Of ethanediol

Ueberreiter and Hager19 rather surprisingly found an overall reaction order of 6 at the beginning of ethanediol esterification. They explained this with the existence of hydrogen-bonded dimers. 

Fig. 3. Long range and one-bond carbon-13 satellite spectrum of a 5% w/w solution of ethanediol in D2O at 94°C. 16 transients were measured on a Varian Associates Unity 500 spectrometer using the sequence of fig. 1, with 2.5 s presaturation, a t value of 100 ms, spin lock pulses of 450 ps, no homospoil pulse, and no homodecoupling during acquisition.

Warren and Malec [80] determined nitriloacetic acid and related amino polycarboxylic acids (iminodiacetic acid, glycine and sarcosine in inland waters and sewage effluents by converting to the butyl or A-trifluoracetyl esters followed by chromatography on dual glass U-shaped columns (1.9mx2mm) packed with 0.65% of ethanediol adipate on acid-... 

Taylor pointed out that the kinetics observed for the oxidation of ethanediol are equally consistent with a mechanism involving the direct formation of the products, and an inactive diol-periodate ester, C, in equilibrium with the reactants, viz. 

Ethylene acetal formation from a 4-hydroxy-4-en-3-one (191) gave the 3,5-dieno[3,4-fo]-dioxan (192), as well as the expected 3,3-ethylenedioxy-4-ketone (193). The abnormal product (192) was also obtained from the 4 6,5jS-epoxy-3-ketone (194). Similar reactions, using 2-hydroxyethanethiol instead of ethanediol. 

Alkene isomerization. Homoallylic alcohols are converted to allylic alcohols, and in the presence of ethanediol, monoethers are obtained. ... 

Aryl ethyl ethers are deethylated selectively without affecting aryl methyl ethers on exposure to microwaves in the presence of r-BuOK and 18-crown-6. An interesting reversal of selectivity by the addition of ethanediol is also noted. ... 

As mentioned in CHEC-I, the standard method for formation of l,3-dioxolane-2-thione (28) is reaction of ethanediol with thiophosgene, but other methods include the reaction of (289) with CSj to give (291) as described above, and reaction of diols (293) with base and CS2 followed by Mel which gives the thiones corresponding to (294) in addition to bis(dithiocarbonates) (230) <78S286>. 

The 2-imino-l,3-dioxolanes such as (301) may be prepared either from the cyclic tin compound (300) and PhNCS (Equation (47)) <77BCJ3271> or from PhN=CCl2 and the disodium salt of ethanediol <61CB3287>. 

Figure 2. Spectral changes associated with electron reduction of metmyoglobin in an ethanediol-water glass at —150°C. Glass was formed from an equimolar mixture of ethanediol and water containing 1 g/liter of metMh, irradiated to approximately 8 kGy at —196°C, and exposed to visible light to bleach the trapped electrons at —150°C. Solid curve corresponds to the unirradiated system dotted curve, which is displaced vertically for clarity, corresponds to the final spectrum. Change of scale is indicated by the +1 designation.

Ciernik and Mistr (66CCC4669) (Scheme 113) studied the addition of bispyrazol-3-one derivatives 367a onto salts of heterocyclic quaternary bases 368a and determined that the elimination of ethanediol, A--pheny 1 acetam ide or aniline provided bispyrazol-3-ones 369a. The reactions were performed in refluxing ethanol containing triethylamine. The yield was moderate. 

The enzymes cellulase, mannanase, and aryl-/ -glucosidase showed no significant decrease in activity as determined in the presence of up to 60% of ethanediol. Xylanase, / -glucosidase, and mannosidase lost approximately half of their initial activity at this ethanediol concentration while xylosidase lost most of its activity. The inhibition caused by ethanediol was found to be reversible. 

Cyclic sulfites and cyclic sulfates of ethanediol undergo hydrolysis with acids to furnish glycol. The substituted cyclic sulfate, such as tetramethyl-1,3,2-dioxathiolane 2-dioxide, may undergo a pinacol type of rearrangement under acidic conditions to furnish pinacolone in good yield (74JOC3415). The mechanistic pathway is rationalized in Scheme 17. 

Mono- and di-esters of ethanediol (ethylene glycol) - especially the stearates - are used in cosmetics such as emulsion shampoos and foam bath products as opacifiers and pearlescent agents. 

The [Co(III)Mo602i] ion oxidation of ethanediol to HCHO in H2SO4-H2O was first order in oxidant and substrate. The rate acceleration by H+ ion was attributed... 

Esters of long-chain fatty acids with ethanediol and other diols occur in beef lung [22], beef suet and pig lard [22] and in rat liver [12], Diesters, ether esters and dialkyl ethers of ethanediol cannot be separated from the corresponding glycerol derivatives through adsorption TLC but this separation succeeds with reversed phase partition TLC [9]. 

Hg(II) in these media, can oxidize the lower hydrocarbons, but with poor selectivity owing to the formation of free radicals. Hashiguchi et al. (2014) describe the successful oxidation of methane, ethane, and propane in trifluoro-acetic acid to trifluoroacetate esters, using thallium (III) and lead (IV) trifluoro-acetates. Yields of the esters were better than 75% in most cases. The products from ethane oxidation typically consisted of the ethyl ester and the diester of ethanediol in about 3 1 ratio. From propane the main product was the ester of 2-propanol. 

The so-called triglycerides of starfish contain 35% of the monoacyl monoalkyl (or monoalk-l -enyl) derivatives of ethanediol. It is considered that the fatty tissues in the melon and jaw oils of dolphins, porpoises, and toothed whales may play a major role in the echolocation system of these animals. Litchfield et al. have examined the melon oil and blubber of the Beluga whales, and report that the former remains clear at temperatures well below 0 °C, a property which is related to its unusual triglyceride composition. 

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