Alkyl sulfate esters, from alcohols

Mannitol hexanitrate is obtained by nitration of mannitol with mixed nitric and sulfuric acids. Similarly, nitration of sorbitol using mixed acid produces the hexanitrate when the reaction is conducted at 0—3°C and at —10 to —75°C, the main product is sorbitol pentanitrate (117). Xylitol, ribitol, and L-arabinitol are converted to the pentanitrates by fuming nitric acid and acetic anhydride (118). Phosphate esters of sugar alcohols are obtained by the action of phosphorus oxychloride (119) and by alcoholysis of organic phosphates (120). The 1,6-dibenzene sulfonate of D-mannitol is obtained by the action of benzene sulfonyl chloride in pyridine at 0°C (121). To obtain 1,6-dimethanesulfonyl-D-mannitol free from anhydrides and other by-products, after similar sulfonation with methane sulfonyl chloride and pyridine the remaining hydroxyl groups are acetylated with acetic anhydride and the insoluble acetyl derivative is separated, followed by deacetylation with hydrogen chloride in methanol (122). Alkyl sulfate esters of polyhydric alcohols result from the action of sulfur trioxide—trialkyl phosphates as in the reaction of sorbitol at 34—40°C with sulfur trioxide—triethyl phosphate to form sorbitol hexa(ethylsulfate) (123). 

Alkyl sulfates, also called alcohol sulfates, are formed by making the sulfuric acid esters of linear alcohols. Alkyl chain lengths range from Cp) to Cig. The properties of the alkyl sulfates vary with the alkyl chain length distribution. The alcohol source can be either natural (linear) or synthetic oxo (some branching) alcohols. About 15% of the detergent range alcohols in the United States come from saponification of natural oil and fat. Products are called, for example, tallow alcohol sulfate or coconut alcohol sulfate. They tend to... 

Ethylenimine is conveniently prepared from ethanolamine by heating the inner salt of the sulfate ester with aqueous alkali (37%). The method has been applied to other /3-amino alcohols to form the C-alkyl homologs of ethylenimine in which one to three of the four hydrogens may be substituted. The general procedure is illustrated by the synthesis of 2,2-dim ethyl ethylenimine (51%). The N-alkyl analogs can be made by treating the N-alkylethanolamine hydrochlorides with chlorosulfonic acid followed by the action of base on the intermediate sulfuric acid esters, as in the preparation of N-ethylethylenimine (70%). ... 

This reaction is analogous to similar methods for the preparation of ethers (methods 113 and 116), Both simple and mixed sulfides may be made from aliphatic mercaptans or thiophenols. The sodium mercaptides are formed from the mercaptans and aqueous or alcoholic solutions of sodium hydroxide or alcoholic sodium ethoxide. Alkylation is effected by halides, alkyl sulfates, or esters of sulfonic acids. The over-all yields of sulfides are usually above 70%. r-Butyl mercaptan is alkylated directly by /-butyl alcohol in strong sulfuric acid to give /-butyl sulfide in 87% yield. ... 

Coco-Based Surfactants. The most important coconut oil-based surfactants are fatty alcohol sulfate, fatty alcohol ether sulfate, and fatty alcohol polyglycol ether. Two relatively new coco-based surfactants are fatty acid methyl ester sulfonate and alkyl polyglycoside, which is produced from fatty alcohol and starch or sugar, both renewable materials. 

Examples of such developments are sulfation of transesterified rapeseed oil phosphatides (17) and the use of bicontinuous microemulsions obtained by the addition of aliphatic alcohols (18, 19). The stability of these systems promises to be more reliable than those in present use. Oils from wood (tall oil) can be sulfo-nated for self-emulsifying fatliquors (20). Polymerizable oils have been used in fatliquors (21). We expect more progress on the use of high polymers, such as the already commercial alkyl acrylate esters developed by Hodder et al. (22-24), and material based on elastomers (6). We anticipate the development of novel systems to be encouraged by the demand for leather in washable garments and automobile upholstery. 

Thus the reaction of sodium eugenoxide with various alkyl iodides in dry alcohol solution was shown to be in accord with second-order kinetics.1 The reaction of sodium ethoxide with optically active 2-bromo or 2-chlorooctane proceeded with complete inversion,2 and etherification of ethanol containing O18 with diethyl sulfate and alkali indicated that the ethyl group came from the sulfuric ester and that the alkoxide fragment was derived from the alcohol.8... 

Definition Sodium salt of the sulfate ester of the PEG ether of coconut alcohol Formula R-(0CH2CH2)n0S03Na, R rep. alkyl groups from coconut oil, avg. n = 1-4 Uses Surfactant in cosmetics... 

In general, Hofmann alkylations are carried out with appropriate alkyl halides or dialkyl sulfates. These reagents may have to be prepared from the related alcohols, often by rather troublesome methods. A more convenient conversion of alcohols to amines involves the alkylation of amines with toluenesulfonate esters of alcohols. These tosylates are generally prepared quite easily and may then be used as alkylating agents [1-14]. If the alcohol which is to be converted to an amine has the proper structural features, the Ritter reaction (see below) is another useful approach to the preparation of primary amines (by hydrolysis of the amide formed in the reaction) and of some secondary amines (by reduction of the amides). 

CAS 8052-504 68140-10-3 EINECS/ELINCS 232-494-0 Synonyms Fleshing grease, sulfated sodium salt Sodium tallow alcohol sulfate Sulfated fallow, sodium salt Sulfuric acid, monotallow alkyl esters, sodium salts Tallow, sulfated, sodium salt Definition Mixture of sodium alkyl sulfates Formula ROSOjNa, R rep. alkyl groups from tallow Properties Brn. paste (as 55% act. matter In water)... 

Fig. 1. Sulfonated and sulfated acid products viscosities after 98% conversions at varying temperatures where the vertical line indicates the maximum temperature for batch sulfonation using SO to minimi2e color deterioration lines A—C represent branched C 2 alkyl ben2ene (BAB) sulfonic acid from SO, oleum (settied), and oleum (whole mixture), respectively lines D and E, lauryl alcohol 3-ethoxylate sulfuric ester (SO ) and lauryl alcohol sulfuric ester...

For extraction of uranium from sulfate leach Hquors, alkyl phosphoric acids, alkyl phosphates, and secondary and tertiary alkyl amines are used in an inert diluent such as kerosene. The formation of a third phase is suppressed by addition of modifiers such as long-chain alcohols or neutral phosphate esters. Such compounds also increase the solubihty of the amine salt in the diluent and improve phase separation. 

As esters of sulfuric acid, the hydrophilic group of alcohol sulfates and alcohol ether sulfates is the sulfate ion, which is linked to the hydrophobic tail through a C-O-S bond. This bond gives the molecule a relative instability as this linkage is prone to hydrolysis in acidic media. This establishes a basic difference from other key anionic surfactants such as alkyl and alkylbenzene-sulfonates, which have a C-S bond, completely stable in all normal conditions of use. The chemical structure of these sulfate molecules partially limits their conditions of use and their application areas but nevertheless they are found undoubtedly in the widest range of application types among anionic surfactants. 

These compounds contain the fragment R as an alkyl or aryl moiety. In other words, they result from the esterification of an alcohol or a phenol with nitrous acid, nitric acid, phosphoric acid, sulfuric acid, or sulfamic acid, respectively. Many of the esters to be examined in this chapter must be activated prior to eliciting their effects, e.g., the organic nitrites and nitrates, which act as donors of nitric oxide or an analogous molecule, and phosphates, which are activated by hydrolysis or even by phosphorylation (antiviral agents). Sulfates are very seldom active or used as prodrugs, but they have significance as metabolites and as industrial xenobiotics. 

Industrial surfactants find uses in almost every industry, from asphalt manufacturing to carpet fibers, from pulp and paper production to leather processing. Examples of the types of chemicals used as surfactants are fatty alcohol sulfates, alkanolamides, alkoxylates, sulfosuccinates, amines, quaternaries, phosphate esters, acid esters, blockcopolymers, betaines, imidazolines, alkyl sulfonates, etc. 

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