Method for preparing aliphatic amines

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing aliphatic amines by addition reaction of ammonia to (C2-C8)-alkenes, for example, to isobutylene in gaseous phase and reaction is catalyzed by heterogeneous, preferably zeolite catalyst. Process is carried out in system comprising two sections - separating and reaction that are interrelated and interdependent and one cooling zone working under the same pressure from 2 to 8 MPa. Liquid mixture of ammonia and alkene is fed to upper part of separating section fitted with dephlegmator and then mixture is fed to reaction section containing catalyst, for example, zeolite catalyst of type ZSM-5 wherein alkene reacts with ammonia partially and forms amine. Temperature in reaction section is maintained usually from 220oC to 320oC and the molar ratio of ammonia to alkene at inlet to reaction section is from 1.5 to 20 usually. Then reaction mixture removing reaction section is cooled in cooling zone to temperature about the condensation point by heat-exchange with mixture that is recovered for repeated utilization from separating section to reaction section. Cooled reaction mixture is recovered to separating section fitted with built in packing for intensification of mutual contact of countercurrent of liquid and gaseous phases wherein the amine concentrate is separated from reaction mixture and removed from heated vat of separating section. Indicated concentrate is purified additionally and unreacted mixture of alkenes and ammonia in common with fresh parent compounds is recovered for repeated processing in gaseous form from condenser of this section to reaction section. Method provides reducing energy consumptions due to reducing heat consumptions and pressure.

EFFECT: improved preparing method.

12 cl, 1 dwg, 2 ex

 

The technical field

The present invention relates to a method for producing aliphatic amines by the addition of ammonia to alkenes.

The level of technology

Most aliphatic amines obtained by aminating alcohols or possibly aminating carbonyl compounds. Only recently have started to use the accession of ammonia to alkenes scheme

The reaction is exothermic, while the equilibrium constant decreases with increasing temperature. In addition, the active catalysts, providing a sufficient rate of reaction at a temperature of from 200 to 250°conducive to shift the equilibrium from the alkene to the amine.

Of course, increasing the pressure increases the balance shift from the alkene to the amine, and in most published in current publications and patents cited the pressure is higher than 2 MPa, and in some cases even 70 MPa.

The reaction rate depends on the activity of the catalyst, but also on the activity of the alkene. Isobutene is highly reactive, propene reacts slower and ethylene has the lowest activity. While the isobutene reacts with ammonia on the catalyst of the zeolite fast enough even at a temperature of 250°for ethylene require a temperature of about 350°C.

Megavista tested as homogeneous and heterogeneous catalysts accession of ammonia to alkenes. The greatest attention was paid to the catalysts of the zeolite type. U.S. patents 4307250 and 4375002 describe as catalysts zeolites Y - and X-type, including various modifications, which operate in the following conditions:

Pressure2.06 to 41,3 MPa
Temperature200-450°
The molar ratio0,2-20

NH3/alkene

When using H-mordenite as catalyst at a temperature of 300-320°C, a pressure of 5 MPa, and a molar ratio of INL/isobutan 3,95 conversion of isobutylene in separate experiments reaches 15-26%, but the selectivity of conversion in respect of tert-butylamine is relatively low and reaches 24 to 72%. In the above patent publications by-products not described, but they, apparently, are oligomers of isobutylene. In EP 0305564 A1 describes a partially dealumination zeolite catalyst having high activity and selectivity, leading to the conversion of 3.8-13.6 per cent at a temperature of 220-260°C, a pressure of 5 MPa, and a molar ratio of INL/isobutylene equal to 4.

In DE 3326579 A1 describes a method for amine by aminating alkene in the presence of a catalyst pintasilgo type. Advantages of a specified catalyst in comparison with the Y-type is more selectively lower formation of carbon deposits, that is, in a relatively small excess of ammonia. The pressure of 30 MPa is considered optimal, and the highest conversion of isobutylene, 12%, is achieved at a temperature of 330°C, a pressure of 59 MPa, and a molar ratio of NH3/isobutylene, equal to 1.5. When aminating of isobutylene by the method according to DE 3327000 A1 on the catalyst on the basis of moralita at a molar ratio of NH3/isobutylene, equal to 1.5, a temperature of 300°and a pressure of 30 MPa, is reached, the conversion of isobutylene to 17.3%.

The use of alkali metals and their hydrides as catalysts accession of ammonia to alkenes is described in U.S. patent 2501556, where the recommended pressure of at least 50 MPa and a temperature of 100-250°C. the Use of rare metals of group VIII, in particular palladium on a carrier, as catalysts for the amination of alkenes is known from U.S. patent 3412158. The use of homogeneous catalysts based on solutions of complexes of ruthenium and iron, upon receipt of aliphatic and aromatic amines by the addition of ammonia to olefin at a temperature of 100-250°and a pressure of 0.1-83 MPa is described in EP 0039061 B1, but the results of experiments evaluated quantitatively. The use of ammonium halides as catalysts for the above reaction is known from EP 0200923 A2, and the use of organic nationalgeneral from U.S. patent 4536602.

The n is less only suitable thermostable types on the basis of fluorine compounds. Apparently, other types of catalysts accession of ammonia to olefin can't compete with zeolites. Zeolites have excellent thermal stability and are easily regenerated with air at a temperature of 400-500°C. Some of homogeneous catalysts have a corrosive action, whereas zeolites practically inert.

A large part of the patent literature relating to the receipt of amine catalyzed by zeolite accession of ammonia to olefin, recommends the above reaction at a relatively high pressure. For example, in DE 3326579 A1 and DE 3327000 A1 discusses a pressure in the range from 4 to 70 MPa, but it is recommended that the pressure from 20 to 30 MPa. When using a lower pressure, for example, 5 MPa (U.S. patent 4307250, 4375002, EP 0305564 A1), conversion of alkene to amine of about 10% is reached only when a large excess of ammonia. The reaction mixture turned into liquid cooling and unreacted educt separated by distillation. If you have a higher excess ammonia must be one stripped off more than 10 kg of ammonia, having a high heat of vaporization, per 1 kg of the obtained amine. At a pressure of 30 MPa is similar to the conversion of isobutylene can be achieved when the molar ratio of NH3/isobutylene, equal to 1.5. One is to the high pressure apparatus is very expensive, and the injection of fluids into the atmosphere high pressure requires high energy costs to actuate the injection pumps.

Synthesis of tert-butylamine at a pressure of 30 MPa is also described in Hoelderich, W.F. et al: "Synthesis of intermediate and fine chemicals on heterogeneous catalysts with respect to environmental protection" Catal. Today, vol. 38, no. 2, 1997, pages 227-233, XP002161264. Because of the excessively high pressure this synthesis is characterized with high energy needs (very high energy costs).

Description of the invention

Presently discovered that you can get aliphatic amines by the addition of ammonia to C2-C8alkenes, using the method according to the present invention, which eliminates the high thermal inputs known methods.

The essence of the method of producing aliphatic amines from ammonia and alkenes C2-C8in the gas phase with the use of heterogeneous catalysts is that the synthesis system includes two sections - the separation and reaction - are interrelated and interdependent, and one cooling zone operating at almost the same pressure of 2 to 8 MPa, where in the upper part of the separating section having a reflux condenser, served the original liquid mixture of ammonia and an alkene, and then the mixture is fed into the reaction section containing the catalyst, where the alkene partially reacts with ammonia, forming AMI the, after that the reaction mixture leaving the reaction section, after cooling in the cooling zone is returned to the separating section, equipped with built-in attachment for the intensification of mutual contact of the counter-current liquid and gas phases, where the concentrate amine is separated from the reaction mixture, the amine concentrate out through the heated cube of the separation section, the specified concentrate additionally cleaned and unreacted mixture of alkenes and ammonia together with fresh parent compound return for reprocessing in gaseous form from the condenser of this section in the reaction section.

Technological scheme of the process shown in the drawing, where 1 - reactor, 2 - heater, 3 - heat exchanger-condenser 4 to the compressor for recirculation, 5 - separation column.

Synthesis of amines from alkenes and ammonia in the system of two vzaimorezerviruemym sections operating at almost equal pressure, according to the present invention allows for easy synthesis at a relatively narrow range of pressure, from 2 to 8 MPa.

The term "practically equal pressure" means the pressure differences in the partitions is determined only by the pressure loss in the apparatus and pipes. The upper limit of the operating pressure due to the proximity of the critical pressure of ammonia or an sm is si with the alkene. The operation of the separation section is due to the simultaneous presence in gas and liquid phases. Critical pressure of ammonia is equal to 11.2 MPa, the critical pressure, for example, isobutylene equal to 4.0 MPa.

Only a small part of amines can be separated by simple partial condensation in the separation section of the system pressure. The content of amine in the mixture leaving the reaction (catalytic) section, is limited to the balance and is just 1-3 mole % amine. Conversion of alkenes in the amine under the conditions according to the invention is 3-10%, and the content of the amine addition is reduced by an excess of ammonia. Therefore, according to the present invention, the efficiency of the allocation of amine from the gas mixture preferably is enhanced by the built-in nozzle, which increases the interfacial surface contact of gas and liquid at the same time as the gas and liquid pass countercurrent separation section. Suitable built-in showerhead consists of a valve, bubble cap or sieve plates, oriented or unoriented nozzles have low efficiency at a pressure close to the critical one.

The countercurrent gas and liquid in the separation section can be guaranteed partial condensation of the unreacted portions of the original mixture of the alkene, and ammonia in the upper part razdelitel the second section, perhaps also due to the supply of fresh liquid reagents in the upper part of the separating partition. Suitable separation efficiency, expressed in terms of the number of gas-liquid equilibrium (theoretical) plates equal to 10-30.

The reaction section of the reaction system contains any catalyst which accelerates the accession of ammonia to the alkene at a pressure caused by the operation of the dividing partition, i.e. from 2 to 8 MPa. The reaction temperature as such is not an essential characteristic of the invention, but it should be such that together with the catalyst to provide a practically acceptable rate of formation of amine. The lower temperature limit is 220°is determined by the kinetics, the upper limit, 320°S, is determined by the attainable equilibrium conversion at a pressure system. Additional selection condition temperature is the gas form of the mixture leaving the reaction section.

A relatively large number of gaseous reactants is circulated in the reaction system, while through the cube of the separation section is given to liquid crude amine, which is then purified in the usual way. The crude amine contains a number of original substances, i.e. alkenes and ammonia. Circulation of the gas mixture in the sections is provided with a suitable pumping device that is capable of working the AMB at a temperature of from 80 to 120° C. At lower temperature the reagents will condense. It should be noted that the pressure loss in both sections and in the cooling zone is usually only 3-10%, relative to the pressure of the synthesis, the energy consumption for the circulation of the reactants is very low. Under normal conditions the amine synthesis from alkenes and ammonia at a pressure of from 20 to 30 MPa can be obtained a higher conversion of the alkene, but the liquid reaction mixture should be cleaned on a separate line, and the selected source materials returned to the liquid phase. Reagents, thus evaporated twice, first in distillation columns, then before entering the reactor. On the other hand, teplostroy in Cuba dividing section for the synthesis of amine of the present invention is very low, and the energy consumption for the internal circulation of the gaseous reagents are also low. Energy expenditure during the synthesis of the present invention is about half the cost of conventional methods. Due to the low energy consumption during the synthesis of amines of the present invention can also be employed with very low conversion of alkenes in the reaction section, which is important for the amination of alkenes with low reactivity, such as propylene and ethylene.

The equipment for operation at pressures of from 2 to 8 MPa is much cheaper than the equipment for Oba the aqueous synthesis of amines at a pressure of from 20 to 30 MPa.

The molar ratio of NH3/alkene-defined type alkene, plays a role in the synthesis of amines of the present invention. More than the boiling point of the alkene, the greater the molar ratio should be used. Preferably the molar ratio of ammonia and alkene at the inlet to the reaction section is from 1.5 to 20. On the one hand, when a larger excess of ammonia equilibrium conversion of alkenes to amines increases, on the other hand, the number of chemicals circulating in the system of separation and reaction sections, increases. If you are using heterogeneous acid catalysts, strong sorption of ammonia reduces the speed of the connection. For example, if exercised by the interaction of isobutylene to obtain tert-butylamine using zeolites ZSM-5 in the reaction section of the system and at a pressure of 4 MPa, the rate of formation of amine in a molar ratio of NH3/isobutylene equal to 4, 30% less than when the molar ratio equal to 2. When using the method according to the present invention, the optimum molar ratio of NH3/isobutylene at the inlet to the reaction section is in the range of 2 to 4.

A large excess of ammonia is required when attaching ammonia to alkenes, boiling at higher temperatures. For example, upon receipt of cyclohexylamine from Ziklag Xena circulation of the gas components from the separation in the reaction section at a pressure of 3 MPa is only possible when a molar ratio of from 15 to 20.

Preferably, the reaction mixture is cooled in a cooling zone to a temperature near the dew point by heat exchange with the mixture, which is returned for reuse of the dividing partition in the reaction section.

Examples of embodiment of the invention,

Example 1

Forcing the pump delivers a fresh mixture of isobutylene and ammonia in the upper part of the separating section, the specified mix, together with the condensate resulting from the reflux condenser, creates phlegm separation section. The reaction mixture is moved to the center of the dividing partition, cooled to 120°C. Separating section is equipped with a built-in nozzle efficiency 15 the equilibrium of the plates, which, along with the coefficient of reverse flow of 0.35 is sufficient to allocate 95% of tert-butylamine of the mixture. Gases leaving a reflux condenser having a temperature of 90°C, heated to 100°and serves them through a membrane compressor through the heater in the reaction section filled with two liters of the zeolite catalyst ZSM-5 in molded form, where they interact with the formation of tert-butylamine at a temperature of 250°and a pressure of 3.9 MPa. The conversion of isobutylene in tert-butylamine equal to 5%, and the selectivity of 99.5%. In the separation section serves such a quantity of fresh ammonia and Isobe who Elena, 70 moles of isobutylene and 210 of moles of ammonia per hour is fed to the reaction section. Through the cube of the separation section, heated to 165°With that comes a liquid mixture containing 50% tert-butylamine, about the same amount of isobutylene and only 0.02% of the dimers of isobutylene.

Example 2

Using the same equipment as in example 1, carried out the synthesis of 2-aminopropane from propylene and ammonia at a temperature of 320°and a pressure of 5 MPa. When using a molar ratio of NH3/propylene equal to 4, the conversion of alkenes in Amin equal to 3%. The dividing section synthesis system works when the coefficient reverse flow of 0.25, providing office 95% of the amine contained in the mixture leaving the reaction section. In the upper part of the separating section temperature is 95°With the cube of the separation section is heated to 134°C. Through the cube of the separation section divert crude 2-aminopropan containing 7 mass % ammonia and 18 mass % of propylene.

1. The method of obtaining aliphatic amines by the addition of ammonia to alkenes2-8in the gas phase, catalyzed by a heterogeneous catalyst, wherein the process is conducted in a system that includes two sections - the separation and reaction, which are interrelated and interdependent, and one cooling zone operating at almost the same pressure of 2 to 8 MPa, where ver is the Nuits part separating section, having a reflux condenser, served the original liquid mixture of ammonia and an alkene, and then the mixture is fed into the reaction section containing the catalyst, where the alkene partially reacts with ammonia to form the amine, then the reaction mixture leaving the reaction section is cooled in the cooling zone and is returned to the separating section, equipped with built-in attachment for the intensification of mutual contact of the counter-current liquid and gas phases, where the concentrate amine is separated from the reaction mixture and exits through the heated cube of the separation section, the specified concentrate additionally cleaned, and unreacted mixture of alkenes and ammonia together with fresh parent compound return for reprocessing in gaseous the form of the capacitor of this section in the reaction section.

2. The method according to claim 1, wherein the alkene is isobutylene.

3. The method according to claim 1, characterized in that in the reaction section use heterogeneous zeolite catalyst.

4. The method according to claim 3, characterized in that in the reaction section using the zeolite catalyst ZSM-5.

5. The method according to claim 1, characterized in that the temperature in the reaction section of the support from 220 to 320°C.

6. The method according to claim 1, characterized in that the molar ratio of ammonia and alkene at the inlet to the reaction section is from 1.5 to 20.

7. With whom persons according to claim 1, characterized in that the reaction mixture is cooled in a cooling zone to a temperature near the dew point by heat exchange with the mixture, which is returned for reuse of the dividing partition in the reaction section.



 

Same patents:

The invention relates to an improved process for the preparation of sulfurylchloride, sulfurylchloride or foramerica carboxylic acid of General formula (I): RC(O)F, where R is C1-C7alkyl or C1-C7alkyl, substituted by at least one chlorine atom and/or at least one fluorine atom, without adding a base or solvent connecting the HF interaction of the corresponding acid chloride of the carboxylic acid (a) adduct of hydrogen fluoride and hydrohloride ammonium or hydrohloride pyridine, or hydrohloride piperidine, or an adduct of hydrogen fluoride and hydrohloride secondary or tertiary apophaticism amine of the formula BmHF, where In the means of secondary or tertiary aliphatic amine, a m has the value 1<m<4, as a fluorinating agent, and the reaction m is equal to or greater than 1, or (b) with HF as a fluorinating tools, and HF is used in the amount of at least 1 mol per mol of the replaceable chlorine atom, in the presence of an adduct of hydrogen fluoride with gidroftoridakh ammonium or adduct of hydrogen fluoride with gidroftoridakh secondary or tertiary aliphatic amine of the formulamHF, where In the means of secondary or tertiary aliphatic amine or pyridine, and m has the value 1<m<4, with triperoxonane acid, (C) and optionally with subsequent regenerierung HF-adduct and separation of the formed HCl

The invention relates to a new compound NlNlN2N2N3N3-hexa(2-oksipropil)-2,4,6-triaminotoluene formula I, which can be used as a crosslinking agent upon receipt rigid and flexible foams, and the method of its production Method is that 2,4,6-triaminotoluene subjected to interaction with propylene oxide in an autoclave at a temperature of 50-100Since, in the presence of a hydroxyl-containing solvent, preferably polyester or water

The invention relates to the chemistry of adamantane derivatives, and in particular to a new method of obtaining amino adamantane General formula AdR, where R=NH2, NHBu-t,

< / BR>
< / BR>
< / BR>
which are biologically active substances and can find application in pharmacology and adamant-1-ylamine is the basis of the drug midantana"

The invention relates to methods of obtaining salt corrosion inhibitor

The invention relates to the production of stabilizers on the basis of substituted amines and can be used to obtain rubber, vulcanization agents and other polymeric materials

The invention relates to a vapor-phase process for the production diarization amines by the catalytic condensation of the corresponding primary amines, specifically, diphenylamine (DFA) of aniline

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing aliphatic amines by addition reaction of ammonia to (C2-C8)-alkenes, for example, to isobutylene in gaseous phase and reaction is catalyzed by heterogeneous, preferably zeolite catalyst. Process is carried out in system comprising two sections - separating and reaction that are interrelated and interdependent and one cooling zone working under the same pressure from 2 to 8 MPa. Liquid mixture of ammonia and alkene is fed to upper part of separating section fitted with dephlegmator and then mixture is fed to reaction section containing catalyst, for example, zeolite catalyst of type ZSM-5 wherein alkene reacts with ammonia partially and forms amine. Temperature in reaction section is maintained usually from 220oC to 320oC and the molar ratio of ammonia to alkene at inlet to reaction section is from 1.5 to 20 usually. Then reaction mixture removing reaction section is cooled in cooling zone to temperature about the condensation point by heat-exchange with mixture that is recovered for repeated utilization from separating section to reaction section. Cooled reaction mixture is recovered to separating section fitted with built in packing for intensification of mutual contact of countercurrent of liquid and gaseous phases wherein the amine concentrate is separated from reaction mixture and removed from heated vat of separating section. Indicated concentrate is purified additionally and unreacted mixture of alkenes and ammonia in common with fresh parent compounds is recovered for repeated processing in gaseous form from condenser of this section to reaction section. Method provides reducing energy consumptions due to reducing heat consumptions and pressure.

EFFECT: improved preparing method.

12 cl, 1 dwg, 2 ex

FIELD: organic chemistry.

SUBSTANCE: target products is produced by ethylene diamine transamination. Reaction is carried out at 135-180°C at pressure of 5-40 MPa in presence of hydrogen and catalyst particles containing 26-65 wt.% of metallic nickel on porous carrier.

EFFECT: high ethylene diamine conversion ratio and high selectivity in relate to target acyclic polyethylene polyamines under advantageous reaction conditions.

10 cl, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: proposed invention pertains to organic chemistry, more specifically to the method of producing N,N-dimethyl-3-phenyl-2-propyne-1-amine. The method involves reacting phenylacetylene with excess bisamine in the presence of a vanadyl acetylacetonate catalyst (VO(acac)2) in an argon atmosphere at 85°C temperature and atmospheric pressure for a period of 4-8 hours. N,N-dimethyl-3-phenyl-2-propyne-1-amine output is 84-98%.

EFFECT: invention can be used in thin organic synthesis, particularly for making not easily accessible polycyclic compounds, as well as in synthesis of biologically active substances.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing N,N,N,N-tetramethylalkadiynediamines, which can be used in fine organic synthesis, particularly for producing not easily accessible polycyclic compounds, as well as in synthesis of biologically active substances. Desired compounds are obtained from reacting diacetylene alkanes with excess N,N,N,N-tetramethylmethane diamine in the presence of a vanadyl acetylacetonate (VO(acac)2) catalyst, in molar ratio diacetylene alkane: N,N,N,N-tetramethylmethane diamine: VO(acac)2 = 10:(25-35):(0.2-0.4) in an argon atmosphere at temperature ranging from 70 to 100°C, mostly at 80°C, and atmospheric pressure for 4 to 8 hours.

EFFECT: method considerably simplifies synthesis schematic due to use of accessible initial reagents and significantly increases output of desired products, and allows for obtaining new and known compounds.

1 cl, 3 dwg, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing N1,N1,N4,N4-tetramethyl-2-butyne-1,4-diamine, which is used in synthesis of polycyclic compounds, as well as in synthesis of biologically active substances. The method involves reaction of N,N,N,N-tetramethylmethane-diamine with excess gaseous acetylene in the presence of a VO(acac)2 catalyst, taken in molar ratio of N,N,N,N-tetramethylmethane-diamine: (VO(acac)2) = 10 : (0.3-0.5), preferably 10:0.4, at temperature 65-75°C and atmospheric pressure for 1-3 hours.

EFFECT: method increases output of the desired product.

1 cl, 3 dwg, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: method involves reaction of bisamine with 3-fold excess acetylene in the presence of a vanadyl acetylacetonate (VO(acac)2) catalyst in an argon atmosphere at temperature 70°C and atmospheric pressure for 3 hours, followed by addition of diisobutylaluminium hydride and stirring the reaction mixture for 4-6 hours at room temperature. The method enables to obtain N1,N1,N4,N4-tetramethyl-2-butene-1,4-diamine from available reagents with quantitative output of (82-97%).

EFFECT: high output of end product.

1 tbl, 3 dwg, 1 ex

Purification method // 2444511

FIELD: chemistry.

SUBSTANCE: present invention relates to versions of a method of purifying terbinafine from nonmetallic impurities, primarily a substance A of formula

, as well as to use of said methods to obtain purified terbinafine. One of the versions of the method involves molecular distillation of crude terbinafine in form of a free base and extraction the obtained purified terbinafine in form of a free base or acid-addition salt (method A). In another version (method B), crude terbinafine in form a free base undergoes molecular distillation combined with formation of a salt of the obtained product with simultaneous deposition of a purified trans-isomer, and the obtained highly pure terbinafine is extracted in form of a free base or acid addition salt.

EFFECT: method enables to obtain terbinafine containing less than approximately 5 ppm of substance A.

13 cl, 2 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing at least one product from acrolein and acrylic acid via partial oxidation of propylene, where a) purified propane is converted at the first reaction step in the presence and/or absence of molecular oxygen, at least one dehydrogenation from a group comprising homogeneous dehydrogenation, heterogeneous catalytic dehydrogenation, homogeneous oxydehydrogenation and heterogeneous catalytic oxydehydrogenation, wherein a gaseous mixture 1 is obtained, which contains unconverted propane and the formed propylene, and b) optional separation from the total amount or partial amount of the gaseous mixture 1 of a partial amount of components other than propane and propylene contained therein, e.g., hydrogen, carbon monoxide, water vapour and/or optional conversion thereof to other compounds, e.g., water and carbon dioxide, and where a gaseous mixture 1' is obtained, which contains propane and propylene, and on at least one of the following reaction steps, c) the gaseous mixture 1 or gaseous mixture 1' or a mixture from the formed gaseous mixture 1' and the remaining gaseous mixture 1 as a component of a gaseous mixture 2 are subjected to heterogeneous catalytic gas-phase partial oxidation of propylene contained in gaseous mixture 1 and/or gaseous mixture 1', wherein a gaseous mixture 3 is obtained, which contains at least one product, d) on at least one separation step, the product is separated from gaseous mixture 3 and from the remaining residual gas, at least propane is returned to the first reaction step, where purified propane is obtained from crude propane which contains ≥90 wt % propane, ≤99 wt % propane and propylene, ≥100 ppm hydrocarbons, having 2 carbon atoms, and ≥100 ppm hydrocarbons, having 4 carbon atoms, under the condition that crude propane is fed into the fractionation column and purified propane is obtained higher than the feeding point under the condition that content of hydrocarbons having 2 carbon atoms, in wt %, in terms of the contained propane, in the purified propane is more than 100% of the corresponding content in crude propane and content of hydrocarbons having 4 carbon atoms, in wt %, in terms of content of propane, in the purified propane is at most 50% of the corresponding content in crude propane.

EFFECT: method enables to cut design expenses owing to no separation of C2-hydrocarbons during distillation.

48 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing N1,N1,N4,N4-tetramethyl-2-butyne-1,4-diamine, which can be used in fine organic synthesis, particularly for producing scarce polycyclic compounds, as well as in synthesis of biologically active substances. The method involves reaction of bisamine with excess gaseous acetylene in the presence of a VO(acac)2 catalyst at temperature 65-75°C and atmospheric pressure for 1-3 hours.

EFFECT: method enables to obtain N1,N1,N4,N4-tetramethyl-2-butyne-1,4-diamine from available reactants with quantitative output of 76-98%.

1 tbl, 3 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing novel N-alkyl-3-methyl-4-nitrosoanilines of formula where R=i-Pr, cyclohexyl. The compounds can be used as modifiers and stabilisers of rubber mixtures and as starting compounds for synthesis of N-substituted n-phenylene diamines, which are used to produce a wide range of azo dyes and in colour photography. The method involves cyclocondensation of acetone and the corresponding amine with a product of nitrosation of 4,4-dimethoxybutan-2-one, which is first held in aqueous hydrochloric acid solution.

EFFECT: improved method.

2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing aliphatic amines by addition reaction of ammonia to (C2-C8)-alkenes, for example, to isobutylene in gaseous phase and reaction is catalyzed by heterogeneous, preferably zeolite catalyst. Process is carried out in system comprising two sections - separating and reaction that are interrelated and interdependent and one cooling zone working under the same pressure from 2 to 8 MPa. Liquid mixture of ammonia and alkene is fed to upper part of separating section fitted with dephlegmator and then mixture is fed to reaction section containing catalyst, for example, zeolite catalyst of type ZSM-5 wherein alkene reacts with ammonia partially and forms amine. Temperature in reaction section is maintained usually from 220oC to 320oC and the molar ratio of ammonia to alkene at inlet to reaction section is from 1.5 to 20 usually. Then reaction mixture removing reaction section is cooled in cooling zone to temperature about the condensation point by heat-exchange with mixture that is recovered for repeated utilization from separating section to reaction section. Cooled reaction mixture is recovered to separating section fitted with built in packing for intensification of mutual contact of countercurrent of liquid and gaseous phases wherein the amine concentrate is separated from reaction mixture and removed from heated vat of separating section. Indicated concentrate is purified additionally and unreacted mixture of alkenes and ammonia in common with fresh parent compounds is recovered for repeated processing in gaseous form from condenser of this section to reaction section. Method provides reducing energy consumptions due to reducing heat consumptions and pressure.

EFFECT: improved preparing method.

12 cl, 1 dwg, 2 ex

FIELD: organic chemistry, chelating compounds, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 1-{[1-(hydroxymethyl)propyl]amino}-1,2-dihydro[60]fullerene of the formula (1) . Method involves interaction of fullerene-C60 c 2-amino-1-butanol of the formula in the mole ratio fullerene-C60 : 2-amino-1-butanol = 0.01:(0.01-0.011) in the presence of titanocene dichloride (Cp2TiCl2) as a catalyst taken in the amount 15-25 mol.% with respect to fulelrene-C60 in toluene medium as a solvent at room temperature (˜20°C) for 42-54 h. The yield of the end product is 67-90%. Synthesized compound can be used as chelating agents, sorbents, biologically active compounds, and in creature of novel materials with desired electronic, magnetic and optical properties.

EFFECT: improved method of synthesis.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention refers to cyanoguanidine derivatives of the general formula I in which A, A, X1, X2, X3, Y1, Y2, Y3, R1, R2, R5, R6 and n have the values indicated in the formula of the invention. The invention also refers to the pharmaceutical composition which has antiproliferative activity on the basis of the compound of the formula I, and application of these compounds for medicinal preparation aimed at treatment and alleviation of proliferative disease and conditions.

EFFECT: new compounds can be useful at proliferative disease treatment.

25 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing amines of the following formula: , which can be used in agricultural chemicals, pharmaceutical preparations, detergents and personal hygiene products. The method involves reduction of amides of the following formula: with hydrogen (H2) in the presence of an auxiliary amine of the following formula: , where R1 is H or a saturated or unsaturated hydrocarbon group containing 1-23 carbon atoms, R2 and R3 independently represent H or a hydrocarbon group containing 1-8 carbon atoms and R4 corresponds to R1, but can distinguished by a different degree of saturation, in which the said H2, the said auxiliary amine and the said amide are all supplied in completely gaseous state in form of a gas stream over a hydrogenation catalyst at reaction pressure above 2 bars but below 50 bars. The said gas stream contains at least Nc moles of carrier gases per mole of the said amide, where the carrier gases include at least the said auxiliary amine and the said H2 in the ratio

where Ptol is the reaction pressure and VPa is the pressure of saturated amide vapour at the reaction temperature.

EFFECT: obtaining target amine with high output and high selectivity.

9 cl, 6 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to an improved method of removing organic amine from liquid hydrocarbon stream containing amine, having a boiling point higher than 100 °C, which is liquid at room temperature and normal pressure. Invention can be used in processes, in which a crude stream or product flow contains hydrocarbons and amines. Method includes the following steps: a) adding water to hydrocarbon stream containing an amine in an amount of 5-70 wt% with respect to total amount of hydrocarbon stream, b) bubbling carbon dioxide through hydrocarbon stream containing an amine at temperature 30-80 °C, and c) separating formed solid phase containing amine from liquid phase by filtration and optionally, extraction of amine from solid phase by heating in water or aqueous solution. Preferably hydrocarbon stream, containing an amine, selected from 2-ethylhexylamine and/or n-dodecylamine, is output stream from reactor for producing linear alpha-olefins (LAO) or fraction of said output flow. Water is added in amount of 15-60 %, more preferably 25-50 % in relation to total amount of hydrocarbon stream, bubbling is performed for 5-60 min, preferably 10-50 minutes, more preferably 20-40 minutes. Volume rate of carbon dioxide is in range of 50 to 150 cm3/min, depending on total amount of a mixture of liquid hydrocarbons in reactor. Added water is usually at least once partially replaced with fresh water during bubbling of carbon dioxide in temperature range 50-80 °C through hydrocarbon stream.

EFFECT: method simplifies process, since it simplifies extraction of amines due to formation of a solid gel-like phase, which is insoluble in organic or aqueous phase; wherein method does not require additional means for extracting and amines easily react.

14 cl, 1 tbl, 3 ex

Up!