The method of producing phthalonitrile
(57) Abstract:The invention relates to the field of organic chemistry, in particular to a method for production of aromatic NITRILES, namely phthalonitrile used as an intermediate product in the synthesis of pigments and dyes, paints, varnishes, stabilizing agents, and other materials. The inventive method of producing phthalonitrile comprising passing the gas mixture in the ratio of phthalic anhydride : ammonia = 1 : (40 - 100), at 420-480oWith a stationary catalyst bed and the selection of solid phthalonitrile condensation sprayed with liquid ammonia, and the process is carried out on a stationary layer of the catalyst is aluminum oxide, the regeneration of the catalyst is carried out at 430-550oC for 50-70 min oxygen periodically through 950-1050 h his work, with before and after regeneration, the catalyst is rinsed with an inert gas, the exhaust amigadave gases are sent to the joint processing of products of coking. table 2. The invention relates to the field of organic chemistry, in particular to a method for production of aromatic NITRILES, namely phthalonitrile used as an intermediate product with the EN method for the production of phthalonitrile oxidative ammonolysis of o-xylene by reacting with ammonia and air at a molar ratio of o-xylene: ammonia: air, equal 1:15:30, fluidized bed microspherical alumina, processed complex component composition containing oxides of metals Sb, B1, V, Mo, CR [Rizaev R., and others Receive phthalonitrile oxidative ammonolysis of o-xylene.- Chemical industry, 9, 1983, S. 16-18].In the industrial implementation of production phthalonitrile method of oxidative ammonolysis of the whole difficulty lies in the extraordinary explosion of technology. Aromatic hydrocarbons, ammonia, oxygen give explosive mixture and process with heat. The use of equipment during the ammonolysis of the fluidized bed of the catalyst, but also extremely difficult microspherical catalyst allows you to get phthalonitrile in good yield (90%), but at the same time, the process remains complex, energy-intensive, and the production of phthalonitrile high cost. All these factors hinder the implementation of industrial technology phthalonitrile. In addition, o-xylene is currently scarce raw materials.The known method for preparation of aromatic NITRILES, toluenethiol, terephthalonitrile by reacting p-xylene and ammonia in the gas phase at a temperature of 400 to 500oLow yield of NITRILES and duty cycle 30 min, nepriemlim for practical implementation, since all the operations for the preparation and transition to the stage of oxidative regeneration itself and the stage of regeneration is longer than the immediate stage of obtaining phthalonitrile, which makes this method ineffective and unprofitable.The closest in technical essence and the achieved result is a method of producing phthalonitrile comprising passing the gas mixture talamini vapor in the ratio of phthalic anhydride: ammonia = 1: (40100), at a temperature of 420-480oWith a stationary catalyst bed, which is used as the silicate, bentonite, phosphoric acid on silica gel and phosphoric acid on silicate, contact time 0.15 emitting solid phthalonitrile condensation sprayed with liquid ammonia, the exhaust amigadave gases is directed to the irrigation water and concentrated ammonia water dispersed under a pressure of 12 ATM of dry ammonia and water [Dobrovolsky S. Century /P> With all the benefits of this method of obtaining phthalonitrile (the yield of the target product 85-94%) not clear on the question of the regeneration of the catalyst. According to the publication, the catalyst is put through the loop and replaced with a new one. Purification of exhaust gases from ammonia is very complicated and expensive.The objective of the invention is to provide explosion-proof way of getting phthalonitrile with increased productivity due to the implementation of the periodic regeneration of the catalyst, recycling admixtures exhaust gases and a product with a low cost.This object is achieved in that in the method of producing phthalonitrile comprising passing the gas mixture in the ratio of phthalic anhydride: ammonia = 1:(40100) at a temperature of 420-480oWith a stationary catalyst bed and the selection of solid phthalonitrile condensation sprayed with liquid ammonia according to the invention the process is performed on the stationary layer of the catalyst is aluminum oxide, the regeneration of the catalyst is carried out at a temperature 430-550oC for 50-70 min periodically through 950-1050 h his work, with before and after regeneration, the catalyst is rinsed with an inert gas, the exhaust admixtures is auchenia of phthalonitrile with the specified set of features ensures the achievement of the technical result introducing explosion-proof technologies for phthalonitrile by optimizing the regeneration mode, periodic implementation, utilization admixtures waste their joint processing with products of coking coal.This technical result is achieved by solving the problem on inventive step, in particular the implementation process periodically with regeneration of the catalyst is stationary layer of aluminum oxide as the loss of activity due to the intensive education on the surface of the carbon compounds and the direction of exhaust admixtures gases on joint processing of products of coking coal.Research is set to the optimum temperature range for regenerating catalyst - 430-550oWith stores physico-chemical properties of the catalyst layer of aluminum oxide and its subsequent activity. When the temperature of the regeneration of the catalyst is below 430oWith burnout resinous deposits of low-intensity. Increasing the regeneration temperature above 550oWith undesirable because it is not stored porous structure of the catalyst.The regeneration time of catalogados regeneration per unit volume of catalyst. When regeneration of the catalyst is less than 50 min burnout resinous carbon deposits is not enough. To increase the regeneration time of over 70 minutes is impractical because already there was a complete burnout of carbon compounds.To set the interval between regenerations of the catalyst over 1050 h economically and technically impractical because significantly reduces the yield of phthalonitrile. The period between regenerations of the catalyst to take less than 950 h is undesirable, as yet not lose the activity of the catalyst.The need for and feasibility of joint processing of waste admixtures gases forming during the manufacture of phthalonitrile, with products of coking coal is based on the fact that the exhaust gases from the synthesis and condensation of phthalonitrile contain about. %: 4-5 ammonia, 1-2 carbon monoxide and traces of aromatic hydrocarbons, the volume is 50 m3/h, and the products of coking coal - direct coke oven gas coke production also contains ammonia, carbon monoxide, aromatic compounds, the volume is 1600003/H. Served in the products of coking coal urea gases obtained in the production of phthalonitrile, neznachitelinoe catalyst caused by the security management processes: synthesis phthalonitrile and catalyst regeneration.Example. The proposed method of obtaining phthalonitrile carried out on pilot plant was assembled in the workshop of phthalic anhydride by-product coke production JSC "West-Siberian metallurgical plant. Phthalic anhydride was evaporated at a temperature of 160oC. Ammonia and phthalic anhydride was filed in the ratio of 1:80, the obtained gas mixture was passed at a temperature of 450oWith over a stationary layer of the catalyst is aluminum oxide. Regeneration of the catalyst was carried out at a temperature of 510oC for 70 min oxygen periodically through 1000 hours of operation catalyst. The volumetric feed rate of regeneration gases was 6400 h-1the content of oxygen in the regeneration gases amounted to 7%. Before and after the regeneration was carried out by purging the catalyst with an inert gas. Synthesis products, contact with liquid sprayed ammonia, cooled and settled, by condensation stood firm phthalonitrile. With 1 t of phthalic anhydride was formed to 0.55 wt.% resinous deposits on the catalyst. Limit, to total loss of activity of the catalyst, the content of seal products was 14-15 wt.%, had the following composition. wt.%: carbon 86-92, hydrogen 4-7, nitrogen 4-7. Exhaust gases from the synthesis is in, sent on joint processing of products of the coking - direct coke oven gas.The experimental data obtained by implementing the proposed method of obtaining phthalonitrile, summarized in the table: in the table.1 shows the conditions and results of the synthesis of phthalonitrile in the table.2 - conditions and results of regeneration of the catalyst is aluminum oxide.These data confirm that the optimum results are obtained when the parameters specified in the present method of obtaining phthalonitrile.The development of the claimed proof method will allow to increase the production of phthalonitrile, to reduce its cost by carried out periodically regenerate the catalyst and recycling admixtures exhaust gases (reducing operating costs and capital expenditures by 30%).The inventive method of obtaining phthalonitrile industrially applicable by-product coke enterprises with the production of phthalic anhydride. The method of producing phthalonitrile comprising passing the gas mixture in the ratio of phthalic anhydride : ammonia = 1: (40-100), at 420-480oWith a stationary catalyst bed and the allocation of solid Pnom layer of catalyst aluminum oxide, regeneration of the catalyst is carried out at 430-550oC for 50-70 min oxygen periodically through 950-1050 h his work, with before and after regeneration the catalyst purge inert gas, the exhaust ammonia on holding gases are sent to the joint processing of products of coking.
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for preparing fluorinated dicyanobenzene represented by the formula (2): wherein m means a whole number from 1 to 4; n means 0 or a whole number from 1 to 3, and m + n = 4. This substance is useful as an intermediate and the parent compound for synthesis of medicinal and pharmaceutical products, agricultural reagents and polymers. Method involves interaction of tetrachlorodicyanobenzene represented by the formula (1): with a fluorinated agent at temperature from 80oC to 200oC in the presence of a non-protonic polar solvent taken in the amount from 0.1 to 3 parts by mass per 1 part by mass of indicated tetrachlorodicyanobenzene. Method involves carrying out the reaction with destruction of volume solid materials containing in the reaction mixture and/or by removing volume solid materials adhered inside of reaction vessel. Method provides preparing fluorinated dicyanobenzene with high yield at low temperature for short time.
EFFECT: improved preparing method.
13 cl, 7 ex
SUBSTANCE: invention relates to a method of producing substituted 4-[cyano(phenyl)methyl]-5-nitrophthalonitriles of general formula
, where R denotes CH3, OCH3, CI, F, which can be used as semi-products in synthesis of biologically active substances, fluorescent materials and phthalocyanines. The method involves reaction of 4-bromo-5-nitrophthalonitrile with sodium salts of 2-substituted oxobutene nitriles in molar ratio 1:2, respectively, at temperature T = 19-25°C for 1-2 hours in dimethyl formamide solution, after which the reaction mass is diluted with ten-fold excess water with T = 0-25°C. The released gum residue is extracted with methylene chloride, thoroughly washed with water and chromatographed on silica gel. The eluent (solvent) is evaporated and the residue is filtered and recrystallised from alcohol.
EFFECT: method enables to obtain novel compounds of the formula given above.
SUBSTANCE: invention relates to a method of producing substituted 4-nitro-5-(2-oxoethyl)phthalonitriles of formula , where R=4-Me-C6H4, 4-MeO-C6H4, 2-thienyl, which can be used as precursors for producing biologically active substances and synthesis of phthalocyanines. The method involves use of 4-bromo-5-nitrophthalonitrile and sodium salts of 2,4-dioxobutanoic acid derivatives as initial reagents for synthesis of substituted 4-nitro-5-(2-oxoethyl)phthalonitriles. Reaction of said reagents takes place at temperature 18…35°C and molar ratio 1:2, respectively, for 18-24 hours in dimethylformamide solution. The reaction mass is then diluted with ten-fold excess 5% hydrochloric acid solution. The crystalline precipitate is filtered off and recrystallised from alcohol.
EFFECT: method enables to obtain substituted compounds with good output.
1 tbl, 3 ex
SUBSTANCE: invention relates to synthesis of novel 4-(azacycloalkyl)phthalonitriles. Novel 4-(azacycloalkyl)phthalonitriles of general formula
are obtained. The method of obtaining said compounds involves nucleophilic substitution of the bromine atom in 4-bromophthalonitrile (BPN) with N,N-cycloalkyleneamines.
The reaction takes place in the presence of a deprotonation agent K2CO3 and a catalytic complex Cul/dipyridyl formed in situ at temperature 90-95°C for 12 hours. Molar ratio of reactants BPN: amine: Cul: dipyridyl: K2CO3=1:1.2:0.1:0.1:1.5. After the reaction, the mixture is cooled and filtered. The filtered residue is washed with water and recrystallised.
EFFECT: obtaining novel 4-(azacycloalkyl)phthalonitriles using a method which is safe for this class of compounds.
2 cl, 4 ex
SUBSTANCE: invention relates to a method of producing 4,4'-oxydiphthalonitrile of formula used as a monomer for synthesis of polyhexazocylanes and polyphthalocyanines, as well as a product in synthesis of polyether imides. The method involves reaction of 4-nitrophthalonitrile with potassium nitite in the medium of an alkylaromatic solvent in the presence of potassium carbonate and a quaternary ammonium salt while heating, wherein the quaternary ammonium salt used is Adogen® 464 (trialkyl(C8-C10)-methylammonium chloride) or Aliquat® 336 (trioctylmethylammonium chloride). At the end of the reaction, the reaction mass is cooled and the product is separated. The mother solution formed during separation is used in the second and subsequent cycles of producing 4,4'-oxydiphthalonitrile.
EFFECT: method enables to significantly increase output of 4,4'-oxydiphthalonitrile.
SUBSTANCE: invention relates to chemistry, specifically to an improved method of producing 4,4'-(m-phenylene-dioxy)diphthalonitrile (tetranitrile P) of formula I, which can be used as a monomer in synthesis of polyhexazocylanes and polyphthalocyanines, as well as a semi-product in synthesis of polyether imides. The method involves, for example, reaction of 4-nitrophthalonitrile and resorcinol in the medium of an aprotic dipolar solvent in the presence of a base at 80-90°C in 1 hour. The starting compounds - 4-nitrophthalonitrile and resorcinol - are dissolved in N,N-dimethylacetamide and a solution of sesquihydrate potassium carbonate K2CO3·1.5H2O in water is added to the obtained solution. The residue of the end tetranitrile P I separated from the reaction mass is then washed on a filter with an aliphatic alcohol selected from a group comprising methanol or ethanol or 2-propanol.
EFFECT: method enables to obtain tetranitrile P of higher purity with high output.
SUBSTANCE: invention relates to a novel phthalonitrile derivative, which is the starting compound for producing phthalocyanine dyes. Described is 4-[4'-(4"-methylphenylazo)phenoxy]phthalonitrile.
EFFECT: compound has properties of a fat dye for dyeing paraffins, wax and polymer materials while providing a uniform saturated green colour.
3 dwg, 5 ex
SUBSTANCE: invention relates to azo compounds based on 4-amino-2,3',4'-tricyanodiphenyl of general formula I, which can be used in synthesis of phthalocyanines and complexes thereof. In formula I , R denotes , , , , .
EFFECT: high efficiency of using the compounds.
SUBSTANCE: invention relates to chemistry and specifically to a novel 4-tert-butyl-5-nitrophthalonitrile of formula .
EFFECT: compound can be used as a starting substance for synthesis of phthalocyanine metal complexes which can be used as dyes for polyester fibres or as catalysts for oxidation of sulphur compounds.
5 dwg, 4 ex
SUBSTANCE: according to the disclosed method, di(4-cyanphenyl)methane is obtained from di(4-aminophenyl)methane. The method includes a diazotation step and is characterised by that the step for substituting diazo groups with nitrile groups is carried out at temperature of 75-80°C under the action of a copper-cyanide complex solution obtained from an alkali metal cyanide and copper sulphate in molar ratio of 4:1.
EFFECT: method enables to obtain a pure product with stable output.