxidation and therefore it is prepared just prior to synthesis dimethylzinc. The synthesis is carried out by introducing iodotope bromide to crushed zinc-copper alloy is added dropwise in an inert gas atmosphere with constant stirring of the reaction mass. The process proceeds in two stages, the first of which interact iodotope bromide with alloy education promezhutochnoC) and lasts for 9 to 15 hours Of which 3 hours is spent on the gradual addition iodotope methyl, and the remaining time to complete its interaction with the alloy and the formation of methylsergide
< / BR>In the second stage, the temperature of the reaction mixture rises to 60 - 65oC is the disproportionation of methylsergide education dimethylzinc:
2CH3ZnI _ (CH3)2Zn+Zn+I2< / BR>Phase disproportionation continues for 7 to 9 h, the reaction mass Argonauts target product. Contained in the copper alloy of direct participation in the reaction does not accept or after the distillation dimethylzinc remains in a solid non-volatile reaction slurry.The total duration of the process of obtaining dimethylzinc in a known manner (without taking into account the time of its isolation from the reaction mass reaches one-day (16 - 24 h). Despite guidance on quantitative (100%) the yield of the target product by a known method, its real reproducible value is only 70 - 80% of theoretical.This known method of obtaining dimethylzinc selected by the authors as a prototype of the invention as closest to him tenia dimethylzinc is the long duration of the process, not a high yield of the target product, the impossibility of making alloy zinc-copper in advance due to its oxidation.The problem solved by the invention is the increased activity of the zinc-copper alloy, leading to reduced synthesis time dimethylzinc and increase its output.The problem is solved in that in the known method of obtaining dimethylzinc interaction iodotope bromide with zinc-copper alloy, the alloy further added silver in an amount of 0.1 to 1.0 wt.% when the following concentrations of all ingredients, wt.%:
Zinc - 89 - 91,9
Copper - 8 - 10
Silver - 0,1 - 1,0
Due to the introduction of silver in the zinc-copper alloy increases its chemical activity and stage of formation of the intermediate methylsergide significantly reduced in time and ends almost simultaneously with the completion of the addition iodotope bromide. After 0.5 h after boiling iodotope bromide in the reactor stops. Approximately 1.5 times (up to 5 - 6 h) and reduced phase disproportionation of methylsergide education dimethylzinc. The total duration of the process of obtaining dimethylzinc according to the invention, the composition is portsionirovaniem). Thus, the duration of the process of obtaining dimethylzinc reduced 1.7 - 2.8 times (8,5 - 9,5 h by the proposed method; 16 to 24 h in the prototype). Simultaneously, 87 - 95% of theoretical increases the yield of the target product, that is 1.2 - 1.3 times in comparison with the prototype. In addition, the addition to the alloy of silver in an amount of 0.1 to 1.0 wt.% increases its resistance to oxidation and contributes to the conservation of chemical activity in a long time. For example, the syntheses dimethylzinc carried out immediately after preparation of ternary alloy zinc-copper-silver and one month after its storage in the air gave the same results on the yield of the target product and the duration of the process. It allows you to separate in time the processes of preparation of the alloy and its use, that is, to produce the alloy in advance, which is particularly beneficial during production dimethylzinc.Used according to the invention, an expensive noble metal (silver) after synthesis dimethylzinc and its distillation from the reaction mass remains in the sludge and can be selected from it for reuse in the preparation of the alloy.The essential features offers the becoming of this alloy, wt. %: 89 - 91.9 zinc; 8 - 10 copper; 0.1 to 1.0 silver. These features combine to provide a positive effect, which consists in reducing the duration of the process of obtaining dimethylzinc and increase the yield of the target product. If the content of silver in the alloy is less than 0.1 wt.%, the specified positive effect is not achieved. Increasing the concentration of silver in the alloy above 1.0 wt.% does not increase the positive effect, and therefore impractical. Only the silver content in the concentration range of 0.1 - 1.0 wt.% provides maximum effect: reduce process time: 1.7 - 2.8 times and increase the yield of the target product 1.2 - 1.3 times.Claimed in the present invention the combination of features - the presence of additional ingredient (silver) at a concentration of 0.1 - 1.0 wt.% - it is not known from open sources of scientific, technical and patent information and is new.The following is a specific example of the invention:
Preparation of alloy zinc - copper - silver.In a quartz Cup thoroughly mixed with 900 g of zinc powder, 95 g of copper powder and 5 g of silver powder. Cup us is with argon. After being dismissed from the office of air the mixture is heated to a temperature of 400 - 420oC and incubated for 30 to 45 minutes While the zinc is melted and forms a gray-black mass of the alloy, which after cooling is easily crushed to a granular powder.The result is 1 kg of an alloy containing 90 wt.% zinc; 9,5% wt. % of copper and 0.5 wt.% silver.Getting dimethylzinc.In all-metal synthesis reactor with a capacity of 3 l was placed 500 g of crushed alloy. The reactor is equipped with a "face", which circulates liquid coolant (water), allow to heat it in the temperature range 5 - 80oC. Reactor provided with a mechanical agitator with electric and reflux condenser and addition funnel, completely made of metal and provided with viewing Windows to monitor the feed rate and the rate of boiling in the reactor liquid reagents.In an addition funnel pour 367 g (161 ml) iodotope bromide, after which the reactor was rinsed with argon. Then into the reactor at a rate of 1 ml/min serves modesty methyl. The interaction of the reagent with a triple alloy zinc-copper-silver begins immediately. Since this reaction is exothermic, heat is was ivalsa. With this aim, adjust the feed rate to the reactor new portions iodotope bromide and temperature of the reactor due to its external cooling or heating. Within 3 hours into the reactor dropwise poured all modesty methyl. After this boiling iodotope methyl slows, and then stops. To complete the process of its interaction with alloy reactor is forcibly heated to a temperature of 42 - 45oC for half an hour. When boiling iodotope methyl again slows down, the reactor is heated to 60 - 65oC and maintained at these conditions for 6 hours After that, the reflux condenser is replaced by a direct and conduct the distillation dimethylzinc. Obtain 115 g of the target product.Output dimethylzinc is 93% of theoretical (eudistoma the stands). The method of obtaining dimethylzinc the interaction of methyl iodide with zinc-copper alloy, characterized in that the zinc - copper alloy additionally contains silver at the following ratio of ingredients, wt.%:
Zinc - 89 - 91,9
Copper - 8 - 10,0
Silver - 0,1 - 1,01
FIELD: chemistry of organometallic compounds, chemical technology.
SUBSTANCE: invention relates to the improved method for preparing the chelate compound bis-(1-vinylimidazole)zinc diacetate (I) representing the medicinal preparation of acizol that is the effective antidote and antioxidant. Method for preparing the compound (I) is carried out in the absence of organic solvents at temperature 20-35°C in the mole ratio 1-vinylimidazole : zinc diacetate in the range from 10:1 to 3:1. Method provides exclusion fire hazard and explosion hazard solvent from the technological process and enhancement of the yield of highly pure acizol satisfied for Pharmacopoeia requirements.
EFFECT: improved method for preparing.
2 cl, 4 ex
FIELD: luminescent materials.
SUBSTANCE: invention provides novel electroluminescent material comprised of injecting layer, metal chelate complex-based active luminescent layer, hole-transition layer and hole-injecting layer. Luminescent substance is selected from oxyquinolate metallocomplexes of zinc 8-hydroxy-2-methoxyquinolate and zinc 8-hydroxy-2-methylquinolate. Electroluminescent material shows emission in green spectrum region.
EFFECT: increased heat resistance and widened choice of stable green-emitting materials.
2 cl, 3 ex
FIELD: organic chemistry, medicine, oncology.
SUBSTANCE: invention relates to photosensitizing agents used in photodynamic therapy of neoplasm and some other diseases. Invention describes tetraazachlorines of the general formula: wherein R1R2 mean -C6H4; R3 = R4 = R5 mean -CH3; M means HH (H2TBTAC); R1R2 means 1,2-C10H6; R3 = R4 = R5 mean -CH3; M means Zn(Zn-1,2-TNTAC); R1 = R2 mean -C6H5; R3 = R4 = R5 mean -CH3; M means HH (H2TACPh6); R1 = R3 mean hydrogen atom (H); R2 =R4 mean -C6H5; R5R5 mean -CH2N(CH3)CH2; M means HH (H2PyrTACPh4); R1R2 mean 4-C(CH3)3C6H3; R3 = R4 mean hydrogen atom (H); R5R5 mean -CH2N(CH3)CH2; M means HH (H2TBtTACPyrN-Me) used as photosensitizing agents in the near IR-region of spectrum for carrying out the photodynamic therapy. These photosensitizing agents possess the intensive absorption in spectral region 710-750 nm and can be used in treatment of deep tumor tissues by the photodynamic therapy method.
EFFECT: valuable medicinal properties of compounds.
1 cl, 4 ex
FIELD: production of high temperature superconductors.
SUBSTANCE: invention relates to electrochemical synthesis of metal β-diketonates, in particular acetylacetonates. Synthesis of Cu(II) and Zn(II) acetylacetonates in carried out by electrolysis of acetylacetone solution and base electrolyte in acetonitryl in ratio of (1:10):0.5:100, with electrodes made of metal presenting in produced acetylacetonate, at current density not more mA/cm2 by using pulse current. Pulse time is controlled by pulse forming unit connected in parallel to elecrtolyzer. As base electrolyte preferably lithium perchlorate or lithium chloride is used.
EFFECT: controlled process for production of metal acetylacetonates.
5 cl, 2 ex, 1 dwg
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to the improved method for synthesis of zinc phthalocyanine of high purity degree that can be used as a photosensitizing agent for photodynamic therapy. Method is carried out by interaction of phthalonitrile with zinc salt at heating in the presence of a tertiary amine - N,N-dialkylaniline, N,N-dialkylethanolamine or trialkylamine in an aprotonic dipolar solvent medium, for example, dimethylformamide. Method provides preparing the end product with 97-99% content of the basic substance. Method shows the technological effectiveness as it suggests using inexpensive reagents, small amount of solvent and it doesn't require the complex purifying procedures.
EFFECT: improved method of synthesis.
2 cl, 4 ex
FIELD: chemistry, chemical technology.
SUBSTANCE: invention relates to quaternized phthalocyanines and their using for treatment of water against bacterial pollution. Invention describes novel quaternized phthalocyanines representing poly-(trialkylammoniomethyl)-substituted zinc and aluminum phthalocyanines that are sensitizing agents in formation of singlet oxygen by effect of visible light. Also, invention relates to a method for photodisinfection of water by using these quaternized phthalocyanines or their mixtures with dyes of acridine, rhodamine or phenothiazine series and radiation in visible range in the presence of oxygen that provides the effective treatment of water against bacterial pollution.
EFFECT: valuable properties of compounds, improved method of water treatment.
3 cl, 5 tbl, 16 ex
FIELD: medicine, in particular photosensitizing agents for photodynamic therapy.
SUBSTANCE: invention relates to quaternary phthalocyanines of general formula MPc(CH2X)nCln, wherein Pc is phthalocyanine rest C32H16N8; M is Zn, AlY; n = 6-8; X is Y is Cl, OH, OSO3H, useful as photosensitizing agents in photodynamic therapy having high photoinduced activity in vivo and in vitro.
EFFECT: new class of effective photosensitizing agents useful in treatment of various tumors by photodynamic therapy.
1 dwg, 8 ex
FIELD: medicine, in particular photosensitizing agents for antimicrobial photodynamic therapy.
SUBSTANCE: invention relates to new photosensitizing agents for antimicrobial photodynamic therapy namely cationic phthalocyanines of general formula MPc(CH2X)nCln, wherein Pc is phthalocyanine rest C32H16N8; M is Zn, AlY; n = 6-8; X is Y is Cl, OH, OSO3H. Claimed agents is characterized by wide range of antimicrobial activity. Single complex action of nontoxic in darkness micromolar (up to 2.0 muM) concentration thereof and low dose of red irradiation make it possible to produce high inactivation levels (up to 97-99 %) both gram-negative bacteria and yeast fungi of genus Candida.
EFFECT: improved agents for treatment of various severe complications of inflammation diseases.
3 dwg, 13 ex, 2 tbl
FIELD: organic chemistry.
SUBSTANCE: invention relates to novel compounds, namely zinc bis-[2-(tosylamino)benzylidene-N-alkyl(aryl, hetaryl)aminates] of the general formula (I): wherein Ts means tosyl; R means (C1-C6)-alkyl with exception isopropyl, (C1-C6)-alkyl-substituted phenyl, (C1-C6)-alkoxy-substituted phenyl with exception para- and ortho-methoxyphenyl, pyridyl, (C1-C6)-alkylpyridyl, or R + R form in common disulfidodialkyl group -(CH2)n-S-S-(CH2)n- wherein n = 1-3, but preferably to zinc bis-[2-(tosylamino)benzylidene-N-alkylidenemercaptoaminates] of the general formula (Ia): Compounds can be used for synthesis of light-radiating organic diode of white and visible light. Fluorescence can be observed in blue region of spectrum with fluorescence bands maximum at 428-496 nm. Quantum yields are 0.2-0.25.
EFFECT: valuable physical properties of compounds.
5 cl, 8 ex
FIELD: luminescent substances, organic chemistry.
SUBSTANCE: invention relates to electroluminescent materials containing organic luminescent substance. Invention describes novel electroluminescent material consisting of injection layer, active luminescent layer based on chelate metal complex, hole-transporting layer and hole-injecting layer. Material comprises metal complexes based on sulfanyl derivatives of 8-aminoquinoline as a luminescent substance, in particular, zinc complexes of 8-(methylsulfanylamino)-quinoline and 8-(3,5-difluorophenylsulfanylamino)-quinoline. Material comprises a mixture of triphenylamine oligomers as a hole-transporting layer. Invention provides creature of electroluminescent material showing the enhanced moisture resistance, enhanced resistance to crystallization and enhanced thermal stability.
EFFECT: improved and valuable properties of material.
4 cl, 5 ex