Alcohols and alkoxylates

Alcohols are very common surfactants, acting alone, as a solvent for other surfactants, or in combinations forming, amongst others, esters and ethers. 

Simple straight-chain alkyl esters, such as stearyl stearate, exhibit a carbonyl stretch between 1750 and 1730 cm and C-O stretches at 1250 and 1170 cm In aryl esters the carbonyl stretch is reduced in frequency to 1720 cm  

Polyethoxylates and polypropoxylates also form surface-active esters. Their spectra exhibit the classic EO or PO bands described in section 10.6.2. The alkoxy component may or may not contain terminal O-H groups, which should be evident from the spectrum. 

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Alcohols and Alkoxylates. The preferred method of sulfation uses some form of a continuous thin-film SO3 reactor. 

The partially alkoxylated chlorotitanates, (RO) TiCl, can be prepared in high purity by reaction of TiCl with an organosilane ester, Si(OR)4 (see Silicon compounds). The degree of esterification of the titanium can be controlled by the amount of silane ester used. When is 3 or 4, the addition of the appropriate alcohol and an amine receptor is required (5). 

The inferior activation in the 3- or 6eto-position is illustrated by the very large difference in reactivity in the following aminations and alkoxylations. In the reaction of 2-chloro-5-iodopyridine or 2,3-dibromopyridine (cf. 295) with boiling methanolic methoxide, only the 2-halogen is displaced as is also the case in the amination of 2-chloro-3,5-diiodopyridine and of 2,3,6-tribromopyridine. 4-Amination of 3,4-dibromo-, 2,3,4,5-tetrabromo-, and 3-bromo-4-chloro-pyridine occurred. Only 2-amination (aqueous NH3, 190°, 36 hr) occurred with 2,3-dichloropyridine (295) and only 4-ethoxyla-tion (alcoholic ethoxide, 160°, 4 hr) with 3,4-dichloropyridine. ... 

PD—S) to yield phosphates and alcohols, see Scheme 5 reaction a. Sterically hindered aryl phosphites (e.g., AO 14) have an additional chain breaking activity, i.e. they react with peroxyl and alkoxyl radicals during their function as antioxidants (reactions 5b and 5c) [18]. 

Amine salts of acrylate ester polymers, which are physiologically acceptable and useful as surfactants, are prepared by transesterifying alkyl acrylate polymers with 4-morpholinethanol or alkanolamines and fatty alcohols or alkoxyl-ated alkylphenols and neutralizing with phosphoric acid. This polymer salt (pH of a 10% aqueous solution = 5.1) was used as an emulsifying agent for oils and waxes [70]. 

The development of monoalkyl phosphate as a low skin irritating anionic surfactant is accented in a review with 30 references on monoalkyl phosphate salts, including surface-active properties, cutaneous effects, and applications to paste and liquid-type skin cleansers, and also phosphorylation reactions from the viewpoint of industrial production [26]. Amine salts of acrylate ester polymers, which are physiologically acceptable and useful as surfactants, are prepared by transesterification of alkyl acrylate polymers with 4-morpholinethanol or the alkanolamines and fatty alcohols or alkoxylated alkylphenols, and neutralizing with carboxylic or phosphoric acid. The polymer salt was used as an emulsifying agent for oils and waxes [70]. Preparation of pharmaceutical liposomes with surfactants derived from phosphoric acid is described in [279]. Lipid bilayer vesicles comprise an anionic or zwitterionic surfactant which when dispersed in H20 at a temperature above the phase transition temperature is in a micellar phase and a second lipid which is a single-chain fatty acid, fatty acid ester, or fatty alcohol which is in an emulsion phase, and cholesterol or a derivative. 

Label scrambling in propene occurs through the framework-bound alkoxyl intermediate 23, which is seen at 89 ppm in studies of propene-2-l3C on HZSM-5 (45). Analogous alkoxyl species have been reported on acidic zeolites from the reactions of certain alcohols and acetylene. In the latter case, structure 24 was proposed as the product obtained by heating acetylene on HZSM-5 (126). Evidence for this assignment included the formation of acetaldehyde as a hydrolysis product. Acetylene also reacts... 

Different approaches to the kinetics of alcohol dehydration were attempted by two groups of authors [118,119]. In one case, it has been assumed that the active surface of alumina is formed either by free hydroxyl groups or by surface alkoxyl groups. The rate equation was then derived on the basis of the steady-state assumption a good fit to the experimental data was obtained [1118]. The second model was based on the fact that water influences the adsorption of an alcohol and diminishes the available surface. The surface concentrations of tert-butanol and water were taken from independent adsorption measurements and put into the first-order rate equation a good description of integral conversion data was achieved [119]. 

In the first stage of the reaction an alkoxyl anion and the nitrohydrazine cation are formed which afterwards react together to give the corresponding alcohol and nitrohydrazine. Nitrohydrazine reacts with excess hydrazine to produce tetrazene, nitrous acid and di-imid. Then the tetrazene decomposes to form ammonia and nitrogen from di-imid on the other hand tetrazene, hydrazine and nitrogen are formed. Hydrazoic acid and ammonia are then formed as decomposition products of tetrazene. 

No analogous reactions take place with carboxylic acid esters. Cristol and his co-workers [49] therefore suggest that initially an alkoxyl ion is formed and afterwards the corresponding alcohol and nitrate ion are produced ... 

Phosphites are known to act by a preventive mechanism, i.e. preventing the formation of initiating radicals from hydroperoxides by reducing the latter to alcohols, see reaction 4 [20]. In addition to their peroxidolytic activity (PD), sterically hindered aromatic phosphites, e.g. Ultranox U626, act also by chain breaking (CB) mechanism. These phosphites react with the propagating alkylperoxyl (ROO ), reactions 5, and alkoxyl (RO) radicals, reactions... 

The extremely large number of lanolin derivatives has been reviewed by Barnett8 and Steel.16 Lanolin derivatives can be formed by acetylation, ethoxylation, propoxylation, alkoxylation, and isobutylation of hydroxy groups, as well as hydroxylation of the double bond in the sterol ester component. Hydrolysis of lanolin can also produce lanolin alcohols and lanolin acids, which like lanolin can be ethoxylated, acetylated, and hydoxylated. 

Carbonate and carbamate derivatives, prepared from the reaction of alcohols and amines with phosgene and /V-hydroxy-2-thiopyridone, provide the corresponding alkoxyl radicals and aminyl radicals respectively, via radical decarboxylation [71-81]. For example, photolytic treatment of carbamate (57) derived from 4-pentenylamine generates the corresponding 4-pentenylaminyl radical, as shown in eq. 8.24. Under neutral conditions in the presence of tert-BuSH, a direct reduction product (A) of 4-pentenylaminyl radical is formed, while, in acidic conditions, cyclized product (C), pyrrolidine, via 5-exo-trig manner from 4-pentenylaminyl radical is formed. Under the latter conditions, the real reactive species is an electrophilic 4-pentenylaminium radical which rapidly cyclized via 5-exo-trig manner. 

With the slow demise of the nonylphenol ethoxylate market due to legislation, the fatty alcohol market has the chance to design alternatives by subtle changes to the hydrophobe chain lengths and alkoxylate levels. The effects must be achieved with biodegradability as... 

Ruetgers Organics Corp.) Ethoxylated and alkoxylated alcohols... 

The following substances are recommended starting materials for unsaturated polyesters fumaric acid, maleic acid, methacrylic acid, adipic acid, phthalic acid, resi-nic acid, isophthalic acid, terephthalic acid, hydrated or halogenated phthalic acids, aliphatic and substituted aliphatic single and multi-functional alcohols up to C)8, alkoxylated and hydrated phenols and bisphenols, styrene, vinyltoluene, acrylic acid and methacrylic acid esters of the Ci-C4 alcohols, and tricyclodecane dimethanol. 

Reactions of Esters Esters are much more stable than acid chlorides and anhydrides. For example, most esters do not react with water under neutral conditions. They hydrolyze under acidic or basic conditions, however, and an amine can displace the alkoxyl group to form an amide. Lithium aluminum hydride reduces esters to primary alcohols, and Grignard and organolithium reagents add twice to give alcohols (after hydrolysis). 

Besides oxidation reactions, MTO supported on AI2O3/ Si02, niobia, or zeolites also catalyzes the metathesis of functionalized alkenes, 1,2 transposition of allylic alcohols, addition of epoxides to ketones, alkoxylation of epoxides, dehydration and amination of alcohols, and... 

Alcohols containing heterocyclic nuclei, halo, and alkoxyl groups as well as double bonds may be prepared. Without doubt, this is the best general procedure for the formation of the primary alcohol grouping from compounds at the oxidation level of a carboxylic acid. Reductions by this reagent were reviewed in 1951. °°... 

The chlorine atom in furftiryl chloride, like that in benzyl chloride, is very reactive and is readily replaced by the alkoxyl group (80%). On. the other hand, the chlorine atom in tetrahydrofurfuryl chloride is unreactive, so that the corresponding ethers are prepared from the alkali alcoholate and alkyl halides (80%). ... 

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