DE764891C - Process for the preparation of halogen-substituted, sulfonated ureas - Google Patents

Description

It has been found that valuable halogen-substituted, sulphonated ureas can be obtained the benzene series and the heterocyclic series are obtained when one is reactive Carbonic acid derivatives or substances or mixtures of substances that form such compounds with hydrogen-containing aminosulfonic acids which can be replaced on the nitrogen atom ßenzölreihe and the heterocyclic series ίο converts, with the reaction components be chosen such that at least one halogen atom is present in the end product.

One arrives at the same or similar compounds if one uses the aminosulfonic acids corresponding, sulfonic acid group-free amines are used and the sulfonic acid groups introduces by post-sulfonation.

As carbonic acid derivatives that can be used for condensation, are suitable chlorides or esters, amides, imides or anhydrides of carbonic acid, where carbonyl chloride and carbamic acid chlorides to be sold under carbonic acid chlorides

are standing. Halogen and / or alkyl-substituted ones have proven to be particularly valuable aromatic, aliphatic-aromatic and heterocyclic carbamic acid chlorides er-S grasslands. By warming or by melting or heating the aminosulfonic acids with ureas or urethanes in suitable Solvents or suspending agents are obtained from ammonia or alcohol ίο splitting off valuable products as well.

The condensation products claimed can also be obtained by accumulation " of isocyanates, in particular halogen- and / or alkyl-substituted aromatic Isocyanic acid esters, aminosulfonic acids of the benzene series or the heterocyclic ones Line. Similar bodies are formed during the conversion of carbamic acid chloride sulfonic acids the benzene series and the heterocyclic series with suitable amines the benzene and heterocyclic series or with the addition of corresponding isocyanate sulfonic acids of these amines. Alkyl and aryl carboxylic acid azides also lead to the Condensation with aminosulfonic acids with evolution of nitrogen to form urea derivatives. In all of these methods, the components must be substituted in such a way that that at least one halogen is present in the end product ·. This can be done in any of the Reaction components. at> he also stand in both at the same time.

The carbamic acid chlorides and isocyanic acid esters used as starting materials can be obtained by known processes. By reacting primary or secondary amines, such as 4-chloroaniline, 3, 4-dichloroaniline, 2, 4-dichloroaniline, 3, 4-D1-chloro-6-methoxyaniline, 4-xitraniline, 4, 4'-dichloro-2- aminodiphenyl ether, 4'-chloro-4-aminodiphenyl sulfone, 3, 4, 5-trichloroaniline, 2, 4, 5-triethaniline or α-dodecylbenzylamine with phosgene produce the carbamic acid chlorides in a simple reaction. By means of suitable reactions known per se, the latter, obtained from the corresponding primary amines, can easily be converted into isocyanic acid esters.

Suitable aromatic aminosulfonic acids are the sulfonic acids of the aminodiphenyls, the aminodiphenyl ethers, the aminodiphemimethanes, and the aminodiphenylsulde. the aminodiplienylsulfoxides, the aminodiplienylsulfones, the aminodiphenylamines, the aminodiphenylketenes, the aminobenzanilides, the aminodiphenylureas, the aminodiphenylthioureas; but simple sulfonic acids of aniline, anisidine or xitraniline are also valuable. Particularly suitable here are halogen- and / or alkyl-substituted derivatives of the amino or polyamino sulfonic acids mentioned, such as 3,4-dichloroanilino-sulfonic acid, 4-chloro-4'-amino-i, i'-diphenyl ether-2'- sulfonic acid, 4, 4 ' - dichloro- 2- aminoi. i'-diphenyl ether-2'-sulfonic acid, 2'.4-dichloro-4'-amino-i, i'-diphenyl ether -'-sulfonic acid, 3-methyl-4-chloro-4'-amino-1. i'-diphenyl ether-2'-sulfonic acid, 3, 4-dichloro-4'-amino-1, 1- diphenyl sulfide -2'-sulfonic acid, 3. 4-dichloro-2'-amino-1, ι'-diphenyl sulfide 4'-sulfonic acid, 4, 4'-dichloro-2-amino-i, i'-diphenylmethane-2'-sulfonic acid or 3'-aminol) enzoyl-3, 4-dichloroaniline-6-sulfonic acid. Of heterocyclic aminosulfonic acids, the aminobenzothiazole sulfonic acids may be mentioned

Aminocarbazole sulfonic acids, the aminoacyl- ^! carbazole sulfonic acids, the aminodiphenylene [oxydsulfonic acids and the aminophenothioxinsulfonic acids; Here, too, the halogen substitution products have proven to be particularly verbose.

A suitable choice of substitution makes it possible to obtain products with one or more sulfonic acids. For example, when phosgene acts on halogenated aminodiphenyl ether monosulfonic acids, ureas with two sulfonic acid groups are formed. On the other hand, the action of carbamic acid chlorides on aminosulfonic acids produces ureas with a sulfonic acid group. The invention thus claims symmetrical and asymmetrical urea sulfonic acids, as well as those which are more or less fully alkylated, aralkylated or arylated on nitrogen. By condensing aminosulfonic acids or alkylaminosulfonic acids with carbamic acid chlorides substituted on the nitrogen, it is possible to produce di-, tri- and tetrasubstituted ureas. Mono- and di-substituted unsymmetrical urea derivatives are formed by reaction of i _O o aminosulfonic acids and Alkylaminosulfonsäuren with Xitroharnstoff or cyanate.

The claimed symmetrical and, in particular, asymmetrical urea sulfonic acids are great for estimating wool, feathers. Furs, hair, paper, textiles. Leather, natural or artificial fibers or objects containing these substances from moths and others Textile pests. In particular, the neutral drawability, which is already relative 'low temperature, e.g. B. at 45 °, is very pronounced, and the pronounced washing and flexing fastness of the treated textiles is worth mentioning. In these properties, in particular in their combination in a single chemical compound, they are the commercially available 120 ■ Superior to protective agents.

For the process of making the

Starting materials is given in the context of this Invention not seeking protection.

Example ι

16 parts of 4-amino-4'-chloro-5'-methyli, i'-Diphenylether-2-sulfonic acid are dissolved in 250 parts of water in the required amount 10% soda solution brought into solution. 30 parts of crystalline are added to this solution.

Add sodium acetate and pass at 40 to 50 ° phosgene until a sample shows no more free amine. This will be the solution exactly neutralized by means of soda, the urea, an N, N '- 4, 4' - (3 ", 3 '" - dimethyl

4 ", 4 ^/ "-dichlo> rdiphenoxy) -3, 3'-disulfonic acid diphenylurea, precipitates as a pasty mass; it is separated off, dried, ground and obtained as a light, water-soluble powder. The yield is quantitative.

ao Instead of 4-amino-4'-chloro-5'-methyli, i'-diphenyl ether ^ -sulfonic acid, 4- or 2-amino-4'-amyl-6 ^/ -chlor-i, 1'- Diphenyl ether-2- or -4-sulfonic acid, the 4-amino-2'- or -4'-chloro-1, 1'-diphenyl ether-2-sulfonic acid or the corresponding 'i' ⁿ 3 '. Compounds substituted 5'- by two methyl groups or in the 3 ', o'-position by a methyl and an isopropyl group or the analogous compounds derived from 2-amino-4'-chloro-i, i'-diphenyl ether-4-sulfonic acid derivative compounds, the 2-amino ~ 4 ', 5-, "3'j 6'- or -4', 6'-dichloro-i, i'-diphenyl ether-4-sulfonic acid or its homologues, the 4-amino 3 ', 6'- or -4', o'-dichloro-i, i'-diphenyl ether-2-sulfonic acid, the 2- or 4-amino-2 ', 4', s'-trichloro-1, 1 ' Diphenyl ether-2- or -4-sulfonic acid can be used These diphenyl ether sulfonic acids are obtained by known processes by condensation and subsequent reduction of p-chloronitrobenzenesulfonic acid or o-chloronitrobenzoilsulfonic acid with appropriate phenols.

Example 2

17.8 parts of 2-amino-4 _i 4'-dichloa-1, i'-diplienylether-2'-sulfonic acid sodium, prepared by gently suIf oning 2-amino-4,4'-dichloro-1, i'-diphenyl ether are dissolved in 200 parts of water and 30 parts of crystalline. Sodium acetate added; at 40 to 50 ⁰ phosgene is then passed in. The separated product is taken up in soda and then treated with saturated sodium chloride solution.

salted, whereupon the urea precipitates nicely crystalline. The yield of N, N '~ 2, 2'- (4 ", 4" '- dichloro-2 ", 2'" - disulfonic acid diphenO'Xy) -5, s'-dichlorodiphenylurea quantitatively.

In place of the above-mentioned sulfonic acid, other diphenyl ether sulfonic acids can be used, namely those that are obtained by Nachs'ulfurierung unsulfated diphenyl ethers, z. B. 4-Amino-4'-chk> ri, 1 '- diphenyl ether - 2' - sulfonic acid, the 2-amino "4, 4'- or -4 ', 6'-dichloro-i, 1'-diphenyl ether- 2'-sulfonic acid, the analogous 2 ', 4'-dichloro-4'-sulfonic acid or similar, substituted by alkyl, such as methyl or amyl groups © derivatives, the 4-amino-2,4'- or -4', 6'-dichloT- (possibly - 5'-methyl) - 1, i'-diphenyl ether- 2 '- sulfonic acid, the 2 - amino-4, 4', S -, - 4, 4 ', 5' -or4, 4 ', o'-trichloro-i, i'-diphenyl ether-2'-sulfonic acid or the analogous' 4 ~ amino-2, 4', s'-trichloro compound.

Example 3

20 parts of 3-amino-4'-chloro-4- (4 "-chars" - methyl - 2 "- sulfonic acid phenoxy) -1, 1'-diphenylsulfone (produced by condensation of 4,4'-dichroic> r -3-nitro-i, i'-diphenylsulfone and 3-methyl-4-chlorophenol using potassium hydroxide solution at 120 to 150 ⁰ , reduction and sulfonation of the condensation product at 95 ° with monohydrate for 3 hours) are dissolved in 250 parts of water using soda , 30Te ¹ Ue of sodium acetate is added, then ^{phosgene is passed in at 40 to 50 0} until no more amine can be detected; Acetate may have to be added. When acidified, the urea sulfonic acid turns out to be doughy. It is pressed and dried. Quantitative yield.

It is also possible to use other phenoxydiphenylsulphone sulphonic acids, such as 3-amineO'-4'-chloro-2- (4 "-cblo'r-3" -metihyl-2 "-sulphonic acid phenoxy) -1, i'-diphenylsulphone or the 3-amino-4 ', s'-dichloro-4- (4 "-chloro-3" - methyl - 2 "- sulfonic acid phenoxy) -1, 1'- diphenyl sulfone.

Example 4 ■

17 parts of 2-amino-4'-chloro-i, i'-diphenyl sulfide-4-sulfone: acid Sodium, obtained through condensation and subsequent reduction of 4-chlorothiophenol and o-chloronitrobenzenesulfonic acid, are dissolved in 250 parts of water and 30 parts of crystalline. Sodium acetate brought to it; then phosgene is passed in at 40 to 50 ° until no more amine is demonstrable. The excreted doughy mass is separated into the sodium salt transformed and evaporated in vacuo. The urea forms a light colored powder that dissolves clearly in water. Quantitative yield.

Other aminodiphenyl sulfide sulfonic acids, such as. B. the 4-amino ^ 4'-chloro-i, i'-diphenyl ₁ sulfide-2-sulfonic acid or the 2-amino-4 ', s'-dichloro-i, i'-diphenyl sulfide-4-sulfonic acid :, used will.

Analogous urea derivatives can be obtained by phosgenating 4-amino-4'-chlorodiphenylamine - 2 - sulfonic acids, 4-amino-3 '. 4'- or -4 ', 6'-dichlorodiphenylamine - 2 - sulfonic acid or z. ß. of 4-amino-4'-chlori. i'-Diphenylsulfon-2-sulfonsätire shown will.

Example 5

10 parts of 2-amino-4, 4'-dichloro-i, i'-diphenylmethane-2'-sulfonic acid (prepared from 2-xitro-4-chlorobenzyl chloride and chlorobenzene, reduction and sulfonated with sulfuric acid monohydrate, a white powder with an intensely sweet taste , are dissolved in 150 parts of water using soda and mixed with the necessary amount of crystalline sodium acetate; then phosgene is passed in at 30 to 40 ³ until the diazotization reaction has disappeared. The diphenylmethane urea is worked up as in Example 1. It reproduces drying in vacuo gives a light powder, which dissolves clearly in water.

Example 6

22 parts of 4-amino-4'-chloro-i, i'-diphenyl ether and 19 parts of 3,4-dichlorophenyl isocyanate (Kp _18118-120 ', F. 45-46 *, prepared from 3, 4-dichloroaniline and phosgene by known method) are mixed thoroughly and heated to I2o ~. At this temperature the reaction begins, the temperature rises by itself to 145 - ~. ^{It is then heated to 160 to 170 5} for a further 3 hours and then left to cool. 39 parts of an asymmetrical urea derivative are obtained. 39 parts of this X- (4 "-ChIorphenoxy) -pbenyl-X'-3, 4-dichIorphenylharnstoffes are introduced into 200 parts by weight of monohydrate at 10 is then cooled to -10 to -5 ^C;. Then added dropwise at this temperature, 35 parts by weight 25% oleum and stirred at this temperature until a sample is soluble in dilute alkali, then poured onto ice, neutralized and salted out. Yield 41 parts of a clear water-soluble product.

Example 7

16.5 parts of those described in Example 5 2-amino-4. 4'-dichloro-i, i'-diphenylmethane-2'-sulfanic acid are dissolved in 100 parts by volume of dry pyridine; in this solution be at 10 to 15- with good stirring 10 parts of 3,4-dichlorophenyl isocyanate entered in small portions. After 1 hour the diazotization reaction has disappeared; the reaction mixture is then with Treated with steam until no more pvridine passes over. The residue is in 1 1 Water absorbed and nitrated while hot. The X-2 '- (4 "- Chlorine - 2 "- sulfonic acid benzyl) - 5'-chlorophenyl - X '- 3, 4- dichlorophenylurea l> eim Cool off in white flakes. These are suctioned off and washed with a little water and dried in vacuo. Quantitative yield.

Instead of 3, 4-dichlorophenyl isocyanate, z. B. also the 2-, 3- or 4-chlorophenyl isocyanate or the 3.4. 5-trichlorophenyl isocyanate can be used.

Example 8

9 parts by weight of 2-amino-4. 4'-dichloro, i'-diphenyl ether-2'-sulfonic acid are dissolved in 50 parts by volume of dry pyridine. The solution is mixed with 10 parts of 3,4-dichlorophenylcarbamic acid chloride in small portions at 10 to 15 ° ^{C. while stirring well.} After all the carbamic acid chloride has been entered, it is heated for 1 hour for 40 to 50 minutes. 100 parts by volume of 10% sodium carbonate solution are then added and the mixture is treated with steam until all of the pyridine has passed over. The residue is cooled, the deposited resin is separated off and taken up in 500 parts of hot water, nitrated while hot, and the X-2 '- (4 "-chloro-2" -sulfonic acid phenoxy>^' - chloro-X '^. 4 -dichlorophenylurea precipitated with a little brine as a thick, light-colored resin, separated from the aqueous layer and dried in vacuo, the product being obtained as a light-colored, brittle mass, quantitative yield.

Other sulfonic acids of the diphenyl ether series can also be used, e.g. B. 4-Amino-4'-chloro-5'-methyl-1.i'-diphenyl ether-2-sulfonic acid, the 4-amino-4 ', 5'-dichloro-1, i'-dipheny} ether-2-sulfonic acid, the 4-Amino-2, 4 ', 5'-trichloro-i, i'-diphenyl ether-2'-sulfonic acid or others of the aminodiphenyl ether sulfonic acids listed in the preceding examples. But also the aminodiphenyl sulfides, such as the 4-amino no 4 ', 5'-dichIor-i, i'-diplieny] suIfid-2-sultonic acid, condenses quantitatively with 3,4-D1-chlorophenylcarbamic acid chloride. Instead of 3, 4-bichlorophenylcarbamic acid chloride can also use the equivalent amount of 3. 4-D1-chlorophenyl isocyanate with the aminosulfonic acids listed implemented.

Example 9

-

12 parts 1 - Amino-3. 4-dichIorIxMizol- (i-sul Fonsäure are in 7 ^ parts by volume

dissolved dry pyridine. 15 parts of 3,4-Dichlorphenylcarbaminsäurechlorid now be introduced with stirring at ⁰ to 15 io in small portions; darm is stirred at 40 to 50 ^{0 for 1 hour.} After no more free amine can be detected, Soda solution is added and the reaction mixture is treated with steam until no more pyridine passes over. The residue is boiled with water, filtered and a little sodium chloride solution is added. The condensation product that. N - 3,, 4- dichloro -: 6 -stilf onsäurephenyl N '- 3', 4 '- dichlorophenylurea is obtained in this way in beautiful leaves. Yield very much

Well.

Instead of i-amino-3, 4-dichlorobenzene-6-sulfonic acid Another halogenated anilinesulfonic acid can also be used, e.g. the 4-chloroaniline sulfonic acid or the

ao 2,4-Dichlo'raniline-5-sulfc »nsäuτe.

Exactly as in the example above, metanilic acid can be mixed with 3-chloro> r-5- (4'-chlorophenoxy) -phenylcarbamic acid chloride, (prepared from 2 - amino - 4, 4 '- dichloro -1, 1' - diphenyl ether and phosgene condense by a known method).

Example 10

44 parts of 4-amino-4'-chloro-i, i'-diphenyl ether are mixed with 7 parts of urea intimately and slowly heated to 160 to 170 ⁰ until no more ammonia escapes, which is achieved usually in. After 3 hours.

The yield of N, N'-4, 4 '- (4 ", 4"' - dichlorodiphenoxy) - diphenylurea is 46 parts.

The above urea is introduced into 200 parts of monohydrate at 10 °; then it is cooled to -io °. 65 parts of 26 "/ 0IgC ¹ S oleum are then added dropwise. After two and a half hours a sample is readily soluble in water; the reaction mixture is poured onto ice and salted out. After drying, in vacuo, 48 parts of a water-soluble disulfonic acid are obtained.

Example 11

¹ mol of m-aminobenzoyl-3,4-dichloaranilide ^and 6-sulfonic acid are dissolved in 100 parts by volume of dry pyridine; 10 parts of 3,4-DieMoirphenylcarbamic acid chloride are then slowly added to the solution, while stirring and cooling, at 10 to 15 °. After the latter has been entered, stirring is continued for 1 1/2 hours until the diazotization reaction disappears. A little soda is then added and the pyridine is blown off with steam. The residue is taken up in 1 l of hot water, quickly boiled, filtered hot and brine is added to the filtrate. The co-oxidation product is precipitated as a gray resin; it is separated off and dried in vacuo.

m-aminobenzoyl-3,4-dichloroanilide-6-sulfonic acid is obtained by reacting 3-nitrobenzoyl chloride with i-amino-3,4-dichlorobenzene-6-sulfonic acid in pyridine. The nitro body is reduced with iron according to a known method and from the obtained soda-alkaline filtrate precipitated with hydrochloric acid.

Example 12

V20 mole of the 4-amino-4'-amyl-i, i'-diphenyl-2-sulfonic acid is dissolved in 200 parts by volume of dry pyridine or acetone, and added in portions with stirring at 10 to 15 ⁰ with 10 parts of 3, 4-DichlorphenyliiSocyansäureester; stirring is continued at room temperature until the diazation reaction has disappeared. After adding 50 parts of 10% sodium carbonate solution, the pyridine or acetone is blown off with steam, the residue is boiled with water while passing in steam, filtered hot and the condensation product is precipitated as a thick resin from the filtrate with brine. It is separated off and dried in vacuo. The N, 4'- (4 "- amylphenoxy) -5 '- sulfonic acid phenyl-N', 3, 4-dichlorophenylureaF is readily soluble in warm water.

A similar product is also obtained from 2, s-dichlorophenylcarbamic acid chloride.

Example 13

6 parts of 2-aminobenzothiazoil-o-sulfonic acid are suspended in 50 parts by volume of dry pyridine; a solution of 5.25 parts of 3,4-diehlophenyl isocyanate in pyridine is then added. to this and heated to 90 ^{0 for} 6 hours with stirring. Then 30 parts by volume of a 10% sodium carbonate solution are added and the pyridine is blown off with steam. The aqueous solution that remains is filtered and saline solution is added while it is warm, whereupon a white precipitate crystallizes out. After cooling, it is filtered, washed with water and dried. Yield:. 6 parts of N-3,4-dichlorophenyl-N '- 6' - sulfonic acid -2'-benzothiazolylurea in the form of a white powder which is soluble in hot water. _

4-Aminoantipyrine can be reacted with 3,4-dichlorophenyl isocyanate in exactly the same way. Subsequent sulfonation gives the N-3, 4-dichlorophenyl-N'-i '- (sulfophenyl) -2', 3'-dimethyl-5'-oxo-4'-pyrazolidylurearin In the form of a gray-tinged powder that is soluble in soda solution.

Claims (4)

Example 14 35 parts of 4-amino-4'-bn> m-3'-inethyI-i, i'-Diphenylether-2-sulfonic acid (shown in the usual way by condensation of p-bromo-m-cresol with p-nitrochlorobenzenesulfonic acid and subsequent reduction) are in 500 parts by volume of water and the necessary Dissolved amount of soda, with 60 parts of crystalline. Sodium acetate added and to 40 to 50 ° warmed; then phosgene is passed through for 1 hour. From the failed Paste is decanted off and dissolved in hot soda. When it cools down, a gelatinous one falls Mass that hardens to a solid, brownish-white mass when it dries Genati can also use 2-amino-4'-bromi, i'-diphenylether-4-sulfonic acid (sodium salt) (produced by condensation of p-bromophenol with o-xitrochlorobenzenesulfonic acid and Reduction) are phosgenated. Example 15 19 parts of 4-amino-4'-bromo-3-methyl-1. 1'-Diphenylether-2'-sulfonic acid in 50 parts by volume of anhydrous pyridine are mixed with 70 parts of a 15% solution of 3,4-dichlorophenyl isocyanate in nitrobenzene in a stirred flask. The temperature rises by itself to over 30 ⁰ . Then, it is stirred at 1 hour at 50 ^0th If the reaction with Xitrite is still positive, some isocyanate solution is added. Then, after adding a little soda solution, it is distilled with steam, the residue is taken up in 1000 parts of hot water and filtered hot with a little charcoal. The filtrate is mixed with brine, the condensation product separating out as a dark, soon-to-solidify resin. It is separated off and dried in vacuo at 70 °. A gray powder which is soluble in hot water is obtained. As an aminodiphenyl ether compound, 2-amino-6'-bromo-i, i'-diphenyl ether-4-sulfonic acid can also be used be used. Example 16 9 parts of 4-amino-4'-iododiphenyl ether-2-sulfonic acid (prepared from p-iodophenol and p-nitrochlorobenzenesulfonic acid and subsequent reduction of the nitro compound) are dissolved in 200 parts by volume of water, neutralized with soda solution, mixed with 20 parts of crystalline sodium acetate and made up to 40 .. heated to 50 ⁰ Then as long as phosgene is passed through until the precipitation stops increasing ■ are separated by decanting from the somewhat sticky precipitate, washed with a little water, the precipitate is dissolved in Sodalösimg and evaporated to dryness yield.: 8 parts of a light brownish powder. Example 17 36 parts of the sodium salt of 2-amino-4,4'-dichloro-i, i'-diphenylether-2'-sulfonic acid are suspended in 150 parts by volume of xitrobenzene, and 18.5 parts of p-chlorobenzoic acid azide dissolved in 50 parts by volume of nitrobenzene are added at 25-30 and heated for 24 hours 40 to ^50: then the Xitrobenzol is blown with steam. After filtration, the colorless end product, which is readily soluble in water, is salted out from the clear filtrate with common salt. Λ η place of p-chlorobenzoic acid azide can also another azide, e.g. B. the 3, 4-D1-chloro> enzoic acid azide. P-VENT REQUIREMENTS: i. Process for the preparation of halogen-substituted, sulfonated ureas of the benzene series and the heterocyclic series, characterized in that reactive carbonic acid derivatives or substances or mixtures of substances forming such compounds are reacted with aminosulfonic acids g _{0 of} the benzene series and the heterocyclic series containing hydrogen that can be replaced on the nitrogen atom, with the reaction components are chosen so that at least one halogen atom is present in the end product. 2. The method according to claim 1, characterized in that one is on the nitrogen atom replaceable hydrogen-containing, unsulfonated amines of the benzene series and the heterocyclic series used for condensation and the sulfonic acid groups by post-treatment ' treatment with sulfonating agents in the end product. 3. Process according to Claims 1 and 2, characterized in that one instead of the reactive carbonic acid derivatives, analogous isocyanic acid esters used. 4. Process according to Claims 1 and 2, characterized in that one Instead of the reactive carbonic acid derivatives, analogous carlionic acid azides are used. To distinguish the subject matter of the invention from the state of the art, the establishment procedure the following publication has been considered: German patent specification No. 289 107. 5031 5.52