Alcohols and Glycols

Ktj era [55] has separated several diols on alumina layers. He used layers impregnated with 3% ammonium borate solution in order to separate the 1,2-diols from other glycols. Silver nitrate solution was used for visuahsation. TLC-separation of stereoisomeric diols also has been achieved by Fischer and Koch [30] on layers of fibrous alumina. 

The terpene- and sesquiterpene alcohols, used as food flavouring agents in the food industry, are treated in Chapter J on p. 225 and the sugar alcohols in Chapter X. 

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The catalyst, which may be regarded as complementary to Raney nickel (Section VI,5) is largely used for the hydrogenation of esters (esters of monobasic and of dibasic acids to alcohols and glycols respectively) ... 

Table 5 Hsts the principal commercially available acetylenic alcohols and glycols Tables 6 and 7 Hst the physical properties of acetylenic alcohols and glycols, respectively.

Table 5. Commercial Secondary and Tertiary Acetylenic Alcohols and Glycols...

Economic Aspects. A number of secondary and tertiary acetylenic alcohols and glycols are manufactured by Air Products and Chemicals Co. In 1990, U.S. bulk prices of ethyloctynol, methylbutynol, and tetramethyldecynediol were about 8.35/kg, 3.95/kg, and 8.00/kg, respectively. 

Sulfonamide groups can be introduced into phthalocyanines to make them soluble in alcohols and glycol ethers. Their main appHcations are transparent paints, flexo and gravure printing inks, wood stains, plastics, and ballpoint inks. This includes products Hke Solvent Blue 24 (Cl 74380),... 

The nitrous oxide merely suppresses reduction of ferricyanide by by converting the latter to 0 . For a number of alcohols and glycols and also polyethylene oxide of molecular weight 200-2 x lO, the values of A (R +ferricyanide) fall in the range 2-5 x 10 l.mole sec ... 

Although expansion and drainage are still increasing together, it can be easily seen that the polymer-stabilized foam has a drainage far below that of the typical foam (each with the same basic formulation) shown in Table III. The foam base is an alkoxy/1 inear alkyl sulfate, fatty alcohol, and glycol/glycol ether mixture, as outlined in Table VII. 

Boisselle, A.P. and Meinhardt, N.A., Acetylene-allene rearrangement reactions of trivalent phosphorus chlorides with a-acetylenic alcohols and glycols,. Org. Chem., 27, 1828, 1962. 

Apart from nitrobenzene, trichlorobenzene in particular was the preferred solvent up until a few years ago. It has now been replaced by other solvents such as high-boiling hydrocarbons (kerosene, naphthalene) and also alcohols and glycols, because traces of polychlorinated biphenyls may be formed. These are not easily degradable. With hydrocarbons, however, the possibility of fire and explosion must be considered in designing suitable production units. 

Nitronium tetrafluoroborate is a very efficient reagent for the D-nitration of alcohols and glycols containing both primary and secondary hydroxy functionality (Equation 3.7). Yields of nitrate ester are high and frequently quantitative. 0-Nitration with nitronium salts produces a strong acid and so an acid-binding agent should be present for acid sensitive substrates. 

Various alcohols and glycols can be used as antifreezes and are effective freeze point depressants for water. However, because glycols raise the boiling point of water while alcohols lower it, only glycol bases are recommended for use by engine manufacturers. 

The hexitols form the typical derivatives of alcohols and glycols— esters, ethers, acetals and ketals, and metallic complexes. Because of the multiplicity of reactive groups and because of stereoisomerism, the number of theoretically possible derivatives of a given type is enormous. For example, D-mannitol on reacting with a mono reagent such as an etherifying agent or an acid, can form 35 different compounds ... 

Colorless monoclinic crystals hygroscopic decomposes slowly in moist air density 1.67 g/cm at 17°C melts at 151°C (decomposes) highly soluble in water (84g/100g at 20°C) soluble in lower alcohols and glycols pH of 0.1 molar solution 3.4. 

FORMAMIDE. Form amide (meibanamide), HCONHi. is the lirsi member of the primary amide series and is the only one liquid at room temperature. II is hygroscopic and has a faint odor of ammonia. Formamide is a colorless to pale yellowish liquid, freely miscible with water, lower alcohols and glycols, and lower esters and acetone. It is virtually immiscible in almost all aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, and ethers. By virtue of its high dielectric constant, close to that of water and unusual for an organic compound, formamide has a high solvent capacity lor many heavy-metal salts and for salts of alkali and alkalinc-carth metals. It is an important solvent, in particular for resins and plasticizers. As a chemical intermediate, formamide is especially useful in the synthesis of heterocyclic compounds, pharmaceuticals, crop protection agents, pesticides, and for the manufacture of hydrocyanic acid. 

Harris et al. (15) carried out similar hydrogenations in aqueous and 1% alkaline media over Raney nickel for 6-10 hours at 225°-250°C. and 1500-2500 p.s.i.g. hydrogen pressure the products were identical with those found in dioxane. In 1941 lignin from soda black liquors was hydrogenated over copper chromite in dioxane at 250°-300°C., and colorless saturated products were obtained (/). Cyclohexane and four alkylcyclo-hexanes were detected, but the major part of the lignin was converted to alcohols and glycols related to polycyclic hydrocarbons of 20-70 (or more) carbon atoms. 

Similarly, the last two variables in the above list (volume/density and phase amounts) are difficult to measure with commonly available instruments. As a result, hydrate phase equilibria are normally determined in terms of four variables (1) pressure, (2) temperature, (3) water-free hydrocarbon phase composition, and (4) the free-water phase composition (excluding hydrocarbons but including salts, alcohols, and glycols). 

Small alcohols and glycol ethers (3-5 C s) as synergists for VC polymers... 

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