The method of obtaining aliphatic alpha,omega-aminonitriles

 

(57) Abstract:

The invention relates to the field of organic chemistry. Describes how to obtain aliphatic alpha, omega-aminonitriles partial hydrogenation of aliphatic alpha,omega-dinitriles at elevated temperature and pressure in the presence of a hydrogenation catalyst, solvent, ammonia and lithium hydroxides, or connection, of which, during the hydrogenation of the formed lithium hydroxide. This method allows to increase the efficiency of the process by increasing yield and selectivity. 3 C.p. f-crystals, 2 tab.

The invention relates to the production technology of aminonitriles, in particular to a method for producing alpha,omega-aminonitriles.

A method of obtaining aliphatic alpha,omega-aminonitriles partial hydrogenation of aliphatic alpha,omega-dinitriles at elevated temperature and elevated pressure in the presence of a hydrogenation catalyst and solvent - alcohol or ammonia, in the case of using an aliphatic alcohol as solvent, the process is carried out in the presence of inorganic bases such as ammonia, sodium hydroxide, potassium, lithium (see U.S. patent No. 5 151 543, MKI: C 07 C 253/30, is the solvent, the output is only depending on the conversion, 60-62%, and formed a relatively large amount of diamine. When using methanol as solvent and sodium hydroxide as inorganic bases yield and conversion are comparable with those obtained when using ammonia. When using alcohol and alkali metal hydroxide as the base drawback is along with unsatisfactory outputs large amounts of solvent, so as dinitrile can only be used in an amount of about 10 weight. %, while when using ammonia as a solvent dinitrile can be used is almost five times the number (47 wt.%).

The objective of the invention is to develop a method of producing aliphatic alpha, omega-aminonitriles, allowing to increase the efficiency of the process by increasing yield and selectivity.

The problem is solved in a method of producing aliphatic alpha,omega-aminonitriles partial hydrogenation of aliphatic alpha,omega-dinitriles at elevated temperature and elevated pressure in the presence of a hydrogenation catalyst and solvent ammonia, due to the fact that the hydrogenation wire the party.

According to the method according to the invention as starting compounds used aliphatic alpha,omega-dinitrile General formula I

NC-(CH2)n-CN, (I)

in which n denotes an integer from 1 to 10, in particular 2, 3, 4, 5 and 6. Especially preferred compounds of formula I are dinitrile succinic acid, dinitrile glutaric acid, dinitrile adipic acid ("adiponitrile"), dinitrile pipelinewall acid and dinitrile cork acid (superolateral"), in particular the preferred adiponitrile.

According to the invention partially hydronaut above dinitrile formula I in the presence of ammonia and lithium hydroxides or compounds giving at reaction conditions lithium hydroxide, using catalytic hydrogenation in the alpha,omega-aminonitriles General formula II

NC-(CH2)-CH2-NH2(II)

and n has the above meaning.

Especially preferred aminonitriles formula II are those in which n has a value of 2, 3, 4, 5 or 6, in particular 4, i.e., the nitrile 4-aminobutanoic acid, nitrile 5-aminopentanoic acid, nitrile 6 aminohexanoic acid (6-aminocaproyl), nitrile 7-aminoheptanoic acid and nitrile 8-amine is 40 - 120, preferably 50 to 100, even more preferably 60 to 90oC. the Pressure is usually selected from 2 to 12, preferably from 3 to 10, even more preferably from 4 to 8 MPa. The residence time in the reaction zone depends mainly on the desired outputs, the selectivity and the desired degree of conversion. Usually it is chosen in such a way as to achieve maximum output, for example, when using adiponitrile it ranges from 50 to 275, preferably from 70 to 200 minutes.

Preferably the pressure and temperature is chosen so that the interaction could take place in the liquid phase.

Ammonia is used usually in an amount such that the weight ratio of ammonia to dinitrile was in the field from 9:1 to 0.1: 1, preferably from 2.3:1 to 0.25:1, particularly preferably from 1.5:1 to 0.4:1.

The amount of lithium hydroxide is chosen usually in the range from 0.1 to 20, preferably from 1 to 10 wt.%, counting on the amount of used catalyst.

As lithium compounds, giving at reaction conditions lithium hydroxide, should be called: metallic lithium, alkyl and aryl lithium compounds, for example, n-utility and finality. A number of these compounds are usually selected so that the joined connection, containing Nickel, ruthenium, rhodium and cobalt, the preferred are compounds of the Raney type, in particular Raney Nickel and Raney cobalt. You can also use the catalyst on the carrier, and the carrier can be, for example, aluminum oxide, silicon dioxide, zinc oxide, activated carbon or titanium dioxide. Especially preferred is a Raney-Nickel (e.g., companies BASF AG, Degussa and grace).

Nickel, ruthenium, rhodium and cobalt catalysts can be modified with metals of group VI (Cr, Mo, W) and group VIII (Fe, Ru, Os, Co (only in the case of Nickel), Rh, lr, Pd, Pt) of the Periodic system of elements. According to the observations using, in particular, the catalysts of the Raney Nickel, modified, for example, chromium and/or iron leads to increased selectivity for aminonitriles.

The amount of catalyst is chosen so that the amount of cobalt, ruthenium, rhodium or Nickel ranged from 1 to 50, preferably from 5 to 20 wt.%, counting on the entered number of dinitrile.

The catalysts can be used in a fixed bed method of feeding on the bottom or irrigation, however, the preferred suspension catalysts.

According to the method according to Isabey are valuable starting compounds for obtaining cyclic lactam, in particular, 6-aminocaproate is the starting compound for caprolactam.

The following example illustrates the proposed method.

Example. Reactor: 300 ml autoclave. Load: 60 g adiponitrile, 7 g of Raney Nickel (BASF, H1-50, moist, about 6 g of Raney-Nickel), 0.1 g of lithium hydroxide.

The autoclave is filled with adiponitrile (ADN), lithium hydroxide and Raney Nickel in argon, then closed and pump 100 ml of ammonia. The mixing occurs a magnetic stirrer.

After heating to 80oC (own a pressure of about 30 bar) increase the total pressure up to 70 bar of hydrogen. This pressure support continuous pumping of hydrogen. Take samples later 30, 60, 90, 120, 180, 240, 300 and 360 minutes and subjected to gas chromatographic analysis. The results of the experiments can be seen from table 1.

Comparative experience

Application hydroxide instead of sodium hydroxide lithium

I repeat the example using 0.2 g of sodium hydroxide instead of 0.1 g of lithium hydroxide ceteris paribus. The results are summarized in table 2.

Comparing the data of tables 1, 2 shows that the use of sodium hydroxide instead of lithium hydroxide leads to worse results selectivity of the bright feast of aliphatic alpha,omega-dinitriles at elevated temperature and pressure in the presence of a hydrogenation catalyst and solvent ammonia, characterized in that the hydrogenation is carried out in the presence of lithium hydroxide or compounds, of which, during the hydrogenation of the formed lithium hydroxide.

2. The method according to p. 1, characterized in that the hydrogenation is carried out at 40 - 120oC.

3. The method according to p. 1 or 2, characterized in that the hydrogenation is carried out at 2 - to 12 MPa.

4. The method according to PP.1 to 3, characterized in that aliphatic alpha, omega-dinitrile use adiponitrile obtaining 6-aminocaproate.

 

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