US1025652A - Chlor-aralkyl-sulfonic acids and process of making such compounds. - Google Patents

Description

UNITED STATES PATENT OFFICE.

OTTO SCHMIDT, 0F MANNHEIM, GERMANY, ASSIGNOR T0 BADISCHE ANILIN & SODA FABRIK, 0F LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, A CORPORATION.

CHLOR-ARALKYL-SULDONIC ACIDS AND PROCESS OF MAKING SUCH COMPOUNDS.

No Drawing.

Patented May '7, 1912.

To all whom it may concern:

Be it known'that I, Orro SCHMIDT, Ph. 1)., chemist, subject of the King of Prussia, residing at Mannheim, Germany, have invented new and useful Improvements in Chlor- Aralkyl- Sulfonic Acids and Processes of Making Such Compounds, of which the following is a specification.

I have discovered that chlor-aralkyl-sulfochlorids containing chlorin in the alkyl group can be converted into the corresponding chlor-aralkyl sulfonic acids by treating them with a saponifying agent undermild conditions, that is to say, by such treatment that the sulfochlorid group is saponified to the sulfonic acid group, while the chloralkyl group remains unattacked. This can be eflected, for instance, by treatment with limited quantities of water in the presence of alcohol. Chlor-aralkyl-carboxylic-acid chlorids containing chlorin in the alkyl group can also be converted into the corresponding chlor-aralkyl-carboxylic acids, for

' instance by treatment with cold concentrated sulfuric acid.

The chlor-aralkyl-sulfonic acids which can be obtained according to my invention are new and are characterized by being colorless and hygroscopic, and upon boiling with water they give rise to aralkyl-alcohol-sulfonic. acids, and upon treatment with dimethyl-anilin give rise to sulfonic acids of dimethyl-phenyl-aralkyl-ammonium hy droxids,in the form of an inner anhydrid thereof.

The chlor-aralkyl sulfochlorids which are employed in carrying out my invention and their preparation are described in the specification of the application for Letters Patent Serial No. 616,449, while the sulfonic acids of dimethyl-phenyl-aralkyl-ammonium hydroxids are described and claimed in the specification of the applicationfor Letters Patent Serial No. 584,131.

The following examples will serve to illustrate further the nature of my invention and how it can be carried into practical effect, but the invent-ion is not confined to these examples. The parts are by weight.

Example 1: Dissolve two hundred and twenty-five parts of benzyl-chlorid-parasulfochlorid in eighty parts of alcohol, heatthe solution on the water-bath and add, gradually, while stirring, eighteen parts of water.

Continue heating until the evolution,

Application filed March 23, 1911. Serial No. 616,448. I I

of hydrochloric acid ceases and then distil off the excess of alcohol at about eighty degrees centi'grade, preferably in cacao. The residue consists chiefly of benzyl-chloridpara-sulfonic acid and solidifies after standing. for a considerable time. It is easily soluble in cold water and, on neutralization with a base in the cold, the corresponding salt can be obtained. The reaction which takes place can be represented by the following formula I SihCl Salli In a similar manner, other chlor-aralkylsulfonic acids can be obtained from the corresponding chlorids, for instance 2'chlor-1- benzyl-chlo'rid-4-sulfochlorid gives rise to 2- chlor-1-benzyl-chloridl-sulfonic acid. The foregoing example can also be carried out by allowing the benZyl-chlorid-sulfochlorid to stand for some time in admixture with cold alcohol, whereupon water is added and the whole is warmed; or the. sulfochlorid can be directly heated with dilute alcohol. Instead of alcohol, other organic solvent can be employed, such for instance as acetone, or a benzyl-chlorid-sulfonic acid itself which has the power of dissolving both benzylchlorid-sulfochlorid and water. If desired, however, such additions can be dispensed with. If, in the foregoing example, the benzyl-chlorid-para-sulfochlorid be replaced by an equivalent quantity of benzal-chloridmet-a-sulfochlorid, the corresponding benzalchlo'rid-meta-sulfonic acid is obtained.

Example 2: Introduce thirty parts of benzyl-chlorid-para-carboxylic-acid chlorid (obtainable by chlorinating para-toluic acidchlorid in the presence of heat) into two hundred parts of ninety-eight-per cent; sulfuric acid while maintaining a temperature of from zero to five degrees centigrade. When the evolution of hydrochloric acid ceases, pour the solution onto ice and filter off the benzyl-chlorid para-carboxylic acid and wash it with cold water. It is almost insoluble in cold water and melts at about from one hundred and ninety to one hundred' and ninety-two degrees centigrade under decomposition. The reaction which takes place can be represented by the following formula 011,01 OHaCl r f -l c 01 coon Now what I claim is 1. The process of producing omega-chloraralkyl acids by treating omega-chloraralkyl acid chlorids with a saponif ing agent under mild conditions substantially as hereinbefore described.

2. The production of benzyl-chlorid-parasulfonic acid by heating benzyl-chloridpara-sulfo-chlorid with water in the presence of alcohol.

3. As new articles of manufacture chlor- 'aralkyl-sulfonic acids which when pure are colorless and hygroscopic and which upon treatment with boiling Water give rise to aralkyl-alcohol-sulfonic acids and which upon treatment with dimet-hyl-anilin give rise to sulfonic acids of dimethyl-phenylaralkyl-ammonium hydroxids in the form of an anhydrid thereof.

4. As a new article of manufacture benzylchlorid-para-sulfonic acid which when pure is colorless and hygroscopic, upon boiling with water gives rise to benzyl-alcohol-parasulfonic acid and upon treatment with dimethyl anilin gives rise to dimethylphenyl para sulfo benzyl ammonium hydroxid in the form of an anhydrid thereof.

In testimony whereof I have hereunto set my hand 'in the presence of two subscribing witnesses.

OTTO SCHMIDT. Witnesses:

J. ALEO. LLOYD, S. H. SHANK.