Method for semi-hydrogenation of dinitriles to aminonitriles

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for semi-hydrogenation of dinitrile of the general formula: NC-R-CN wherein R means linear or branched alkylene group comprising from 1 to 12 carbon atoms to the corresponding aminonitrile in the liquid medium. Method is carried out in the presence of a catalyst, such as nickel or Raney nickel comprising an activating element taken among rhodium or iridium wherein the weight ratio (Rh or Ir)/Ni is from 0.05% to 10%. Method provides enhancing yield of aminonitrile.

EFFECT: improved and enhanced method.

21 cl, 3 ex

 

The present invention relates to providerone of dinitriles to the appropriate aminonitriles.

Typically, the hydrogenation dinitriles conducted to obtain the corresponding diamines; in particular, the hydrogenation of adiponitrile leads to the formation of the diamine, which, in turn, is one of the two starting compounds used to obtain polyamide-6,6.

However, you may want to gain diamine, and intermediate aminonitriles. A non-limiting example of such a case is providerone adiponitrile with getting aminoacetonitrile, which can then be converted into caprolactam, which is the source for obtaining polyamide-6, or polyamide-6.

Thus, in U.S. Patent US 4389348 describes a method of hydrogenation of dinitrile to omega-aminonitriles hydrogen in the environment aprotic solvent and ammonia in the presence of rhodium deposited on alkaline media.

In U.S. Patent US 5151543 describes how partial hydrogenation of dinitriles to aminonitriles in a solvent, in twofold excess in relation to dinitrile and containing liquid ammonia or alkanol containing mineral base, soluble in the above alkanol, in the presence of a catalyst of the type of Nickel or Raney cobalt.

U.S. patent US 5981790 refers to the ways which the partial hydrogenation of dinitriles to aminonitriles in the presence of a catalyst based on Raney Nickel or Raney cobalt, in which the reaction medium containing the inhibiting compounds and products of hydrogenation, includes at least 0.5% weight. water. The catalyst is used together with the base.

These various methods allow to obtain aminonitriles and diamine in a more or less different ratios, together with the more or less large number of by-products which are difficult to separate. Further research is constantly held to change these ratios, aimed, in particular, to increase the yield of aminonitriles in relation to the diamine, as well as to reduce the formation of by-products.

Thus, in the patent application WO 00/64862 describes how partial hydrogenation of dinitrile to obtain aminonitriles in the presence of a hydrogenation catalyst, liquid ammonia or alkanol as a solvent and a compound that increases the selectivity of the reaction aminonitriles.

There had also been a catalyst system Nickel-based activated one or more other metals such as titanium, copper, or iron, to improve the activity of the catalyst, to increase its selectivity for aminonitriles or reduce the release of unwanted side products. Such catalytic systems described in the French Patent FR 2785608 and U.S. Patent US 5801286.

One for the Ah of the present invention is to develop a method for the selective hydrogenation of one nitrile group dinitrile (referred to in this text providerone), with the aim of obtaining more relevant aminonitriles and only a smaller number of diamine with a minimum formation of by-products.

The invention in particular relates to a method for providerone aliphatic dinitriles to the appropriate aminonitriles with hydrogen and in the presence of a hydrogenation catalyst. This method differs in that the hydrogenation catalyst comprises Nickel or Raney-Nickel and the activating element selected from rhodium or iridium.

In accordance with another feature of the present invention, the catalyst according to the invention may contain one or more additional activators, which are selected from groups 3 through 12 of the Periodic system of the elements (IUPAC nomenclature used in: Handbook of Chemistry and Physics - 80thedition 1999-2000). In particular, preferred is the group which consists of titanium, chromium, iron, zirconium, vanadium, manganese, bismuth, tantalum, ruthenium, platinum, palladium, niobium, hafnium, bismuth and rare earth elements. The catalyst according to the invention does not contain copper, silver and/or gold.

In accordance with the preferred method of carrying out the invention in the reaction mixture in the hydrogenation impose a strong mineral base, which is derived from alkali or alkaline earth metal or am is one. However, if the hydrogenation is carried out in the presence of liquid ammonia, a strong mineral base is not required.

In accordance with another preferred feature of the invention the initial mixture when carrying out the hydrogenation contains water in an amount of at least 0.5% weight. of the total liquid content of the above components of the mixture of diamine and/or aminonitriles able to form of gidrirovannogo of dinitrile, as well as unreacted dinitrile, the total content of these three components is from 80% to 99.5%.

In accordance with another method of the invention, the reaction can be carried out in the presence of a solvent, such as alcohol. In this case, the presence of water is optional.

The reaction providerone can be carried out in the presence of additives that increase the selectivity for aminonitriles compared with the selectivity that can be achieved in the above-described system without the use of additives, the total selectivity for aminonitriles and the diamine is at a level that is at least equivalent to the level achieved without additives. Such additives are described in particular in patent application WO 00/64862.

In accordance with the invention, the activating element, rhodium or iridium, is contained in the catalyst, mainly in the weight soo is wearing (Rh or Ir)/Ni in the range from 0.05% and 10% and preferably from 0.1% to 5%.

The catalyst may contain additional activator different from rhodium or iridium, the amount of which is usually from 0% to 5% weight. by weight of Nickel.

The catalyst was prepared in accordance with conventional methods of producing metal catalysts.

For example, nicely Raney are catalysts commonly used in the industry in the hydrogenation reactions. These catalysts receive alkaline etching of aluminum-Nickel alloy (Al/Ni), enriched in aluminum and including, if necessary, other metals, usually called activators or promoters. The catalyst consists of agglomerates of crystallites of Nickel with a large specific surface and changing the concentration of the aluminum alloy. The activator may be added at any stage of the preparation of the catalyst: in the process of producing an alloy by fusing various metals, the activation process of the alloy alkaline etching in the presence of a salt of rhodium or iridium or after activation of the alloy (see patent applications WO 95/17959 and WO 95/17960).

The catalyst typically contains aluminum in an amount, expressed as weight ratio of aluminum to Nickel is less than or equal to 10%.

The catalyst according to the invention can be used in various forms, such as granules, tablets, powder.

The method according to the invention allows the t to achieve when the degree of conversion of dinitrile more than 70%, the selectivity for aminonitriles more than 55% and the total selectivity for aminonitriles and diamine more than 90%.

Aliphatic dinitrile that can be used in the method according to the invention are, in particular, dinitrile General formula (I):

NC-R-CN (I),

where R denotes a linear or branched alkylenes or alkenylamine group containing from 1 to 12 carbon atoms.

In the method according to the invention preferably use dinitrile formula (I), where R denotes a linear or branched alkalinity radical containing from 2 to 6 carbon atoms.

As examples of such dinitriles can be called, in particular, adiponitrile, methylglutaronitrile, ethylsuccinate, malononitrile, succinonitrile, glutaronitrile and their mixtures, in particular mixtures of adiponitrile and/or methylglutaronitrile and/or ethylsuccinate, which can be obtained by the method similar to the method of synthesis of adiponitrile.

In practice, the most often use dinitrile, where R=(CH2)4and it is this value corresponds to adiponitrile (ADN), which is used in examples of the present invention.

A strong mineral base is typically hydroxides, carbonates and alkanoate alkali or alkaline earth metal or ammonium. His wybir who are mainly from hydroxides, carbonates and alkanoates alkali metal or ammonium.

Used strong mineral base is chosen preferably from the following compounds: LiOH, NaOH, KOH, RbOH, CsOH, NH4OH and mixtures thereof.

In practice we often use NaOH and KOH, although RbOH and CsOH can give very good results.

The reaction mixture has a composition varying depending on the conditions of the method.

Water is usually present in the reaction mixture in a quantity less than or equal to 20 wt%. Preferably, the water content in the reaction mixture ranges from 2% to 15% weight. with respect to the total content of the liquid components of the above mixture.

In addition to the water or instead of water you can use at least one other solvent, typically an alcohol type. The most suitable alcohols are methanol, ethanol, propanol, isopropanol, butanol or mixtures of these compounds.

If an alcohol solvent is used along with water, its content ranges from two to four weight parts per one weight part of water, preferably three weight parts of alcohol per one weight part of water.

In accordance with another preferred feature of the invention the initial mixture hydrogenation contains diamine, education which accompanies hydrogenation reactions. An example of such a product to serve the hexamethylenediamine were, formed when source dinitrile use adiponitrile.

The average concentration of aminonitriles and/or diamine in the reaction mixture during the continuous mode, the hydrogenation is preferably from 35% to 99 wt%. with respect to the total weight of the solvent introduced into the reaction mixture, more preferably from 45% to 89% (wt./weight.).

The total concentration of the target aminonitriles and/or the corresponding diamine and neprevyshenie of dinitrile in the reaction mixture typically ranges from 85% to 99 wt%. with respect to the total content of the liquid components introduced into the reaction mixture.

The reaction mixture may include a liquid or dissolved ammonia. Ammonia is usually from 0% to 50% weight. the weight of the reaction mixture, preferably from 0% to 15% weight.

The number of hydroxide of alkali or alkaline earth metal or ammonium in the reaction mixture varies depending on the nature of the above reaction mixture.

If the reaction mixture as a liquid environment contains only water, the reaction products and possible ammonia or diamine as a liquid solvent medium, the amount of hydroxide of alkali or alkaline earth metal is preferably greater than or equal to 0.1 moles per kg of catalyst, preferably from 0.1 to 2 moles per kg of catalyst, more pre is respectfully from 0.2 to 1.0 moles per kg of catalyst.

The amount of catalyst may vary within wide limits, in particular, depending on the chosen method of carrying out the reaction or the selected reaction conditions. So, if dinitrile injected into the reaction mixture gradually, the weight ratio catalyst/GearWay dinitrile much higher than in the case when all dinitrile used immediately in the beginning of the reaction. For example, you can use from 0.5% to 50% weight. catalyst relative to the total weight of the reaction mixture and most often from 1% to 35%.

In accordance with the preferred method of carrying out the invention the catalyst before you enter it into the mixture to providerone, subjected to pre-treatment. The specified pre-processing is carried out mainly according to the method described in the unpublished application for a Patent in France, No. 00.02997. This method is briefly consists of the following: mixed hydrogenation catalyst with a certain amount of the original strong mineral base and solvent, in which a strong mineral base malorastvorima. In accordance with the invention, the mixture containing the pre-treated catalyst, is fed into the hydrogenation reactor, the hydrogenation reaction is carried out in normal conditions and in accordance with the procedures already described in the literature.

The selectivity of p is aminonitriles with the same degree of conversion of dinitrile depends in particular, on the nature and percentage of activator, the amount of water in the reaction mixture, from the nature of the base and from the relationship of the Foundation to Nickel.

The method according to the invention is usually carried out at a temperature less than or equal to 150°S, preferably less than or equal to 120°S, more preferably less than or equal to 100°C.

More specifically, the temperature is in the range from room temperature (approximately 20° (C) to 100°C.

Previously, simultaneously or after heating the reactor to create the necessary pressure of hydrogen, i.e. hydrogen pressure, almost amounting to 1 bar (0,10 MPa) to 100 bar (10 MPa) and preferably between 5 bar (0.5 MPa) to 50 bar (5 MPa).

The duration of the reaction varies depending on the conditions of its implementation and the used catalyst.

When using periodic carrying out of the reaction duration of the reaction may vary from several minutes to several hours.

It should be noted that the expert can change the timing of stages of the method according to the invention in accordance with the selected operating conditions.

Other conditions that affect the conduct of the hydrogenation according to the invention (continuous or periodic mode), are defined by traditional technological regulations and, known by themselves.

The invention is illustrated by examples, which describe the process of providerone adiponitrile to obtain amino-6-kapronasia.

In these examples can be used the following abbreviations:

- ADN = adiponitrile

- AKN = aminocaproate

- GMI = hexamethylenediamine were

- SP = the degree of transformation

- ARTICLE = the selectivity of the original connection to the product (in this case in relation to the ADN).

Comparative example

In the reactor of stainless steel with a capacity of 100 ml, equipped samasamajaya stirrer type rushton, means for loading reagents and supply of hydrogen, and a temperature regulation system, put:

- hexamethylenediamine were 24 g

water 5.3g

CON 0.33 mmol

the Raney - Nickel (1.7% Cr) of 0.65,

In this example, the amount of KOH is 0.5 moles per kg Ni.

The reactor is rinsed with nitrogen and then with hydrogen; the hydrogen pressure was adjusted to 2 MPa and the reaction mixture is heated to 50°C. Then quickly insert 24 g adiponitrile through the addition funnel, which is equipped with a pressure of 2.5 MPa by using a reducer with manometer placed in the vessel for storing hydrogen under a pressure of 5 MPa. Begin timing the reaction. Over the course of the reaction being followed by the consumption of hydrogen in the tank for the storage of hydrogen, the pressure in the reactor under arrivalsa constant at 2.5 MPa, and according to analysis by gas chromatography of samples taken from the reaction mixture. When the output of aminoacetonitrile reaches its maximum, the reaction is interrupted by stopping the stirring, the reaction mixture cooled down and relieve the pressure.

Get the following results:

- duration of reaction: 33 min

The JV adiponitrile: 79,6%

- selectivity for aminoacetonitrile: 70,1%

- selectivity on hexamethylenediamine were: 29,5%

the selectivity for other products 0,4%

Example 1: Ni, activated Rh

In the reactor of stainless steel with a capacity of 100 ml, equipped samasamajaya stirrer type rushton, means for loading reagents and supply of hydrogen, and a temperature regulation system, put:

- hexamethylenediamine were 24 g

water 5.3g

CON 0.66 mmol

the Raney Nickel, activated 2,7% Rh, 1.3 g

In this example, the amount of KOH is 0.5 moles per kg Ni.

The reactor is rinsed with nitrogen and then with hydrogen; the hydrogen pressure was adjusted to 2 MPa and the reaction mixture is heated to 50°C. Then quickly insert 24 g adiponitrile through the addition funnel, which is equipped with a pressure of 2.5 MPa by using a reducer with manometer placed in the vessel for storing hydrogen under a pressure of 5 MPa. Begin timing the reaction. Over the course of the reaction is monitored to paraschou hydrogen storage tanks for hydrogen, the pressure in the reactor is kept constant at 2.5 MPa, and according to analysis by gas chromatography of samples taken from the reaction mixture. When the output of aminoacetonitrile reaches its maximum, the reaction is interrupted by stopping the stirring, the reaction mixture cooled down and relieve the pressure.

Get the following results:

- duration of reaction: 66 min

The JV adiponitrile: 83,3%

- selectivity for aminoacetonitrile: 71,7%

- selectivity on hexamethylenediamine were: 28%

the selectivity for other products 0,3%

Example 2: Ni, activated Ir

In the reactor of stainless steel with a capacity of 100 ml, equipped samasamajaya stirrer type rushton, means for loading reagents and supply of hydrogen, and a temperature regulation system, put:

- hexamethylenediamine were 24 g

water 5.3g

CON 0.13 mmol

the Raney Nickel, activated 2,8% Ir, 1.3 g

In this example, the amount of KOH is 0.2 moles per kg Ni.

The reactor is rinsed with nitrogen and then with hydrogen; the hydrogen pressure was adjusted to 2 MPa and the reaction mixture is heated to 50°C. Then quickly insert 24 g adiponitrile through the addition funnel, which is equipped with a pressure of 2.5 MPa by using a reducer with manometer placed in the vessel for storing hydrogen under pressure MPa. Begin timing the reaction. Over the course of the reaction being followed by the consumption of hydrogen in the tank for the storage of hydrogen, the pressure in the reactor is kept constant at 2.5 MPa, and according to analysis by gas chromatography of samples taken from the reaction mixture. When the output of aminoacetonitrile reaches its maximum, the reaction is interrupted by stopping the stirring, the reaction mixture cooled down and relieve the pressure.

Get the following results:

- duration of reaction: 72 min

The JV adiponitrile: 81,2%

- selectivity for aminoacetonitrile: 73,8%

- selectivity on hexamethylenediamine were: 25,4%

the selectivity for other products 0,8%

1. How providerone of dinitrile to the appropriate aminonitriles in a liquid medium, characterized in that it is carried out in the presence of a catalyst, such as Nickel or Raney-Nickel, containing an activating element selected from rhodium or iridium, and the weight ratio (Rh or Ir)/Ni ranges from 0.05% to 10%, and denitely have the formula (I):

NC-R-CN, (I)

where R denotes a linear or branched alkylenes group containing 1 to 12 carbon atoms, preferably linear or branched alkalinity radical containing 1 to 6 carbon atoms.

2. The method according to claim 1, characterized in that Viseu omanyte the weight ratio is in the range of 0.1 to 5%.

3. The method according to any one of claims 1 and 2, characterized in that the catalyst contains one or more activators selected from titanium, chromium, iron, zirconium, vanadium, manganese, bismuth, tantalum, ruthenium, platinum, palladium, niobium, hafnium, and rare earth elements, provided that there is no copper, silver and/or gold.

4. The method according to claim 3, characterized in that the number of additional activator, other than rhodium or iridium, which contains the catalyst, ranges from 0 to 5 wt.% by weight of Nickel.

5. The method according to any one of claims 1 to 4, characterized in that it is carried out in the presence of a strong base.

6. The method according to any one of claims 1 to 5, characterized in that the average concentration of dinitrile in the reaction mixture during the continuous mode of hydrogenation is 10 to 45% (wt./weight.).

7. The method according to any one of claims 1 to 6, characterized in that it is carried out in the presence of LiOH, NaOH, KOH, RbOH, CsOH or NH4OH, or mixtures thereof.

8. The method according to any one of claims 1 to 7, characterized in that the source of the liquid reaction mixture contains water, the content of which is 1 to 20 wt.% relative to the total weight of the reaction mixture.

9. The method according to claim 8, characterized in that the water content is 1 to 15 wt.% in relation to the weight of the reaction mixture.

10. The method according to any one of claims 1 to 9, characterized in that the reaction mixture contains rastvoritelya alcohol.

11. The method according to claim 10, characterized in that the alcohol is chosen from methanol, ethanol, propanol, isopropanol, butanol and mixtures of the above compounds.

12. The method according to any one of claims 1 to 11, characterized in that the reaction mixture contains a diamine, which is formed during the hydrogenation of dinitrile.

13. The method according to item 12, wherein the average concentration of aminonitriles and/or diamine in the reaction mixture during the continuous mode of hydrogenation is 35 to 99 wt.% with respect to the total weight of the solvent included in the above reaction mixture.

14. The method according to item 13, wherein the average concentration of aminonitriles and/or diamine is 45 to 89 wt.% with respect to the total weight of the solvent in the reaction mixture.

15. The method according to any one of claims 1 to 14, characterized in that the reaction mixture contains a liquid or dissolved ammonia.

16. The method according to item 15, wherein the ammonia is 0 to 50 wt.% weight of the reaction mixture.

17. The method according to any of pp.5-16, characterized in that the content of the hydroxide of alkali or alkaline earth metal or ammonium hydroxide is greater than or equal to 0.1 moles per kg of catalyst.

18. The method according to 17, characterized in that the content of the above-mentioned hydroxide is 0.1 - 2 moles per kg of catalyst.

19. The method according to any of PP-18, characterized the eat, the content of the above-mentioned hydroxide is 0.2 to 1.0 moles per kg of catalyst.

20. The method according to any one of claims 1 to 19, characterized in that it is carried out at a temperature less than or equal to 150°S, preferably less than or equal to 120°C.

21. The method according to any one of claims 1 to 20, characterized in that it is carried out under hydrogen pressure, which is 0.10 to 10 MPa.



 

Same patents:

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for semi-hydrogenation of dinitriles of the general formula: NC-R-CN (I) wherein R means linear or branched alkylene or alkenylene group comprising from 1 to 12 carbon atoms to the corresponding aminonitriles. Method involves using hydrogen in the presence of catalyst based on nickel, cobalt, Raney nickel or Raney cobalt comprising, possibly, an activating element that is taken among the 6 group of the Periodic system of element by the IUPAC nomenclature in the presence of strong mineral base representing a derivative of alkaline or earth-alkaline metal or ammonium hydroxide. In carrying out the hydrogenation process the parent mixture comprises water in the weight concentration at least 0.5 weight% of the total content of liquid components of the above said mixture, diamine and/or aminonitrile that can be form from the hydrogenating dinitrile and non-converted dinitrile wherein the weight concentration of all three indicated components is from 80% to 99.5%. The semi-hydrogenation reaction is carried out in the presence of at least one the selectivity-enhancing agent that is taken among the group comprising the following components: - compound comprising at least one cyano-group not bound with carbon atom that is taken among the group comprising hydrogen cyanide, lithium, sodium, potassium, copper cyanide, chelate cyanides of K3[Fe(CN)6], K4[Fe(CN)4], K3[Co(CN)6], K2[Pt(CN)6], K4[Ru(CN)6], ammonium or alkaline metal cyanides, tetrabutyl ammonium cyanide, tetramethyl ammonium thiocyanide, tetrapropyl ammonium thiocyanide; - organic isonitrile that is taken among the group including tert.-octylisonitrile, tert.-butylisonitrile, n-butylisonitrile, isopropylisonitrile, benzylisonitrile, ethylisonitrile, methylisonitrile and amylisonitrile; - tetraalkyl ammonium or tetraalkylphosphonium hydroxide or fluoride is taken among the group comprising tetramethyl ammonium, tetraethyl ammonium, tetrapropyl ammonium, tetrabutyl ammonium, tetrabutylphosphonium; - the chelate coordination compound formed by at least one metal atom and at least carbonyl radicals that is taken among the group comprising organic compounds including carbonyl, phosphine, arsine or mercapto-groups bound with metal and taken among the group comprising iron, ruthenium, cobalt, osmium, rhenium, iridium and rhodium. Method provides enhancing the selectivity by the aminonitrile group.

EFFECT: improved preparing method.

13 cl, 2 ex

The invention relates to a method of partial hydrogenation of dinitrile in aminonitriles, including the state of contact of dinitrile General formula R(CN)2where R represents alkylenes group, with a hydrogen containing medium in the presence of (a) solvent-containing liquid ammonia, alcohol, or both; catalytic composition (b) containing a hydrogenating catalyst, which may be in the form of a foam metal or supported on a carrier, and (C) additives to increase the output of aminonitriles and/or selectivity for aminonitriles selected from the group consisting of oxides of carbon, compounds of tetraalkylammonium hydroxide, connection hydroxide tetraallylsilane, polycentric cluster carbonyl metal containing (i) at least two transition metal atoms inside the cluster, (ii) at least three bridge between metal atoms inside the cluster, and (iii) at least one carbonyl group associated with the metal atom, where the metal is a metal of group VIII; organic isonitrile; cyanide compounds having at least one cyano associated with an atom other than carbon; and fluoride compounds
The invention relates to a method of providerone of dinitriles General formula NC-R-CN in which R is a normal or branched alkylenes group having from 1 to 12 carbon atoms into the corresponding aminonitriles in liquid medium at elevated temperature and pressure

The invention relates to variants of the method of selective hydrogenation of aliphatic dinitriles formula NCRCN, where R is alkylenes group having from 2 to 25 carbon atoms, to aminonitriles by shielding dinitrile with a hydrogen-containing fluid medium in the liquid phase in the presence of a hydrogenation catalyst on a carrier and solvent-containing liquid ammonia, alcohol or both of these substances, using a catalyst selected from the group consisting of Nickel, cobalt, iron or a combination of two or more of them, deposited on magnesium oxide, or in the presence of organic additives containing a carbonyl group selected from the group consisting of organic amides, such as formamide, N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N-metalloceramic, ndimethylacetamide, organic esters of carboxylic acids, such as methylformate, ethyl formate, salts of carboxylic acids, such as formate, sodium formate, ammonium, and urea
The invention relates to a method of producing aminonitriles and diamine by catalytic hydrogenation of aliphatic dinitrile, in particular the production of 6-aminocaproate and diamine
The invention relates to a method of providerone of dinitriles to the appropriate aminonitriles using hydrogen and a catalyst selected from Raney Nickel, Raney cobalt and Raney Nickel contains one activating element selected from elements of groups IVb, VIb, VIIb and VIII of the Periodic system of elements and zinc, and cobalt, Raney contains one activating element selected from elements of groups IVb, VIb, VIIb and VIII of the Periodic system of elements and zinc, and in the presence of a strong inorganic bases - derived alkaline or alkaline earth metal, namely, what source environment hydrogenation contains in the absence of any other solvent water at the rate of 0.5 - 20 wt.% in relation to the total number of liquid components of the reaction medium, the diamine and/or aminonitriles formed from gidrirovannogo of dinitrile and untransformed dinitrile, on the basis that all three compounds comprise from 80 to 99.5 wt.% in relation to the total number of liquid components of the environment, while achieving the degree of conversion of dinitrile constituting 95%, and achieving selectivity for aminonitriles at least 60%
The invention relates to organic chemistry

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for semi-hydrogenation of dinitriles of the general formula: NC-R-CN (I) wherein R means linear or branched alkylene or alkenylene group comprising from 1 to 12 carbon atoms to the corresponding aminonitriles. Method involves using hydrogen in the presence of catalyst based on nickel, cobalt, Raney nickel or Raney cobalt comprising, possibly, an activating element that is taken among the 6 group of the Periodic system of element by the IUPAC nomenclature in the presence of strong mineral base representing a derivative of alkaline or earth-alkaline metal or ammonium hydroxide. In carrying out the hydrogenation process the parent mixture comprises water in the weight concentration at least 0.5 weight% of the total content of liquid components of the above said mixture, diamine and/or aminonitrile that can be form from the hydrogenating dinitrile and non-converted dinitrile wherein the weight concentration of all three indicated components is from 80% to 99.5%. The semi-hydrogenation reaction is carried out in the presence of at least one the selectivity-enhancing agent that is taken among the group comprising the following components: - compound comprising at least one cyano-group not bound with carbon atom that is taken among the group comprising hydrogen cyanide, lithium, sodium, potassium, copper cyanide, chelate cyanides of K3[Fe(CN)6], K4[Fe(CN)4], K3[Co(CN)6], K2[Pt(CN)6], K4[Ru(CN)6], ammonium or alkaline metal cyanides, tetrabutyl ammonium cyanide, tetramethyl ammonium thiocyanide, tetrapropyl ammonium thiocyanide; - organic isonitrile that is taken among the group including tert.-octylisonitrile, tert.-butylisonitrile, n-butylisonitrile, isopropylisonitrile, benzylisonitrile, ethylisonitrile, methylisonitrile and amylisonitrile; - tetraalkyl ammonium or tetraalkylphosphonium hydroxide or fluoride is taken among the group comprising tetramethyl ammonium, tetraethyl ammonium, tetrapropyl ammonium, tetrabutyl ammonium, tetrabutylphosphonium; - the chelate coordination compound formed by at least one metal atom and at least carbonyl radicals that is taken among the group comprising organic compounds including carbonyl, phosphine, arsine or mercapto-groups bound with metal and taken among the group comprising iron, ruthenium, cobalt, osmium, rhenium, iridium and rhodium. Method provides enhancing the selectivity by the aminonitrile group.

EFFECT: improved preparing method.

13 cl, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: process comprises hydrogen reduction of halogenated aromatic nitrile represented by general formula 1:

in which X denotes chlorine or fluorine atom, m integer from 1 to 5, n integer from 1 to 5, and m+n ≤ 5, provided than when n≥ 2, all X can be the same or different, using hydrogenation catalyst selected from group consisting of optionally modified porous nickel and optionally modified porous cobalt and in presence of organic acid in solvent to form halogenated aromatic methylamine represented by general formula 2: , in which X, m, and n are as defined above and "a" is integer from 1 to m).

EFFECT: enabled efficient large-scale production of desired product with high output.

20 cl, 7 ex

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

The invention relates to a method for producing 2,2'-azobisisobutyronitrile used as a blowing agent and polymer initiator of radical polymerization of unsaturated hydrocarbons

The invention relates to the chemistry of adamantane derivatives, and in particular to a new method of obtaining adamantylidene NITRILES of General formula

where R1=H: R2=H, CH3WITH2H5, (CH3)2CH2WITH6H5WITH10H5C5H10N, C5H10NCH2, (CH2)3JV; R1=CH3: R2=CH3,

which are important intermediates in the synthesis of some biologically active substances

The invention relates to a new method of obtaining compounds of formula (I), where W represents nitrogen or CR3; R1represents halogen, halogenated, preferably trifluoromethyl, halogenoalkane, preferably triptoreline, R4S(O)n- or-SF5; R2represents hydrogen or halogen, for example chlorine or bromine; R3represents a halogen, for example chlorine or bromine; R4represents an alkyl or halogenated; and n is 0, 1 or 2; which comprises the reaction of an acid additive salt arylhydrazines formula (III), where R1, R2and W are defined above, (A) with the compound of the formula (II), where R5and R6independently represent alkyl or together represent alkylenes chain containing two or three carbon atoms, or (B) with the compound of the formula (IV), where R7represents alkyl, preferably methyl or ethyl; or which involves the oxidation of compounds of formula (V)

The invention relates to a method of partial hydrogenation of dinitrile in aminonitriles, including the state of contact of dinitrile General formula R(CN)2where R represents alkylenes group, with a hydrogen containing medium in the presence of (a) solvent-containing liquid ammonia, alcohol, or both; catalytic composition (b) containing a hydrogenating catalyst, which may be in the form of a foam metal or supported on a carrier, and (C) additives to increase the output of aminonitriles and/or selectivity for aminonitriles selected from the group consisting of oxides of carbon, compounds of tetraalkylammonium hydroxide, connection hydroxide tetraallylsilane, polycentric cluster carbonyl metal containing (i) at least two transition metal atoms inside the cluster, (ii) at least three bridge between metal atoms inside the cluster, and (iii) at least one carbonyl group associated with the metal atom, where the metal is a metal of group VIII; organic isonitrile; cyanide compounds having at least one cyano associated with an atom other than carbon; and fluoride compounds

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

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