Ketones, volatile

An alternative method of working up the distillate, which has its advantages when dealing with volatile ketones or when it is suspected that conversion into the ketone is incomplete, is to treat the combined ketones with sodium hydroxide pellets until the mixture is alkaline. Should solids separate, these may be dissolved by the addition of a little water. The ketone is then separated, dried over anhydrous potassium carbonate, and fractionated. 

Unsaturated hydrocarbons are present in nearly all products of the Clemmensen reduction of aromatic ketones and must be removed, if the hydrocarbon is requiral pure, by the above process. Secondary alcohols, often produced m small amount are not appreciably steam-volatile. 

The ester and catalj st are usually employed in equimoleciilar amounts. With R =CjHs (phenyl propionate), the products are o- and p-propiophenol with R = CH3 (phenyl acetate), o- and p-hydroxyacetophenone are formed. The nature of the product is influenced by the structure of the ester, by the temperature, the solvent and the amount of aluminium chloride used generally, low reaction temperatures favour the formation of p-hydroxy ketones. It is usually possible to separate the two hydroxy ketones by fractional distillation under diminished pressure through an efficient fractionating column or by steam distillation the ortho compounds, being chelated, are more volatile in steam It may be mentioned that Clemmensen reduction (compare Section IV,6) of the hj droxy ketones affords an excellent route to the substituted phenols. 

The following are examples of the above procedure. A mixture of diethylamine and re-butyl alcohol may be separated by adding sufficient dilute sulphuric acid to neutralise the base steam distillation will remove the alcohol. The amine can be recovered by adding sodium hydroxide to the residue and repeating the distillation. A mixture of diethyl ketone and acetic acid may be treated with sufficient dilute sodium hydroxide solution to transform the acid into sodium acetate and distilling the aqueous mixture. The ketone will pass over in the steam and the non-volatile, stable salt will remain in the flask. Acidification with dilute sulphuric acid hberates acetic acid, which can be isolated by steam distillation or by extraction. 

Kinetic measurements were performed employii UV-vis spectroscopy (Perkin Elmer "K2, X5 or 12 spectrophotometer) using quartz cuvettes of 1 cm pathlength at 25 0.1 C. Second-order rate constants of the reaction of methyl vinyl ketone (4.8) with cyclopentadiene (4.6) were determined from the pseudo-first-order rate constants obtained by followirg the absorption of 4.6 at 253-260 nm in the presence of an excess of 4.8. Typical concentrations were [4.8] = 18 mM and [4.6] = 0.1 mM. In order to ensure rapid dissolution of 4.6, this compound was added from a stock solution of 5.0 )j1 in 2.00 g of 1-propanol. In order to prevent evaporation of the extremely volatile 4.6, the cuvettes were filled almost completely and sealed carefully. The water used for the experiments with MeReOj was degassed by purging with argon for 0.5 hours prior to the measurements. All rate constants were reproducible to within 3%. 

Many esters occur naturally Those of low molecular weight are fairly volatile and many have pleasing odors Esters often form a significant fraction of the fragrant oil of fruits and flowers The aroma of oranges for example contains 30 different esters along with 10 carboxylic acids 34 alcohols 34 aldehydes and ketones and 36 hydrocarbons... 

Emulsives are solutions of toxicant in water-immiscible organic solvents, commonly at 15 ndash 50%, with a few percent of surface-active agent to promote emulsification, wetting, and spreading. The choice of solvent is predicated upon solvency, safety to plants and animals, volatility, flammabiUty, compatibihty, odor, and cost. The most commonly used solvents are kerosene, xylenes and related petroleum fractions, methyl isobutyl ketone, and amyl acetate. Water emulsion sprays from such emulsive concentrates are widely used in plant protection and for household insect control. 

Many mercury compounds are labile and easily decomposed by light, heat, and reducing agents. In the presence of organic compounds of weak reducing activity, such as amines (qv), aldehydes (qv), and ketones (qv), compounds of lower oxidation state and mercury metal are often formed. Only a few mercury compounds, eg, mercuric bromide/77< 5 7-/7, mercurous chloride, mercuric s A ide[1344-48-5] and mercurous iodide [15385-57-6] are volatile and capable of purification by sublimation. This innate lack of stabiUty in mercury compounds makes the recovery of mercury from various wastes that accumulate with the production of compounds of economic and commercial importance relatively easy (see Recycling). 

In the wood rosin process, rosin is isolated from aged pine stumps that have been left in fields cleared for farming or lumbering operations. The stumps are cut and shredded to pieces the size of matchsticks. The wood chips are then extracted with an appropriate solvent, eg, aUphatic or aromatic petroleum hydrocarbons or ketones. The extract is fractionally separated into nonvolatile cmde rosin, volatile extractibles, and recovered solvent. The dark rosin is usually refined further to lighter-colored products using selective solvents or absorption. 

Volatiles or Aroma. The essential oil, or aroma, of tea provides much of the pleasing flavor and scent of green and black tea beverages. Despite this, volatile components comprise only - 1% of the total mass of the tea leaves and tea infusions. Black tea aroma contains over 300 characterizing compounds, the most important of which are terpenes, terpene alcohols, lactones, ketones, esters, and spiro compounds (30). The mechanisms for the formation of these important tea compounds are not fully understood. The respective chemistries of the aroma constituents of tea have been reviewed... 

Ketones are more stable to oxidation than aldehydes and can be purified from oxidisable impurities by refluxing with potassium permanganate until the colour persists, followed by shaking with sodium carbonate (to remove acidic impurities) and distilling. Traces of water can be removed with type 4A Linde molecular sieves. Ketones which are solids can be purified by crystallisation from alcohol, toluene, or petroleum ether, and are usually sufficiently volatile for sublimation in vacuum. Ketones can be further purified via their bisulfite, semicarbazone or oxime derivatives (vide supra). The bisulfite addition compounds are formed only by aldehydes and methyl ketones but they are readily hydrolysed in dilute acid or alkali. 

Solvents acetone, methyl ethyl ketone (MEK), toluene, xylene, glycol, ethers, alcohol defats and dries skin some may be absorbed may carry other components through skin high volatility, exposure possible irritation central nervous system depression (e.g. dizziness, loss of coordination) low to high toxicity, longterm effects... 

While discussing ethers we should mention that the presence of unreacted anisoles or methyl anisoles is highly undesirable in the manufacture of phenol-formaldehyde resoles. These materials tend to be unreactive relative to phenol under normal resole conditions. They are also volatile and have odors detectable at very low concentrations. They have been the source of worker complaints and costly claims in the wood products industry. Benzophenones and methyl phenyl ketones are also common phenol contaminants that are problematic in this regard. 

Sources. Methyl ethyl ketone (MEK) is used in some r neries as a solvent in lube oil dewaxing. Its extremely volatile characteristic makes fugitive emissions its primary source of releases to the environment. 

Volatile organic compounds (VOCs) include organic compounds with appreciable vapor pressure. They make up a major class of air pollutants.I his class includes not only pure hydrocarbons but also partially oxidized hydrocarbons (organic acids, aldehydes, ketones), as well as organics containing chlorine, sulfur, nitrogen, or other atoms in the molecule. 

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