Патент USA US2120557код для вставки
Patented June 14, 1938 I ' UNITED stares ems? orrics SULPHONIC ACIDS 0F CARBOXYLIC ACID ADIIDES AND PROCESS FOR rm PRO DUCTION THEREOF , Hans Haussmann, Mannheim, Germany, . as signor to I. G. Farbenindustrie Aktiengesell schaft, Frankfort-on-the-Main, Germany - No Drawing. Application May 6, 1936. Serial No. 78,196. In Germany May 16, 1935’ 20 Claims.‘ (Cl. 260—124) The present invention relates to-a process for the production of sulphonic acids of carboxylic resin acids, bile acids and naphthenic acids may be employed. » _ ' \ ' f ' ' acid amides which are suitable as assistants in ' The conversion‘ of the said initial materials the textile and related industries. , into halogenated carboxylic acids or their con I have found that especially valuable washing, - version products, such as fatty acid chlorides, 5 wetting, cleansing, dispersing and like agents are obtained by condensing halogen-containing aliphatic carboxylic acids or their derivatives, maybe effected ‘by known methods; whenintro- . ducing halogen into saturated initial materials, the‘ reaction may be accelerated by increasing such as halides, anhydrides or esters, with amino ‘ the‘temperature, by the action of light or by the 10 sulphonic acids the amino groups of which still addition of catalysts. vUnsaturated carboxylic 10 . contain at least one replaceable hydrogen atom and the sulphonic group of which is- combined to an aromatic radicle. In the present case the term aliphatic carboxylic acid is intended to 15 comprise open chain as well as’ cycloaliphatic carboxylic acids. - ‘ ‘ acids generally speaking absorb the necessary amounts of halogen under very mild conditions.» As amino-sulphonic acids having aromati cally-combined sulphonic groups may be men tioned in particular the aromatic amino-sul- '15 phonic acids, as for example sulphanili'c acid, Suitable halogenated carboxylic acids or carboxylic acid derivatives for the process accord,ing to this invention are in particular the halo20 genated chloride of saturated or unsaturated fatty acids from naturally-occurring fatty acid metanilic acid, , N-ethyl-metanilic acid, ortho aminobenzene sulphonic acid, toluidine sulphonic acids and naphthylaminosulphonic acids as well as their derivatives or substitution products. In 20 many cases those amino-sulphonic acids the containing substances for example oils, fats, waxes or resins, such as coconut oil, palm kernel oil, olive oil, soy bean oil, castor oil, hydro25 genated train‘ oil (which may still contain un- nitrogen atoms of which only contain one re placeable hydrogen atom and the second hydro-‘ gen atoms of which are replaced by aromatic, saturated acids), tallow or Montan wax or 001- ophony. Products which contain fatty acid radicles having a long carbon chain in the molecule have a specially good‘ action. The degree 30 of halogenation may be of any desired value depending on the nature of the condensation products and the purpose for which they are to be employed. Generally speaking it is advantageous when employing fatty acids of high movi lecular weight to introduce up to two or more .5 aliphatic, cycloaliphatic, aliphatic-aromatic or 25 radicles are especially valuable. heterocyclic Polynuclear amino-sulphonic acids of the said kind may also be employed in the same way and also amino-sulphonic acids which still contain hydroxy, carboxylic, ether, ester or nitro groups 30 or which are substituted by halogen atoms. Amino-sulphonic acids which contain two or more basic groups of which at least one con tains a replaceable hydrogen atom, or which contain two or more, sulphonic groups are also 35 atoms of halogen into the aliphatic or‘ cyclo- suitable for the process according to this inven valiphatic radicle of the carboxylic acid; when employingv carboxylic acids of low molecular tion. For example dimethyl-para-phenylenedi amine sulphonic acid, naphthylaminedisulphonic weight, a smaller content of halogen is frequent40 1y sufficient in order to obtain products having Valuablé propel‘ties- When employing fatty acid acids and naphthylamine-trisulphonic acids may be mentioned. The amino-sulphonic acids to be 40 employed according to this invention may also mixtures as the initial material it is sometimes be interrupted in the chains or between are sui?cient to halogenate only a part of the fatty ' matic rings or both by hetero atoms or atomic acids. '45 - ' Instead/of simple aliphatic carboxylic acids or groups._ The amino groups may also have a purely aliphatic character, as for example in 45v their derivatives; substituted carboxylic acids or benzylamine sulphonic acid or in compounds of their derivatives may be employed or also carbox he acids which contain hetero atoms, such as gxygen or sulphur, or hetero-atomic groups, the composition: 50 such as carboxylic amide groups, in the aliphatic "radicles. Carboxylic acids having branched chains and the like may also be employed for the process according to this invention; for example carboxylic acids obtainable by the oxi55 dation of para?in wax and the like, and also , _ NHZ'CH2'CHZ'O'CGH4'SO3NQ‘ The said interruption may occur in any desired 50 manner, as for example by oxygen or sulphur atoms or by carboxylic amide groups or other atomic groups or also by tertiary nitrogen atoms. 7 The reaction of the halogenated fatty acid de- 55 2 " ' 2,120,587 rivatives with the amino-sulphonic acids con sorption of 50 parts has taken place. The re- ' taining aromatic sulphonic groups may be car sulting chlorination product is freed from dis- ' ried out under the working conditions usual for , solved hydrochloric acid by leading in air and the Schotten-g-Baumann reaction is so far as then introduced at a temperature of zero C. into 5 acid chlorides and acid anhydrides are employed. In ‘this case, the condensation may also be car ried out in organic solvents with an addition of agents combining with acids. vIn the reaction of fatty acids or fatty acid esters with amino 10 sulphonic acids or their salts it is preferable to work in the presence of organic solvents; butanol for example is suitable for this purpose. It is preferable to employ salts of the amino-sul phonic acids which are soluble in organic sol 15 vents, as for example those ‘of tertiary bases, such as triethylamine or dimethylaniline; pyri dine may also be employed in many, cases. In some cases the said bases themselves are suitable ' 20 as solvents. The products obtained in the said ‘manner have an excellent washing power for- substances of all kinds. They have a high stability when em a solution of 173 parts of metanilic acid rendered 5 alkaline with sodium carbonate. The mixture is stirred for some time at ordinary temperature and the resulting paste is- evaporated to dryness. A very active. washing agent is obtained which is stable in hard water. . ~ Instead of metanilic acid also N-ethyl meta nilic acid can be employed; in this manner a. product is obtained which possesses a high wash ing power. ' 10 ' Example 2 15 Chlorine is led into. 200 parts of coconut oil fatty acid chloride at about 90° C. until an in , crease in weight of 40 parts hastaken place. The resulting acid chloride is condensed in the man ner described in Example 1 with 223 parts of 20 naphthionic acid and worked up. A product is ployed in hard water; when the content of halo- ' obtained which has in particular a very good gen is su?icient, their aqueous solutions give no [emulsifying power. Example 3 25 deposits in the cold even in very hard water. By reason of their valuable properties they may "70 parts of chlorine are led into 300 parts of 25 be employed in a very general and varied manner oleic acid chloride while cooling with ice. The and they are especially suitable for all domestic resulting product is reacted with 300 parts of an and industrial purposes. They may also fre amino-sulphonic. acid having the formula: 30 quently be employed for the production of prep~ arations. Since they also have an excellent dis persing power for liquid and solid substances, it is possible for example to convert large amounts of solvents, oils, fats and waxes into aqueous solu 35 tions with their aid. The said- products may also at a temperature of from 25° to 30° C., the reac tion being alkaline to phenolphthalein and being among these may be mentioned for example in organic salts, such as waterglass, Glauber’s salt, kept so by the addition of corresponding amounts of caustic soda solution. When the reaction is completed, the reaction mixture is heated for 35 some time at from" 45° to 50° C.,~neutralized and evaporated to dryness. A product is obtained perborates, ortho-, pyro- and meta-phosphates, which is eminently suitable especially for dis be employed together with other . substances; 40 organic salts, such as soaps, sodium salts of tetra- . persing calcium soaps. hydronaphthalene sulphonic acids or Turkey red oils, or other wetting and cleansing agents, as for example salts of fatty alcohol sulphuric esters or which comprises condensing an aliphatic carbox true aliphatic sulphonic acids. ylic ‘acid substance selected from the class con Organic sub What I claim is: 40 1. The. process for the production of amides ' 45 stances of a colloidal nature are also suitable as sisting of carboxylic acids, carboxylic halides, an ' additions, as for example glue, starch, traga hydrides and ,esters, containing outside the car ,canth, reaction products of ethylene oxide on ' boxylic group. at least one halogen atom with an organic compounds which contain reactive hy aromatic amino sulphonic acid the amino group drogen atoms, as for example in the form of of which contains at least one replaceable hydro 50 hydroxy, carboxyl amino or mercapto groups, gen atom and the sulphonic group of which is 50 and also ?llers, such as clay, china clay and ben attached to‘ an aromatic nucleus. , tonite may be employed with the said products. .2. The process for the production of amides Mixtures of the said products with disinfecting or pharmaceutical substances can be prepared to 55 a greater extent than in the case of soaps. ' The products according to this invention may be converted into all the forms known for the use of soaps. In particular, ?akes, threads, cut tings, coarse and ?ne powders, solid pieces, such 60 as hand and grained soap, or concentrated solu tions, as for example liquid soaps may be pre pared therefrom. Generally speaking the sodium salts of the said products are most suitable for the said purposes, but the other alkali salts and 65 in particular the saltswith ammonia or water soluble organic bases, as for example hydroxy alkylamines, are distinguished by an excellent activity. > ‘~ The following examples will further illustrate 70 the nature of this invention but the invention is ‘not restricted to these examples. I The parts are by weight. Example 1 Chlorine is vled into 300 parts of stearic acid 76 chloride at a temperature of 90° C. until an ab which comprises condensing a soap-forming ali phatic carboxylic acid substance selected from the class consisting of carboxylic acids, carbox ylic halides, ,anhydrides and esters, containing outside the carboxylic group at least one halogen atom with an aromatic amino sulphonic acid the amino group of which contains at least one re placeable hydrogen atom and the sulphonic group 60 of which is attached to an aromatic nucleus. 3. The process‘ for the production of amides which comprises condensing a halogen-contain ing aliphatic acid obtainable from high molecular organic substances of natural origin with an aro matic amino sulphonic acid -the amino group 65 of which contains at least one replaceable hydro gen atom and the sulphonic group of which is attached to an aromatic nucleus. 4. The process for the production of amides 70 which comprises condensing a derivative of an aliphatic carboxylic acid selected from the class consisting of ,carboxylic halogenides, anhydrides , and esters, containing outside the carboxylic groups at least one halogen atom with an aromat- 75 3 . 3,120,557 ic amino sulphonic acid the amino group of which the class consisting of carboxylic acids, carboxylic 5 contains atleast one replaceable hydrogen atom halides, anhydrides and esters, containing outside and the sulphonic group of which is attached to an aromatic nucleus. with an amino sulphonic acid containing at least 5. The process for the production of amides which comprises condensing a halogen-contain ing hydrogenated fatty acid obtained from un saturated fatty acids with an aromatic amino sulphonic acid the amino group of which con 10 tains at least one replaceable hydrogen atom and ' the sulphonic group of which is attached to an aromatic nucleus. _ one alkyl radicle and the amino group of which contains at least one replaceable hydrogen atom and the sulphonic group of which is attached to an aromatic radicle. ' - 11. The process for the production of amides which comprises condensing a halogen-contain ing soap-forming aliphatic carboxylic acid sub stance selected from the class consisting of car ».. 6. The process for the production of amides boxylic acids, carboxylic halides, anhydrides and which comprises ‘condensing a halogen-contain esters, containing outside the carboxylic group 15 ing hydrogenated train oil fatty acid with an aromatic amino sulphonic acid the amino group of which contains at least one replaceable hydro gen atom and the sulphonic group of which is attached to an aromaticnucleus. 20 " '7. The process for the production of amides which comprises condensing’ a soap-forming ali phatic carboxylic acid substance selected from the class consisting of carboxylic acids, carboxylic halides, anhydrides and esters, containing out 25 side the carboxylic group at least one halogen atom with an aromatic amino mono sulphonic acid the amino gsoup of which contains at least one replaceable hydrogen atom and the sulphonic group of which is attached to an aromatic nucleus. 80 8. The process for the production of amides which comprises condensing a soap-forming ali phatic carboxylic acid substance selected from the class consisting of carboxylic acids, carboxylic at least one halogen atom with a toluidine sul phonic acid. 12. A colorless carboxylic acid amide derived from a halogen-containing aliphatic carboxylic ‘ acid with at least eight carbon atoms containing in the amino radicle at least one aromatic radicle 20 and at least one sulphonic group attached to the aromatic radicle. ' ' 13. A colorless amide of a halogenated soap forming acid containing in the amino radicle at least one aromatic radicle and at least one sul phonic group attached to the aromatic radicle‘. 14. A colorless amide of a halogenated soap forming acid containing in the amino‘ radicle at least one mono-nuclear aromatic radicle and at least one sulphonic group attached to the arc 30 matic radicle. 15. A colorless amide of a halogenated soap forming acid and metanilic acid. ‘ halides, anhydrides and esters, containing outside ' 16. A colorless amide of a halogenated soap the carboxylic group at least one halogen atom forming acid and amino-sulphonic acids contain 35 with a mono nuclear amino mono sulphonic acid ing in the amino radicle at least one aromatic radicle and at least one 'alkyl radicle and a sul phonic group attached to the aromatic radicle. the amino group of'which contains at least one _ replaceable hydrogen atom and the sulphonic 40 the carboxylic group at least one halogen atom group of which is attached to the nucleus. 9. The process for the production of amides which comprises condensing a soap forming ali phatic carboxylic acid substance selected from 17. A colorless amide of a halogen-containing soap-forming acid and —N-ethyl metanilic acid. .40 18. A colorless amide of a halogen-containing ' the class consisting of carboxylic acids, car soap-forming acid and toluidine sulphonic acid. 19. A colorless amide of halogen-containing boxylic halides, anhydrides and esters, contain _ hydrogenated train oil fatty acids and metanilic. 45 ing outside the carboxylic ‘group at least one halogen atom with metanilic acid. 10. The process for the production ofv amides which comprises condensing a soap-forming alla ‘phatic carboxylic acid substance selected from acid. 45 20. A colorless amide of halogen-containing hydrogenated train oil fatty acids and toluidine sulphonic acid. HANS HAUSSMANN.