DE2233679B2 - Process for the preparation of azines - Google Patents

Description

R,

IO

in which R ₁ and R, is hydrogen, straight-chain C, _ ,, - alkyl, branched C ₃ - ₁₂ -alk yl radicals or C ₃ _ ₁₂ cycloalkyl, C "^ hydrocarbon radicals and are the same or different or together with a benzene ring a Form chain-like or branched C ₃ -C -cycloalkyl radicals and the radicals can optionally be substituted by chlorine, bromine, fluorine, nitro or methoxy groups, characterized in that ammonia and hydrogen peroxide are mixed with a carbonyl compound R ₁ —CO-R ₂ , in which R ₁ and R _{2 have} the meanings given, in the presence of a catalyst which is a hydroxide or a soluble salt of ammonium or a metal from group I a or 11 a of the periodic table.

2. The method according to claim 1, characterized in that the reaction is carried out in solution will.

3. The method according to claim 1 and 2, characterized in that the solvent is a C ₁ _ ₄ -Alkylmonoalkohol.

4. The method according to claim 1 to 3, characterized in that the reaction temperature between O and 100 C.

5. The method according to claim 1 to 4, characterized in that the molar ratio is carbonyl compound used and ammonia used to hydrogen peroxide used is between 2 and 4.

6. The method according to any one of claims 1 to 5, characterized in that the reaction

carried out in the presence of a known stabilizer for hydrogen peroxide.

The invention relates to a method of manufacture of azines of the general formula

R,

R,

R,

C = N N = C

in whichR, and R _{2 are} hydrogen, straight-chain C ₁ _ ₁₂ -alkyl radicals, branched C ₃ _ _I2 -alkyl radicals or C ₃ _ _I2 -cycloalkyl radicals, Q, ^ -hydrocarbon radicals with a benzene nucleus and are identical or different or together are chain-like or branched Form C ₃ _ ,, - Cycloalkyl · est and where the radicals can optionally be substituted by chlorine, bromine, fluorine, nitro or methoxy groups.

It is known that aldehydes with ammonia give rise to various addition, condensation or polymerization products (see / for example S. Pat., _: The Chemistry of the Carbon-Nitrogen Bond. Interscience. London, 1970, p. 67), the can react with hydrogen peroxide to form unstable peroxidic compounds and which, when reacted with ammonia and hydrogen peroxide, lead to peroxidic products (see / for example J. C hem. Soc 1969, C. 2678).

It is known that the reaction of ammonia Hydrogen peroxide and a ketone / u aminoperoxides leads Is. For example J. Chem. Sik- .. C. 2663) and that this reaction in the presence of tungstic acid or molybdic acid as a catalyst / u a Oxime leads (see for example J. Gen. Chem. LRSS. 1960.30. 1635).

In the German disclosure documents 21 27 229. 21 43 516 and 22 10 790 describes that azines by reacting ammonia with a Carbonyl compound and hydrogen peroxide in the presence a nitrile or a cvanide. the mechanism of the reaction is unclear. where the Nitnl or the cyanide but intervene as reactants and not as catalysts, with a corresponding Form amide, can produce.

According to FR-PS 1162413, oxidation occurs aromatic imines / u Diary Iketa / inen carried out with the help of atmospheric oxygen in the presence of copper. This method requires the prior synthesis of imines. which is difficult and practical can only be performed with aromatic ketones. This procedure therefore does not allow others To produce compounds as pure aromatic amines.

The invention is based on the object of a simple Generally applicable process to be carried out for the production of A / inen from cirbonyl compounds to create that no prior s \ iithetisierung the corresponding imine makes necessary.

The invention relates to a process for the preparation of A / ines of the general formula

R,

R ₁

C = N-N = C

in which R ₁ and R _{2 are} hydrogen, straight C, _, _r

Alkyl radicals, branched C3_, _2- alkyl radicals or C ₃ , ₂ -cycloalkyl radicals. C "_, ^ hydrocarbon radicals with a benzene nucleus and are identical or different or together form a chain or branched C ₃ _" - cycloalkyl radical and where the radicals

may optionally be substituted by chlorine, bromine, fluorine, nitro or methoxy groups, which is characterized. that ammonia and hydrogen peroxide with a carbonyl compound R ₁ CO-R ₂ , in which R and R _{2 are} the ones indicated

Have meanings in the presence of a catalyst which is a hydroxide or a soluble salt of ammonium or a metal of group Ia or Ha of the periodic table.

The reaction taking place when the process according to the invention is carried out, its reaction mechanism has not yet been clarified, can be described by the following schematic reaction equation will:

3 ₄

-CO-R ₁ +? NH,, IU>,

The carbonyl compounds suitable for the present invention are aldehydes, where one of the radicals R ₁ and R ₂ denotes a hydrogen radical, and ketones, where none of the radicals denotes a hydrogen radical. The type of carbon compound or compounds used determines the Nature of the azine (s) obtained: The use of an aldehyde leads to an alda / in and the use of a ketone to a keta / in, ^

According to the process according to the invention, mixtures of two different aldehydes, of two different ketones, of an aldehyde and a ketone or of even more complex carbonyl mixtures can also be used. If one with R ₁ -CO-R, (U) uüü · R ₁ -CO-R; (ID. Where R | and R, "can be the same or different from R ₁ and R, and have the abovementioned meaning for R ₁ and R, denotes two carbonyl compounds present in a complex mixture, mixtures of symmetrical and asymmetrical azines are obtained . which correspond to the following formulas:

R ₁

R;

R,

(1)

C = N-N = C

(Γ)

R,

C = N-N = C

R. '

R ₂

[V)

40

45

Carbonyl compounds (II) for the inventive Procedures come into question are, for example:

the following aldehydes: formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, n-valeraidehyde, trimethyl azelaldehyde, n-heptaldehyde, Ethyl-2-hexanal, hexahydrobenzaldehyde, benzaldehyde, p-chlorobenzaldehyde, p-nitrobenzaldehyde, ff-methoxypropionaldehyde, and

the following ketones: acetone, butanone-2, pentanone-2, pentanone-3, methyl isopropyl ketone, methyl isobutyl ketone, Methylcyclohexyl ketone, acetophenone, benzophenone, cyclobutanone, cyclopentanone, cyclohexanone, Methyl-2-cyclohexanone, methyl-3-cyclohexanone, Methyl-4-cyclohexanone, 2,4-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, cycloheptanone, Cyclooctanone, cyclodecanone, cyclododecanone.

The reaction is carried out in solution in the presence of a catalyst consisting of a hydroxide or a soluble ammonium salt or a soluble salt of a C - N - NC + 4H ₂ O
R- R,

tilt

Metal of group la or Ha of the periodic table seen, carried out. Preferred are the S. «. Lze from Li. Na. K, Mg. Ca. Sr and Ba. As ammonium salts the ammonia derivatives or mono-, Di- and Tnalky! Amines, where the alkyl radicals 1 to 12 carbon atoms can be used. Man can look for the hydroxides and the quaternary ammonium salts, such as B. tetraalkylammonium hydroxide and tetraalkylammonium salts, where the alkyl radicals have the given meaning, or, for example Use benzyhrimethylammonium salts. As salts, insofar as they are soluble in the reaction mixture, inorganic salts of hydrazine and it oxazine. of carboxylic acids or aliphatic or aromatic Sulphonic acids with no more than 20 carbon atoms are used if the anions are subject to reaction conditions are stable. Examples of these are fluorides. Chlorides, nitrates. Sulfates. Phosphates. Pyrophosphates, borates. Carbonates. Formates. Acetates. Propionate. Butyrate. Isobuly rate. Hexanoates. Octunoate. Dodecanoate. Stearates. Oxalates. Succmaie. Glutarate. Adipates, benzoates, phthalates. Mcihansulfonate. Aihansulfonate. Benzenesulfonals. p-toluenesulfonates etc. These salts can be used as such, but they can also be used in the case of the ammonium salts Manufacture in situ by putting / u a submitted Amount of ammonia to add the corresponding acid. The catalyst is preferably in a Amount of 0.01 to 10 percent by weight, based on the total weight of the reaction mixture, used.

The preferred method, which is used to ertindungsgcmaßen representation of the azines, is that the three Rcaktandcii with the catalyst in aqueous solution or in the presence of a solvent that facilitates the homogenization of the solution, durchfuhrt along This solvent is preferably a C _{1 4} -Alkyl monoalcohol. z. B methanol, ethanol. n-propanol. Isopropanol. n-Butanol, Isobutanol, Sec-Butanol You can work at atmospheric pressure or increase the pressure up to 10 atmospheres if necessary. to reverberate the ammonia in solution / u. The temperature is preferably between 0 and 100 C.

The reactants are preferably equimolecular Quantities before. but you can also have one or more compounds in excess or in deficit insert. For example, 0.2 to 5 moles of aldehyde or ketone and ammonia can be used per mole of water use substance peroxide. However, preference is given to using 2 to 4 mol of aldehyde or ketone and ammonia per mole of hydrogen peroxide. The reagents can be used in commercially available form. The hydrogen peroxide can be an aqueous 30 to 90% solution and the ammonia anhydrous or be used in the usual aqueous solution. The reagents can be combined at the same time be or in a certain order, over a period of time and at a temperature that is particular allow the heat of reaction generated to be kept under effective control. One can also

combine the aldehyde or the ketone and the hydrogen peroxide in a known manner beforehand, to obtain a peroxidic intermediate which is then used in the reaction. One can first let the aldehyde or the ketone react with ammonia and then hydrogen peroxide and add catalyst. Finally, one can react with an aldehyde or ketone Ammonia and hydrogen peroxide produce an amine peroxide and then the catalyst for Give reaction solution.

It may be advantageous. a stabilizer for the hydrogen peroxide, such as phosphoric acid. Nitrilotriacetic acid or ethylenediaminetetraacetic acid and their sodium salts to be added to the reaction mixture.

The azines are important intermediates, especially in the production of hydrazine.

The following examples illustrate the invention. In the examples, the azines obtained were by Separated preparative chromatography and identified by IR spectrum and mass spectrum as well Quantitatively determined by chemical means or gas chromatography.

Example I.

A solution of 20 g of sodium hydroxide in 2 (K) ml of methanol is placed in a flask equipped with a stirrer 10 ml of water. Then 73.5 g of cyclohexanone, 25 ml of 19% ammonia and 0.5 g are added one after the other Add disodium ethylenediamine traacelate. To this solution is added over 30 minutes and below Maintaining a temperature of 20 C 12.25 g 70% hydrogen peroxide. After 24 hours of reaction, 8.6 g of cyclohexanone azine are obtained.

Example 2

The experiment according to Example 1 is repeated, the sodium hydroxide being replaced by 10 g of lithium chloride replaced. When the addition of hydrogen peroxide is complete, the mixture is heated to 50 ° C. for 2 hours and obtained 15.4 g of cyclohexanonazine in the reaction solution.

Example 3

According to J. Chem. Soc, 1969. C. 2678. Peroxy-U'-dicyclohexylamine by mixing 98 g of cyclohexanone, 20 ml of water, 45 ml ^! Methanol. 50 ml of 19% ammonia and 1 g of Dmatriumäthylcndiaminletraacclal. Gaseous ammonia is introduced. cools to 0 C and gradually adds 24.5 g of 7% strength hydrogen peroxide. You stand for 24 hours at room temperature and receive

s K) Ig Perox} - !. I -dicyclohcnvlamin in the reaction mixture.

Take an aliquot of this mixture which contains 53 g of peroxy- !. I'-dicclohexylamine, and adds 24.5 g cyclohexanone and 2 g sodium hydroxide.

ίο dissolved in KKImI methanol, added. The reaction mixture is kept 6.5 hours at 50 ° C., saturating it by introducing it with ammonia, and maintaining it after completion of the reaction 2.3 g of cyclohexanonazine.

Example 4

A mixture of 42 g of peroxy-1,1-dicyclohexylamine is produced. which was produced as in Example 3. 20 grams (0.22 moles) of cyclohexanone. 10 g lithium chloride and KK) ml of methanol. Ammonia is passed in until it is saturated and heated to 35 C. After 6 hours of reaction, 3.1 g of cyclohexanonazine are obtained.

Example

According to the literature, one puts perox 1,1'-diisopropylamine by adding 58 g of Azelon and 70 ml of 30% strength hydrogen peroxide in Presence of ammonia previously dissolved by introduction and I g of disodium ethylenediamine octraacetai and 1 g of ammonium acetate are mixed. One holds then for 24 hours at 0 C.

An aliquot of this solution, the 13.1 g of peroxy-Ι, Γ-diisopropylamine contains, is dissolved in 50ml methanol. 5.8 g of acetone and 20 g of lithium chloride are added added, ammonia passes in until saturation and then warmed to 35 C. After 2 hours of reaction obtained one 0.22 g of azelonazine.

B e i s ρ i e 1 6

According to J.Chem.Soc. 1969. C. 2678. 20g Peroxy-1,1'-diisobutylamine by reacting hydrogen peroxide with isobulyraldehyde in the presence from ammonia. 7 g of isobutyraldehyde are added to the crude mixture obtained. 10 g lithium chloride and introduces ammonia to saturation. The mixture is heated to 35 ° C. and obtained after 6 hours 1.4 g isobutyraldehyde azine.

Claims (1)

Patent claims:
1. Process for the production of A / inen der general formula
R, C = -N- N = C R ₁