Secondary olefin sulfates

The direct sulfation of wax olefins has been perfected in Europe but has not been commercialized to any extent in the United States. More work has been done in this country on alcohols that have been prepared by Fischer-Tropsch syntheses, oxo process reactions, and reduction of the fatty acid mixtures obtained by paraffin wax oxidation. In most instances these alcohols as well as the olefins have been branched chain or secondary products, both of which have been reported to give inferior detergent and sudsing properties (13, 2Jf). 

Isoalkanes can also be synthesized by using two-component catalyst systems composed of a Fischer-Tropsch catalyst and an acidic catalyst. Ruthenium-exchanged alkali zeolites288 289 and a hybrid catalyst290 (a mixture of RuNaY zeolite and sulfated zirconia) allow enhanced isoalkane production. On the latter catalyst 91% isobutane in the C4 fraction and 83% isopentane in the C5 fraction were produced. The shift of selectivity toward the formation of isoalkanes is attributed to the secondary, acid-catalyzed transformations on the acidic catalyst component of primary olefinic (Fischer-Tropsch) products. 

Tertiary amines do not react with nitrous acid, acetyl chloride, benzoyl chloride, benzenesulfonyl chloride, but react with alkyl halides to form quaternary ammonium halides, which are converted by silver hydroxide to quaternary ammonium hydroxides. Quaternary ammonium hydroxides upon heating yield (1) tertiary amine pins alcohol (or, for higher members, olefin plus water). Tertiary amines may also be formed (2) by alkylation of secondary amines, e.g., by dimethyl sulfate, (3) from amino acids by living organisms, e g, decomposition of fish in the case of trimethylamine. 

The results are shown in Figure 27. It can be seen the all the anionics tested show significant effects of the combination with SAE on their sequestering ability. For this effect, the optimum EO mole number for each anionic is different. Since the combination of LAS with STPP gives a calcium ion sequestering ability of only 165 mg/g-detergents by this procedure, the combination of SAE with LAS(Linear Alkyl-benzene Sulfonate), AOS (4-Olefin Sulfonate), SAS(Secondary Alkane Sulfonate) or SDS (Sodium Dodecyl Sulfate) would be recommended for use in heavy-duty detergents. 

Linear internal monoolefins can be oxidized to linear secondary alcohols. The alpha (terminal) olefins from ethylene oligomerization, described earlier in this chapter, can be converted by oxo chemistry to alcohols having one more carbon atom. The higher alcohols from each of these sources are used for preparation of biodegradable, synthetic detergents. The alcohols provide the hydrophobic hydrocarbon group and are linked to a polar, hydrophilic group by ethoxylation, sulfation, phosphorylation, and so forth. 

The classical method for making tert-butyl esters involves mineral acid-catalysed addition of the carboxylic acid to isobutene but it is a rather harsh procedure for use in any but the most insensitive of substrates [Scheme 6.33].80-82 Moreover, the method is hazardous because a sealed apparatus is needed to prevent evaporation of the volatile isobutene. A simpler procedure [Scheme 6.34] involves use of tert-butyl alcohol in the presence of a heterogeneous acid catalyst — concentrated sulfuric acid dispersed on powdered anhydrous magnesium sulfate. 3 No interna] pressure is developed during the reaction and the method is successful for various aromatic, aliphatic, olefinic, heteroaromatic, and protected amino acids. Also primary and secondary alcohols can be converted into the corresponding /erf-butyl ethers using essentially the same procedure (with the exception of alcohols particularly prone to carbonium ion formation (e.g. p-... 

Detergents, which now rival soap in demand, are based largely on petroleum the variety of structures which confer detergent properties have led to some interesting syntheses. Alkyl aryl sulfonates are made by alkylation of benzene either with chlorinated kerosene or with a highly-branched olefin made from propylene. Long chain olefins for secondary sulfates were made from paraffin wax. Secondary alkyl sulfonates were made by direct sulfonation of paraffins with sulfur dioxide and chlorine, a reaction discovered in America in the 193O s. 

The chemistry of aromatic alkylation is more complicated than implied by equations (15, 16, 17). Polymerization, CP production, and the isomerization of heavier olefins also occur. Olson (32) has reported many details of the positional isomerization of 1-aIkenes in the Ce—Cm range. Using 1-dodecene as an example, the alkylated product is a mixture of 2- through 6-dodecyl benzenes. In the absence of isomerization, only 2-dodecyl benzene is produced. Attachment at the first carbon atom is not expected when propylene or heavier olefins are employed since primary cations would then be obtained. Secondary cations are however more stable (or preferred) and lead to the attachment at the second or higher carbon atom of the cation. Olson suggests that positional isomerization involves the formation of dodecyl acid sulfates or dodecyl fluorides when sulfuric acid or HF are used as catalysts reverse reactions then lead to the formation of olefins with double bonds in a new position on the chain. In one example reported, at least 80% of the dodecene isomerized before alkylation (by reactions similar to eqs. 16 and 17). Olson also found that some of the initial dodecylbenzene produced were isomerized. The 2-dodecyl benzene that was initially produced isomerized in the presence of AICI3 catalysts to give from 3-dodecyl to 6-dodecyl benzenes. 

Secondary and tertiary alcohols can be dehydrated in dimethyl sulfoxide when heated to 160 -185°C for 14-16 hr to give olefins in yields of 70-85% [6]. The solution is diluted with water, extracted with petroleum ether (30°-60 C), dried, and then distilled. Other acid catalysts that have been reported for dehydration of alcohols are anhydrous or aqueous oxalic [7, 8], or phosphoric acid [9], and potassium acid sulfate [10,11]. In addition, acidic oxides such as phosphorus pentoxide [10-12] and acidic chlorides such as phosphorus oxychloride or thionyl chloride [13] have been reported to be effective as catalysts for the dehydration reaction. 

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