US2316538A

US2316538A - Sulphonic acids and process of preparing them

Info

Publication number: US2316538A
Application number: US351153A
Authority: US
Inventors: Orthner Ludwig; Langbein Werner
Original assignee: Individual
Current assignee: Individual
Priority date: 1939-07-13
Filing date: 1940-08-03
Publication date: 1943-04-13
Anticipated expiration: 1960-04-13

Description

Patented Apr. 13, 1943 FFICE 'sULPnoNro ACIDS AND rnocnss or raamama mm Ludwig .Orthner and Werner Langbein, Frank i'ort-on-the-Main, Germany; vested in the Alien Property Custodian No Drawing. Application August 3. 1940, Serial No. 351,153. In Germany July 13, 1939 Claims. (Cl. 260-513) The present invention relates to sulphonic acids and to a process of preparing them. It is an object of the invention to prepare sulphonic;

acids from beta-halogenether compounds and alkali sulphites, the new compounds having capillary active properties and being suitable as adjuvants in the textile industry, for instance as wetting, dispersing and washing agents.

We have found that sulphon-ic acids are obtained by reacting alkali sulphites with betahalogen-ethers prepared by condensing alkylene oxides with a. member of the group consisting of halogen-methyl-ethers derived from: aliphatic and carbocyclic compounds containing an ali phatic radical with at least four carbon atoms and further containing at least one hydroxyl group, and halogenmethylamides derived from aliphatic and carbocyclic carboxylic and sulphonic acids containing an aliphatic radical with at least four carbon atoms. The products obtained may be designated by the following general formula wherein R stands for a member of the group consisting of aliphatic and carbocyclic radicals containing an aliphatic radical with at least four carbon atoms, and X stands for a member of the group consisting of oxygen, carboxylic acid amide and sulphonic acid amide.

As aliphatic or carbocyclic compounds containing at least one aliphatic radical with four carbon atoms and further containing at least -0ne alcoholic hydroxyl group, there may be and oils, in the synthesis of methanol or in the hydrogenation of the products obtained by the oxidation of parafilne, for lnstance the alcoholic mixtures obtained by the hydrogenation of palm oil or coconut oil. The carbon skeleton of the compounds containing at least one alcoholic hydroxyl group maybe interrupted by hetero atoms or hetero atom groups. As such compounds there may be named, for instance: isooctylphenylmonoglycolether and p-dodecyl-N- dihydroxyethylaniline. I I

The halogenmethyl-ethers may be obtained in the usual manner from the compounds named, for instance by the action oi'vformaldehyde and hydrochloric acid, if necessary in the presence of an indifferent solvent or diluent.

In order to obtain halogenmethyl-a'mides, there may be used as starting materials the amides of the following acids: butyric acid, caproic acid, caprylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linolic acid, further the amides of the carboxylic acids obtained by the saponification of whale oil or by the oxidation of parafines. Moreover there may be used sulphamides, especially those obtained'by the simultaneous action of sulphur dioxide and chlorine upon paraifine hydrocarbons and the subsequent reaction with ammonia. 'Moreover there are suitable for the process of the present invention the amides from alkylated aromatic, hydroaromatic or araliphatic carboxylic or sulphonic acids. I

From the amides the halogenmethyl-amides may be obtained, for instance by'the action of formaldehyde and hydrochloric acid, if necessary in the presence of an indifferent solvent or diluent.

The beta-halogenethers obtainable by reacting the halogen-methyl-ethers or -amides with a suitable alpha, beta-alkylenoxide, for instance ethylene oxide, propylene oxide, butylene dioxide, glycide, if necessary at a raised temperature and 'under pressure, are transformed into ether sulphonic acids by the action of alkali sulphite, for instance by heating them to about 160-170 C. in an aqueous or aqueous-alcoholic solution.

' The process of the present invention makes use of easily obtainable alcohols or alcoholic mixtures or of amides or mixtures of amides, products with valualble capillary active properties being obtained in a simple manner. The ethersulphonic acids so obtained constitute in the form of their salts in some cases viscous masses, in other cases .white to yellowish, water-soluble powders. The products have an excellent sta bility towards the agents which cause the hardness of water and a good wetting, foaming, emulsifying and washing power. Some of the products may also be used as leveling, through-dyeing and softening agents As washing agents the products serve for cleansing household articles and textile materials, especially wool, cotton, silk, artificial silk, as well as for hygienic pur- The products may be used either alone or in admixture with each other or with other capillary active substances, such as soap and other adiuvants of the textile industry, with colloidal substances, as for instance mucilage, glue, water- 2 Somme cellulose derivatives, starch, bentonite,

- saponine or the like, as well as in admixture with C., while stirring, until the solution is saturated.

After the separation of the aqueous layer the product is dried by means of calcium chloride and filtered, whereupon the methylene chloride is separated by distillation. The octylchloromethylether obtained is then distilled under reduced pressure.

178.5 parts of octylchloromethylether are heated with 60 parts of ethylene oxide for 6 hours in a closed vessel at 160 C. to 170 C. The ethylene oxide in excess is then separated. By the absorption of 1 moi. of ethylene oxide the octylmethyl-ether-beta-chloroethylether has been formed. 7

222.5 parts of the above ether are heated for 10 hours, while stirring, at 150-160 C. with a solution of 170 parts of sodium sulphite in 400 parts of water and 800 parts of methanol. After cooling the product is filtered with suction and recrystallized from methanol.

(2) 234.5 parts of dodecyl-chloromethyl-ether V are heated for 6 hours at 160-170 C. with 60 parts of ethylene oxide, the solution being worked up in the manner indicated in Example 1. 278.5 parts of the dodecyl-methylether-betachloroethylether obtained having the formula C12H25-OCHPO- H:-CH:-Cl are heated for 10 hours at 150-160 C. with a solution of 210 parts of potassium sulphite in 400 parts of water and 800 parts of methanol. After coolin the product is filtered with suction and recrystallized from methanol,

(3) 360.5 parts of oleylchloromethylether are heated for 6 hours at 160-170 C. with 60 parts of ethylene oxide. 316.5 parts of the oleylmethylether-beta-chloroethylether obtained are heated for 10 hours, while stirring, at 150-160 C. with a solution of 170 parts ofsodium sulphite in 400 parts of water and 800 parts of methanol. The product is redissolved from methanol.

(4) 262.5 parts of the chloromethylether from the mixture of alcohols obtainable by the reduction of palm oil, are heated for 8 hours at ISO-170 C. with 60 parts of ethylene oxide. 306.5 parts of the beta-chloroethylether obtained are heated for 10 hours, while stirring, at 150-160 C.

with a solution 1'70 parts of sodium sulphite in 400 parts of water and 800 parts of methanol. The product obtained may be redissolved from methanol. I

(5) 178.5 parts of the chloromethylether derived from a mixture of alcohols containing 7 to 9 carbon atoms, obtainable by the oxidation of paramne, are heated for 6 hours at 160-170 C. with 60 parts of ethylene oxide. 222.5 parts of the beta-chloroethylether obtained are heated for 10 hours, while stirring, at 150-160 C. with a solution of 1'70 parts of sodium sulphite in 400 parts of water and 800 parts of methanol. The product obtained may be redissolved from methanol.

(6) 250 parts of octyiphenylmonoglycolether are dissolved in twice the quantity of methylene chloride. 45 parts of para-formaldehyde are then added and hydrochloric acid gas is introduced at 0-5 C., while stirring, until the solution is saturated. After the separation of the aqueous layer, the solution is dried by means of calcium chloride. After filtering, the methylene chloride is separated by distillation. 298.5 parts of octylphenyl monoglycoletherchloromethylether are heated for 6 hours at 160-170 C. with 60 parts of ethylene oxide. 342.5 partsof the octylphenylmonoglycolether methylether-beta-chloroethylether obtained are heated for 10 hours, while stirring, at l50-l60 C. with a solution of 170 parts of sodium sulphite in 400 parts of water and 800 parts of methanol. The product obtained is purified by redissolving it from methanol.

(7) 375.5 parts of stearic acid beta-chloroethoxymethylamide are heated for 10 hours. whilestirring, at 150-160 C. with a solution of 170 parts of sodium sulphite in 400 parts of water and 800 parts of methanol. After cooling, the sodium salt of the sulphonic acid having the formula is filtered with suction and recrystallized from methanol. Instead of sodium sulphite there may be used potassium sulphite. The initial material is obtained as follows:

283 parts of stearic acid amide are dissolved in twice the quantity of methylene chloride. 45 parts of paraformaldehyde and parts of pulverulent calcium chloride are then added, hydrochloric acid gas being introduced at 0 C.-5 C., while stirring, until the solution is saturated. The solution is filtered with suction and rapidly dried by means of further calcium chloride. After filtering the methylene chloride is separated by distillation: the stearlc acid chloromethylamide remains in form of a fatty mass.

331.5 parts of stearic acid chloromethylamide are heated for 6 hours at ISO-170 C. in a closed vessel with 60 parts of ethylene oxide, whereupon the ethylene oxide in excess is separated. With absorption of l mol of ethylene oxide the stearic acid beta-chloroethoxymethylamide has been formed.

roethoxymethylamide obtainable in the manner fdescribed below, are heated for 10 hours at C. with a solution of 210 parts of potassium sulphite in 400 parts of water and 800 parts of methanol. After cooling, the product is filtered with suction and redissolved from methanol.

The initial material is obtained as follows:

By treating parafilne hydrocarbons having a boiling point of 220-320 C., with equimolecular amounts of sulphur dioxide and chlorine, a mixture of aliphatic sulphochlorides is obtained. By reacting this mixture with ammonia, a mixture of aliphatic sulphamides having an average carbon chain of 14 atoms is obtained. By proceeding in the manner indicated in Example v7, a mixture of aliphatic sulphochloromethylamides is finally obtained.

326.5 parts of this mixture are heated 1on6 hours at 160-170 C. with 60 parts of ethylene oxide, the product being worked up as indicated in e 7. (0) 312 parts of dodecylcyclohexylmonoglycolether are transformed into the chloromethylether by the action of 45 parts of 'paraiformaldehyde and hydrochloric acid. 'By' reacting this chloromethylether with ethylene oxide, the dodecylcyclohexylmonoglycolether methylether beta chloroethylether is obtained, which is then transformed into the corresponding sulphonate' by means of sodium sulphite in an aqueous methanol solution. The sulphonate obtained may be redissolved from methanol.

(.10) 263 parts of octylphenoxyacetic acid amide are dissolved in twice the amount of methylene chloride. 45 parts of paraformaldehyde and 90 parts oi. anhydrous sodium sulphate are then added, hydrochloric acid gas being introduced at C.- 0., until the solution is saturated. After filtering, the methylene chloride is separated by distillation.

311.5 parts of the octylphenoxyacetic acid chloromethylamide are heated at 160-170 C. with parts of ethylene oxide, whereupon the ethylene I til we claim: 0 g 1. The process which comprises reacting a halogemnethyl-etherot an aliphatic compound containing an aliphatic radical of at least 4 carbon atoms and at least 1 hydroxyl group with an alv kyienoxideand reacting the resulting compound with an alkali sulphite.

2. The process which comprises reacting chlormethyi-ether o1 dodecyl alcohol with ethylene oxids and reacting the resulting beta-chlor-ethylether with an alkali sulphite to replace the betachlor group :by a sulphonic acid group.

3. The process as defined in claim 1 wherein the reaction with the alkali sulphite is effected at a temperature ranging from to C.

4. ,As new compounds the sulphonic' acids of the general formula wherein R stands for an aliphatic radical with at least iour carbon atoms, and X stands for oxygen.

' 5'. The compound 01' the formula cmms-mcna-o-cns-cni-soan LUDWIG oamna WERNER moans.