US2169998A - Sulpho-carboxylic esters suitable - Google Patents

Sulpho-carboxylic esters suitable Download PDF

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US2169998A
US2169998A US2169998DA US2169998A US 2169998 A US2169998 A US 2169998A US 2169998D A US2169998D A US 2169998DA US 2169998 A US2169998 A US 2169998A
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups

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  • assistants for the textile and related industries particularly wetting, cleansing and emulsifying agents, having excellent properties are obtained by esterifying saturated or non-saturated aliphatic, i. e. open chain or cycloaliphatic, monoor polyhydric alcohols containing more than 8 carbon atoms in their molecule with the carboxylic groups of aliphatic sulpho-carboxylic acids (C-SO2OH) containing up to 8 carbon atoms in their molecule.
  • C-SO2OH carboxylic groups of aliphatic sulpho-carboxylic acids
  • aliphatic, sulphonatable carboxylic acids containing up to 8 carbon atoms in their molecule and comprising no sulphonic group may also be used, the esters obtained being then sulphonated.
  • alcohols is to be understood in a broad sense and is meant to include alcohols which contain further substituents as for example halogen and/or carboxylic radicles.
  • octodecyl alcohol As suitable alcohols may be mentioned octodecyl alcohol; dodecyl alcohol, oleic 'alcohol, octodecane diol (obtainable by reductioncf castor oil with the aid of hydrogen), alcohplxmixtures which may be obtained by reduction with the aid of hydrogen of fats and oils of vegetalyi. e. 30 animal and vegetable origin, alcohols which are formed by the oxidation of paraflins, such as paraffin wax or paraflin oil, and alcohols corresponding to resinic, naphthenia-and montanio acids and obtainable therefrom by reduction with the aid of hydrogen.
  • paraflins such as paraffin wax or paraflin oil
  • derivatives thereot may also be esterified to yield similar products, suitable derivatives being for example dichlor-octodecyl alcohol and ricinoleic acid.
  • suitable derivatives being for example dichlor-octodecyl alcohol and ricinoleic acid.
  • the alcohols obtainable by introducing alkyl or cycloalkyl groups into one hydroxyl group of polyhydric alcohols containing up to 8 carbon atoms in their molecule may also be employed provided the total amount of carbon atoms in the final molecule is greater than 8; 45 as examples of such alcohols may be mentioned propylene-glycol mono-octodecyl ether and butylene-glycol mono-hexyl ether.
  • sulpho-carboxylic acids sulphoacetic acid, a-sulpho-propionic and sulpho-iso- 50 butyric or -valeric acids may be mentioned.
  • carboxylic acids containing no sulphonic groups are those which contain up to 8 carbon atoms in their molecule and one or more groups which render sulphonation to true sulphonic acids possible without destructive attack on the ester, such as double l g g n a om 7 Claims. (Cl. 260-481) for example crotonic acid, dimethyl acrylic acid mono-chlor acetic acid, or u-brom propionic acid.
  • Carboxylic acids containing up to 8 carbonatoms in their molecule may also be employed into which the said sulphonatable groups can be introduced after esterification, for example by halogenation of the radicle of a saturated aliphatic acid.
  • the esterification is usually carried out by' acting with the alcohols on the acids, or acid chlorides, under the usual conditions, as for example by treating the.alcohols with the acids in the presence of an acid reacting catalyst such as hydrochloric or sulphuric acid, or by heating the alcohols with the acids, or their chlorides, at elevated temperatures such as from about-50 to about 100 C., or above the boiling point of water for removing the latter, or halogen hydride respectively; when working with acid chlorides the alcohols may be employed in the form of alcoholates.
  • an acid reacting catalyst such as hydrochloric or sulphuric acid
  • esters which do not contain sulphonic groups must, as has already been mentioned, subsequently be sulphonated.
  • This sulphonation is generally carried out in the usual manner, by a treatment with sulphonating agents stronger than concentrated sulphuric acid until true sulphonic acids are obtained which can be ascertained by the fact that a sample does not split 01? the sulphonic groups when boiled with dilute mineral acids, as for example a 10 per centaqueous hydrochloric acid.
  • the esters may be sulphonated for example by means of oleum, sulphur trioxide or chloro-sulphonic acid if desired in the presence of inert organic diluents, such as carbon tetrachloride, trichlorethylene, and/0r catalysts such as the superficially active charcoal or bleaching earth, and/or agents capable of removing water, as for example acetic or propionic anhydrides and the like.
  • inert organic diluents such as carbon tetrachloride, trichlorethylene, and/0r catalysts such as the superficially active charcoal or bleaching earth, and/or agents capable of removing water, as for example acetic or propionic anhydrides and the like.
  • Esters obtained from carboxylic acids containing a halogen atom may be converted into esters of sulpho-carboxylic acids by a treatment with salts of sulphurous acid such as alkali, alkaline earth metal or heavy metal salts, the reaction being preferably carried out with alkali metal sulphites or ammonium sulphite. It is particularly advantageous to carry out this treatment by heating at about C. the mixture of the ester with an aqueous solution of an alkali metal sulphite together with a small amount of an organic solvent soluble in water, such as ethyl alcohol, or of an emulsifying agent for which purpose use may be made of the products obtained by the process itself.
  • the esters, the acid radicles of which contain halogen atoms may also be converted into true sulphonic acids by a treatment with alkali metal hydrosulphide and subsequent oxidation.
  • Esters which already contain a sulphonic group may, if so desired, be subjected to one of the sulphonation methods described, so that the final product contains two or more sulphonic groups, such products being also obtainable from esters of poly-halogen carboxylic acids with the aid of sulphites.
  • R--COO-R1 The products according to the present invention correspond to the general formula R--COO-R1 in which R denotes an aliphatic radicle containing up to '7 carbon atoms and at least one 'sulphonic radicle and R1 denotes a radicle of an aliphatic monoor polyhydric alcohol containing more than 8 carbon atoms.
  • R1 will usually contain from 10 to 18 carbon atoms, the products from alcohols containing from 12 to 18 carbon atoms being particularly valuable.
  • The;;1i 1'oducts obtained according to the present invention are excellent washing, cleansing and emulsifying agents for many purposes in daily and commercial use. They may be employed alone or together with various additions such as salts as for example sodium chloride. sodium sulphate or sodium perborate, diluted acids, such as dilute hydrochloric or acetic acid, glue, organic solvents such as carbon tetrachloride, cyclohexanol, oil of turpentine and/or mineral, vegetable or animal oils. l
  • Example 1 162 parts of the mono-sodium salt of sulphoacetic acid are heated with 270 parts of octodecyl,
  • Example 2 325 parts of the mono-sodium salt of sulphoacetic acid are heated with 500 parts of oleic alcohol (CisHgsOH) for 15 hours at 180 C. while stirring, the water set free during the esterification being removed from the reaction vessel by means of a current of nitrogen. After removing the oleic alcohol which has not reacted and small quantities of other water-insoluble matter as described in Example 1, an excellent, water-soluble washing agent is obtained, which consists of practically pure oleyl sulpho-acetate.
  • oleic alcohol CiHgsOH
  • Example 3 1 part of the mono-sodium salt of sulpho-acetic acid is heated at 180 C. during 18 hours while stirring, with 1 part of a mixture of alcohols such as is obtained by the catalytic reduction of coconut oil, the water being removed as in the preceding examples.
  • the reaction product is worked up in the usual manner; it is an excellent wetting and detergent agent.
  • free sulpho-acetic acid may be employed, the reaction being then carried out at about C. and preferably at about 20 millimeters mercury gauge.
  • Example 4 parts of the ester prepared by treating the mixture of alcohols resulting from the catalytic reduction of coconut oil with chloracetic acid are boiled for some time with an aqueous solution of 70 parts of anhydrous sodium sulphite containing about 30 per cent of ethyl alcohol, until a sample of the reaction product forms a clear solution with water.
  • the reaction mixture itself,. containing some sodium chloride, as well as the product obtained by evaporation of the liquid is an excellent detergent and wetting agent.
  • Example 5 50 parts of the mixture of esters, obtained by the esterification of crotonic acid with the mixture of alcohols of high molecular weight prepared by a catalytic reduction of coco fat, are mixed at 20 C. with a mixture of 25 parts each of sulphuric acid monohydrate and of acetic anhydride. After stirring for several hours the reaction product is poured onto ice and rendered neutral with the aid of aqueous caustic soda solution. Non-sulphonated constituents are removed whereupon the water-soluble sulphonation product is recovered by salting out. The sodium salt of the sulphonic acid of the initial ester possesses a high wetting power.
  • Example 6 36 parts of an ester obtained by esterifying one molecular proportion of chloro-acetic acid with one molecular proportion of octodecane-'l,18-diol, obtainable by the catalytic reduction of castor oil, are stirred for 5 hours at 83 C. with a solution of 15 parts of sodium sulphite in parts of a 30 per cent aqueous solution of ethyl alcohol. An eflicient washing and scouring agent is obtained, the efiicient constituent of which may be obtained in the solid form by evaporating the aqueous alcoholic solution.
  • Example 7 38 parts of the chloro-acetic ester of ricinoleic acid, presumably corresponding to the formula and obtainable for example by heating equimolecular proportions of chloro-acetic acid and of ricinoleic acid to 160 C., are refluxed for 2 hours with a solution of 15 parts of sodium sulphite, and 5 parts of sodium carbonate in 150 parts of an aqueous 30 per cent solution of ethyl alcohol. After evaporation of the alcohol a product having a good washing and foaming power is obtained.
  • Sulpho-carboxylic esters suitable for use as assistants in the textile and related industries, corresponding to the general formula R,COOR1 in which R denotes an aliphatic radicle, containing up to 7 carbon atoms and at least one sulphonic radicle, and R1 denotes a radicle of an aliphatic alcohol obtainable by resaturated aliphatic alcohols, said esters containing a sulphonic group on the alkyl portion of the acyl group of the ester molecule.
  • Esters suitable for use as assistants in the textile and related industries corresponding to the general formula R--COO-R1 in which R denotes an aliphatic radicle containing up to 7 carbon atoms and a. substance selected from the group consisting of Cl and 803K and R1 denotes a radicle of an aliphatic alcohol obtainable by reduction of the unsaturated fatty" acids of vege- FRITZ GUENTHER. KARL SAF'TIEN.

Description

Patented Aug. 22, 1939 UNITED STATES PATENT OFFICE Fritz Guenther and Karl saitiemLudwigshafenon-the-Rhine, Germany, assignors to I. G. Farbenindustrie Aktiengesellschaft, Frankfort-onthe-Main, Germany No Drawing. Application May 13, 1931, Serial No. 537,208. In Germany May 23, 1930 The present invention relates to the production of assistants for the textile and related in- ,dustries, particularly of wetting, cleansing and emulsifying agents.
We have found that assistants for the textile and related industries, particularly wetting, cleansing and emulsifying agents, having excellent properties are obtained by esterifying saturated or non-saturated aliphatic, i. e. open chain or cycloaliphatic, monoor polyhydric alcohols containing more than 8 carbon atoms in their molecule with the carboxylic groups of aliphatic sulpho-carboxylic acids (C-SO2OH) containing up to 8 carbon atoms in their molecule. Instead of the sulpho-carboxylic acids, aliphatic, sulphonatable carboxylic acids containing up to 8 carbon atoms in their molecule and comprising no sulphonic group may also be used, the esters obtained being then sulphonated.
The term alcohols is to be understood in a broad sense and is meant to include alcohols which contain further substituents as for example halogen and/or carboxylic radicles.
As suitable alcohols may be mentioned octodecyl alcohol; dodecyl alcohol, oleic 'alcohol, octodecane diol (obtainable by reductioncf castor oil with the aid of hydrogen), alcohplxmixtures which may be obtained by reduction with the aid of hydrogen of fats and oils of vegetalyi. e. 30 animal and vegetable origin, alcohols which are formed by the oxidation of paraflins, such as paraffin wax or paraflin oil, and alcohols corresponding to resinic, naphthenia-and montanio acids and obtainable therefrom by reduction with the aid of hydrogen. Instead of the said simple alcohols, derivatives thereot may also be esterified to yield similar products, suitable derivatives being for example dichlor-octodecyl alcohol and ricinoleic acid. The alcohols obtainable by introducing alkyl or cycloalkyl groups into one hydroxyl group of polyhydric alcohols containing up to 8 carbon atoms in their molecule may also be employed provided the total amount of carbon atoms in the final molecule is greater than 8; 45 as examples of such alcohols may be mentioned propylene-glycol mono-octodecyl ether and butylene-glycol mono-hexyl ether.
As suitable sulpho-carboxylic acids, sulphoacetic acid, a-sulpho-propionic and sulpho-iso- 50 butyric or -valeric acids may be mentioned. -Suitable carboxylic acids containing no sulphonic groups are those which contain up to 8 carbon atoms in their molecule and one or more groups which render sulphonation to true sulphonic acids possible without destructive attack on the ester, such as double l g g n a om 7 Claims. (Cl. 260-481) for example crotonic acid, dimethyl acrylic acid mono-chlor acetic acid, or u-brom propionic acid. Carboxylic acids containing up to 8 carbonatoms in their molecule may also be employed into which the said sulphonatable groups can be introduced after esterification, for example by halogenation of the radicle of a saturated aliphatic acid.
The esterification is usually carried out by' acting with the alcohols on the acids, or acid chlorides, under the usual conditions, as for example by treating the.alcohols with the acids in the presence of an acid reacting catalyst such as hydrochloric or sulphuric acid, or by heating the alcohols with the acids, or their chlorides, at elevated temperatures such as from about-50 to about 100 C., or above the boiling point of water for removing the latter, or halogen hydride respectively; when working with acid chlorides the alcohols may be employed in the form of alcoholates. When mineral acid esters of the alcohols such as octodecyl mono-iodide are used, it is preferable to employ salts of the organic acidsfor the esterification; When employing sulpho-carboxylic acids it is particularly advantageous to heat the alcohols with the acids in the -free state to say 100." C. preferably in vacuo or the mono-sodium salt of the acid with the alcohols to a temperature of say 120 C. preferably above 150 C. Thus for example the aliphatic alcohols containing more than 8 carbon atoms in their molecule which are obtainable by reduction with the aid of hydrogen of fatty acids may be esterified by heating with the monosodium salt of sulpho-acetic acid at 200 C. or an alkyl ester, such as the methyl ester, of the mono-sodium salt of sulpho-acetic acid may be re-esterified with the alcohol desired.
The esters which do not contain sulphonic groups must, as has already been mentioned, subsequently be sulphonated. This sulphonation is generally carried out in the usual manner, by a treatment with sulphonating agents stronger than concentrated sulphuric acid until true sulphonic acids are obtained which can be ascertained by the fact that a sample does not split 01? the sulphonic groups when boiled with dilute mineral acids, as for example a 10 per centaqueous hydrochloric acid. The esters may be sulphonated for example by means of oleum, sulphur trioxide or chloro-sulphonic acid if desired in the presence of inert organic diluents, such as carbon tetrachloride, trichlorethylene, and/0r catalysts such as the superficially active charcoal or bleaching earth, and/or agents capable of removing water, as for example acetic or propionic anhydrides and the like. Esters obtained from carboxylic acids containing a halogen atom may be converted into esters of sulpho-carboxylic acids by a treatment with salts of sulphurous acid such as alkali, alkaline earth metal or heavy metal salts, the reaction being preferably carried out with alkali metal sulphites or ammonium sulphite. It is particularly advantageous to carry out this treatment by heating at about C. the mixture of the ester with an aqueous solution of an alkali metal sulphite together with a small amount of an organic solvent soluble in water, such as ethyl alcohol, or of an emulsifying agent for which purpose use may be made of the products obtained by the process itself. The esters, the acid radicles of which contain halogen atoms, may also be converted into true sulphonic acids by a treatment with alkali metal hydrosulphide and subsequent oxidation.
Esters which already contain a sulphonic group may, if so desired, be subjected to one of the sulphonation methods described, so that the final product contains two or more sulphonic groups, such products being also obtainable from esters of poly-halogen carboxylic acids with the aid of sulphites.
Products of the nature hereinbefore defined are also obtained by employing for the esterification polyhydric alcohols containing 8 or less carbon atoms in their molecule in which case alkyl or cycloalkyl groups must be introduced into at least one free hydroxyl group of the ester, for example with the aid ci 'alkylene oxides containing the required number of carbon atoms, so that the resulting alcoholic radicle contains more than 8 carbon atoms.
The products according to the present invention correspond to the general formula R--COO-R1 in which R denotes an aliphatic radicle containing up to '7 carbon atoms and at least one 'sulphonic radicle and R1 denotes a radicle of an aliphatic monoor polyhydric alcohol containing more than 8 carbon atoms. R1 will usually contain from 10 to 18 carbon atoms, the products from alcohols containing from 12 to 18 carbon atoms being particularly valuable.
The;;1i 1'oducts obtained according to the present invention are excellent washing, cleansing and emulsifying agents for many purposes in daily and commercial use. They may be employed alone or together with various additions such as salts as for example sodium chloride. sodium sulphate or sodium perborate, diluted acids, such as dilute hydrochloric or acetic acid, glue, organic solvents such as carbon tetrachloride, cyclohexanol, oil of turpentine and/or mineral, vegetable or animal oils. l
The following examples will further illustrate the nature of this invention but the invention is not restricted to these examples. The parts are by weight.
Example 1 162 parts of the mono-sodium salt of sulphoacetic acid are heated with 270 parts of octodecyl,
Example 2 325 parts of the mono-sodium salt of sulphoacetic acid are heated with 500 parts of oleic alcohol (CisHgsOH) for 15 hours at 180 C. while stirring, the water set free during the esterification being removed from the reaction vessel by means of a current of nitrogen. After removing the oleic alcohol which has not reacted and small quantities of other water-insoluble matter as described in Example 1, an excellent, water-soluble washing agent is obtained, which consists of practically pure oleyl sulpho-acetate.
Example 3 1 part of the mono-sodium salt of sulpho-acetic acid is heated at 180 C. during 18 hours while stirring, with 1 part of a mixture of alcohols such as is obtained by the catalytic reduction of coconut oil, the water being removed as in the preceding examples. The reaction product is worked up in the usual manner; it is an excellent wetting and detergent agent. Instead of the monosodium salt, free sulpho-acetic acid may be employed, the reaction being then carried out at about C. and preferably at about 20 millimeters mercury gauge.
Example 4 parts of the ester prepared by treating the mixture of alcohols resulting from the catalytic reduction of coconut oil with chloracetic acid are boiled for some time with an aqueous solution of 70 parts of anhydrous sodium sulphite containing about 30 per cent of ethyl alcohol, until a sample of the reaction product forms a clear solution with water. The reaction mixture itself,. containing some sodium chloride, as well as the product obtained by evaporation of the liquid is an excellent detergent and wetting agent.
- Example 5 50 parts of the mixture of esters, obtained by the esterification of crotonic acid with the mixture of alcohols of high molecular weight prepared by a catalytic reduction of coco fat, are mixed at 20 C. with a mixture of 25 parts each of sulphuric acid monohydrate and of acetic anhydride. After stirring for several hours the reaction product is poured onto ice and rendered neutral with the aid of aqueous caustic soda solution. Non-sulphonated constituents are removed whereupon the water-soluble sulphonation product is recovered by salting out. The sodium salt of the sulphonic acid of the initial ester possesses a high wetting power.
Example 6 36 parts of an ester obtained by esterifying one molecular proportion of chloro-acetic acid with one molecular proportion of octodecane-'l,18-diol, obtainable by the catalytic reduction of castor oil, are stirred for 5 hours at 83 C. with a solution of 15 parts of sodium sulphite in parts of a 30 per cent aqueous solution of ethyl alcohol. An eflicient washing and scouring agent is obtained, the efiicient constituent of which may be obtained in the solid form by evaporating the aqueous alcoholic solution.
Example 7 38 parts of the chloro-acetic ester of ricinoleic acid, presumably corresponding to the formula and obtainable for example by heating equimolecular proportions of chloro-acetic acid and of ricinoleic acid to 160 C., are refluxed for 2 hours with a solution of 15 parts of sodium sulphite, and 5 parts of sodium carbonate in 150 parts of an aqueous 30 per cent solution of ethyl alcohol. After evaporation of the alcohol a product having a good washing and foaming power is obtained.
What we claim is:
1. Sulpho-carboxylic esters, suitable for use as assistants in the textile and related industries, corresponding to the general formula R,COOR1 in which R denotes an aliphatic radicle, containing up to 7 carbon atoms and at least one sulphonic radicle, and R1 denotes a radicle of an aliphatic alcohol obtainable by resaturated aliphatic alcohols, said esters containing a sulphonic group on the alkyl portion of the acyl group of the ester molecule. I
table oils and fats.
4. The chloroacetic acid ester of an unsaturated non-cyclic alcohol containing a chain of 18 carbon atoms in its structure.-
5. The process which comprises reacting with chloroacetic acid upon an unsaturated non-cyclic alcohol containing a. chain of 18 carbon atoms in its structure, whereby to produce the chloroacetic acid ester of said alcohol.
6. Sulpho-acetates of aliphatic alcohols obtainable by reduction of unsaturated fatty acids of oils and fats of vegetable origin.
7. Esters suitable for use as assistants in the textile and related industries corresponding to the general formula R--COO-R1 in which R denotes an aliphatic radicle containing up to 7 carbon atoms and a. substance selected from the group consisting of Cl and 803K and R1 denotes a radicle of an aliphatic alcohol obtainable by reduction of the unsaturated fatty" acids of vege- FRITZ GUENTHER. KARL SAF'TIEN.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2447619A (en) * 1946-08-21 1948-08-24 Standard Oil Dev Co Sulfurized esters of oxalic acid
US3121071A (en) * 1959-09-25 1964-02-11 Dow Chemical Co Polymers of 2-sulfo-1-sulfomethyl ethyl methacrylate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2447619A (en) * 1946-08-21 1948-08-24 Standard Oil Dev Co Sulfurized esters of oxalic acid
US3121071A (en) * 1959-09-25 1964-02-11 Dow Chemical Co Polymers of 2-sulfo-1-sulfomethyl ethyl methacrylate

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