CH621128A5 - Process for the preparation of aliphatic diesters of diaminoalkylphosphonic acid. - Google Patents

Description

621128

2nd

PATENT CLAIM Process for the preparation of aliphatic diesters of diaminoalkylphosphonic acid of the formula I.

CH2NH2

RïO O (CH2) x (I),

\ ll I

P- (CH2) j- C- (CH2) n-CH2NH2

/ I

R2O H

wherein the radicals R1 and R2 can be identical or different and each represent an aliphatic radical with at least 2 carbon atoms, x and y are identical or different and denote the number 0 or 1 and n denotes the number 0.1, 2, 3 or 4 stands, by hydrogenation of aliphatic diesters of dicyanalkylphosphonic acid, characterized in that aliphatic diesters of dicyanalkylphosphonic acid of the formula II

CN

I.

R * 0 O (CH2) x (H)

\ ll I

) P- (CH2)> - C- (CH2) n-CN

/ I

R20 H

with hydrogen in the presence of a nickel catalyst and / or cobalt catalyst and in the presence of ammonia for 0.1 to 50 minutes.

The invention relates to a process for the preparation of aliphatic diesters of diaminoalkylphosphonic acid by hydrogenation of aliphatic diesters of dicyanalkylphosphonic acid in the presence of nickel and / or cobalt catalysts and ammonia.

DOS 2 301 411 describes a process for the preparation of amino-substituted phosphonic acid esters from cyano-substituted phosphonic acid esters by catalytic hydrogenation in the presence of rhodium catalysts and a complexing agent. Diaminoalkyl compounds are neither described, nor mentioned in the list of single products which can be prepared in the description. Instead, ß-aminoethylphosphonic acid dialkyl esters are emphasized as a typical group of compounds in their individual individuals. The German patent application only mentions the production of diethyl, diphenyl and dimethyl-2-aminoethylphosphonate as exemplary embodiments. It is expressly pointed out that the hydrogenation catalysts commonly used, e.g. Raney nickel, cobalt, palladium and platinum, are unsuitable for the process according to the invention because they either do not catalyze the hydrogenation of the cyano group or disadvantageously side reactions, e.g. tend to favor the polymerization of imines formed as intermediates (Section 2, catalyst, 2nd paragraph).

German Offenlegungsschrift 2,032,712 describes that the hydrogenation of co-cyanoalkanophosphonic acid dialkyl esters does not lead to the corresponding (o-amino-alkanophosphonic acid dialkyl esters) but to non-investigated, non-volatile condensation products. The assumption is made that the hydrogenation inter- or intramolecular conversions occur that the

Prevent the formation of the desired connections. The published patent teaches that the hydrogenation can only be achieved if the esters are first converted into the monoesters by saponification. The alkali metal salts of co-aminoalkanephosphonic acid monoalkyl esters are therefore obtained by this hydrogenation.

DE-OS 2 358 835 describes a process for the preparation of monoaminoalkylphosphonic acid esters by batchwise hydrogenation of cyanoalkylphosphonic acid esters in the presence of nickel, cobalt or noble metal catalysts and ammonia. Diaminoalkylphosphonic acid compounds are not mentioned. As the exemplary embodiments show, only Raney nickel can be used as a catalyst and residence times of 2 to 12 hours, as a rule over 5 hours. If these conditions are applied to the hydrogenation of dicyano compounds such as 1,4-dicyano-2- (diethylphosphono) butane, which has not been described previously, a mixture of 1,6-diamino-3- ( diethylphos-phonoVhexane and 4-diethylphosphono-perhydroazepine with 31% yield.

It has now been found that aliphatic diesters of diaminoalkylphosphonic acid of the formula I

CH2NH2

I.

R1 ° \ 0 (CH2) x (I),

/ P- (CH2) r- C- (CH2) ir-CH2NH2

/ I

R20 H

wherein the radicals R1 and R2 can be identical or different and each represent an aliphatic radical with at least 2 carbon atoms, x and y are identical or different and denote the number 0 or 1 and n denotes the number 0.1, 2, 3 or 4 is obtained advantageously by hydrogenation of aliphatic diesters of dicyanalkylphosphonic acid if one obtains aliphatic diesters of dicyanalkylphosphonic acid of the formula n

CN

I.

rio o (CH2) x (n),

\ ll I

^ /> P- (CH2)> - C- (CH2) n-CN

R20 H

wherein R1, R2, x, y and n have the abovementioned meaning, with hydrogen in the presence of a nickel catalyst and / or cobalt catalyst and in the presence of ammonia for 0.1 to 50 minutes.

Among the new compounds of formula I are aliphatic diesters of diaminoalkylphosphonic acid of formula Ia

CH2NH2

I.

C2HsOn ^ O (CH2) x (Ia),

^ / P- (CH2) r- CH- (CH2) a-CH2NH2 C2H5O

where x and y denote the number 0 or 1 and n stands for the number 0.1, 2 or 3, preferred.

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621128

The reaction can be represented by the following formulas in the case of the use of 3-diethylphosphonodiponitrile.

+ 4H2

NC-CH2-CH2-CH-CH2-CN> H2N-CH2-CH2-CH2-CH-CH2-CH2-NH2

OP (OC2H5) 2 OP (OC2H5) 2

In view of the prior art, the process according to the invention provides the new aliphatic diesters of diaminoalkylphosphonic acid in a good yield and purity in a simpler and more economical way. These advantageous results are surprising with regard to the aforementioned publications, the catalysts used and the reaction conditions according to the invention. One hydrogenates e.g. 1,4-dicyano-2- (diethylphosphono) butane continuously under. the conditions according to the invention, the yield of 1,6-diamino-3- (diethylphosphono) hexane is 80%.

With regard to Houben-Weyl, Methods of Organic Chemistry, Volume XII / 1, pages 411 and 524, one would also have an at least partial ester cleavage in the basic reaction medium given by ammonia and the starting diamine itself, and possibly also the formation of corresponding ones Must expect monophosphate mixtures; Also, as Houben-Weyl (loc. cit., page 412) teaches, hydrogen can also cause a hydrogenolytic cleavage of the dialkyl esters to monoalkyl esters in the presence of catalysts 30. With regard to Houben-Weyl (loc. Cit., Pages 354, 358, 359), ring closure reactions and the formation of cyclic amines were also suspected.

The starting materials II can be obtained by adding dialiphatically substituted phosphite to the corresponding α, β-35 unsaturated dinitriles, e.g. according to the procedure described in German Offenlegungsschrift 2 301 411. Preferred starting materials II and correspondingly preferred end products I are those in the formulas of which the radicals R1 and R2 can be the same or different and each 40 represent an alkyl radical with 2 to 10, preferably with 2 to 4, carbon atoms, the two designations x and y being the same or can be different and each denote the number 0 or 1 and n stands for the number 0.1, 2, 3 or 4, preferably for the number 0, 1, 2 or 3, in particular for 0.1 45 or 2. The abovementioned radicals can also be replaced by groups which are inert under the reaction conditions, e.g. Alkyl groups or aminoalkyl groups with 1 to 4 carbon atoms.

For example, the following can be used as starting materials of the formula II:

2-diethylphosphonobutane-l, 4-dinitrile, 3 -diethylphosphonobutane nitrile,

2- (diethylphosphonomethyl) glutaronitrile; ss

2-diethylphosphonosuccinonitrile,

2-diethylphosphono-l, 5-pentandinitrile,

2-diethylphosphono-1, 6-hexane nitrile;

(Diethylphosphonomethyl) malononitrile,

1- (diethylphosphonomethyl) butane-1,4-dinitrile, 60

1- (diethylphosphonomethyl) -1,5-pentaninitrile;

correspondingly substituted for the diethyl esters

Di- (n-propyl) -,

Di (isopropyl) -,

Di- (n-butyl) -, 6S

Di- (isobutyl) -,

Di (pentyl) -,

Di (n-hexyl) -,

Di- (n-heptyl) -,

Di- (n-octyl) -,

Di- (n-nonyl) -,

Di- (n-decyl) -,

Di (2-ethylhexyl) ester;

corresponding esters with 2 aforementioned but different radicals, e.g. the O-propyl-O-ethyl ester.

The reaction is generally carried out at a temperature of from 0 to 250 ° C., preferably from 30 to 100 ° C., in particular from 35 to 70 ° C., without pressure or expediently under pressure, batchwise or, as a rule, advantageously continuously. If appropriate, solvents are used which are inert under the reaction conditions, such as water; Alkanols, e.g. Methanol, ethanol, n-butanol; Ether such as diethyl ether, cyclic ether such as tetrahydrofuran or dioxane.

Preferred hydrogenation catalysts are also several metals, suitably copper and manganese, containing cobalt and / or nickel catalysts, e.g. corresponding sintered catalysts. The metals can be present in the catalyst in the form of their oxides and / or in a mixture with phosphoric acid. Advantageous catalysts of the type mentioned contain between 3 and 30% by weight of copper, 0.5 and 10% by weight of manganese and 60 to 90% by weight of cobalt or nickel. This is optionally supplemented by 0.1 to 5% by weight of phosphoric acid, based on the amount of metal. The hydrogenation catalyst is generally used in the reaction in an amount of 0.5 to 30% by weight, based on starting material II. It can be mixed with a carrier material suitable for the reaction e.g. Silicon dioxide, are used, the amount of the catalyst advantageously being 10 to 40% by weight of the mixture of catalyst and carrier. As a rule, such quantities of hydrogen are added to the reaction mixture at the beginning and in the course of the reaction that a corresponding reaction pressure, expediently between 50 and 300, preferably 150 and 300 bar, is always established at the reaction temperature. Inert gases such as nitrogen can also be used to adjust the pressure accordingly. Cobalt or nickel sintered catalysts which can contain up to 30% by weight of copper, manganese, iron and / or chromium are also advantageous.

Raney nickel and Raney cobalt are preferably used. Such hydrogenation catalysts are generally added in amounts of 0.5 to 50% by weight, based on starting material II. Hydrogen is generally used in an excess, based on starting material II. The reaction advantageously takes place at a reaction pressure between 50 and 300, preferably 100 and 290 bar, discontinuously or, as a rule, preferably continuously; the reaction temperature is generally between 20 and 120 ° C, preferably between 50 and 90 ° C. The hydrogenation is carried out in the presence of hydrogen, generally in an amount of 4 to 40, preferably 5 to 20, mol, based on 1 mol of starting material II. The hydrogen can be fed to the reaction discontinuously or expediently continuously and / or the catalyst can be freshly mixed with hydrogen even after a certain reaction time

621128

4th

loaded. As a rule, such amounts of hydrogen are added to the reaction mixture at the beginning and in the course of the reaction that a corresponding reaction pressure is always set at the reaction temperature.

Ammonia can be used in the form of its expedient aqueous solution or advantageously in gaseous or liquid form. Quantities of 5 to 100, preferably 10 to 60, mol per mol of starting material II are generally suitable. The reaction is carried out for 0.1 to 50, preferably 0.1 to 10, in particular 0.2 to 1 minutes.

The hydrogenation can be carried out as follows: the starting material II, hydrogen and ammonia, if appropriate together with the solvent, are passed through a reactor with the hydrogenation catalyst at the reaction temperature and the reaction pressure. Then the reaction mixture is cooled, optionally mixed with a solvent such as ethanol and filtered. The end product I is removed from the filtrate by the usual methods, e.g. by evaporating the filtrate and fractional distillation.

The new compounds which can be produced by the process according to the invention are flame retardants for foams or cellulose-containing textiles and starting materials for dyes, textile auxiliaries and flame retardants. These compounds can also be used as fungicides. They also have antibacterial and algicidal activity. Furthermore, the compounds are valuable as phytotoxic materials which, for example, impart flame retardancy to products which are formed by cocondensation with aminocarboxylic acids or diamine dicarboxylates. Compared to known substances such as diethylphosphonoethylamine or phosphono-propylamine, in combination with epoxides they have wash-resistant flame retardant effects on textiles and can also be anchored on them with polyfunctional epoxies. They are also valuable intermediates for the production of complexing agents and micronutrients.

For these uses are aliphatic diesters of dia-monoalkylphosphonic acid of the formula Ia

CH2NH2

I.

C2H5O. O (CH2) x (Ia),

\ ll I

P- (CH2) y- CH- (CH2) D-CH2NH2

C2HsO //

where x and y denote the number 0 or 1 and n stands for the number 0, 1, 2 or 3, preferably.

The parts mentioned in the examples mean parts by weight. They relate to parts by volume like kilograms to liters.

example 1

H2N-CH2-CH2-CH2-CH-CH2-CH2-NH2

I.

OP (OC2Hs) 2

a) Preparation of the starting material: To a solution of 212 parts of 1,4-dicyanbutene- (1) and 552 parts of diethylphosphite are added with stirring and external cooling for 30 minutes at 40 ° C. 25 parts of a 3-molar solution of sodium slowly add methanolate in methanol. After the evolution of heat has ended, fractional distillation gives 266 parts of diethyl phosphite and 415 parts of 3-diethylphosphonodipaditrile at 179 ° C. and 0.2 Torr.

b) 100 parts per hour of a solution of equal parts of 3-diethylphosphono-adiponitrile and ethanol and 350 parts by volume of liquid NH3 are passed together with 100,000 parts by volume of hydrogen per hour at 60 ° C. and 280 bar through a high-pressure reactor which contains 500 parts of a catalyst of the following composition : 89 wt% Co, 7 wt% Mn and 4 wt% H3PO4. Before the hydrogenation, the catalyst is depressurized with hydrogen at 240 ° C. for 1440 minutes and then at a pressure of 30 atm for 1440 minutes. The amount of exhaust gas is 100,000 parts by volume of hydrogen per hour. The residence time in the reaction space is 0.25 minutes.

The raw output is fractionated using a thin-film evaporator and 60 parts of 3-diethylphosphono-hexamethylenediamine are obtained per hour from the boiling point 130 ° C. at 0.01 Torr, corresponding to a yield of 80% of theory.

Example 2 H2N-CH2-CH2-CH2-CH-CH2-NH2

I.

CH2-P (OC2Hs) 2

II

O

a) Preparation of the starting material: To a solution of 212 parts of a-methylene glutaronitrile in 552 parts of diethyl phosphite, 20 parts of a 3 molar solution of sodium methanolate in methanol are added with stirring and external cooling at 40 ° C. for 30 minutes. After the evolution of heat has ended, fractional distillation gives 263 parts of diethyl phosphite and 440 parts of 1,3-dicyano-4- (diethylphosphono) butane at 180 ° C. and 0.2 Torr.

b) 100 parts per hour of a solution of equal parts of 1,3-dicyano-4- (diethylphosphono) butane and ethanol and 350 parts by volume of liquid NEb are passed through p.inp together with 100,000 parts by volume of hydrogen at 60 ° C. and 280 bar. n High-pressure reactor which contains 500 parts by volume of a catalyst of the following composition: 89% by weight of Co, 7% by weight of Mn and 4% by weight of H3PO4. Before the hydrogenation, the catalyst is depressurized with hydrogen at 240 ° C. for 1440 minutes and then at 14 bar for 1440 minutes. The amount of exhaust gas is 100,000 parts by volume / hour. The residence time in the reaction space is 0.26 minutes.

The raw output is fractionated using a thin-film evaporator and 50 parts of 2- (diethylphos-phonomethyl) -1,5-diamino-pentane having a boiling point of 128 ° C. at 0.01 Torr are obtained per hour, corresponding to a yield of 78% of theory.

Use 1

A cotton body with a weight of g / m 2 is treated on an two-roll pad with an aqueous solution of 1,6-diamino-3-diethylphosphonohexane (0.094 part / volume part). The roller pressure on the foulard is set so that the liquor absorption is 100%. The fabric is dried at 80 ° C. and then pulled through an aqueous solution of the tris (2,3-epaxypropyl) phosphate (0.201 parts / volume part) and squeezed under the same conditions as after the 1st bath. The fabric finished in this way is dried at 80 ° C. and heated to 135 ° C. in the stenter for 5 minutes. Then it is washed with a 0.2% by weight soda solution for 2 minutes at 70 ° C. After neutral rinsing is dried again.

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621128

A good washable flame retardant according to DIN 53 906 is achieved (see table 1).

Use 2

A cotton body with a weight of 180 g / m2 is equipped in a wet-on-wet procedure using a two-bath process.

Table 2

1. Bath: aqueous solution of 0.134 parts l, 6-diamino-3-diethylphosphonohexane per part by volume. Fleet intake: 70%.

2nd bath: aqueous solution of 0.450 parts of tris (2,3-epoxypropyl) phosphate per part by volume. Fleet intake: 40%.

It is then dried at 80 ° C. and condensed at 135 ° C. for 6 minutes. This is followed by further washing with a 0.2% by weight soda solution (2 minutes at 70 ° C), neutral rinsing and drying.

The flame retardant test according to DIN 53 906 shows the result listed in Table 2.

The fabrics treated in this way show no impairment of the strength properties (tear resistance, abrasion resistance) compared to the non-finished goods.

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Table 1

after use 1 treated fabric untreated according to d. after machine-cooked laundry +) fabric soda (number of washes)

treat-

lung 12 3 4

Test duration

(sec)

6

6

6

6

6

6

Burn time

(sec)

28

0

0

0

0

0

Glow duration

(sec)

29

0

0

0

0

0

Tear length through

(mm) at burned

50 g load

90

90

95

80

100

Fiber application

(%)

24.3

24.0

24.0

23.4

23.1

+) Wash duration 2 hours at 95 ° C

(with 5 g / 1 commercial detergent)

40

45

50

after use 2 treated fabric untreated according to d. after machine-cooked laundry +) fabric soda

treat-

lung 12 3 4

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Test duration

(sec)

6

6

6

6

6 6

Burn time

(sec)

27th

0

0

0

0 1

Glow duration

(sec)

30th

0

0

0

0 0

Tear length through

(mm) at burned

50 g load

95

90

95

100 115

Fiber application

(%)

21.4

20.2

20.2

20.0 19.5

->. o

+) Washing time 2 hours at 95 ° C

(with 5 g / 1 commercial detergent)

Use 3

If you try to cross-link diethylphosphonopropylamine with the tris (2,3-epoxypropyl) phosphate in analogy to the examples given with 1,6-diamino-3-diethylphosphonohexane on the textile, no washing permanence is achieved. Already during the post-treatment of the finished fabrics, practically the entire amount of product applied is washed off, as shown in Table 3.

Table 3

Two-bath equipment with intermediate drying analogous to use 1.

Baths: a) 0.098 parts / volume diethylphosphonopropylamine b) 0.201 parts / volume tris (2,3-epoxypropyl) phosphate

Untreated tissue

After the equipment

After use 1 finished fabric After the soda treatment

Test duration

(sec)

6

6

6

Burn time

(sec)

27th

0

31

Glow duration

(sec)

26

0

0

Tear length through

by

(mm) at burned

85

burned

50 g load

Fiber application

(%)

-

29.0

2.8

B