DE618109C - Process for the production of amines - Google Patents

Description

Process for the preparation of amines, the subject of main patent 599 ro3 is a process for the production of amines, in which one carboxylic acids or their functional derivatives at elevated temperature and with the addition of catalysts treated with a mixture of ammonia or its derivatives and hydrogen.

It has now been found that instead of derivatives of ammonia Can use compounds that under the applied working conditions in amines are transferred, which in turn react with the carboxylic acids, etc. For the present proceedings. suitable starting materials are, for example, nitrites, such as aeetonitrile, butyric acid nitrile, nonylene acid nitrile, stearic acid nitrile, benzonitrile, Phenylessigsäurenitril, Mandelsäurenitrl, also oximes, z. B. aetaldoxime or benzaldoxime. Nitro compounds such as nitromethane, nitrobenzene, Nitrophenols etc., as well as pyridines, quinolines, isoquinolines and the like.

In the present process, substances can also be used, dealing with ammonia or primary. Amines in the presence of catalytically excited Convert hydrogen to primary or secondary amines, which then convert the organic, Contains residues of these substances bound to nitrogen. For this come z. B. Consider: Aldehydes or ketones, such as acetaldehyde, propionaldehyde, butyraldehyde, enanthaldehyde, Oleic aldehyde, benzaldehyde, phenylaoetaldehyde, acetone, methyl ethyl ketone, methyl undecyl ketone, Benzophenone, cyclohexanone, etc. For example, acetone forms with ethylamine in the presence of catalysts and hydrogen easily isopropylethylamine, which in turn is then can continue to react with the simultaneously applied carboxylic acid, etc. It can also mixtures of different nitrites or mixtures of nitrites with aldehydes or ketones, pyridine and the like are used instead of ammonia or amines.

If you treat z. B. a. Mixture of lauric acid nitrile and methyl butyrate in the presence of a reduced cobalt catalyst with hydrogen at high pressure, so takes place during the heating of the reaction mixture at about 8o to zao ° the Conversion of the lauric acid nitrile into dodecylamine. The educated Dodecylamine is able to continue to react with the butyric acid methyl ester, butyldodecylamine is formed at temperatures above 2oo °.

Subjecting a reaction mixture of Palna kernel fat, A-ethaldehyde and ammonia from the action of catalytically excited hydrogen, so forms initially an amine mixture, the ethylamine, diethylamine, triethylamine, butanolethylamine etc. contains and that continues. as well as the remaining ammonia and the amines with the carboxylic acids formed from the glycerine of the palm kernel fat: and ammonia etc. -implemented. Such amine mixtures of primary, secondary and tertiary amines, which is partially bound to a higher molecular weight aliphatic radical on the nitrogen atom can contain, as such or in the form of their salts or after further reactions Use as textile auxiliaries and the like.

The catalysts in the present case are those in the main patent mentioned hydrogenation catalysts into consideration. For example, those for the catalytic reduction of fatty acids: and their derivatives to the corresponding Suitable alcohols. Catalysts are generally capable of producing nitrites at the same time and in the presence of ammonia or amines also carboxylic acids etc. into the corresponding To transfer amines. However, it must be taken into account that the nitrites z. B. with Nickel-containing catalysts mainly form secondary amines., While Catalysts containing cobalt promote the formation of primary amines. One has it is thus in hand, by the choice of certain. Catalysts the formation to effect certain end products. Mixtures of catalysts, of which z. B. a component for the transfer of nitrites, oximes, ketones, etc. into the corresponding. Amines and their other components to form the from this amine with the. Acid residue emerging. Amines are particularly suitable, are often advantageous.

The procedure is generally carried out in the same way as at then. Process of the main patent, although it is appropriate to specify the working conditions even; the nitrile reduction or: the recovery of amines from aldehydes. or ketones or to adapt to the reduction of Pyridn, etc. One can do the hydrogen pressure as well adjust the temperature of the process accordingly, e.g. B. the reaction mixture first heat to 100 ° for a long time and only then increase the temperature. Further one can get the gas mixture, which at the beginning of the process from ammonia and hydrogen existed, make the lapse of a certain time or / and before reaching one's conscience Replace the temperature limit with pure hydrogen.

EXAMPLE i A mixture of 107 parts of methyl laurate, 117 parts of benzyl cyanide and 10 parts of a catalyst obtainable by reduction of basic cobalt carbonate at 325 ° in a stream of hydrogen is treated with hydrogen at 270 ° and pressure. The benzyl cyanide is converted under the specified working conditions into (3-phenylethylamine, which continues to react with the methyl laurate. (3-Phenylethyldodecylamine) is obtained in good yield. (3-Phenylethylamine and di-ß-phenylethylamine. Example 2 100 parts by weight Methyl laurate, 2,000 parts by weight of cyclohexanol and 50 parts by weight of ammonia are treated together with 100 parts by weight of a catalyst prepared according to Example 1 in a stirred autoclave at 270 ° and under a hydrogen pressure of 25 ° at until the pressure no longer decreases Separation of the catalyst is an amine mixture which consists essentially of cyclohexylamine, dicyclohexylamine, dodecylamine and the cyclohexyldodecylamine which boils under 12 mm pressure at 180 to 181 ° Presence of io o Parts by weight of a cobalt catalyst: ators produced by reduction. is available from cobalt carbonate in a hydrogen stream at 325 °, at 24o ° and under a pressure of 200 at - treated with hydrogen. The reaction product freed from the catalyst boils under 10 mm pressure to 60% between 6o and 25o °. The amine mixture obtainable in the manner described with formic acid, acetic acid or hydrochloric acid 'u. The like. Obtained products have a high wetting and foaming power. .

EXAMPLE Zoo parts by weight of pyridine and 100 parts by weight of methyl laurate are heated to 280 ° in a stirred autoclave under a hydrogen pressure of 200 to 25 ° at in the presence of 25 parts by weight of a cobalt catalyst, which can be obtained by heating cobalt carbonate to 35 ° for 4 hours in a stream of hydrogen . After the uptake of hydrogen has ceased, the reaction mixture is separated off from the catalyst and subjected to distillation in vacuo. Under a pressure of 15 mm, the N-dodecylpiperidine formed distills over at igo to i95 °. The excess pyridine present has been converted into piperidine in the course of the reaction. EXAMPLE 5 A mixture of 100 parts by weight of coconut fatty acid methyl ester and zoo parts by weight of acetonitrile is treated in the presence of 20 parts of a tungsten sulfide catalyst which, according to the; According to British patent specification 379335 is produced at 29o ° in a stirred autoclave for 6 hours with hydrogen from Zoo at pressure.

When the reaction product separated off from the catalyst is distilled, diethylamine is mainly obtained as the forerun. The main fraction (98 parts by weight) boils between 90 and 250 ° at a pressure of 20 mm. The main fraction is diluted with the same volume of ligroin and, while cooling and stirring well, enough of a dilute aqueous, methyl alcoholic hydrochloric acid (methanol / water - i: i) is allowed to flow in until the bases are neutralized. At the. Evaporation. In the aqueous-alcoholic solution, the hydrochloric acid salts of the amines are obtained as a pale yellow, viscous, slightly solidifying oil. Example 6 Silica gel is impregnated with a solution of copper nitrate, dried and the catalyst is heated to 350 to 0.00 °. The catalyst, which has a particle size of about 5 to 10 mm in diameter, is then filled into a high-pressure tower and reduced in a stream of hydrogen at 150 to 25 °.

Under a pressure of 200 at of hydrogen, the pump is pumped at 270 ° at the top At the end of the oven, add the same volume of acetonitrile and palm kernel fatty acid while you cook the hydrogen circulates in the same direction. The reaction product is at the bottom Withdrawn from a collecting vessel at the end of the furnace. It works in the example 5 and thus wins the hydrochloride of the fatty acids from the fatty acids bases formed.

Claims (1)

PATENTANsPRUcFI- process for the preparation of amines as a modification of the process of patent 599 103, characterized in that organic compounds which are converted into amines under the working conditions used are used for the reaction with the carboxylic acids or their functional derivatives instead of ammonia derivatives will.