Method of production of the bromine derivatives of the fullerene c60
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
The invention relates to the field of organic synthesis, in particular the chemistry of bromine derivatives of fullerene C60.
Fullerene is one of the allotropic modifications of carbon and is a polyhedral (spherical) cluster consisting of 60 or more carbon atoms. [1. Whishaw, Ivemania: USP. chemistry. 62(5), (1993)].
Derivatives of fullerene widely used as superconductors, solid carbon films, materials for nonlinear optics, and useful properties often exhibit a fullerene derivative obtained on the basis of chemical reactions With60with metals, volatile organic molecules. For this reason, globally deployed extensive studies of chemical reactions of fullerenes (Whishaw, Ivemania: USP. chemistry. 62(5), (1993)).
Reactivity of fullerenes is very unusual. The behavior of fullerenes appear in the most simple chemical reactions: hydrogenation, galogenirovannyie, oxidation, etc.
Due to the presence in the molecule of a large number of double bonds (hence, reaction centers), the interaction of fullerene With60with many reagents is very tricky and leads to the formation of a mixture of isomers. This property of fullerene evident in the synthesis galoidoproizvodnykh, in particular, bromine derivatives of fullerene
In 1991-1992, it was found that the fullerene C60interacts with liquid bromine, giving a complex mixture of products joining With60Brn. Further, these studies have not been great development because of the difficulty of allocating individual compounds and monitoring the process of halogenation [2. Engkaulah, Ehimare. USP. chemistry. 62(5), (1993)].
In order to obtain the brominated products with low content of bromine, the reaction was carried out at the ratio of bromine to the fullerene 1÷3:1. However, bromination at a concentration of reagents is not. [3. R.Taylor, A.G.Avent, P.R.Birkeu, T.J.S.Dennis, J.P.Hare et al. Pure and Appl. Chem. Vol. 65, No. 1, p.135, 1993]. And only by using a substantial excess of bromine fullerenes With60/S70(a mixture of 85:15) or clean With a60are bromirovanii liquid bromine at 20°s and 50°With up With60Brn(n=2-4)with the IR spectrum, the absorption at 515-545 cm-1characteristic of the C-Br. [4. G.Olah, J.Bucsi, C.Lambert, R.Aniszfeld, N.J.Trivedi et al. J. Am. Chem. Soc., V.113, p.9385, 1991].
The outputs of the products obtained and the conversion of the original fullerene60/S70in the work not specified.
Fullerene C60it is soluble in CS2and holding the synthesized excess of liquid bromine in a solvent leads to the formation of dark brown crystals with a yield of 80%. Coz the ACLs data of x-ray analysis of this compound is 1, 3, 6, 11, 13, 18, 28, 31-octabromodiphenyl-C60. Bromination of fullerene C60in benzene or CCl4gives red crystals in the form of plates, the structure of which is defined as 1, 6, 9, 12, 15, 18-hexabromobenzene-C60. This same product was obtained when carrying out the reaction in chloroform [5. F.N.Tebbe, R.L.Harlow, D.B.Chase, D.L.Thorn, G.C.Campbell et al. Science V.256, p.882, 1992; 6. P.P.Birkett, P.B.Hitchcock, H.W.Kroto, R.Taylor, D.R.M.Walton. Nature V.357, p.479, 1992].
Processing of fullerene C60liquid bromine is completed by formation of the product composition With60Br24in the form of crystals yellow-orange color. The reaction of the synthesized reversible. Polybromide fullerene easily helps eliminate bromine, turning into dibromide (C60Br2and tetrabromide (C60Br4) .
Disadvantages of the method:
1. Method of ethnological, inconvenient and difficult to instrument design.
2. Bromine is corrosive, poisonous compound, especially at elevated temperatures; acts on the respiratory organs, the skin.
3. Low selectivity.
4. High consumption brainwashes agent.
The authors of this application has proposed a method of obtaining bromine derivatives of fullerene C60that does not have these disadvantages.
The method consists in the interaction of bromoform (CHBr3) and tetrabromomethane (CBr4with fullerene C60in prisutstvie and homogeneous metal complex registeruser catalyst - complex Wilkinson [RhCl(PPh3)3] at a temperature of 100°C for 10-20 hours. The reaction CHBr3(or CBr4with fullerene C60formed hydrobromide (or bromo derivatives) fullerene with a content of from 1 to 6 bromine atoms in the molecule With60and the number of bromine atoms in the resulting product is determined by the reaction conditions
Special experiments were optimal molar ratio of catalyst and reagents:[Rh]:[C60]:[CHBr3or CBr4]=1:100:100 to 500, preferably 1:100:300. The reaction can be performed in two ways:
1) upon prolonged heating at 100°20 hours;
2) at 100°10 hours with an activated form of the catalyst, which had been pre-heated solution of catalyst [RhCl(PPh3)3] CHBr3(or CBr4) in 1 ml of toluene at 180°C for 0.5-1 hours
The advantages of the proposed method.
1. High output bromo derivatives of fullerene C60(70-81%).
2. Availability pomeroyi and hydrobromide reagents.
3. The simplicity of instrumentation.
4. The versatility of ways depending on the reaction conditions to selectively receive bromo derivatives of fullerene with 1-6 halogen atoms.
5. Minor consumption of catalyst.
6. Reducing waste.
7. Reducing labor and energy costs and environmental safety.
The method is illustrated by examples.
Example 1. In a glass ampoule (V=20 ml), or in mikroavtobus stainless steel (V=20 ml) (the results of parallel experiments do not differ) under argon was placed 0.1 mmole RhCl(PPh3)3added 10 mmol of fullerene C60, 10-50 mmol tetrabromomethane (CBr4) in 5 ml of toluene. The ampoule was sealed (autoclave was closed and heated at 100°C for 20 hours with constant stirring. After the reaction, the ampoule (autoclave) was cooled to 20°C, dissected, the resulting reaction mass was filtered through a layer of alumina (eluent - chloroform), and then the solvent was evaporated in vacuum. To remove traces of the solvent the residue was kept under vacuum at 50°C for 5 hours
The reaction mass was analyzed by high performance liquid chromatography (C18 column, eluent: toluene-chloroform).
The purified product is a crystal dark brown color. IR range (νcm-1, 525, 575 (C-Br).
According to elemental analysis dibromopropane fullerene has the following composition. Found: C, 81.74%; Br, 18.26%. With60Br2.
Elemental analysis data of other bromine derivatives are listed below:
With60Br4: C, 68.99%; Br, 31.01%
(Calculated, %: C, 59.93; Br, 30.75)
With60Br6: C, 59.93%; Br, 40.07%
(Calculated, %: C, at 60.05; Br, 39.95)
Example 2. Activation of the catalyst: in a glass ampoule under argon was placed 0.1 mmole RhCl(PPh3)3, 10 mmol CBr4in 1 ml of toluene, the ampoule was sealed and heated at 180°With 1 hour. After cooling, the ampoule was opened, was added 10 mol fullerene in 4 ml of toluene, sealed ampoule was heated for 10 h at 100°C. Upon completion of the reaction, the treatment of the reaction mixture and isolation of the reaction products as in example 1.
Example 3. In a glass ampoule (autoclave) under argon was placed 0.1 mmol RhCl(PPh3)3added 10 mmol of fullerene, 10-50 mmol of bromoform (CHBr3) in 5 ml of toluene. Ampoule (autoclave) was heated at 100°C for 20 hours with constant stirring. Upon completion of the reaction, the treatment of the reaction mixture and isolation of the reaction products as in example 1.
Found, %: C, 89.73; H 0.12; Br, 10.15. C60HBr.
Calculated, %: C, 89.90; N, 0.13; Br, 9.97
Elemental analysis data of other bromine derivatives of fullerene to the following:
With60H2Br2: C, 81.58%; N, 0.22%; 18.20%
(Calculated, %: C, at 81.66; N, 0.23; Br, 18.11)
With60H3Br3: C, 74.85%; N, 0.29%; Br, at 24.86%
(Calculated, %: C, 74.80; H, 0.31; Br, 24.89)
The results of the experiments are shown in the table.
|The results of experiments on bromirovanii and hydrobromination fullerene C60using CBr4and CHBr3under the action of RhCl(PPh3)3(solvent - toluene)|
|№ №||Booking agent||The molar ratio of [Rh]:[C60]:[CBr4or CHBr3]||Temperature, °C||Pro-have-tel-ness, h||Con-version60, %||The composition of the reaction products, %|
|12.*||-"-||-"-||-"-||10||80||10td align="center"> 10||80|
Experiments 4, 5, 10, 12 carried out with an activated form of the catalyst.
The method of obtaining bromine derivatives of fullerene C60, characterized in that as pomeroyi agents use tetrabromomethane CBr4or bromoform CHBr3that react with fullerene C60in the presence of registeruser catalyst complex Wilkinson [RhCl(PPh3)3], and the molar ratio of the catalyst, fullerene and brainwashes agent is 1:100:100÷500, the reaction is carried out at a temperature of 100°C for 10-20 hours
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: 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: 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: chemical industry; method of production of the carbon-mineral materials.
SUBSTANCE: the invention is pertaining to the field of the production of the carbon-mineral materials. The method of production of the carbon-mineral materials with the high ash percentage and the homogeneous distribution of the phases includes the carbonization of the lignocellulose material chosen from the group of the husks of the rice or the oats, or the wheat straw, by the partial oxidation in the boiling layer at the temperature of 400-800°С in the presence of the catalyst representing the metal oxides deposited on the oxide carrier composed of the "d" elements of the 4-th period of the Periodic system. The method allowed to produce the material possessing the homogeneous distribution at least of two phases, the high ash percentage up to 95 % and the high specific surface up to 250 m2/g in one phase from the high ash percentage lignocellulose wastes of the plant growing.
EFFECT: the invention ensures production of the carbon-mineral materials with the high ash percentage and the homogeneous distribution of the phases.
2 cl, 8 ex, 1 tbl
FIELD: chemical industry; methods of production of the nitrogen-bearing porous carbonic material.
SUBSTANCE: the invention is pertaining to production of the nitrogen-bearing porous carbonic material. The nitrogen-bearing carbonic material is produced from the mixture of the aromatic phenols and о-nitroaromatic amines, or from the mixture of 1,2,3-benzotriazoles and 8-oxiquinoline, either parabanic acid or carbamide in the water solution with hydroxides of the metals of the first (Ia) group of the Periodic table of the elements in the mass ratio of 1:(2-10)of the organic mass to the mass of the hydroxide. The produced mixture is steamed, melted and the formed fusion cake is exposed to the carbonization at 600-1000° C in the reducing or inert medium. The invention ensures production of the nitrogen-bearing porous carbonic materials with the high specific surface and the microporosity.
EFFECT: the invention ensures production of the nitrogen-bearing porous carbonic materials with the high specific surface and the microporosity.
2 cl, 15 ex
FIELD: chemical industry; methods of production of the nanocarbonic materials.
SUBSTANCE: the invention is intended for chemical industry and may be used at production of the heterogeneous catalysts for synthesis of the isoalkanes from the methane, the natural gas, the synthesis gas, the catalytic oxidation of carbon monoxide. The source raw is schungite, which is sequentially treated at heating with the melted alkali at the temperature of no more than 500°C; and in the mode of boiling it is treated with the concentrated inorganic acid, in the capacity of which they use НСl or HF; and with the strong oxidant from the row including HClO4 and ВаО2 in the mode of boiling treatment at the temperature of up to 150°С within no more than 2 h. After treatment with each of these reactants the formed intermediate product is flushed and dried. Then conduct the thermal treatment with the high-temperature gaseous oxidation in the oxygen or air medium in the high-temperature furnace at the temperature of 700-1200°С with production of the target product - the nanocarbonic material. The invention allows to produce the nanocarbonic material containing up to 90 mass % of the nanotubes and others nanocarbonic forms, and up to 70 mass % of the open nanocarbonic forms; and also one time to treat of no less than 100 kg of schungite in one apparatus with the volume of no more than 70 l. At that the output of the nanocarbonic material is up to 20 mass % from the initial mass of mass of schungite.
EFFECT: the invention allows to produce up to 20 mass percent of the nanocarbonic material from the initial mass of schungite.
7 cl, 1 dwg, 7 ex
FIELD: carbon materials.
SUBSTANCE: invention relates to inorganic chemistry of carbon and can be utilized when obtaining stable nano-diamond sols. According to an embodiment of invention, synthetic diamond-containing substance contains 82-91% carbon, 0.8-1.5% hydrogen, 1.1-2.2% oxygen, and 1.1-1.3% metallic impurities with content of non-diamond carbon 2-25% based on total weight of carbon. diamond-containing substance is characterized by ζ(zeta) potential from -40 to -85 mV. According to second embodiment, substance contains 97.5-98.5% carbon, 0.09-0.2% hydrogen, 0.3-0.5% oxygen, and 0.5-0.8% metallic impurities with content of non- diamond carbon 0.2-5% and zeta potential from 0 to -75 mV. Synthetic diamond-containing substance according to invention manifest high colloidal particle stability and are susceptible to be fractioned with narrow particle size distribution: 3 to 1700 nm and 3 to 8000 nm, respectively. Present substances are recovered by treating dry nano-diamond powder obtained from mixture of explosives (trinitrotoluene-hexogen or graphite-hexogen) in boiled organic solvents, succession of solvents going from hydrophobic solvents to hydrophilic ones so that each precedent solvent dissolves well in subsequent one.
EFFECT: increased economical efficiency and commodity of transportation of raw material and diamond-containing substances obtained thereof.
3 cl, 9 dwg, 4 ex
FIELD: medical and biological instrumentation industry; methods of modification of the hydrophobic surfaces.
SUBSTANCE: the invention is pertaining to the method of modification of hydrophobic surfaces and may be used for upgrading the hydrophobic surfaces used in the scanning probe microscopy, in the immune-enzyme analysis, at development of the biochips. The method of modification of hydrophobic surfaces includes deposition on the surface of the modifying monolayer of the complex composition molecules containing the functional group, the section forming the hydrogenous ties and the hydrophobic section. At that as the functional group the molecule contains, at least, one group sampled from the following row:NH2, СООН, СНО,ONH2, SH; as the section forming the hydrogen ties the molecule contains the fragments -NH(CH2)nCO- ,where п=1-5, and as the hydrophobic section the molecule contains the fragment -(СН2)n , where n=5-12, or the similar fragment with one or several insertions of the heteroatoms sampled from the row of O, S, NH. In particular, such molecules may have the following composition[Gly4-NHCH2]2C10H20. The invention allows to ensure the high quality evenness of the modified surfaces, reproducibility of their properties and reduction of the time interval of the modification.
EFFECT: the invention ensures the high quality evenness of the modified surfaces, reproducibility of their properties and reduction of the time interval of the modification.
2 cl, 3 dwg
FIELD: carbon materials.
SUBSTANCE: invention relates to electrochemistry of carbon materials, namely to removing carbon-containing impurities from diamond powders. Method comprises electrochemical treatment of diamond powder in sulfuric acid electrolyte, more specifically in sulfuric acid solution of manganese sulfate while electrochemical treatment is effected at concentration of manganese in electrolyte 15-30 g/L, solids/liquids ratio 1:(3-5), anodic current density 0.10-0.20 A/cm2. and temperature 125 to 170°C for 2 to 7 h. Degree of purification reaches 99.8%.
EFFECT: increased degree of removing residual graphite under relatively low temperature preventing oxidation of diamond.
1 tbl, 7 ex
FIELD: carbon materials.
SUBSTANCE: invention relates to manufacture of activated carbons based on anthracite and process according to invention consists in treating starting material with hydrochloric acid and/or ammonia solution at 50-60°C followed by filtration, drying, and subsequent gradual (10-30°C/min) raise of temperature to 750-800°C to perform activation.
EFFECT: shortened manufacturing time, increased specific surface, adsorption capacity, and crushing resistance of activated carbon.
2 cl, 1 tbl, 9 ex
FIELD: catalyst carrier production.
SUBSTANCE: invention relates to petrochemical and chemical industry and can be used to manufacture carbon catalyst carriers and sorbents. Granulated carbon black is treated at stirring with hydrocarbon gases at 750-1200°C until material compacted by pyrocarbon is formed. Material is the treated in two steps with gaseous oxidant, in particular overheated water steam. In the first step, treatment is carried out in fluidized bed wherein consumption of oxidant is 3.0 to 30.0 kg per 1 kg of pyrocarbon-compacted material to achieve summary pore volume 0.2-0.5 cm3/g. In the second step, product is placed into drum rotating at peripheral velocity 0.2-4.0 rpm and treated with overheated water steam consumed at a rate 2.0-10.0 kg per kg material. Treatment is continued until achieve summary pore volume achieve value 0.5-1.5 cm3/g. Thus obtained porous carbon material is characterized by specific surface 450-700 m2/g and resistance of granules against abrasion 92-96%. Yield of the product is raised by a factor 1.5-2.
EFFECT: improved performance characteristics of product and increased yield.
2 cl, 1 dwg
FIELD: production of nanodiamond suspensions in various media for conducting of plating processes.
SUBSTANCE: method involves providing thermal processing of nanodiamond powder in air at temperature of 440-600 C until powder weight losses reach 5-85%. Thermally processed powder forms stable suspensions in water, ethyl alcohol and other solvents upon common mixing. Sediment stability of nanodiamond suspensions thermally processed in accordance with invention and produced using supersonic treatment is at least 1.5 times as high as similar parameter of nanodiamond suspensions produced by prior art processes.
EFFECT: simplified method allowing stability of nanodiamond suspension in various media to be improved.
FIELD: chemical industry; tire industry; technical rubber industry; other industries; production of the carbon-silica composite.
SUBSTANCE: the invention is pertaining to the sorbents, which may be used, in particular, as the reinforcing fillers in the tire industry and the technical rubber industry, the sorbents for purification from the organic and inorganic impurities and in other processes. The carbon-silica composite including silicon oxide and the carbonic material represents the geometrically structured system consisting of the microspheres of SiO2 and the carbonic fragments bound with SiO2 and having the specific surface areaSBET = 480-760 m2/g, the pores volumeVprs = 0.5-1.1 cm3/g, the mean diameter of the pores of 3-8.2 nanometers measured by the BET method by the nitrogen heat desorption. At that in the infrared spectrum the state of silicon is characterized by availability of the adsorbing bands of the siloxane groups with the wave number v = 1070-1090 cm-1 and the half-width of 55-75 cm-1, availability in the spectra of the RFES of the spectrum lines of silicium Si 2s with the binding energy of 101-102 eV, and the state of carboneum is characterized by availability in the infrared spectrum of adsorbing bands of the carboxyl groups with the wave number v = 1440-1460 cm-1 and the half-width of 60-70 cm-1, availability in the spectra of the RFES of the spectrum lines of Carboneum C 1s with the binding energy of 282-283 eV, the specific surface SBET = 400-600 m2/g, the pores volumeVprs = 0.3-0.9 cm3/g, measured by the BET method by the nitrogen heat desorption. At that the microspheresofSiO2 have the diameter of 3-10 nanometers, the carbonic fragments have the dimension of 20-200 nanometers, the silicon oxide is structured in the form of the secondary globules with the diameter of 100-300 nanometers, the carbonic fragments have the forms of the solid fragments, the tubes and the plates. The invention ensures production of the material with the high reinforcing properties in the elastomers at preparation of the rubbers.
EFFECT: the invention ensures production of the material with the high reinforcing properties in the elastomers at preparation of the rubbers.
7 cl, 2 dwg, 5 ex
FIELD: carbon materials.
SUBSTANCE: invention relates to technology of manufacturing porous carbon materials based on fine-size compositions preferably for use as filter elements in micro- and ultrafiltration processes. According to invention, pore agent is dispersed via diluting it with high-dispersed carbonaceous powder in joint grinding-and-mixing process and resulting mixture is added to charge. Carbonaceous powder utilized is either carbon black or colloidal graphite with particle size not larger than 0.5 μm and pore agent-to-diluent ratio is between 1:1 and 1:2.
EFFECT: increased permeability of materials.
4 cl, 2 tbl, 2 ex