Method for semi-hydrogenation of dinitriles to aminonitriles

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 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, sometimes you may need 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 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 way that cha is partially hydrogenation of dinitriles to aminonitriles in the presence of a catalyst based on Raney Nickel or Raney cobalt, in which the reaction mixture containing gidriruemyi 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 balkanologie solvent and a compound that increases the selectivity of the reaction aminonitriles. However, the number of unwanted by-products remains high.

One of the objectives of the present invention is to develop a new method for 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 education of pomocny.polecam.

More specifically, the invention relates to a method of providerone aliphatic dinitriles to the appropriate aminonitriles with hydrogen and in the presence of a hydrogenation catalyst, for example, Nickel-based, cobalt, Raney Nickel or Raney cobalt, possibly containing an activating element, which is selected from elements of groups 3 through 12 of the Periodic system of the elements according to the IUPAC nomenclature given in Handbook of Chemistry and Physics - 80thedition, 1999-2000, and in the presence of a strong mineral base, which is derived from alkali or alkaline earth metal or ammonium. Original mix (medium) for carrying out hydrogenation includes water, which amount is at least 0.5 wt%. of the total liquid content of the above components of the mixture of diamine and/or aminonitriles able to form of gidrirovannogo of dinitrile and neprevyshenie of dinitrile, while the total weight content of these three components in the mixture ranges from 80% to 99.5%.

In accordance with the invention, the reaction providerone carried out in the presence of at least one additive that increases 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 located is on the level, at least almost equivalent to the level achieved without additives.

Under the selectivity of the product understand the output for the specified product, calculated with respect to the number of dinitrile, transformed by the reaction.

This additive is a compound which is chosen from the group containing:

the compound containing at least one cyano, unrelated to the carbon atom,

- organic isonitrile,

- hydroxide or fluoride of tetraalkylammonium or tetraalkylammonium,

complex coordination compound formed of at least one metal atom and at least carbonyl radicals,

- fluoride compound of the alkali or alkaline earth metal.

As examples of compounds containing at least one cyano, unrelated to the carbon atom, can be called inorganic cyanides, organic/inorganic cyanides, complex compounds or salts of cyanide, such as hydrogen cyanide, lithium cyanide, sodium, potassium, copper, complex cyanides K3[Fe(CN)6], K4[Fe(CN)4], K3[Co(CN)6], K2[Pt(CN)6], K4[Ru(CN)6]thiocyanide ammonium or alkali metal. As organic/inorganic cyanide can be called cyanides of tetraalkylammonium, that is their as tetrabutylammonium cyanide, thiocyanic of Tetramethylammonium, thiocyanic of tetrapropylammonium.

As organic isonitriles according to the invention can be called tert-activiteiten, tert-utilitites, n-utilitites, isopropylidene, benzylidene, utilitites, melilitites and amilitary.

As a complex coordination compounds can be called complexes containing as ligands organic compounds, including carbonyl, phosphine, Arsinoe or mercapto groups associated with metal. Suitable metals can be called metals from groups 7, 8, 9 and 10 of the Periodic system of the elements mentioned above, such as, for example, iron, ruthenium, cobalt, osmium, rhenium, iridium, rhodium.

As organic hydroxides or fluorides tetraalkyllead compounds can be called tetraalkylammonium, tetraalkylammonium compounds containing hydroxyl groups or fluorine atoms, combined with ammonium or phosphonium groups. Alkyl radicals are preferably hydrocarbon radicals containing from 1 to 8 carbon atoms. These radicals can be linear or branched. Examples of suitable compounds according to the invention are Tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrabutylphosphonium.

Rela is availa able scientific C with another preferred feature of the invention the weight ratio of agent, increase the selectivity for catalytic element, expressed in weight of metal, such as Nickel, is from 0.001:1 to 2:1, mainly 0.005:1 to 1:1. The ratio varies depending on the nature of the agent that increases the selectivity.

The method according to the invention allows to achieve selectivity for aminonitriles above 65%and the total selectivity for aminonitriles and diamine above 90%, with a coefficient of transformation of dinitrile more than 70%.

Aliphatic dinitrile that can be used in the method according to the invention are, in particular, dinitrile General formula 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.

Examples of such dinitriles are, in particular, adiponitrile (ADN), 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)used in the examples of the present invention.

A strong mineral base is typically hydroxides, carbonates and alkanoate alkali or alkaline earth metal or ammonium. It is chosen mainly from hydroxides, carbonates, and alkanoates alkali metal.

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

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

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

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%. in relation to the total quantity of liquid substances included in the above reaction mixture.

The original amount of a strong mineral base, preferably higher than or equal to 0.05 moles per kg of catalyst. Preferably it is from 0.1 moles to 3 moles per kg of catalyst, more preferably from 0.15 to 2 is Olga per kg of catalyst.

The catalyst used in the method may be Nickel, cobalt, Raney Nickel or Raney cobalt. These last Raney metals besides Nickel or cobalt contain residual amounts of metal are removed from the original alloy in the process of preparation of the catalyst, which typically is aluminum; and one or more other elements, often called trigger elements, such as, for example, chromium, titanium, molybdenum, tungsten, iron, zinc, copper, rhodium, iridium, cobalt and Nickel. Among these trigger elements chromium and/or iron and/or titanium are considered as the most preferred. The content of these activators are expressed in weight./weight. Nickel is usually from 0% to 10%, preferably from 0% to 5%. These activators are also used with catalysts based on Nickel and/or cobalt.

The amount of catalyst may vary within wide limits, in particular, depending on the selected method of carrying out the reaction or the selected reaction conditions. 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, subject p is adveritising processing. 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 as follows: mix the catalyst hydrogenation with a certain amount of a strong mineral base and solvent, in which a strong mineral base malorastvorima. In accordance with the invention, the mixture containing the thus 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 agent that increases the selectivity can be introduced into the reaction mixture separately from the catalyst. In a preferred method of carrying out the invention, the agent that increases the selectivity is introduced into the catalyst before putting in the reaction mixture, for example, at the stage of pre-processing.

Optimal selectivity for aminonitriles with the same degree of conversion of dinitrile depends on the nature and content of the activator, the amount of water in the reaction mixture, the temperature, the nature and content of the Foundation and/or the agent that increases the selectivity.

The method according to the invention is usually carried out at a reaction temperature less than or equal to 150°S, preferably less than or equal to 12° With and even more preferably less than or equal to 100°C.

More specifically, the specified temperature is between room temperature (approximately 20° (C) to 100°C.

Previously, simultaneously or after heating, the reaction vessel to create the necessary pressure of hydrogen, in practice, the hydrogen pressure is 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.

With 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, known by themselves.

Below are examples that illustrate the invention.

In these examples can be used the following abbreviations:

- ADN = adiponitrile

- AKN = aminocaproate

- GMI = hexamethylenediamine were

- SP = the degree of transformation

- ST = selectivity for Rel is the solution to the transformed source connection (in this case in relation to the ADN).

Comparative example 1

In the reactor of stainless steel with a capacity of 100 ml equipped with a stirrer type samasamajaya, 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) 0.65 g of Nickel

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. 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 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: 33 min

The JV adiponitrile: 79,6%

- selectivity for aminomar is the nitrile: 70,1%

- selectivity on hexamethylenediamine were: 29,5%

the selectivity for other products 0,4%

Example 2

Spend the Example 2 analogously to Example 1, but using the following reactants:

- hexamethylenediamine were 24 g

water 5.3g

CON 0.18 mmol

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

agent that increases the selectivity (2H5)4N+F-H2O 1.09 mmol (rate 0.162 g)

In this example, the amount of KOH is 0.3 moles / kg of Ni, and the attitude of the agent that increases the selectivity for Nickel is 0.25:1.

Get the following results:

- duration of reaction: 63 min

The JV adiponitrile: 83,8%

- selectivity for aminoacetonitrile: 81,6%

- selectivity on hexamethylenediamine were: 17,8%

the selectivity for other products 0,6%

This Example shows the increase of selectivity for ADN and a constant selectivity of side products.

1. How providerone of dinitriles to the appropriate aminonitriles using hydrogen in the presence of a catalyst based on Nickel, cobalt, Raney Nickel or Raney cobalt, containing, perhaps, the activating element, which is selected from 6 groups of the Periodic system of the elements according to the IUPAC nomenclature and in the presence of a strong mineral base, which is derived from alkali or alkaline earth metal sludge is the ammonium hydroxide, the original mix when carrying out the hydrogenation includes water with a weight concentration of at least 0.5 wt.% of the total liquid content of the above components of the mixture of diamine and/or aminonitriles able to form of gidrirovannogo of dinitrile and neprevyshenie of dinitrile, with the weight concentration of all three of these components is 80 - 99.5%pure, characterized in that the reaction providerone carried out in the presence of at least one agent that increases the selectivity, which is chosen from the group comprising a compound containing at least one cyano, unrelated to the carbon atom which is selected from the group including hydrogen cyanide, lithium cyanide, sodium, potassium, copper, complex cyanides To3[Fe(CN)6], K4[Fe(CN)4], K3[Co(CN)6], K2[Pt(CN)6], K4[Ru(CN)6]thiocyanide ammonium or alkali metals, cyanide, tetrabutylammonium, thiocyanic of Tetramethylammonium, thiocyanic of tetrapropylammonium, organic isonitrile chosen from the group comprising tert-activiteiten, tributylstannyl, n-utilitites, isopropylidene, benzylidene, utilitites, melilitites and amilitary, hydroxide or fluoride of tetraalkylammonium or tetraalkylammonium chosen from the group consisting of tetramethyl money, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetramethylphosphonium, complex coordination compound formed of at least one metal atom and at least carbonyl radical which is chosen from the group consisting of organic compounds, including carbonyl, phosphine, Arsinoe or mercaptopropyl associated with the metal selected from the group consisting of iron, ruthenium, cobalt, osmium, rhenium, iridium, rhodium,

and aliphatic dinitrile are denitely General formula (I):

NC-R-CN, (I)

where R denotes a linear or branched alkylenes or alkenylamine group containing 1 to 12 carbon atoms, preferably R is a linear or branched alkalinity radical containing 2 to 6 carbon atoms.

2. The method according to claim 1, characterized in that the mineral base selected from the hydroxides, carbonates and alkanoates alkali metal, alkaline earth metal or ammonium.

3. The method according to claim 1 or 2, characterized in that used a strong mineral base selected from the following compounds: LiOH, NaOH, KOH, RbOH, CsOH and mixtures thereof.

4. The method according to any one of claims 1 to 3, characterized in that the quantity of a strong mineral base, located in the reaction mixture, is greater than or equal to 0.05 moles per kg of catalyst.

5. JV the property according to any one of claims 1 to 4, characterized in that water is present in the reaction mixture in a quantity less than or equal to 20 wt.%, preferably 2 to 15 wt.% with respect to the total content of the liquid components of the above mixture.

6. The method according to any one of claims 1 to 5, characterized in that the concentration of the target aminonitriles and/or the corresponding diamine and neprevyshenie of dinitrile in the reaction mixture is 85 to 99 wt.% with respect to the total content of the liquid components of the reaction mixture.

7. The method according to any one of claims 1 to 6, characterized in that the used catalyst selected from Raney Nickel, Raney cobalt and Raney Nickel and Raney cobalt, comprising one or several other elements, such as chromium, titanium, molybdenum, tungsten, iron, zinc, copper, rhodium, iridium, cobalt, Nickel.

8. The method according to any one of claims 1 to 7, characterized in that a catalyst selected from Raney Nickel, containing at least one activating element selected from chromium and/or iron and/or titanium.

9. The method according to any one of claims 1 to 8, characterized in that a catalyst selected from Raney Nickel, containing at least one activating element in the amount of 0 to 10 wt.%.

10. The method according to any one of claims 1 to 9, characterized in that the catalyst is 0.5 - 50 wt.% with respect to the total weight of the reaction mixture.

11. The method according to any one of claims 1 to 10, characterized in that it is a wasp is estlat at the reaction temperature below or equal to 150° C.

12. The method according to any one of claims 1 to 11, characterized in that it is carried out under hydrogen pressure of 1 bar (0,10 MPa) to 100 bar (10 MPa).

13. The method according to any one of claims 1 to 12, characterized in that the weight ratio of agent that increases the selectivity to the catalyst, expressed in weight of the metal catalytic element is 0.001:1 to 2:1.



 

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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
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The invention relates to organic chemistry

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.

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EFFECT: improved preparing method.

13 cl, 7 ex

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FIELD: organic chemistry, chemical technology.

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EFFECT: improved preparing method.

13 cl, 7 ex

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