DE1643640C3 - Process for the production of omega-carbamoylalkanoic acids, omega-cyanoalkanoic acids and alkane-alpha, omegadicarboxylic compounds - Google Patents

Description

G
draws that one is a compound of the general formula

NH

a)

X C

C Χ

OO

wherein X and X 'are optionally alkyl-substituted, divalent aliphatic radicals having 4 to 6 carbon atoms are in the chain and can be the same or different, at temperatures of Thermally decomposed at 300 to 600 C. 20 and b)

2. The method according to claim 1, characterized in that a solution of IJ'-peroxydicyclohexylamine in 300 to 600 C hot inert gas is sprayed. R ₁₉

■ 13

R ,.

R,

The present invention relates to a method for the production of ω-carbamoylaikansäuren, ω-cyanoalkanoic acids and alkane-rMD-dicarbonimides.

'The compounds prepared by the process according to the invention can be used in the preparation are used by polyamides, as they can be converted into amino acids by hydrogenation will. They can also be used as intermediates in the manufacture of diesters (door plasticizers) or used in condensation resins.

It is known to start from ω-carbamoylalkanoic acids of the u, (u-dicarboxylic acids via their half-esters by reacting the half-esters with thionyl chloride to convert the free carboxy group into a Acid chloride and subsequent reaction with ammonia to replace the chlorine with an amino group and final cleavage of the ester group by mild hydrolysis. Out such an m-carbamoylalkanoic acid can then an α-cyanoalkanoic acid produced by dehydration will.

The object of the invention is to provide a process for the preparation of the compounds mentioned, that in a single step starting from a readily available raw material in a simple way and produced these compounds cheaper, especially suitable for large-scale industrial use.

The inventive method is characterized in that a compound of the general formula

and c)

■ 31

32

R ,. R.

33

35

40

45 where R ₁ to R _{60 are} alkyl groups or hydrogen. The preferred compounds are those

in which R ₁ to Rg _{0 are} hydrogen or lower:

Alkyl, ζ. B. with 1 to 10 carbon atoms in de:

Chain, are, in particular with 1 to 5 carbon atoms in the chain, e.g. B. methyl, ethyl, propyl Specific examples of compounds that give way

-Who can be used in the method according to the invention

NH

ΓΥ

NH

OO

60

OO

X '

wherein X and X 'are optionally alkyl-substituted, divalent aliphatic radicals having 4 to 6 carbon atoms are in the chain and, identically or differently, U'-Peroxydicydopentylamine,

/ y ^NH y \

4,4'-dimethyl-l, ¹ -peroxydicyclohexylamin '.

'J

NH *

1, Γ- peroxydicyclohexy lamin.

-NH

3,3,3 ', 3', 5,5'-hexamethyl-1,1 '-peroxydicyclohexylamine.

OO '

1,1 '-peroxydicycloheptylamine.

The present invention relates to the preparation of derivatives of alkane-fv ^ -dicarboxylic acids in which nitrogen is bonded to the m-carbon atom. This nitrogen atom must therefore form part of a nitrogen-containing carboxylic acid derivative, e.g. B. -CONH ₂ , --CONHCO - or --CN. At the other end of the alkane chain, the "carbon atom of the derivative of the alkane-ivj-dicarboxylic acid, for. B. form part of a carboxylic acid group or a derivative of a carboxylic acid group bound to the nitrogen at the ω-carbon atom.

Examples of derivatives of alkane and fu-dicarboxylic acids with nitrogen bonded to the ^ carbon atom

OC

NH

(CH ₂ ) ,,

CO

(ID

Decane-1,10-dicarbonimide, which is an example of the imide type of derivatives is;

HOOC- (CH ₂ J ₁₀ -CN

(Hl)

11-Cyanundckanoic acid, which is an example of the nitrile or is cyanide type of derivatives;

HOOC (CH ₂ ), ₀ -

(IV)

11-carbamidundecanoic acid, which is an example of the amidic acid type of derivatives is. Also derivatives of these compounds in which the carbon chain has alkyl substituents carries, e.g. 11-cyano-dimethylundecanoic acid c.

The number of carbon atoms in the chain with the carboxyl group or its derivative on both I-.ndcn is equal to the sum of the carbon atoms which form part of the two rings, and this chain carries the substituents originally present on the two rings.

So contains 3,3'-dimethyl-l, l'-peroxydicyclohexyl-

amine

/ \ / ^NH

\ / ^0O

Me

12 atoms that form part of the rings, and the 2 rings together have two methyl substituents,

ίο and it can be thermally decomposed to dimethyl-l 1-cyanundecanoic acid, in which there are 12 carbon atoms in the chain containing the carboxylic acid group and its —CN derivative.
The per-

'5 oxyamin can exist in the form of the pure compound, which has been separated from the reaction mixture in which the peroxyamine was formed. Products rich in peroxyamine resulting from the reaction that produced peroxyamine.

can be easily deposited, but can be used without further purification. In the Production of peroxyamines by reacting cyclic ketones, hydrogen peroxide and Ammonia often separates the peroxyamine as an oily layer that also contains unchanged ketone.

from the aqueous reaction medium. This oily layer can be used without isolation of the Pei oxyamin's thermal decomposition reaction are fed.

The reaction can be carried out in the liquid or in the vapor phase; However, if maximum yield of alkane-i / .ci-dicarboxylic acid derivative is desired, it is preferable to carry out the reaction in the vapor phase. The preferred temperatures are in the range of 300 to 60O ¹ C. When maximum yield of nitrile acid derivative is desired, it is preferred to employ temperatures in the range of 400 to 600 C. Whom. the reaction is to be carried out in the vapor phase, it is preferred to use reduced pressures. Examples of suitable pressures are those in the range 0.1 to 300 mm Hg, preferably 10 to 300 mm Hg.

The vapor phase reaction can be carried out in any suitable manner, e.g. B. by placing a solution of the peroxyamine in a heated column filled with inert material, e.g. B. Glass spheres, which may be packed, above and the product containing the desired derivatives pulls off at the bottom. It is desirable to get the peroxyamines to the reaction temperature as soon as possible to heat. This can be done by putting the peroxyamine, either melted or in Solution sprays into the gas, which goes beyond the desired reaction temperature Temperature is heated, the gas by evaporation of the liquid to the desired reaction temperature is cooled. The pyrolysis can be carried out in an atmosphere of an inert gas, e.g. B. nitrogen, are executed. Any solvent that is inert to the pyrolysis conditions can be used to dissolve the peroxide, e.g. B. ethanol, pyridine, / f-picoline, benzene, chloroform, aqueous ethanol, cyclohexanone. Tributylamine, Ethylcnglykoi. The solution can be of any desired concentration, e.g. B. 10 to 100 percent by weight, for example 50 to 100 percent by weight of peroxide, calculated on the weight of the solvent:; Indeed, the solvent may form a minor part of the mixture, so may

Mixtures consisting of 90 percent by weight of the peroxide (I) and 10 percent by weight of cyclohexanone, be used, because even the small proportions of cyclohexanone are sufficient to produce a liquid To give mixture. The peroxide can also be used as a solvent-free vapor, e.g. B. in a stream an inert gas.

The main nitrogen-containing derivatives of alkane-c ^ to-dicarboxylic acids obtained by reaction Produced in the vapor phase are ι ο imides, acid nitriles and acid amides; when 1,1-peroxydicyclohexylamine When the reaction is heated to an elevated temperature in the vapor phase, decane-1,10-dicarbonimide is used (II) the dicarbonimide, 11-cyanundecanoic acid (III) the nitrile acid and 11-carbamidundecanoic acid (IV) the acidic amide. The structural skeleton of the derivatives produced depends on nature and position of substituents on the rings of the compound (I) fed to the reaction vessel. The type of derivative produced depends on the reaction conditions. Favor high temperatures the formation of nitrile acids. At a given temperature, the fraction becomes nitrile acid by increasing the pressure at which the thermal decomposition is carried out, by decreasing it the speed of feeding into the heated column or by increasing the concentration the peroxide in the solvent, d. H. by increasing the contact time.

The vapor phase reaction is fast. and examples of useful peroxyamine residence times are 0.1 to 2 seconds.

Examples of methods by which the derivative of alkane-ii, c »-dicarboxylic acid from the crude product Can be separated are distillation and recrystallization from solvents.

The nitrogen-containing alkanedicarboxylic acid derivatives generated upon thermal decomposition like ω-carbamide alkanoic acids and ω-cyaiialkanoic acids, can in m-aminoalkanoic acids, the Used in the manufacture of polyamides can be transformed by adding them or theirs Hydrogenated alkali salts in the presence of a hydrogenation catalyst. The mix of products of the Thermal decomposition can be separated into its components, which are separately hydrogenated or the mixture can be hydrogenated without being separated into its components.

If the alkali salts of the nitrogen-containing alkanedicarboxylic acid derivatives can form, can these are used in the hydrogenation and provide the corresponding alkali metal salts of ω-aminoalkanoic acid. Thus, alkali salts of ω-carbamide alkanoic acids and (»-cyanoalkanoic acids can be used.

The hydrogenation to provide 12-aminododecanoic acid is carried out in the presence of a hydrogenation catalyst. Examples of such catalysts are the noble metal catalysts, e.g. B. (a) Platinum catalysts, especially in the form of the finely divided metal. z. B. Adam's catalyst, (b) palladium catalysts, e.g. B. palladium on charcoal, (c) rhodium catalysts. Other useful hydrogenation catalysts are the mixed noble metal catalysts, e.g. B. rhodium-platinum, rhodium-palladium, rhodium-ruthenium and ruthenium-palladium catalysts and nickel and coball catalysts, 7. B. Rancy catalysts.

The reaction can be carried out in the liquid phase by mixing the substance to be hydrogenated with a Solvent to be carried out. Acetic acid works well as a solvent if you have one Noble metal hydrogenation catalyst uses, and aqueous alcohol or aqueous-alcoholic ammonia, when using Raney nickel or cobalt as a catalyst. The catalyst will also intimately mixed with the solution, which is then brought into intimate contact with the hydrogen. This can be conveniently done by bubbling hydrogen through the solution or by stirring the solution in a hydrogen atmosphere.

The optimum of temperature and pressure for the hydrogenation depends on the catalyst used away. When using noble metal catalysts, the hydrogenation is suitably at Room temperature, i.e. between 10 and 25 C and at atmospheric pressure.

When using nickel and cobalt hydrogenation catalysts, temperatures between 10 and 200 C and pressures between 1 and 300 atmospheres are quite useful. The duration of the response depends of course on the reaction conditions. and the response time can be 5 hours or more and also be as short as 20 minutes or less.

The <»- aminoalkanoic acid produced in the hydrogenation can be recovered in any suitable manner. If z. B. is used a noble metal catalyst in acetic acid, the catalyst is filtered off and the solvent evaporated to provide the amino acid, which the latter can then, if desired, be recrystallized, e.g. B. from a large volume of water. When Raney nickel or cobalt alkalis are used in an ammoniacal medium, the amino acid is largely deposited on the catalyst and can be removed by means of a solvent, e.g. B. acetic acid and / or hot water, extracted therefrom. Any amino acid '.m ammoniacal solvent in which the hydrogenation was carried out will be in the form of the ammonium salt. The acid can be released by neutralization or by evaporation of the ammonia.

The invention will now be explained in more detail by the following examples. In this are all pressures as Millimeters of mercury and all temperatures given as degrees Celsius.

example 1

By converting 3-methylcyclohexanone, Hydrogen peroxide and ammonia together became a peroxide of the formula

Me -

OO

Mc

which was likely a mixture of stereoisomers.

5 g of the peroxide were dissolved in 15 cc of ethanol and dripping the solution through a column (1.5 cm internal diameter) which is 20.3 cm its length was packed with glass beads and heated to 400. The pyrolysis was carried out at 150 mm pressure carried out in a slow stream of nitrogen. The addition of the solution took half an hour

saying. The product was distilled to give 0.4 g of 3-methyicyclohexanone, 1.2 g of a methylcaprolactam fraction and 2.6 g of a fraction with a boiling point of 190 to 250714 mm which, as can be seen from the Infrared and nuclear magnetic resonance spectra showed dimethyl-Π-cyanundecanoic acid isomers as well as something Contained lactam and amic acid. The cyanic acids were extracted with base and had a boiling point of 230 up to 240714 mm and acid equivalent 238.

Example 2

By converting 4-methylcyclohexanone, Hydrogen peroxide and ammonia together made a peroxide. The obtained peroxide ^^ '- dimethyl-U'-peroxydicyclohexylamine (5g), was dissolved in ethanol (60 cc) and the solution at 400 and a pressure of 150 mm in 45 minutes allowed to drip through the heated column as in Example 1. Part of the peroxide had not reacted, so that the product is redissolved in 20 cc benzene after evaporation of the ethanol and the solution is within was allowed to drip through the same column for one hour. Distillation gave 0.6 g of 4-methylcyclohexanone, 0.8 g of a 4-methylcaprolactam fraction and 1.8 g of a fraction with a boiling point of 180 bis 240/14 mm, which according to testing by means of infrared spectroscopy, the expected dimethyl-11 -cyanundecanoic acid as well as some contained amides and an unsaturated compound.

Example 3

10 g 3,3,3 ', 3', 5,5 '- hexamethyl-1,1' - peroxydicyclohexylamine were dissolved in 15 cc of ethanol and the solution passed through a heated column, as in Example 1, allowed to drip at 500/150 mm for three quarters of an hour. Distillation of the product resulted 1.7 g of dihydroisophorone, 2.4 g of a trimethylcaprolactam fraction, 1.6 g of a fraction with a boiling point 180 to 220/15 mm and 2.0 g of a fraction with boiling point 240 to 246/15 mm, containing cyanic acids.

Example 4

10 g Ι, Γ-Peroxydicyclopentylamin from cyclopentanone, hydrogen peroxide and ammonia were dissolved in 10 cc of ethanol and the solution through a heated column as in Example 1 in 5,007,150 mm for _^3/4 hour dripped. Distillation of the product gave 0.1 g of cyclopentanone, 0.3 g of valeric acid, 7.8 g of an ω-cyanonanoic acid fraction and 0.5 g of residue. The cyanic acid had a melting point of 50 to 52 ° after recrystallization.

Example 5

32 g of Ι, Γ-peroxydicyclohexyiamine were dissolved in a mixture of 100 cc of ethanol and 4 cc of pyridine, and the solution was introduced dropwise over 3 hours into a 35.6 cm long glass tube, which was half filled with glass spheres and opened through an oven a temperature of 500 (at the center) was heated. The pressure inside the reaction system was 150 mm, and pyrolysis was carried out in a slow stream of nitrogen. The product was condensed, the solvent removed and the residue distilled to give three fractions and 0.9 g of residue. The first fraction (2.8 g) consisted mostly of cyclohexanone but contained some pyridine; the second fraction (5.6 g) was mainly caprolactam; the third fraction (20.0 g) and was mainly consisted of 11-Cyanundekansäure (92.2% according to titration).

Example 6

16 g Ι, Γ-peroxydicyclohexylamine, dissolved in 25 g // - Picolin, were for 115 minutes with a

ίο introduced a temperature of 500 " and a pressure of 150 mm into the reaction tube used in Example 5, through which a slow stream of nitrogen was passed. Distillation yielded cyclohexanone, 3.1 g of a cyprolactam fraction, 9.1 g of a largely 11-cyanundecanoic acid Fraction (88.5% according to titration) and 0.7 g residue.

Example 7

8 g of U'-peroxydicyclohexylamine, dissolved in 40 cc of ethanol and 1 cc of pyridine, were in the reaction tube used in Example 5 , through which a slow stream of nitrogen was passed, at a temperature of 590 x and a pressure of 15 mm for 60 Minutes introduced. Distillation gave 1.2 g of a fraction containing 50% caprolactam together with unreacted peroxide, 5.0 g of a fraction containing 87% 11-cyanundecanoic acid together with caprolactam and decane-1,110-dicarbonimide, and 0.4 g residue.

Example 8

8 g Ι, Γ-peroxydicyclohexylamine, dissolved in 40 cc Ethanol and 1 cc pyridine were in the reaction tube used in Example 5, through which a slower Nitrogen stream was passed for 30 Minu'en at a temperature of 500 and one 150mm pressure introduced. Distillation gave 0.8 g of a caprolactam fraction, 5.7 g of a fraction, which 11-cyanundecanoic acid (82% according to titration) as well as caprolactam, and 0.3% residue.

Example 9

8 g U 'Peroxydicyclohexylamin dissolved in 10 cc of ethanol and 1 cc of pyridine, at a temperature of 500 ° and a pressure of 1 50 mm for 60 minutes in the used for Example 5 reaction tube inserted through which was passed a slow stream of nitrogen . Distillation gave 0.9 g of a caprolactam fraction, 5.4 g of a fraction containing 11-cyanundecanoic acid (86% according to titration) and 03 g of residue.

Example 10

8 g of 1.l'-peroxydicyclohexylamine, dissolved in 40 cc of ethanol and 1 cc of pyridine, were introduced into the reaction tube used in Example 5 for 30 minutes at a temperature of 400 ° and a pressure of 150 mm, through which a slow stream of nitrogen was directed. Destination yielded 0.8 g of a caprolacta fraction, 5.5 g of a fraction which! 1-cyanundecanoic acid (40% according to titration) and decane RO-dicarbonimide, and 0.4 g of residue

Example 11

10 g Ι, Γ-peroxydicyclohexylamine, dissolved in 20 cc chloroform, were at a temperature of 440

609643/49

and a pressure of 15 mm was introduced into the reaction tube used in Example 5 for 35 minutes, through which a slow stream of slurry was passed. The solvent wiggle out of the Product evaporated, the residue treated with light gasoline, the solution cooled and imide (5.6 g) abliltrierl. The filtrate was evaporated and the residue was distilled. This resulted in 0.7 g Cyclohexanone, 0.9 g of a caprolactam fraction and

I 6 g of a fraction which mainly 11-cyanundecanoic acid in addition to some 11-carbamidundecanoic acid.

Example 12

^ g lJ'-Peroxydicyclohxylamine, dissolved in 20 cc Pyiidin and 10 cc of water, were at one temperature of 510 and a pressure of 15 mm for 45 minutes in that used in Example 5 Reaction tube introduced through which a slow stream of nitrogen was passed. The product was dissolved in chloroform and dried with anhydrous magnesium sulfate. The solvent was evaporated, the residue with light gasoline mixed and chilled, yielding 4.2 g of 11-cyanundecuic acid revealed. The filtrate was distilled to yield 0.8 g of one mainly Caprolactam dipping fraction and 1.0g of a fraction that is largely the cyanic acid (11-cyanundecanoic acid) depicted.

Example 13

Xg 1.l'-peroxydicycloxylamine. dissolved in 20 g Cyclohexanone, were for 40 minutes at a temperature of 440 and a pressure of 15 mm introduced into the reaction tube used in Example 5, through which a slow stream of nitrogen was directed. The cyclohexanone was reduced under Pressure removed and the residue treated with light gasoline and cooled, 2.6 g gave some impure dean-UO-dicarbonimide. Distillation of the filtrate yielded 0.6 g of a caprolaclam fraction and 3.2 g of a fraction containing dean-1.10-dicarbonimide. Cyanundecanoic acid and carbamidundecanoic acid.

Example 14

Hg 1.1 '-peroxydicyclohexylamine. dissolved in a mixture of 20 g of ethylene glycol and 8 cc of ethanol, were introduced over 40 minutes at a temperature of 440 and a pressure of 15 mm into the reaction tube used in Example 5, through which a slow stream of nitrogen was passed. The product was diluted with chloroform, washed with water to remove glycol and ethanol , the chloroform solution was evaporated and gasoline was added to the residue. Cooling led to the separation of 4.0 g of imide, and the filtrate was distilled, giving 0.7 g of cyclohexanone, 0.5 g of a caprolactam fraction and 1J g of a fraction, soft decane-1,10-dicarbonimide, 11-cyanundecanoic acid and

I1 -carbamidundecanoic acid. Example 15

16 g i.l'-peroxydicyclohexylamine. dissolved in 8 g of ethanol, were pumped for 9 minutes into a U-tube (43.2 cm long, 9.5 mm inner diameter) made of stainless steel, through which a stream of preheated nitrogen (4.5 l / h at normal temperature and pressure). Both the reaction vessel and the preheater for the nitrogen were immersed in a salt bath heated to 500 'and the pressure inside the reaction system was 150 mm. The product was condensed and the solvent was removed, leaving 13.6 g of residue, which was found to be 8.8 g of 11-cyanundecanoic acid (according to titration and infrared analysis) and 1.7 g of caprolactam (according to gas liquidity kits -Chromatography).

B e i s ρ i e I 16

14.8g of Ll'-peroxydicyclohexylamine were taken under Nitrogen through a 53.3 cm long empty glass reaction vessel, which is through an oven to 500 was heated, distilled. The pressure within the system was 0.1 mm. The product (14.7 g) contained 8.6 g of 11-cyanundecanoic acid, 1.7 g of caprolactam and 1.9 g of cyclohexanone.

Example 17

The procedure of Example 15 was repeated, but instead of solid 1,1'-peroxydicyclohexylamine, an amount of 16 g of the oil was used which had separated from the aqueous layer when aqueous hydrogen peroxide, cyclohexanone and ammonia together for 2 hours have been implemented . The 16 g of oil contained 14.2 g of 1,1'-peroxydicyclohexylamine. The product remaining after removal of the ethanol solvent weighed 13.6 g and contained 7.8 g of 11-cyanundecanoic acid, 1.8 g of caprolactam and 2.5 g of cyclohexanone.

Example 18

8 g of Ι, Γ-peroxydicyclohexylamine in 50 g of pyridine, containing 0.1 cc of a 40% strength aqueous solution of Triton B (Triton B is benzyltrimethylammonium hydroxide), were heated under reflux for 12 \, hours at atmospheric pressure. Distillation of the mixture, which still contained 20% unreacted peroxide, gave, in addition to pyridine and cyclohexanone, 2.0 g of a fraction from the boiling point 125 to 155/15 mm, which contained 40% caprolactam together with the peroxide, and 2.6 g of a fraction from Boiling point 155 to 170 at 15 mm, which contained the C ₁₂ acid amide (11-cavbamidundecanoic acid)

Example 19

8g Ll'-Peroxydicyclohexylamine in 10g / i-Pikohn . were during IV ₄ hours 10 g of boiling i-picoline (bath temperature 175 to 180 ") was added to reflux at atmospheric pressure was continued for another 1 _{'for 4} hours to decompose the remainder of the Peroxydes distillation gave besides / -.? pico -Hn and cyclohexanone 1.6 g of a fraction consisting largely of caprolactam and 2.2 g of a fraction with a boiling point of 250 to 26G ~ at 15 mm, from which the Q, diamide (11-carbamide undecanamide) with a melting point of 187 to 190.5 " and the C ₁₂ acid amide (11-carbamidundecanoic acid) with melting point 132-134 ° were isolated.

Claims (1)

can be thermally decomposed at temperatures of 300 to 600 '. The number of carbon atoms in each of the radicals X and X 'which form part of the rings shown in the general alkanoic acids, ω-cyanoalkanoic acids and alkane 5 formula 1, can vary from 4 to «, (u-dicarbonimides, thereby kenn- that is, there can be from 5 to 7 carbon atoms in each ring. Examples of such compounds are: 1. Process for the production of "j-carbamoyl cheese Ck