Oxidative adducts

Furfuryl alcohol is used alone or in combination with other solvents for various cleaning and paint removing operations. The ethylene oxide adduct of furfuryl alcohol is especially useful in this type of appHcation (80—83). 

Since double bonds are no longer present, these compounds are more stable than the corresponding furan derivatives. Tetrahydrofurfuryl alcohol—ethylene oxide adducts [31692-85-0] are also usehil solvents for paint stripping formulations (136,141,143). 2-Methylfuran is a good solvent, but... 

The product secondary alcohols from paraffin oxidation are converted to ethylene oxide adducts (alcohol ethoxylates) which are marketed by Japan Catalytic Chemical and BP Chemicals as SOFTANOL secondary alcohol ethoxylates. Union Carbide Chemical markets ethoxylated derivatives of the materials ia the United States under the TERGlTOL trademark (23). 

Another subclass of substituted amides that is of great commercial value is the ethoxylated amides. They can be synthesized from alkanolamides by chain extending with ethylene or propylene oxide or by ethoxylation directly from the primary amide (46—48). It was originally beheved that the stepwise addition of ethylene oxide (EO) would produce the monoethano1 amide and then the diethanolamide when sufficient ethylene oxide was added (49), but it has been discovered that only one hydrogen of the amide is substituted with ethylene oxide (50—53). As is typical of most ethylene oxide adducts, a wide distribution of polyethylene oxide chain length is seen as more EO is added. A catalyst is necessary to add ethylene oxide or propylene oxide to a primary or an ethoxylated amide or to ethoxylate a diethoxy alkanolamide synthesized from diethanolamine (54). 

TDA-derived polyols are made by alkoxylation. Polypropylene oxide adducts of I DA (14) and TDA-initiated polyether polyols (13,15) are used in rigid polyurethane foams and continue to be included in new formulations (62) as well as older appHcations. 

Typical commercial ethoxylated sorbitan fatty acid esters are yellow Hquids, except tristearates and the 4- and 5-mol ethylene oxide adducts which are light tan soHds. These adducts, as well as the 20-mol adducts of the triesters, are insoluble but dispersible in water. The monoester 20-mol adducts are water soluble. Ethoxylated sorbitan esters are widely used as emulsifiers, antistatic agents, softeners, fiber lubricants, and solubilizers. In combination with the unethoxylated sorbitan esters or with mono- or diglycetides, these are often used as co-emulsrfiers. The ethoxylated sorbitan esters are produced by beating sorbitan esters with ethylene oxide at 130—170°C in the presence of alkaline catalysts. 

Surfactants and Dispersants. Castor od can be transformed from an od- to a water-soluble surfactant, depending on the moles of ethylene oxide added to its hydroxyl group. A 40 mole ethylene oxide adduct of castor od, known as PEG-40 castor od, is a surfactant that has cosolvent properties and is utilized as a fragrance solubilizer (118). Glycol hydroxystearate emulsifiers are formulated into shampoos to impart finer peadescence and give better stabdity than gylcol stearates (118) (see Hair preparation). 

DET-ethylene oxide adduct 20 16 min room temp. reduced 92 minimum irriation —... 

Clear, surface-active phosphate ester compositions were prepared by heating 1 mol P4O,0 with 2-4.5 mol of a linear or branched chain C6, 8 saturated alcohol, a C4 20 mono- or dialkylphenol, or a 2- to 14-mol ethylene oxide adduct of one of these alcohols or alkylphenols at 25-110°C, and hydrolyzing the reaction product at 60-110°C with 0.5-3.0% H20. The hydrolyzed mixture had a lower Klett color value than the phosphorylation reaction mixture [21]. 

Phosphoric acid esters based on alkylene oxide adducts are of great interest. Their properties can be altered by the length and structure of the hydrophobic alkyl chain. But they are also controlled by the kind and length of the hydrophilic alkyleneoxide chain. The latter can easily be tailored by selection between ethylene oxide and propylene oxide and by the degree of alkoxylation. 

Monoester salts of phosphoric acid derived from fatty alcohol ethylene oxide adduct or alkylphenol ethylene oxide adduct useful as surfactants are prepared by addition of R(OCH2CH2) OH, alkali fluoride and (C12P0)20 in a molar ratio of 0.9-1.5 0.05-1 1.0 at -50 to + 10°C and hydrolysis of the Cl-containing intermediates with a base. The monoester phosphates showed comparable or better washing and foaming efficiency than commercial products [12]. 

Whereas nonionic ethylene oxide adducts discolor badly on contact with sodium hydroxide, phosphate derivatives of these nonionics exhibit good color stability even under these conditions. But in the presence of strong acids poly-oxyethylated phosphate esters undergo hydrolysis to the base nonionic and phosphoric acid. However, the free surface-active acids by themselves show little tendency to hydrolyze. They have a pH value of 2 in aqueous solution. 

Ethylene oxide adducts of alkanephosphonic acids exhibit a better solubility in water and partly an interesting depression of the surface tension in aqueous solutions (Table 9). Although foamability and wetting rate lie in a medium range, they possess no emulsifying ability. 

Rosenfeld, M.E., Palinski, W., Yla-Herttuala, S., Butler, S. and Witztum, J.L. (1990). Distribution of oxidation-specific lipid oxidation adducts and apo lipoprotein B in atherosclerotic lesions of varying severity from WHHL rabbits. Arteriosclerosis 10, 336-349. 

Sojka, Z., Che, M. and Giamello, E. (1997) EPR investigation of the electronic structure of mononuclear copper(I) nitric oxide adduct formed upon low-pressure adsorption of NO onto Cu/ZSM-5 zeolite, J. Phys. Chem. B, 101, 4831. 

A radical initiator based on the oxidation adduct of an alkyl-9-BBN (47) has been utilized to produce poly(methylmethacrylate) (48) (Fig. 31) from methylmethacrylate monomer by a living anionic polymerization route that does not require the mediation of a metal catalyst. The relatively broad molecular weight distribution (PDI = (MJM ) 2.5) compared with those in living anionic polymerization cases was attributed to the slow initiation of the polymerization.69 A similar radical polymerization route aided by 47 was utilized in the synthesis of functionalized syndiotactic polystyrene (PS) polymers by the copolymerization of styrene.70 The borane groups in the functionalized syndiotactic polystyrenes were transformed into free-radical initiators for the in situ free-radical graft polymerization to prepare s-PS-g-PMMA graft copolymers. 

Figure 31 The radical initiator (47) based on the oxidation adduct of an alkyl-9-BBN used for the production of poly(methyhnethacrylate) (48) from methylmethacrylate monomer by the radical polymerization route. (Adapted from ref. 69.)...

Triols. One triol used was the propylene oxide adduct of 1,2,6-hexanetriol, designated LHT-240 and supplied by Union Carbide Chemicals Company. After degassing, its hydroxyl, unsaturation, and water contents were 4.31 meq/g, <0.01 meq/g, and 0.004%, respectively. Thus, the material was essentially trifunctional, and its number average molecular weight was 696. If the unsaturation was exactly 0.01 meq/g, then the number-average functionality was 2.99. 

Asymmetric induction by metalloporphyrin is affected not only by the structure of the ligand, but also by other factors the nature of the metal center, the oxidant used, and the donor ligand added.62,63 As shown in Figure 1, oxo-metalloporphyrins have been considered to be the active species in metalloporphyrin-catalyzed oxidation. In some oxidations, however, metal-oxidant adducts have been suggested as the real active species. 

Electroactive 3-(N-phenylpyrazolyl)fullereno[l,2-r/]isoxazolines have been synthesized by using 1,3-dipolar cycloaddition of pyrazole nitrile oxides, generated in situ, to Cgo at elevated temperature or microwave irradiation. The cyclic voltammetry measurements show a strong donor pyrazole ring, and a better acceptor ability of the fullerene moiety than the parent C60 (538). Treating fullerene Cgo with mesitonitrile oxide in toluene gives fullerene-nitrile oxide adduct, which is supposed to be useful for electrical and optical components (539). 

Aulbach M, Ter Meer HU. Preparation of fullerene-nitrile oxide adducts, Ger. Pat. 4240042 1994. [Chem. Abstr. 1995 122 31507],... 

The activation parameters AS" and for formation and dissociation of the nitric oxide adduct of cobalamin... 

A SET process has been postulated between Rh(III) oxidative adducts and an NAD(P)H model compound (cf. Section 18.2.4) [91]. Oxidative adducts formed by Sn2, SNAr, or inner-sphere SET pathways may produce radicals by homolytic M-C bond cleavage [130, 155, 176, 199]. 

Nonionic surfactants contain (Fig. 23) no ionic functionalities, as their name implies, and include ethylene oxide adducts (EOA) of alkylphenols and fatty alcohols. Production of detergent chain-length fatty alcohols from both natural and petrochemical precursors has now increased with the usage of alkylphenol ethoxylates (APEO) for some applications. This is environmentally less acceptable because of the slower rate of biodegradation and concern regarding the toxicity of phenolic residues [342]. 

K. Yeowell O Connell, W. Pauwels, M. Seven, Z. L. Jin, M. R. Walker, S. M. Rappa-port, H. Veulemans, Comparison of Styrene-7,8-oxide Adducts Formed via Reaction with Cysteine, N-Terminal Valine and Carboxylic Acid Residues in Human, Mouse and Rat Hemoglobin , Chem.-Biol. Interact. 1997, 106, 67 - 85. 

A proposed mechanism for the SiCaT reaction using the 1,6,11-triyne system as an example is illustrated in Scheme 7.21. The reaction proceeds through insertion of one of the terminal alkynes into the Si-[Rh] bond of the hydrosilane-[Rh] oxidative adduct, generating an ethenyl-[Rh] intermediate, which undergoes addition to the second and third alkyne moieties to form intermediate III.2a. Subsequent carbocyclization followed by /9-hydride elimination gives the tricyclic silylbenzene derivative 70. Alternatively, ethenyl-[Rh] intermediate can be isomerized to the thermodynamically more... 

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