Derivatives alcohols

Aromatic alcohols (derivatives of carblnol HCHjOH) may be prepared (compare AltpAaltc Alcohols, discussion preceding Section 111,14) ... 

The most stable protected alcohol derivatives are the methyl ethers. These are often employed in carbohydrate chemistry and can be made with dimethyl sulfate in the presence of aqueous sodium or barium hydroxides in DMF or DMSO. Simple ethers may be cleaved by treatment with BCI3 or BBr, but generally methyl ethers are too stable to be used for routine protection of alcohols. They are more useful as volatile derivatives in gas-chromatographic and mass-spectrometric analyses. So the most labile (trimethylsilyl ether) and the most stable (methyl ether) alcohol derivatives are useful in analysis, but in synthesis they can be used only in exceptional cases. In synthesis, easily accessible intermediates of medium stability are most helpful. 

Most manufacturers sell a portion of their alcohol product on the merchant market, retaining a portion for internal use, typically for the manufacture of plasticizers. Sterling Chemicals linear alcohol of 7, 9, and 11 carbons is all used captively. Plasticizer range linear alcohols derived from natural fats and oils, for instance, octanol and decanol derived from coconut oil and 2-octanol derived from castor oil, are of only minor importance in the marketplace. 

Capacity Limitations and Biofuels Markets. Large biofuels markets exist (130—133), eg, production of fermentation ethanol for use as a gasoline extender (see Alcohol fuels). Even with existing (1987) and planned additions to ethanol plant capacities, less than 10% of gasoline sales could be satisfied with ethanol—gasoline blends of 10 vol % ethanol the maximum volumetric displacement of gasoline possible is about 1%. The same condition apphes to methanol and alcohol derivatives, ie, methyl-/-butyl ether [1634-04-4] and ethyl-/-butyl ether. 

Alkoxides. Zirconium alkoxides are part of a family of alcohol-derived compounds (219). The binary zirconium compounds have the general formula ZRX — (OR). They are easily hydrolyzed and must be prepared under anhydrous conditions. They are prepared by the reaction of zirconium tetrahahdes and alcohols ... 

Bromomethyl-5-methylthiophene gives normal displacement products with amines but it is isomerized on attempted reaction with copper(I) cyanide (Scheme 59) 48MI30200. Whereas 2-hydroxymethylthiophene reacts normally with hydrogen halides to give 2-halomethylthiophenes, reaction of 2-hydroxymethylfuran (2-furfuryl alcohol) with hydrochloric acid results in formation of laevulinic acid (151). 2-Furfuryl alcohol derivatives are... 

Ethanol water is a solution of denatured grain alcohol. Its main advantage is that it is nontoxic and thus is widely used in the food and chemic industry. By using corrosion inhibitors it could be made non-corrosive for brine service. It is more expensive than methanol water and has somewhat lower heat transfer coefficients. As an alcohol derivate it is flammable. 

The dibenzosuberyl ether is prepared from an alcohol and the suberyl chloride in the presence of triethylamine (CH2CI2, 20°, 3 h, 75% yield). It is cleaved by acidic hydrolysis (1 N HCl/dioxane, 20°, 6 h, 80% yield). This group has also been used to protect amines, thiols, and carboxylic acids. The alcohol derivative can be cleaved in the presence of a dibenzosuberylamine. ... 

The second phase in resole formation is reaction of the activated phenol with the aldehyde to form the phenol alcohol derivative. When the aldehyde is formaldehyde, the derivative is a hydroxymethyl phenol and the process is known as methylolation. Scheme 2 illustrates this reaction. Since resoles are usually made with excess aldehyde, more than one substitution may be made on the ring. When the reactants are phenol and formaldehyde, up to three methylol groups may be substituted. This reaction has been extensively studied and the rates of... 

Phenol An organic compound that is an alcohol derivative of benzene. 

Other examples of the successful displacement of tosylates are the preparation of 31 -, 16a-,16j - and27- labeled steroids. This displacement reaction fails, however, with certain C-18 and C-19 alcohol derivatives which give mainly O—S instead of C—O bond cleavage. Unsatisfactory results were also obtained with sterically hindered tosylate esters at C-11, C-12 and C-20, which give considerable amounts of olefinic products in addition to O—S bond cleavage. ... 

Although such alkoxides have never been isolated it is assumed that with bulky alcohols such as steroidal alcohols, the main contributing structure in such an equilibrium (especially when excess lead tetraacetate is present) is the one in which n = 1. An advantage of this procedure held in common with the hypoiodite reaction is the fact that the alcohol derivative is formed in situ. Intermolecular hydrogen abstraction e.g., reaction with solvent)... 

During attempted acetonide formation of an amino alcohol derivative, smooth tosyl cleavage was observed. The reaction is general for those cases having a carboxyl group, as in the following example, but fails for simple amino alcohol derivatives that lack this functionality. ... 

Chiral boron(III) complexes can catalyze the cycloaddition reaction of glyoxy-lates with Danishefsky s diene (Scheme 4.18) [27]. Two classes of chiral boron catalyst were tested, the / -amino alcohol-derived complex 18 and bis-sulfonamide complexes. The former catalyst gave the best results for the reaction of methyl glyoxylate 4b with diene 2a the cycloaddition product 6b was isolated in 69% yield and 94% ee, while the chiral bis-sulfonamide boron complex resulted in only... 

Bepridil (59) blocks the slow calcium channel and serves as an antianginal agent and a vasodilator. In its synthesis, alcohol (derived from epichlorohydrin) is converted to the corresponding chloride with thionyl chloride and displaced with the sodium salt of ]i-benzylaniline to give bepridil (59) °... 

Tetrahydroimidazo[5,l-c][l,2,4]triazine 474 was prepared (79KGS1540) by treating imidazole derivatives 472 or 473 with hydrazine. Compound 473 was obtained by reaction of the respective imidazole with 1,2-dibromoethane or by the reaction of the alcohol derivative 471 with phosphorus tribromide. On the other hand, chlorination of471 with thionyl chloride gave 472 (Scheme 100). 

Scheme 8.45 Suzuki-Tsuchihashi rearrangement of epoxy alcohol derivatives.

Alcohol derivatives of saturated cyclic hydrocarbons Steroid alcohols (e.g., cholesterol)... 

Rate expression. The oxidation of SOj- to SO4- by molecular oxygen is catalyzed by traces of Cu2+ and inhibited by small amounts of alcohols. Derive the expression for -d[SO ]/dt by making the usual approximations, assuming the following mechanism ... 

Fatty alcohols were sulfated with concentrated sulfuric acid before World War II, most frequently involving oleyl alcohols or alcohols derived from sperm and whale oil. Low temperatures were often suggested. Oleyl alcohol was sulfated by adding the alcohol to concentrated sulfuric acid, precooled to a temperature only slightly above the melting point of the alcohol [19], or by addition of cooled sulfuric acid (<95.12%) mixed with diethyl ether and phosphorus pentoxide to the alcohol, under constant stirring, for 3 h at 6-7°C, giving a yield of 98% [20]. Oleyl alcohol was also sulfated either by sulfuric acid or by oleum at 15°C [21]. 

It should be noted that sulfation of alcohols and alcohol derivatives with chlorosulfonic acid is the most suitable and most widely used method in batch laboratory sulfation as well as when samples for physicochemical studies are required. This method provides a comparatively simple procedure for sulfation of small samples. 

Branched dodecyl alcohol derived from the oxidation of branched olefins from petroleum feedstocks. 

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