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UNITED STATES PATENT Office Patened Feb. 25, 1 941 2,233,296 UNITED STATES PATENT office 2,233,296 PROCESS OF MARING MONOACYL a AKENE DAM NES Johannes Nelles, Leverkusen-Schiebusca, Ernst Tietze, Bonn, and Otto Bayer, Leveruser-. G. Werk, Germany, assignors, by mesne assign ments, to General Aailine & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Application April 22, 1939, serial No. 269,420. In Germany April 28, 1938 4 Claims. (C. 260 556) The present invention relates to a process of As carboxylic acids, the imides of which, as far preparing acid amides and to certain new prod as they can be prepared, are employed for the lucts obtainable thereby. process of the present invention there may be It has been found that basic acid amides can mentioned, for instance, acetic acid, chloro-acet 5 be prepared in a very simple and economical ic acid, stearic acid, crotonic acid, benzoic acid, manner by causing ethylene imides and/or pro alkyl benzoic acids, phthalic acid and so on. pylene imides of organic sulfonic or carboxylic Instead of the simple imides also the substituted acids to react with primary or secondary amino imides, for instance, C-methylethylene inides compounds. The reaction probably takes place Inay be employed. 0 according to the following general formula: As Suitable primary and secondary amines we 10 may mention, for example, aliphatic mono els R. amines, di- or polya nines, aromatic amines, ali R-x-N 2. Hi-HN a-3 phatic aromatic amines, halogenated amines, CH R Oxyamines etc. More specifically, there may be 5 5 R employed, for instance, methylamine, diethyl / amine, isooctylamine, stearylamine, distearyl R-X-NH-CH-(CH2)-CH-NN amine, ethylene diamine, diethylenetriamine, - Rs polyethylenepolyamines obtainable by the reac in which X represents the group -SO2- or tion of ethylenedichloride with ammonia, poly -CO-, R is an organic radical and R1 and R2 ethyleneimines, chloroethylamine, aminoacetic 20 are hydrogen or also organic radicals and n. acid, methytaurine, ethanolamine, diethanol is the number 0 or . The hydrogen atoms of amine, dicyandiamide, guanidine, piperidine, tet the ethylene or propylerae bridge of the imide rahydroquinoline, aniline, ethylaniline, hydroxy may be replaced by substituents such as, for ethylanline, chloroaniline, nitroaniline, an instance, methyl groups. It is seen therefrom thran lic acid ester, p-aminobenzenesulfoamide, 25 that the products of the reaction are mono naphthylamine, morpholine, benzylamine, dehy acylated derivatives of ethylenediamine and pro drothotoluidine, 2-amino - 5 - diethylamino-n- pylenediamine. Such products which are partly pentane. Also mixtures of such amino com new, are of great interest as such, for instance pounds may be employed. - 30 in the textile and rubber industry, or as inter The reaction of the amino compounds with the 30 mediates for the preparation of other valuable imides may be carried out in the absence or compounds, for example dyestuffs and pharma presence of Solvents or diluents, like for instance ceuticals. Water, carbontetrachloride, benzene, benzine and Ethylene imides and propylene imides of Or the like. In most cases the reaction is accom ganic acids which are used as starting material panied by a considerable rise in temperature. It 35 for the present invention are obtainable, for in is necessary, therefore, in many cases to cool the stance, according to the processes described in reaction mixture Or to add the reaction compo "Berichte der Berliner Chemischen Gesellschaft,' nents by and by. In some cases the mixture volume 28, page 2933 and volume 32, pages 2035 must be warmed at the end in Order to complete 40 and 2037, by causing Organic acid halides to re the reaction. The reaction may also be carried 40 act with ethylene imine, substituted 1.2-ethylene Out at elevated pressure, for instance if gaseous imines or the corresponding propylene innes. amines are used like ammonia and methyl amine. For the process of this invention there may be It has been found that the ethylene imides of employed, for instance, the ethylene imides and sulfonic acids react most easily. When work 45 propylene imides respectively of methane sul ing with carboxylic acid ethylene imides or with 45 fonic acid, chloroethane sulfonic acid, sulfonic propylene imides it is necessary, therefore, in acids obtainable by chlorination of aliphatic or most cases to carry Out the reaction at elevated cycloaliphatic hydrocarbons in the presence of temperature and, if desired, elevated pressure. sulfur dioxide, benzene sulfonic acid, benzene di The reaction may also be carried out in the pres sulfonic acids, chlorobenzene sulfonic acid, ni ence of other substances or of suitable sub trobenzene sulfonic acid, p-acetylaminobenzene strates, for instance, in or on fibers or similar sulfonic acid, sulfosalicylic acid, naphthalenesul material of cellulose or cellulose derivatives. fonic acid, polychloro-naphthalenesulfonic acids, Our invention is furthermore illustrated by the Oxynaphthalenesulfonic acids, naphthalenedi following examples without being limited there 55 sulfonic acids, quinolinesulfonic acids and so on. to, the parts being by weight: - 55 2 2,233,296 Eacample 1 ing, the reaction product separates in the form of 10.1 parts of 3,4-dichlorobenzene-i-Sulfonic crystals which are filtered off. After recrystal acid ethylene imide (melting point 93-94; pre lizing from a benzene-benzine mixture, 5.2 parts pared by reacting dichlorobenzene sulfonic acid of a product melting at 130-132° C. and having chloride with .. ethylene imine as described in the probable formula: N-dichlorobenzene sul Berichte vol. 32, page. 2037) are dissolved in 10 fonyl N'-(2-chloro-5-methyl phenyl) - ethylene parts of benzene. Thereupon a solution of 3.5 diamine are obtained. - parts of n-butylamine in 10 parts of benzene is . Eacample 6 poured thereto within 10 minutes, care being 10 taken by suitable cooling that the temperature If, in the process of Example 5, 3.2 parts B 10 does not surpass 60. After 15 hours, water and naphthylamine are used instead of the chloro ether are added to the reaction mixture and the amino methylbenzene and the mixture is warmed condensation product is extracted by means of to 50-60° C. for three days, a reaction product is dilute sodium carbonate solution. The aqueous obtained having the probable formula 15 Solution is then brought to a pH-value of about 15 8-8.5 by addition of sodium bicarbonate, whereby / the condensation product is separated in form C-K D-s O-NH-CH-CH-N Of an oil. The oil is dissolved in ether. The ether solution is then dried over sodium sulfate 20 and the ether thereafter evaporated. 9.6 parts of 20 a viscous, yellowish Oil are thus obtained which probably represents the N-dichlorobenzene sul which, when crystallized from methyl alcohol, fonyl-N'-butyl ethylene diamine. melts at 96-98° C. 25 Eacdnple 2 Eacample 7 25 10.1 parts of 3,4-dichlorobenzene-1-sulfonic 5.04 parts 3,4-dichloro-1-sulfonic acid ethylene acid ethylene imide are dissolved in 20 parts of imide are dissolved in 10 parts ethanol amine. benzene and added to a solution of 3.5 parts of The mixture warms to about 60° C. The clear diethyl amine in 10 parts of benzene. The tem Viscous solution is kept at this temperature on 30 perature rises to about 60° C. The reaction prod the water bath for 1 hour, whereupon a sample 30 uct is purified by shaking its solution in benzine is clearly soluble in dilute caustic soda lye, such with dilute caustic soda lye. Thereupon the Solution yielding a precipitate with sodium bi product is precipitated at a pH of 10 by adding carbonate. The reaction mixture is worked up Sodium bicarbonate, and is again dissolved in by extracting with caustic soda lye, precipitating 35 ether. Upon Working up as usual, 8.5 parts of With sodium bicarbonate, at a pH of 9 and dis 35 an oil are obtained which soon solidifies, melts at Solving in ether. A viscous, yellowish resin is 36 C. and has the probable constitution N obtained which is very easily soluble in methyl dichloro benzene sulfonyl-N'-diethyl ethylene alcohol. - diamine. The hydrochloride of the compound, Eacample 8 40 when crystallized from ethyl alcohol, melts at 5.5 parts benzene sulfonic acid ethylene imide 40 167-168° C. (melting point: 47-48) dissolved in 10 parts Eacample 3 benzene are mixed with a solution of 3 parts 5.04 parts 3,4-dichlorobenzene-1-sulfonic acid. piperidine in 10 parts benzene. The temperature ethylene imide are dissolved in 12 parts chloro rises to about 40 C. while the reaction proceeds. 45 benzene and mixed with 2 parts aniline. The After isolation and recrystallization from ben clear solution warms slightly; after 36 hours Zene-benzine mixtures, white crystals having a Crystals have formed in large quantity. They melting point of 42-43° C. and constituting a are filtered off, washed with benzine and crys product of the probable formula 50 tallized from a benzene-benzine mixture. There 50 are obtained 4.5 parts of a product melting at CH-CH 101-102° C, which probably is the N-dichloro { X-so-NII-chi-chi-NC oil. benzene Sulfonyl-N'-phenyl ethylene diamine. are obtained. ' CH-CHA Eacample 4 By replacing the above-mentioned benzene sul 55 5.04 parts 3,4-dichlorobenzene-1-sulfonic acid fonic acid ethylene imide by the dichlorobenzene ethylene imide dissolved in 12 parts chloroben Sulfonic acid ethylene imide of Example 1, a zene are heated to 50-60° C. for 24 hours with 3.3 corresponding product melting at 117-118° C. is parts 4-amino benzoic acid methyl ester. The obtained. 60 product is purified by extracting its ether solu Eacample 9 tion with sold dilute caustic soda lye and adding 18.3 gS.
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