Acyl compounds physical properties

Physical Properties. Almost all Hquid diacyl peroxides (20) and concentrated solutions of the soHd compounds are unstable to normal ambient temperature storage many must be stored well below 0°C. Most of the soHd compounds are stable at ca 20°C but many are shock-sensitive (187). Other physical constants and properties have been reviewed (187,188). The melting poiats and refractive iadexes of some acyl peroxides are Hsted ia Tables 10-12. 

The heat of decomposition (238.4 kJ/mol, 3.92 kJ/g) has been calculated to give an adiabatic product temperature of 2150°C accompanied by a 24-fold pressure increase in a closed vessel [9], Dining research into the Friedel-Crafts acylation reaction of aromatic compounds (components unspecified) in nitrobenzene as solvent, it was decided to use nitromethane in place of nitrobenzene because of the lower toxicity of the former. However, because of the lower boiling point of nitromethane (101°C, against 210°C for nitrobenzene), the reactions were run in an autoclave so that the same maximum reaction temperature of 155°C could be used, but at a maximum pressure of 10 bar. The reaction mixture was heated to 150°C and maintained there for 10 minutes, when a rapidly accelerating increase in temperature was noticed, and at 160°C the lid of the autoclave was blown off as decomposition accelerated to explosion [10], Impurities present in the commercial solvent are listed, and a recommended purification procedure is described [11]. The thermal decomposition of nitromethane under supercritical conditions has been studied [12], The effects of very high pressure and of temperature on the physical properties, chemical reactivity and thermal decomposition of nitromethane have been studied, and a mechanism for the bimolecular decomposition (to ammonium formate and water) identified [13], Solid nitromethane apparently has different susceptibility to detonation according to the orientation of the crystal, a theoretical model is advanced [14], Nitromethane actually finds employment as an explosive [15],... 

The physical properties of the fatty acids, and of compounds that contain them, are largely determined by the length and degree of unsaturation of the hydrocarbon chain. The nonpolar hydrocarbon chain accounts for the poor solubility of fatty acids in water. Laurie acid (12 0, Mx 200), for example, has a solubility in water of 0.063 mg/g—much less than that of glucose (Mt 180), which is 1,100 mg/g. The longer the fatty acyl chain and the fewer the double bonds, the lower is the solubility... 

Identification of Alkyl Halides.—On account of their relative inertness at ordinary temperatures the alkyl halides are usually identified by the determination of their physical properties. They are insoluble in concentrated sulphuric acid, and, unlike the acyl halides, they do not react readily with water and alcohols. Unlike the compounds in which halogen is joined to nitrogen, they are not easily changed by an aqueous solution of sodium hydroxide. They are distinguished from many halogen derivatives of benzene and related hydrocarbons, which will be described later, by the fact that they are decomposed when boiled with an alcoholic solution of potassium hydroxide —... 

Acid catalyzed hydrolysis followed by the identification of D-amino acids in the hydrolysate is equally useful. To make this possible the amino acids in the mixture are acylated with an enantiomerically pure amino acid, for instance with the N-carboxyanhydride of L-leucine. In the resulting mixture of dipeptides any racemized residue is revealed by the formation of two dipeptides that are diastereoisomers of each other, for instance L-leucyl-L-phenylalanine and L-leucyl-D-phenylalanine. Since these are compounds with different physical properties they are separable and appear as a doublet on recordings of an amino acid analzyer. In recent years the conversion to diastereoisomers became unnecessary because the availability of chiral supports now permits separation of enantiomers by high pressure liquid chromatography (HPLC) and also by thin layer chromatography on plates covered with a chiral layer. 

Acyl compounds are quite polar and have boiling points substantially higher than those of the alkanes. Amides, like carboxylic acids, form hydrogen-bonded dimers and oligomers, and are exceptionally high boiling. Table 18.1 gives some physical properties of the acyl compounds related to acetic acid. 

Acyl halides, such as acetyl chloride, and acid anhydrides, such as acetic anhydride, are used exclusively as reagents rather than as solvents. Consequently, their physical properties, such as boiling points and dielectric constants, are of less interest than those of other acyl derivatives. Because neither acyl hahdes nor acid anhydrides form tntermolecular hydrogen bonds, their boiling points are similar to structurally related carbonyl compounds of approximately the same molecular weight. 

The physical and chemical properties of the X -phosphorins 118 and 120 are comparable to those of phosphonium ylids which are resonance-stabilized by such electron-pulling groups as carbonyl or nitrile substituents Thus they can be viewed as cyclic resonance-stabilized phosphonium ylids 118 b, c, d). As expected, they do not react with carbonyl compounds giving the Wittig olefin products. However, they do react with dilute aqueous acids to form the protonated salts. Similarly, they are attacked at the C-2 or C-4 positions by alkyl-, acyl- or diazo-nium-ions Heating with water results in hydrolytic P—C cleavage, phosphine oxide and the hydrocarbon being formed. 

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