Alkoxylated alkyl alcohol

Both packed-column SFC [42,68] and capillary SFC [37,65,69] have been successfully used for analysing polyethers and polyglycols. Chester [69] employed a 9m x 100/tm BP-10 (0.1 um dp) capillary column with CO2 and an FID for analysing Triton XI00 and Neodol 23-65 surfactants. Later et al [7] have also reported SFC separations of an alkoxylated alkyl alcohol at 160°C with CO2 and an FID. The average molecular mass of this polyether was approximately 1800. The mobile phase was pressure-programmed from 100 atm to 165 atm at 40 atm min " after a 10-minute hold time, and then from 267 atm to 320 atm at 2 atm min "L... 

Complex 3c, a catalytic precursor for addition reactions to alkynes (65), reacts at room temperature with a variety of terminal alkynes in alcohols to produce stable alkoxyl alkyl carbene ruthenium(II) derivatives 109 in good yields (Scheme 7). Reaction of 3c (L = PMe3), with trimethylsilyacetylene in methanol gives the carbene ruthenium complex 110, by protonolysis of the C—Si bond, whereas with 4-hydroxy-l-butyne in methanol the cyclic carbene complex 111 is obtained (65,66). 

Chem. Descrip. Alkoxylated primary alcohol, alkyl capped Ionic Nature Nonlonic... 

Propoxylates, ethoxylates, and mixed alkoxylates of aUphatic alcohols or alkyl phenols are sulfated for use in specialty appHcations. 

Alkoxyl tion. The nucleophilic replacement of an aromatic halogen atom by an alkoxy group is an important process, especially for production of methoxy-containing iatermediates. Alkoxylation is preferred to alkylation of the phenol wherever possible, and typically iavolves the iateraction of a chloro compound, activated by a nitro group, with the appropriate alcohol ia the presence of alkaU. Careful control of alkaU concentration and temperature are essential, and formation of by-product azoxy compounds is avoided by passiag air through the reaction mixture (21). 

Aromatic ethers and furans undergo alkoxylation by addition upon electrolysis in an alcohol containing a suitable electrolyte.Other compounds such as aromatic hydrocarbons, alkenes, A -alkyl amides, and ethers lead to alkoxylated products by substitution. Two mechanisms for these electrochemical alkoxylations are currently discussed. The first one consists of direct oxidation of the substrate to give the radical cation which reacts with the alcohol, followed by reoxidation of the intermediate radical and either alcoholysis or elimination of a proton to the final product. In the second mechanism the primary step is the oxidation of the alcoholate to give an alkoxyl radical which then reacts with the substrate, the consequent steps then being the same as above. The formation of quinone acetals in particular seems to proceed via the second mechanism. ... 

Dichloro-s-triazine and its 6-alkyl analogs are as easily hydrolyzed by water as trichloro-s-triazine and, on suspension in aqueous ammonia (25°, 16 hr), the first is diaminated in good yield. 2,4-Bistrichloromethyl-6-methyl- and -6-phenyl-s-triazines (321) require a special procedure for mono-alkoxylation (0-20°, 16 hr, alcoholic triethylamine) disubstitution occurs at reflux temperature (8 hr). Aqueous triethylamine (100°, 3 hr) causes complete hydroxy-lation of 2,4,6-tris-trichloromethyl-s-triazine which can be mono-substituted with ammonia, methylamine, or phenoxide ion at 20°. 

Ether carboxylates are used not only in powdered detergents but in liquid laundry detergents for their hard water stability, lime soap dispersibility, and electrolyte stability they improve the suspension stability and rheology of the electrolyte builder [130,131]. Formulations based particularly on lauryl ether carboxylate + 4.5 EO combined with fatty acid salt and other anionic surfactants are described [132], sometimes in combination with quaternary compounds as softeners [133,163]. Ether carboxylates show improved cleaning properties as suds-controlling agents in formulations with ethoxylated alkylphenol or fatty alcohol, alkyl phosphate esters or alkoxylate phosphate esters, and water-soluble builders [134]. 

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. 

The copolymers may be mixed with other demulsifiers, in particular with alkoxylated novolaks and copolymers that are obtainable by copolymerization of one or more polyoxyalkylene ethers of allyl or methallyl alcohol with vinyl esters of alkyl monocarboxylic acids. 

Figure 17.2 Lipid peroxidation scheme. LH, a polyunsaturated fatty acid LOOM, lipid hydroperoxide LOH, lipid alcohol L, lipid radical LOO, lipid hydroperoxyl radical LO, lipid alkoxyl radical. Initiation the LH hydrogen is abstracted by reactive oxygen (e.g. lipid alkyl radical, lipid alkoxy radical, lipid hydroperoxyl radical, hydroxy radical, etc.) to produce a new lipid alkyl radical, L. Propagation the lipid alkyl, alkoxyl or hydroperoxyl radical abstracts hydrogen from the neighbouring LH to generate a new L radical.

In addition to /3-H elimination, olefin insertion, and protonolysis, the cr-metal intermediate has also proved to be capable of undergoing a reductive elimination to bring about an alkylative alkoxylation. Under Pd catalysis, the reaction of 4-alkenols with aryl halides affords aryl-substituted THF rings instead of the aryl ethers that would be produced by a simple cross-coupling mechanism (Equation (126)).452 It has been suggested that G-O bond formation occurs in this case by yy/z-insertion of a coordinated alcohol rather than anti-attack onto a 7r-alkene complex.453... 

Brown and Suzuki have shown that treatment of trialkylboranes with ethenyl-(Scheme 42, Eq. 42a) and ethynyloxiranes (Scheme 42, Eq. 42b) in the presence of a catalytic amount of oxygen, affords the corresponding allylic or allenic alcohols. The mechanism may involve the addition of alkyl radicals to the unsaturated system leading to l-(oxiranyl)alkyl and l-(oxiranyl)alkenyl radicals followed by rapid fragmentation to give alkoxyl radicals that finally complete the chain process by reacting with the trialkylborane [104-106]. 

It is worth mentioning that in a few cases the (3-elimination of the silyl radical from the a-silyl alkoxyl radical (47) with the formation of corresponding carbonyl derivative was observed [63,64]. Evidently the fate of a-silyl alkoxyl radical depends on the method of radical generation and/or the nature of the substrate. Two examples that delineate the potentialities of this rearrangements are reported in Reactions (5.33) and (5.34). In the former, the 5-exo cyclization of secondary alkyl radical on the carbonyl moiety followed by the radical Brook rearrangement afforded the cyclopentyl silyl ether [65], whereas Reaction (5.34) shows the treatment of an a-silyl alcohol with lead tetracetate to afford the mixed acetyl silyl acetal under mild conditions [63]. 

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. 

Linear ethoxylates are tine preferred raw materials for production of ether sulfates used in detergent formulations because of uniformity, high purity, and biodegradahility, The alkyl chain is usually in the C y. to Cy range having a molar ethylene oxide alcohol ratio of anywhere from 1 1 to 7 1. Propoxylates, ethoxylates, and mixed alkoxylates of aliphatic alcohols or alkyl phenols are sulfated for use in specialty applications. 

If alkyl or aryl radicals at the silicon atom should be replaced with alkoxyl or aroxyl, tetraethoxysilane is re-etherified with triethanolamine in the presence of alcohols or phenols. 

Dialkylaminomethyl alkyl (and aryl) sulfides result from the treatment of a-halogeno-amines with mercaptans (thiophenols).325 Dehydrogenation of amino-alcohols with mercuric acetate182,328 is accompanied by the intramolecular nucleophilic addition of the alkoxyl group when formation of a five- or six-membered ring is possible, e.g. ... 

Instead of alkyl nitrite, other alkoxyl radical precursors such as ROOH, ROOR, ROI, ROC1, etc. can also be used for the same type of reaction. The high reactivity of these compounds comes from the weak bond dissociation energies in O-O, 0-1, and O-Cl bonds. Another simple method is as follows. Photolytical treatment of alcohol (5) with NIS (AModosuccinimide) provides the tetrahydrofuran skeleton (6), through the formation of alkyl hypoiodite (ROI), homolytic cleavage of the 0-1 bond to form an alkoxyl radical, 1,5-H shift to form a carbon-centered radical, reaction with ROI to form 8-iodoalcohol, and finally ionic cyclization to form a tetrahydrofuran skeleton, together... 

Syntheses of alkyl phenyl ethers, C,H, OR, are carried out by refluxing aqueous or alcoholic solutions of alkali phenolates with alkyl halides the yields vary with the nature of the alkyl halides (40-80%). The reactive halogen in benzyl halides is easily replaced by an alkoxyl group (95%). ° The choice of a solvent is sometimes important. Thus, in the preparation of the alkyl ethers of o- and p-hydroxybiphenyl from a mixttire of the phenol, alkyl halide, and powdered potassium hydroxide, high yields are obtained using acetone as a solvent, whereas, with alcohol as solvent, only small yields are obtained. Triarylmethyl chlorides react with alcohols directly (97%). ... 

---