Method for preparing aminonitrile, enhancing yield and/or selectivity by aminonitrile and catalytic composition

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to a method for synthesis of aminonitrile from corresponding dinitrile. Method involves contacting dinitrile of the general formula R(CN)2 wherein R means alkylene group comprising from 2 to 25 carbon atoms with hydrogen-containing medium in the presence of a solvent, hydrogenation catalyst and an additive comprising tetralkyl ammonium cyanate for enhancing yield and/or selectivity by aminonitrile as the end product. Also, invention relates to the catalyst composition used in hydrogenation of dinitrile to aminonitrile comprising the combination (1) of the hydrogenation catalyst useful for hydrogenation of dinitrile of the general formula R(CN)2 wherein R means alkylene group comprising from 2 to 25 carbon atoms to aminonitrile, and (2) additive comprising compound of tetraalkyl ammonium cyanate.

EFFECT: improved method of synthesis.

15 cl, 10 ex

 

The SCOPE of the INVENTION

This invention relates to a method for selective hydrogenation to obtain aminonitriles in the presence of additives of Quaternary ammonium cyanate.

BACKGROUND of INVENTION

Aminonitriles are a group of important chemicals that have a variety of industrial applications. For example, aminonitriles can be used as monomers for obtaining high molecular weight polyamides. Specifically, 6-aminocaproate can be used for nylon 6.

Aminonitriles can be obtained by catalytic partial hydrogenation of dinitriles. See, for example, US 2208598, US 2257814, US 2762835, US 3322815, US 3350439, US 3591618, US 4389348, US 4601859, US 5151543, US 5296628, US 5512697, US 5527946, US 5986127, US 6080884, DE 836938, DE 848654, DE-A-19636768, JP-A-9040630 and WO 00/64862, all of which are included in the description by reference for all purposes, as if they represented fully. However, the yield and selectivity for the desired aminonitriles when using some of the known processes can not be so high as is desirable, and the number of fully hydrogenated product (diamine) are also usually higher than desirable.

In the US 5986127 and WO 00/64862, mentioned above, describes the use of certain additives in the process of partial hydrogenation to improve yield and/or selectivity for the desired product aminonitriles and/or reduce the amount of fully hydrogenated product (diamine).

Now found a new group of compounds, which also effectively function as additives to improve the yield and/or selectivity in the process of partial hydrogenation, such as, for example, mentioned previously included in the sources.

SUMMARY of INVENTION

In accordance with one aspect of the present invention proposes a method of obtaining aminonitriles from the corresponding dinitrile by shielding dinitrile with a hydrogen containing medium in the presence of a solvent, a catalyst for hydrogenation and additives to improve yield and/or selectivity for the desired product aminonitriles, characterized in that the preparation contains the compound of Quaternary ammonium cyanate.

Another aspect of this invention relates to a method for improving yield and/or selectivity for aminonitriles obtained by partial hydrogenation of the corresponding dinitrile hydrogen containing medium in the presence of a solvent and a hydrogenation catalyst, comprising a stage of partial hydrogenation of dinitrile with the additional presence of an effective amount of an additive containing compound Quaternary ammonium cyanate.

In another aspect of the present invention proposes a catalyst composition containing a combination of (1) a hydrogenation catalyst suitable for hidri the Finance of dinitrile to aminonitriles; and (2) supplements containing compound Quaternary ammonium cyanate.

The advantage of this invention is that aminonitriles can be obtained with a higher yield and/or with a higher selectivity for aminonitriles, using an additive than without it.

These and other features and advantages of this invention will be more easily understood by the person skilled in the art when reading the following detailed description. It should be clear that some features of the present invention, which, for clarity, described below in the context of separate embodiments, can also be provided in combination in a single embodiment. Conversely, different characteristics of the present invention, which, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.

A DETAILED DESCRIPTION of the PREFERRED EMBODIMENTS

In accordance with this invention dinitrile contact with a hydrogen-containing medium in the presence of a solvent, the catalyst and the compound of Quaternary ammonium cyanate.

Dinitrile suitable for use in the invention have the General formula R(CN)2where R is hidrocarbonetos group selected from the group consisting of alkalinous, Allenova, alkenylamine, alkalinous and Aracinovo groups. You can use the to one dinitrile or a combination of different dinitriles. Preferred hydrocarbonate groups contain from 2 to 25, more preferably from 2 to 15 and most preferably from 2 to 10 carbon atoms per group. In other words, the preferred dinitrile contain from 4 to 27, more preferably from 4 to about 17, and most preferably from 4 to 12 carbon atoms per molecule dinitrile. The preferred type hidrocarbonetos group is Allenova group.

Examples of suitable dinitriles include, but are not limited to, adiponitrile; methylglutaronitrile; alpha, omega-pentanedinitrile; alpha, omega-heptanenitrile; alpha, omega-nonordinary; alpha, omega-dodecanediol; alpha, omega-pentadecanolide; alpha, omega-cosentinii; alpha, omega-tetracosanoate; 3-methylhexanoate; 2-methyl-4-methylenecholesterol and combinations of two or more of them.

Preferably the carbon atoms of the original dinitrile form a branched or linear chain. Preferred examples are adiponitrile (hydronymy to 6-aminocaproate), methylglutaronitrile (GearWay to two isomeric aminonitriles: 5-amino-2-methylvalerate and 5-amino-4-methylvaleramide) and alpha, omega-dodecadienal (GearWay to the appropriate aminonitriles). The preferred dinitrile is adiponitrile as the product of its selective hidri the Finance, 6-aminocaproate, is a well-known monomer for use for polymerization.

According to this invention can be any hydrogen-containing environment, while in this environment there is enough hydrogen to selectively gidrirovanii dinitrile to aminonitriles. The term "environment" refers to liquid, gas or both. The content of hydrogen in the environment can be in the range from 1 to 100%, preferably from about 50 to about 100% and most preferably from 90 to 100% by volume. The currently favored hydrogen-containing environment is essentially pure hydrogen gas.

The molar ratio of hydrogen (hydrogen-containing atmosphere) to dinitrile is not crucial, as there is enough hydrogen to obtain the desired aminonitriles. Hydrogen is usually used in excess. The hydrogen pressure is typically in the range of from about 50 to about 2000 lb/in2(from about 0.45 to about 13,89 MPa), preferably from about 200 to about 1000 lb/in2(from an average of 1.48 to about 7.00 MPa).

In this invention can be used any solvent which contains or liquid ammonia, or alcohol. The concentration of liquid ammonia in the solvent may be in the range from about 20 to about 100%, preferably from about 50 to about 100% and most preferably from about 80 to about 100 wt.% from the solvent as a whole. Preferred essentially pure liquid ammonia. However, if alcohol is also present in the solvent, the concentration of ammonia can be adjusted according to the amount of alcohol that is discussed in more detail below. The molar ratio of ammonia to dinitrile is preferably from about 1:1 or more and generally is in the range from about 1:1 to about 30:1, more preferably from about 2:1 to about 20:1.

For this invention it is possible to use any alcohol, which can facilitate the selective hydrogenation of dinitrile to aminonitriles. Preferred are alcohols with 1-10, preferably 1-4 carbon atoms in the molecule. Examples of suitable alcohols include, but are not limited to, methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, pentanol, hexanol, heptanol, octanol, nonanol, decanol and combinations of two or more of them. The most preferred alcohol (when used) is methanol. Alcohol can usually present in the solvent in a concentration of from about 20 to about 100%, preferably from about 30 to about 99 wt.% from the mass of solvent in General.

Usually when you use alcohol, the solvent further comprises a base, which is essentially soluble in this solvent. The term "essentially the" applies to "more than minor". The preferred bases are ammonia, ammonium base or inorganic base, such as, for example, oxides of alkali metals, oxides of alkaline earth metals, hydroxides of alkali metals, hydroxides of alkaline earth metals, partially neutralized acids in which one or more protons of the acid-substituted ammonium ion, ions, alkali metal ions, alkaline earth metal or a combination of two or more of them. Specific examples of suitable bases include, but are not limited to, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, or a combination of two or more of them. The most preferred bases are ammonia, lithium hydroxide and sodium hydroxide, as they are readily available and they are cheap.

The base may be present in the solvent in any quantity, while this number may facilitate selective hydrogenation of dinitrile to aminonitriles. Typically, the base may be present in the solvent in the range of from about 0.1 to about 10 wt.% of the total mass of the initial dinitrile.

The catalyst in this way is a hydrogenation catalyst suitable for the hydrogenation of dinitrile to aminonitriles. Preferred are catalysts based on transition metal is RH, selected from the group consisting of iron, cobalt, Nickel, rhodium and combinations thereof. The catalyst may also contain one or more promoters in addition to the above-mentioned transition metals, for example one or more metals from group VIB or VII group, such as chromium, molybdenum and tungsten. The catalyst may be in the form of an alloy, including a solid solution of two or more metals, or a separate metal.

The catalytic metal may also be deposited on an inorganic carrier such as aluminum oxide, magnesium oxide and combinations thereof. The metal may be deposited on an inorganic carrier by any means known to the person skilled in the art, such as, for example, impregnation (impregnation, coprecipitation, ion exchange, and combinations of two or more of them. Preferred inorganic carrier is magnesium oxide, and the preferred catalyst on the carrier is a Nickel-iron catalyst on the carrier oxide magnesium.

The catalyst may be present in any suitable form or shape. It can be expected forms, extrudates, tablets, spheres, or combinations of two or more of them. The catalyst may be in the form of spongy metal, such as Nickel Raney® and cobalt, Raney®. The molar ratio of the catalyst to dinitrile can be any ratio, the eye in this respect may kataliziruetsa selective hydrogenation of dinitrile. The mass ratio of the catalyst to dinitrile is usually in the range of from about to 0.0001:1 to about 1:1, preferably from about 0,001:1 to about 0.5:1. If the catalytic metal deposited on an inorganic carrier, or is a part of the alloy or solid solution, the catalytic metal is usually present in amounts in the range of from about 0.1 to about 60, preferably from about 1 to about 50 and most preferably from about 2 to about 50 wt.% from the total mass of the catalyst.

The preferred catalyst is a catalyst of the type of spongy metal. The metal component is iron, cobalt, Nickel or combinations thereof. Commercially available catalysts of this type are promoted or repromotion catalysts Ni Raney® or With Raney®that can be obtained from the firm's Grace Chemical Co. (Columbia, Maryland) or alternative sponge metal catalysts are available, for example, by Activated Metals Corporation (Sevierville, Tenn.) or Degussa (Ridgefield Park, N.J.).

In the case of the preferred Nickel/iron catalyst on a carrier rate of conversion of adiponitrile increases with the amount of Ni deposited on the media. The preferred concentration of Ni is in the range from about 5 to about 50 wt.% and especially in the range of from about 25 to about 35 wt.%by weight of catalyst (metal + media). The preferred concentration of Fe is in the range from about 0.2 to about 20 wt.% and especially in the range from about 0.5 to about 10 wt.% by weight of catalyst (metal + media).

Additional details of the above components can be found in various earlier sources included. Specific information can be obtained, for example, in US 2208598, US 2257814, US 2762835, US 3322815, US 5151543, US 5296628, US 5512697, US 5527946, US 5986127, US 6080884 and WO 00/64862.

Was found a wide range of compounds tiantou Quaternary ammonium compounds, which can influence the improvement of selectivity/yield in this invention.

The term "improvement" refers to increased selectivity aminonitriles product during transformation more than about 70%, preferably transformations more than about 80%, and especially the transformation of more than about 90% compared with selectivity without the use of additives of this invention. "Effective amount" of the additive is a number necessary to achieve the above-mentioned high selectivity and/or improved overall output aminonitriles compared to the process without the use of additives.

Examples of suitable cyanate compounds Quaternary ammonium compounds are compounds of the cyanate of tetraalkylammonium and mixed connection of the cyanate tetraalkyl/arylamine.

In a preferred embodiment of the cyanate of tetraalkylammonium alkyl groups of the cyanate compounds of tetraalkylammonium, individually contains from 1 to 8 carbon atoms and more preferably 1-4 carbon atoms. Preferably, when all four of the alkyl groups in the molecule are the same, but for use in the invention is suitable mixtures having different tetraalkyl deputies. Examples of suitable compounds of the cyanate of tetraalkylammonium include, but are not limited to, the cyanate of Tetramethylammonium, cyanate of tetraethylammonium, cyanate of tetrapropylammonium and tetrabutylammonium cyanate. As indicated above, are also suitable combination of two or more compounds of tiantou of tetralkylammonium. In mixed compounds tiantou tetraalkyl/arylamine alkyl groups are as described above; the aryl groups can be phenyl, naphthyl, or alkyl substituted phenyl or naphthyl, and the description of the alkyl presented above.

The additive is present during the contacting in any quantity, which can improve the selective hydrogenation of dinitrile to its corresponding aminonitriles (for example, an effective amount). Typically, the mass ratio of the additive to the catalyst is in the range from about of 0.01:1 to about 5:1, preferably from approximately 0.05:1 to about 3:1, more preferably from about 0.1:1 to 2:1 and especially from about 0.1:1 to about 1:1.

The catalyst and the additive can be put in contact with on the nitrile separately; however, preferably, when the catalyst whether it is in the form of a metal or alloy or solid solution, or on inorganic media, previously in contact with the additive. This can be accomplished in a solvent such as, for example, alcohol, simple ester, ester, ammonia, or combinations of two or more of them. In addition, preferably prior to the contacting is carried out in a hydrogen-containing atmosphere, such as described above. The contacting of the catalyst and additives gives pre-treated catalyst. Pre-treated catalyst can be washed with a solvent, as described above, preferably under anaerobic conditions to receive processed by the addition of catalyst.

The contacting of the catalyst and additives can be carried out in any conditions effective to obtain a processed additive catalyst, which can improve the selective hydrogenation of dinitrile or selectivity for aminonitriles. Usually the whole process of obtaining a processed additive catalyst can be carried out by contacting the catalyst with the addition described above, at a temperature in the range of from about 20°With approximately 150°C, preferably from about 30°C to about 100°With, at the same total pressure, which is described to enter the, for from about 5 seconds to about 25 hours.

The method of partial hydrogenation of this invention can be carried out at a temperature in the range of from about 25 to about 150°C, preferably from about 40 to about 100°S, most preferably from about 60 to about 80°Since, if the total pressure is usually in the range of from about 50 to about 2000 lb/in2(from about 0.45 to about 13,89 MPa), preferably from about 200 to about 1000 lb/in2(from an average of 1.48 to about 7.00 MPa), during the period of time generally in the range of from about 15 minutes to about 25 hours, preferably from about 1 hour to about 10 hours.

The method of this invention can be carried out in batch or continuous mode in the respective reactor. Stirring or shaking the reaction mixture may be performed in different ways, known to specialists in this field. Partial hydrogenation of the original dinitrile to its corresponding aminonitriles with high selectivity at high conversion of dinitrile makes this method effective and suitable.

Additional General and specific details of the method can be found in different previously included sources. Specific information can be obtained from US 2208598, US 2257814, US 2762835, US 3322815, US 5151543, US 5296628, US 5512697, US 5527946, US5986127, US 6080884 and WO 00/64862.

The following additional examples illustrate the method of this invention and are not intended to unduly restricting the scope of the invention.

The meaning of the terms used in the examples, have the following definitions:

The output of aminonitriles is determined by the measured concentration of aminonitriles divided by the initial concentration of dinitrile.

Turning dinitrile represents the difference between the initial concentration and concentration at this time of dinitrile divided by the initial concentration of dinitrile.

Selectivity for aminonitriles is the measured output aminonitriles divided by the conversion of dinitrile at the moment.

COMPARATIVE EXAMPLE 1

Sponge Ni catalyst (1.2 g), promoted Fe and Cr (Activated Metals, A4000, without any additional additives), was added 50 cm3the autoclave together with 3.2 g of adiponitrile (ADN) and 35 cm3liquid ammonia mixture. Into the autoclave was introduced hydrogen and ADN was first made at 60°at a total pressure equal 1045 lb/in2(7,31 MPa) at about 1500 rpm Full conversion of ADN was achieved within 30 minutes. The maximum output aminoacetonitrile was 57% at 90% conversion of ADN for selectivity of 63%.

COMPARATIVE EXAMPLE 2

300 cm3the autoclave was loaded 7,7 is With Raney (obtained from W.R. Grace Co., catalog number 2724), of 0.77 g of water, 26 g of ADN and 139 g of liquid ammonia. The content was first made in the 70°at a total pressure of 1000 lb/in2(7.00 MPa) at 1000 rpm Total conversion of ADN was achieved within 40 minutes of work. The maximum output aminoacetonitrile was 58% at 90% conversion of ADN for the selectivity of 64%.

COMPARATIVE EXAMPLE 3

50 cm3the autoclave was loaded with 1.2 g of a catalyst of 5% rhodium on alumina (obtained from Engelhard), and 3.2 g of ADN and 35 ml of liquid ammonia. The content was first made in the 80°when the total pressure 1060 lb/in2(7,41 MPa) at 1500 R/min Overall conversion of ADN was achieved within 30 minutes. The maximum output aminoacetonitrile was 41% at 96% conversion of ADN, and the main product is hexamethylenediamine were.

EXAMPLE 1

1.2 g of sponge Ni catalyst (Degussa BLM 112W) was loaded in 50 cm3the autoclave together with 0.25 g of cyanate tetraethylammonium and added to 1.2 g of ADN and 35 ml of liquid ammonia. The mixture was heated to 70°and brought into interaction with hydrogen at a total pressure equal 1052 lb/in2(7.00 MPa). After 25 min output 6-aminocaproate reached approximately 78% at 88% conversion of the ANDES to the selectivity of 89%.

EXAMPLE 2

1.2 g of sponge Ni catalyst (Degussa BLM 112W) was loaded in 50 cm3the autoclave together with 2.0 g of cyanate of tetraethyl is monia. Then was added 35 ml of liquid ammonia and the mixture was heated to 70°under stirring. The pressure is brought up to 1052 lb/in2(7.00 MPa) with hydrogen and the autoclave was kept in these conditions for 1 hour. After cooling, the liquid phase was filtered, leaving a pretreated catalyst inside the autoclave. In the autoclave was injectively 1.2 g ADN and added 35 ml of liquid ammonia. The mixture was heated to 70°and brought into interaction with hydrogen at a total pressure 1052 lb/in2(7.00 MPa). After 60 minutes yield 6-aminocaproate reached approximately 74% at 92% conversion of ADN for selectivity equal to 80%.

EXAMPLE 3

1.2 g of sponge Ni catalyst (Degussa BLM 112W) was loaded in 50 cm3the autoclave together with 0.5 g of cyanate of tetraethylammonium, was added 1.2 g ADN, and 35 ml of liquid ammonia. The mixture was heated to 70°and brought into interaction with hydrogen at a total pressure 1052 lb/in2(7,41 MPa). After 37 minutes yield 6-aminocaproate reached approximately 76% at 93% conversion of ADN for selectivity, 82%).

EXAMPLE 4

1.2 g of sponge Ni catalyst (Degussa BLM 112W) was loaded in 50 cm3the autoclave together with 0.25 g of cyanate tetraethylammonium. Then was added 35 ml of liquid ammonia and the mixture was heated up to 80°under stirring. The pressure is brought up to 1052 lb/in2(7.00 MPa) through the Yu hydrogen and the autoclave was kept in these conditions for 1 hour. After cooling, the liquid phase was filtered, leaving a pretreated catalyst inside the autoclave. In the autoclave was injectively 1.2 g ADN and added 35 ml of liquid ammonia. The mixture was heated up to 80°and brought into interaction with hydrogen at a total pressure 1052 lb/in2(7,41 MPa). After 12 minutes yield 6-aminocaproate reached approximately 75% at 88% conversion of ADN for selectivity equal to 85%.

EXAMPLE 5

1.2 g of sponge Ni catalyst (Degussa BLM 112W) was loaded in 50 cm3the autoclave together with 0.25 g of cyanate tetraethylammonium. Then was added 35 ml of liquid ammonia and the mixture was heated to 60°under stirring. The pressure is brought up to 1052 lb/in2(7.00 MPa) with hydrogen and the autoclave was kept in these conditions for 1 hour. After cooling, the liquid phase was filtered, leaving a pretreated catalyst inside the autoclave. In the autoclave was injectively 1.2 g ADN and added 35 ml of liquid ammonia. The mixture was heated to 60°and brought into interaction with hydrogen at a total pressure 1052 lb/in2(7,41 MPa). After 70 minutes yield 6-aminocaproate reached approximately 77% at 93% conversion of ADN for selectivity equal to 83%.

EXAMPLE 6

1.2 g of sponge Ni catalyst (Degussa BLM 112W) was loaded in 50 cm3the autoclave together with 0.25 g of cyanate tetraethylammonium Then added 35 ml of liquid ammonia and the mixture was heated up to 80° With under stirring. Pressure was brought to 1054 lb/in2(7.00 MPa) with hydrogen and the autoclave was kept in these conditions for 1 hour. After cooling, the liquid phase was filtered, leaving a pretreated catalyst inside the autoclave. In the autoclave was injectively 1.2 g ADN and added 35 ml of liquid ammonia. The mixture was heated to 70°and brought into interaction with hydrogen at a total pressure 1054 lb/in2(7,41 MPa). Through 65 minutes yield 6-aminocaproate reached approximately 77% at 95% conversion of ADN for selectivity equal to 81%.

EXAMPLE 7

1.2 g of sponge Ni catalyst (Degussa BLM 112W) was loaded in 50 cm3the autoclave together with 0.5 g of cyanate of tetraethylammonium. Then was added 35 ml of liquid ammonia and the mixture was heated to 70°under stirring. The pressure is brought up to 1052 lb/in2(7.00 MPa) with hydrogen and the autoclave was kept in these conditions for 1 hour. After cooling, the liquid phase was filtered, leaving a pretreated catalyst inside the autoclave. In the autoclave was injectively 1.2 g ADN and added 35 ml of liquid ammonia. The mixture was heated to 70°and brought into interaction with hydrogen at a total pressure 1054 lb/in2(7,41 MPa). After 42 minutes yield 6-aminocaproate reached approximately 77% at 92% conversion of ADN for selectives and, equal to 84%.

1. The method of producing aminonitriles from the corresponding dinitrile by shielding dinitrile with a hydrogen containing medium in the presence of a solvent, a catalyst for hydrogenation and additives to improve yield and/or selectivity for the desired product aminonitriles, wherein the additive includes a compound of the cyanate of tetraalkylammonium, and dinitrile has the General formula R(CN)2where R is alkalinous group containing from 2 to 25 carbon atoms.

2. The method according to claim 1, characterized in that dinitrile General formula R(CN)2where R is alkalinous group containing from 2 to 25 carbon atoms, selected from the group consisting of adiponitrile, methylglutaronitrile and alpha, omega-dodecanediol.

3. The method according to claim 1, characterized in that the hydrogenation catalyst comprises a transition metal selected from the group consisting of iron, cobalt, Nickel, rhodium and combinations thereof.

4. The method according to claim 3, characterized in that the hydrogenation catalyst is in the form of spongy metal.

5. The method according to claim 3, characterized in that the catalytic metal deposited on an inorganic carrier.

6. The method according to claim 1, characterized in that the mass ratio of the additive to the catalyst hydrogenation is in the range from about of 0.01:1 to about 5:1.

7. The method according to any one of claims 1 and 2-6, characterized in that the alkyl groups of the compounds of the cyanate of tetraalkylammonium, individually, contain from 1 to 8 carbon atoms.

8. The method according to any one of claims 1 and 2-6, characterized in that the connection of the cyanate of tetraalkylammonium selected from the group consisting of cyanate of Tetramethylammonium, cyanate of tetraethylammonium, cyanate of tetrapropylammonium and tetrabutylammonium cyanate.

9. Method for improving yield and/or selectivity for aminonitriles obtained by partial hydrogenation of the corresponding dinitrile General formula R(CN)2where R is alkalinous group containing from 2 to 25 carbon atoms, using a hydrogen containing medium in the presence of a solvent and a hydrogenation catalyst, comprising a stage of partial hydrogenation of dinitrile with the additional presence of an effective amount of an additive containing compound cyanate of tetraalkylammonium.

10. The method according to claim 9, characterized in that the alkyl groups of the compounds of the cyanate of tetraalkylammonium, individually, contain from 1 to 8 carbon atoms.

11. The method according to claim 9, characterized in that the connection of the cyanate of tetraalkylammonium selected from the group consisting of cyanate of Tetramethylammonium, cyanate of tetraethylammonium, cyanate of tetrapropylammonium and tetrabutylammonium cyanate.

12. The composition of the catalyst for hydrogenation of dinitrile to aminonitriles containing a combination of (1) catalytic hydrogenation, suitable DL the hydrogenation of dinitrile General formula R(CN) 2where R is alkalinous group containing from 2 to 25 carbon atoms, to aminonitriles; and (2) an additive comprising a compound of the cyanate of tetraalkylammonium.

13. The composition of the catalyst according to item 12, wherein the hydrogenation catalyst contains a transition metal selected from the group consisting of iron, cobalt, Nickel, rhodium and combinations thereof; and the mass ratio of the additive to the catalyst hydrogenation is in the range from about of 0.01:1 to about 5:1.

14. The composition of the catalyst according to item 12 or 13, characterized in that the alkyl groups of the compounds of the cyanate of tetraalkylammonium, individually, contain from 1 to 8 carbon atoms.

15. The composition of the catalyst according to item 12 or 13, characterized in that the connection of the cyanate of tetraalkylammonium selected from the group consisting of cyanate of Tetramethylammonium, cyanate of tetraethylammonium, cyanate of tetrapropylammonium and tetrabutylammonium cyanate.



 

Same patents:

FIELD: organic chemistry, biochemistry.

SUBSTANCE: invention relates to compounds used as intermediates substances for inhibitors of transfer of cholesteryl ester protein (CETP) and methods for their preparing. Indicated compounds are represented by the following formulae:

, ,

wherein R is taken among methyl and benzyl and by the formula

wherein R represents methyl.

EFFECT: improved preparing method, valuable biochemical properties of inhibitors.

15 cl, 9 ex

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

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

FIELD: organic chemistry, chemical technology, medicine.

SUBSTANCE: invention relates to the improved method for synthesis of 1,3-substituted indenes that are intermediate compounds used in synthesis of aryl-condensed azapolycyclic compounds used in treatment of neurological and psychological disorders. Method for synthesis of 1,3-substituted indenes of the general formula (I) given in the invention description wherein R1 represents electron-accepting group chosen from the group consisting of cyano-group, alkoxycarbonyl, alkylcarbonyl, aryl, nitro-group, trifluoromethyl and sulfonyl; R2 and R3 are chosen independently from hydrogen atom, (C1-C5)-alkyl, (C1-C5)-alkoxy-group, trifluoromethyl, halogen atom, sulfonylalkyl, alkylamino-group, amide, ester, arylalkyl, heteroalkyl and arylalkoxy-group; or R2 and R3 in common with carbon atoms to which they are bound form monocyclic or bicyclic ring; each R4 represents independently (C1-C6)-alkyl, or two groups of R4 form in common (C2-C3)-alkylene bridge involves the following steps: (a) interaction in the absence of solvent between compound of the formula (II) given in the invention description wherein X is chosen from the group consisting of chlorine, bromine and iodine atoms, and R1, R2 and R3 have above given values with monohydric or dihydric alcohol in the presence of sulfuric acid, and (b) treatment of the reaction product with base and water for neutralization o sulfuric acid residue. As a rule, compound of the formula (II) is synthesized by (a) interaction of compound of the formula (III) given in the invention description wherein R1, R2, R3 and X have above given values with 3-ethocyacrylate in the presence of catalyst and inert water-soluble organic solvent, and (b) complete removal of solvent after termination of indicated reaction. Method provides preparing 1,3-substituted indenes with high yield.

EFFECT: improved method of synthesis.

13 cl, 3 sch, 1 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of tetrafluorobenzonitrile of the formula (2): Method involves hydrogenolysis of a single cyano-group of tetrafluorodicyanobenzene of the formula (I): by effect of hydrogen at temperature above 100°C in the presence of the hydrodecyanidation catalyst of platinum group and synthetic zeolite. Invention shows economy profit in the industrial aspect of method for synthesis of tetrafluorobenzonitrile that can be used as agrochemical and medicinal intermediate compound.

EFFECT: improved method of synthesis.

7 cl, 13 ex

FIELD: organic chemistry, chemical technology, medicine.

SUBSTANCE: invention relates to a new method for synthesis of substituted aryl-condensed azapolycyclic compounds of formulas (II) and (VIII) , novel intermediates compounds and methods for their synthesis. Substituted aryl-condensed azapolycyclic compound of the formula (II) show the binding capacity with neurone nicotine/acetylcholine specific receptor sites and can be used for modulation of cholinergic function in treatment of different diseases. Method for synthesis of compound of the formula (II) wherein R represents hydrogen atom; R2 and R3 are chosen independently from hydrogen, halogen atom, (C1-C6)-alkyl optionally substituted with 1-3 fluorine atoms and (C1-C6)-alkoxy-group optionally substituted with 1-3 fluorine atom involves the hydrogenation reaction of compound of the formula: (1a'): synthesized from compound of the formula (III): to yield intermediate compounds of formulas (IX): and (VII): . Compound of the formula (VII) is cyclized in treatment with a base to yield compound of the formula (VIII) that is reduced. Compound of the formula (III) can be prepared by interaction of compound of the formula (IV): with compound of the formula (V): .

EFFECT: improved methods of synthesis.

14 cl, 12 sch, 64 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates to method for production of 4-(ω-hydroxyalkyloxy)-4'-cyanobyphenyls by reaction of 4-hydroxy-4'-cyanobyphenyl with ω-chloro-1-alkanols under heating. Reaction is carried out in boiling dimethylformamide medium in presence of potash for 2-4 h in the next molar ratio: (4-hydroxy-4'-cyanobyphenyl):(ω-chloro-1-alkanol):(potash) = 1:(1-1.2):(1-1.2).

EFFECT: accelerated, simplified method of decreased cots; increased yield of target product.

1 tbl, 1 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to continuous process for hydrogenation of compounds containing nitrile and nitro groups to produce amino or aminonitrile compounds in presence of heterogeneous hydrogenation catalyst and a basic compound. Into reactor, at stirring, are fed: first stream of reactant to be hydrogenised, second stream of catalyst, third stream of alkali compound, fourth stream of hydrogen to maintain hydrogen pressure in reactor. From reactor is withdrawn at least fifth stream composed of reaction mixture and containing hydrogen bubbles dispersed therein. Fifth stream circulates in at least one circulation circuit coming out of lower section into top section of reactor. Fifth stream remove excess heat released in hydrogenation reaction and so temperature of reaction mixture is maintained below 150°C. Fifth stream circulating in one of circuits is passed through filter medium to produce sixth stream containing a part of hydrogenate separated from catalyst. From reactor and one of circulation circuit, seventh stream is picked and sent to liquid and solid phase separation stage to produce liquid phase comprised of hydrogenate without catalyst and catalyst-containing solid phase. The latter is subjected to reduction before being recycled into the second catalyst stream fed into reactor.

EFFECT: increased selectivity and productivity of hydrogenation process and enabled reduction and reuse of catalyst.

18 cl, 2 dwg

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

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

FIELD: hydrocarbon conversion processes.

SUBSTANCE: process consists in catalytic decomposition of hydrocarbon-containing gas at elevated temperature and pressure 1 to 40 atm, catalyst being reduced ferromagnetic cured product isolated by magnetic separation from ashes produced in coal combustion process at power stations. The catalytic product represents spinel-type product containing 18 to 90% iron oxides with balancing amounts of aluminum, magnesium, titanium, and silicon oxides. Prior to be used, catalyst is subjected to hydrodynamic and granulometric classification.

EFFECT: reduced total expenses due to use of substantially inexpensive catalyst capable of being repetitively used after regeneration, which does not deteriorate properties of original product.

2 cl, 6 ex

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