A. J. Stirton

Surface-active properties of salts of alpha-sulfonated acids and esters

SummaryIn a comparison of the solubility, detergency, and surface-active properties of the mono- and disodium salts ofa-sulfonated lauric, myristic, palmitic, and stearic acids, it has been shown that the less solublea-sulfopalmitates anda-sulfostearates, and sodiuma-sulfomyristic acid as well, are the best detergents. The easily soluble disodiuma-sulfolaurate resembles a simple electrolyte with little evidence of surface-active properties. Ammoniuma-sulfopalmitic acid and triethanolammoniuma-sulfopalmitic acid are more soluble surface-active agents and detergents than the sodium salts. Triethanolammoniuma-sulfopalmitic acid is exceedingly soluble in water at room temperature.The sodium salts of alkyla-sulfopalmitates anda-sulfostearates are easily prepared from the isolated crude diacid. The esters of primary alcohols containing from one to six carbon atoms are readily soluble in water and quite stable to hydrolysis, especially in acid solution. Salts ofa-sulfonated esters of secondary alcohols are stable both to acid and to alkaline hydrolysis. This behavior extends the range of possible application.

Synthetic detergents from animal fats. V. Esters from alpha-sulfonated fatty acids and sodium isethionate

SummaryDisodium 2-sulfoethyl α-sulfopalmitate, disodium 2-sulfoethyl α-sulfostearate, and disodium 2-sulfoethyl α-sulfobehenate were prepared by esterification of the corresponding α-sulfonated acid with sodium isethionate. Disodium 1-methyl-2-sulfoethyl α-sulfostearate was made from sodium 2-hydroxypropanesulfonate. The esters were found to be readily soluble surface-active agents and detergents, very responsive to building with inorganic phosphates and sulfates.Compared to sodium 2-sulfoethyl oleate the esters were readily prepared without the necessity of making the acid chloride; they were considerably more resistant to acid or alkaline hydrolysis; they were about equal in their excellent lime soap dispersing power, but inferior in foaming properties, producing a less permanent foam.The esters were easily soluble because of the presence of two sulfo groups and were improved detergents in the presence of inorganic builders. Mixtures of the palmitic and stearic acid derivatives, such as might be obtained from the saturated acids of tallow, containing a total of 20% active ingredient, were effective detergents in hard water.Disodium 1-methyl-2-sulfoethyl α-sulfostearate, an ester of a secondary alcohol, was even more resistant to alkaline hydrolysis than the esters from sodium isethionate.

Fatty acid monoesters of 1-ascorbic acid and d-isoascorbic acid

SummaryFat-soluble fatty acid monoesters of 1-ascorbic acid (vitamin C) and d-isoascorbic acid have been prepared from lauric, myristic, palmitic, and stearic acids in 40–50 per cent yields.Evidence has been presented to show that only the primary hydroxyl group of each of the ascorbic acids has been esterified.Antioxidant properties of these esters are being studied.Preliminary tests on the esters have indicated that they may have useful properties as interfacial modifiers.

Synthetic detergents from animal fats. The sulfation of tallow alcohols

SummarySodium oleyl sulfate (or the trans isomer) is a desirable component in a mixture of sulfated tallow alcohols, principally because of its ready solubility in water at room temperature.The use of moderate sulfating agents, which can be thought of as complexes formed with either sulfur trioxide, chlorosulfonic acid, or sulfuric acid, has been shown to give products having good detergent and surface-active properties. Desirable properties are generally related to the purity of the product and to the extent to which side reactions at the double bond are minimized or avoided.

The course of biodegradation of anionic detergents by analyses for carbon, methylene blue active substance and sulfate ion

Tallow alcohol sulfates, ether alcohol sulfates and esters of α-sulfo tallow fatty acids were degraded aerobically by sewage microorganisms in a system in which detergent was the sole source of C. Biodegradation was followed by loss of C and methylene blue active substance (MBAS) and formation of SO4−−. Tallow alcohol sulfates were rapidly and completely degraded; ether alcohol sulfates not quite as readily. Reduction in MBAS was rapid for the α-sulfo esters but loss of C and SO4−− formation was incomplete, possibly because of the intermediate formation of a resistant sulfosuccinate. Sodiump-(1-methylundecyl) benzenesulfonate (LAS) was the reference standard.

Microaerophilic biodegradation of tallow-based anionic detergents in river water.

Nine anionic detergents from five general classes (alcohol sulfates, ether alcohol sulfates, sulfated alkanolamides, α-sulfo esters and alkylbenzenesul-fonates) were rapidly screened for biodegradability under aerobic and microaerophilic conditions in river water at 25 and 35 C. In decreasing order, the ease of biodegradation under microaerophilic conditions at 35 C was as follows: alcohol sulfates, sulfated alkanolamides, α-sulfo fatty acid esters and ether alcohol sulfates. Linear alkylbenzenesulfonate did not degrade.

Chlorinated alcohols: IV. The chlorination of oleic acid

Chlorination of oleic acid gave mainly 9,10-dichlorosteraic acid but other products were also formed. By-products included the dimer, 9(10)-(9,10-dichlorostearolyoxy)-10(9)-chlorostearic acid, and the related trimer, formed independent of temperature in the range examined (−20 to +29 C). Higher solvent-oleic acid ratios decreased the amounts of dimer and trimer; chlorination in the presence of hydrogen chloride did not. The equivalent weight of 9,10-dichlorostearic acid was found to increase markedly upon treatment with chlorine and light, but in the dark the acid was apparently unchanged. These effects were independent of temperature.

Chlorinated alcohols: I. Preparation from chlorinated acids

Rhenium, ruthenium and rhodium oxides, hydrogenolysis catalysts for stearic acid at 150 C, were tried for the conversion of 9,10-dichloro-stearic acid to the dichloro alcohol but only ReO3 was effective in some degree (yield 14%). Dehydrochlorination or hydrogenolysis at the carbon-chlorine bond was the principal reaction. Reductions with diborane or with lithium aluminum hydride, however, were found to be excellent methods for preparing 9,10-dichloro-stearyl alcohol.

Chlorinated alcohols: II. The chlorination of oleyl alcohol

Chlorination of oleyl alcohol gives mainly 9,10-dichlorostearyl alcohol but a variety of other products are also formed. By-products include 9(10)-(9,10-dichlorostearoxy)-10(9)-chlorostearyl alcohol (14%) and 9,10-dichlorostearyl 9,10-dichlorostearate (3–4%) in addition to three or four less clearly defined products (12%). One group of products is apparently derived from participation of the hydroxyl group in the chlorine addition step while the other products formed by the reaction of the hydroxyl group with chlorine or chlorine and hydrogen chloride.

Chlorinated alcohols: III. 9,10-Dichlorostearylamine

Abstract9,10-Dichlorostearylamine was prepared by the hydrogenation of 9,10-dichlorostearonitrile, catalyzed by Rh/C, and by the chlorination of oleylamine hydrochloride. The dichloro amine was surprisingly heat-stable and could be purified by molecular distillation at 170 C (0.1 mm). Also described are the preparations of 9,10-dichlorostearoyl chloride, 9,10-dichlorostearamide and 9,10-dichlorostearonitrile. The chlorination of oleonitrile is not a simple reaction and the 9,10-dichlorostearonitrile was best prepared by dehydration of the amide.