DE1270037B - Process for the production of C- to C -cycloalkanone oximes or their salts - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN ÄWflSSS PATENT OFFICE Int. α .:

C07c

EDITORIAL

C07d German class: 120-25 12p-5 Number: 1 270 037 File number: P 12 70 037.7-42 Registration date: May 16, 1962 Ausleeetetae: June 12, 1968

The subject of the main patent 1246 719 is a process for the production of cyclododecanone oxime or its salts from reaction mixtures such as those formed in the nitrosation of cyclododecane using nitrosyl chloride or nitrogen monoxide and chlorine under the action of light, possibly in the presence of an organic solvent and in the presence of hydrogen chloride , to the reaction mixture separately with 80 to 100% sulfuric acid or with oleum with up to 10% sulfur trioxide at a temperature below about 7O ⁰ C continuously extracted at the.

It has now been found that this process is also advantageous for the separation of cycloalkanone oximes with 5 to 11 carbon atoms or their salts can be used from reaction mixtures, as in the nitrosation of cycloalkanes with 5 to 11 carbon atoms using nitrosyl chloride or by means of nitrogen monoxide and chlorine under the action of light, optionally in the presence an organic solvent and in the presence of hydrogen chloride.

Suitable cycloalkanes are, for example, cyclopentane, Cyclohexane, cyclooctane, cyclodecane, cycloundecane, also methylcyclopentane, methylcyclohexane.

The other reactants and the reaction conditions correspond to those of the main patent. The process is simplified in that, especially in the case of the cycloalkanone oximes with 5 to 8 carbon atoms, often oily process products are obtained, so that it is then not necessary will resume precipitated crystals.

In principle, the same limits apply with regard to the concentrations in question as in the main patent. The favorable ranges can easily be found for the individual cycloalkanone oximes determine.

In general, it is advantageous if the molar ratio of cycloalkanone oxime to sulfuric acid is smaller as 1: 1, e.g. B. 1: 1.5, but on the other hand at least 1:10 is.

As with the main patent, the advantages of the process are to be seen in the fact that the formation of oily or crystalline, opaque coatings at the points of passage of light does not occur that a separate The addition of hydrogen chloride is no longer necessary as soon as the reaction mixture is saturated and that the oxime solution is immediately converted into a lactam solution by Beckmann rearrangement can convert, from which the lactam can be obtained as usual.

Process for obtaining

C ₅ - to Cjj cycloalkanone oximes or

their salts

Addendum to the patent: 1 246 719

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, 6700 Ludwigshafen

Named as inventor:

Dr. Horst Metzger,

Dr. Dieter Weiser, 6700 Ludwigshafen

example 1

As an open-topped, with Inlet and outlet provided cooling vessel made of glass or quartz is used and in this a mercury immersion lamp of 80 watts of power attached.

800 g of cyclooctane are introduced into the reaction space. This solution is made using a glass centrifugal pump pumped through a wash bottle filled with 60 g of concentrated sulfuric acid, that the solution leaves the reaction vessel at the bottom, flows through the pump and then through the wash bottle and finally flows back into the reaction vessel at the top.

In cyclooctane were dissolved at 15 to 20 ⁰ C 6.0 g of nitrosyl chloride and the mixture irradiated Cunn under cooling at 15 to 20 ⁰ C and with continued pumping the solution. After 2 hours, a further 6.0 g of nitrosyl chloride are added and this is repeated after a further 2 hours, so that a total of 18.0 g of nitrosyl chloride are introduced within 4 hours. The reaction is terminated after an exposure time of 7 hours. During the whole time, no crystals have precipitated, the cyclooctane phase is clear and practically colorless at the end of the reaction. The lower, yellow-brown colored, sulfuric acid solution, which has increased in volume and weight, is drained from the wash bottle and mixed with 300 g of ice while stirring. Man

809 559/520

Claims (1)

3 4 blunt the acidity of the solution by adding Example 3
dilute sodium hydroxide solution to pH 5, this decreases deposited oxime in ether and receives In the reaction chamber of the described in Example 1 by distillation, 35.0 g of cyclooctanone oxime from the apparatus below are introduced into 800 g of cyclodecane Mp. 41 ° C, that is 90% of theory, based on 5 and the procedure is otherwise as described in Example 1, supplied nitrosyl chloride. The remaining cyclo- After reaction with a total of 18 g of nitrosyl chloride The octane layer is left with dilute sodium hydroxide solution and the lower one from the wash bottle turns yellow-brown wash and distilled. This gives 770.5 g of colored, sulfuric acid solution. Half of this Cyclooctane back. The yield of oxime is, the solution is poured onto 500 g of ice, this separates based on the consumption of cyclooctane, 94 ° / ₀ io immediately 22.0 g of the crude free cyclodecanone the theory. oxime of melting point 79 ° C. (hydrochloride melting point 119 ° C.). Example 2 If one proceeds analogously, but extracts the formed if oxime does not mix with sulfuric acid, it separates In the apparatus described in Example 1, in the form of its hydrochloride, a solution of 400 g of cyclooctane in crystalline form is pumped off after a short time, with the 500 g of benzene also being poured in through 100 g of 80% sulfur-permeable glass parts The crystal coating is also acidic. The benzene solution is saturated at 20.degree. C., which very quickly turns dark, and then with hydrogen chloride and the procedure continues as in the case of reducing the light transmission. Example 1 is described for implementation. After the reaction of the abovementioned amount of nitrosyl chloride has ended, the lower sulfuric acid layer is separated off and, as opposed to the procedure with sulfuric acid Ex, it is mixed with 300 g of ice while stirring. That takes 1.8 times the time for traction. Followed by the addition of dilute sodium hydroxide Abfilder trate the crystals obtained after Umlauge to pH 5 with stirring and cooling 48.5 g Cyclodecanonoximhydrochlorid reduction of cyclooctanone oxime precipitated is filtered off and mp. 117 ° C (from Essigester mp. 119 ⁰ C), that is 85 ° / ₀ dry. By shaking out the aqueous mother theory, based on the cyclodecane consumed. lye with ether gives another amount of oxime. _p ,
A total of 35.5 g of oxime are obtained. The assigned claims:
Remaining colorless benzene solution is extracted with 2-n-sodium hydroxide and then distilled. Here recovery of cycloalkanone oximes or their are obtained back 371 g of cyclooctane, the yield of 30 salts according to patent 1246719, characterized by cyclooctanone oxime, based on the amount consumed, that instead of cyclooctane, is 95% of theory. Cyclododecane C ₅ - to Cu-Cycloalkane uses. If you use instead of 80% sulfur acid 100% sulfuric acid, you get completely considered publications: analogous 35.0 g, corresponding to 94% of theory, Cyclo- 35 Deutsche Auslegeschrift F 14757 IVb / 12o (be octanone oxime. made known on October 6, 1955). 809 559/520 5.68 θ Bundesdruckerd Berlin