Phorone

Obtained by reduction of phorone, b.p. 169 C. Very good solvent for aldehyde resins. 

McjC = CHCOCH3. Colourless liquid b.p. 129"C, with a strong peppermint-like odour. Prepared by distilling diacetone alcohol in the presence of a trace of iodine. Converted to phorone by heating in propanone with dehydrating agents such as sulphuric acid. It is a solvent For cellulose acetate and ethyl-cellulose and other polymers. 

C, b.p. 205°C, forms monohydrate m.p. 58°C. Prepared from diacetoneamine and propanone or by passing NH3 gas into pro-panone containing fused CaCl2. Decomposes to phorone and ammonia, reduced to lelra-melhyl-3-hydroxypiperidine. Used in the synthesis of benzamine hydrochloride. 

Primary amines form Schiff bases, (CH3 )2C=NR. Ammonia induces an aldol condensation followed by 1,4-addition of ammonia to produce diacetone amine (from mesityl oxide), 4-amino-4-methyl-2-pentanone [625-04-7] (CH2)2C(NH2)CH2COCH2, and triacetone amine (from phorone),... 

Some unsaturated ketones derived from acetone can undergo base- or acid-catalyzed exothermic thermal decomposition at temperatures under 200°C. Experiments conducted under adiabatic conditions (2) indicate that mesityl oxide decomposes at 96°C in the presence of 5 wt % of aqueous sodium hydroxide (20%), and that phorone undergoes decomposition at 180°C in the presence of 1000 ppm iron. The decomposition products from these reactions are endothermic hydrolysis and cleavage back to acetone, and exothermic aldol reactions to heavy residues. 

DIBK can be produced by the hydrogenation of phorone which, in turn, is produced by the acid-catalyzed aldol condensation of acetone. It is also a by-product in the manufacture of methyl isobutyl ketone. Diisobutyl ketone ( 1.37/kg, October 1994) is produced in the United States by Union Carbide (Institute, West Virginia) and Eastman (Kingsport, Teimessee) (47), and is mainly used as a coating solvent. Catalytic hydrogenation of diisobutyl ketone produces the alcohol 2,6-dimethyl-4-heptanol [108-82-7]. 

The hquid-phase processes are more energy efficient than the vapor-phase processes, however, they iacur costiy high pressure equipment investment and also produce waste streams containing used catalyst (213). Both methods produce substantial quantities of by-products which cause refining difficulties. The by-products consist primarily of mesitylene [108-67-8] phorone [504-20-17, and the foUowiag xyUtone isomers (215) ... 

The oldest of these materials, a poly (trimethylhexamethylene terephthal-amide) was first marketed by Dynamit Nobel in the mid-1960s (Trogamid T). It is a condensation product of trimethylhexamethylenediamine and terephthalic acid (or its dimethyl ester) (Figure 18.25). In practice a 1 1 mixture of 2,2,4- and 2,4,4-trimethyldiamines is used, this being produced from acetone via iso-phorone, trimethyladipic acid and trimethyladiponitrile. 

Dimethyl peroxide Diethyl peroxide Di-t-butyl-di-peroxyphthalate Difuroyl peroxide Dibenzoyl peroxide Dimeric ethylidene peroxide Dimeric acetone peroxide Dimeric cyclohexanone peroxide Diozonide of phorone Dimethyl ketone peroxide Ethyl hydroperoxide Ethylene ozonide Hydroxymethyl methyl peroxide Hydroxymethyl hydroperoxide... 

Kampher-dl, . camphor oil (Pharm.) camphorated oil. -phoron, n. camphorphorone. -saure, /. camphoric acid, -sauresalz, n. camphorate. -spiritus, m. spirit of camphor, -wein, m. camphorated wine. 

Purely parallel reactions are e.g. competitive reactions which are frequently carried out purposefully, with the aim of estimating relative reactivities of reactants these will be discussed elsewhere (Section IV.E). Several kinetic studies have been made of noncompetitive parallel reactions. The examples may be parallel formation of benzene and methylcyclo-pentane by simultaneous dehydrogenation and isomerization of cyclohexane on rhenium-paladium or on platinum catalysts on suitable supports (88, 89), parallel formation of mesityl oxide, acetone, and phorone from diacetone alcohol on an acidic ion exchanger (41), disproportionation of amines on alumina, accompanied by olefin-forming elimination (20), dehydrogenation of butane coupled with hydrogenation of ethylene or propylene on a chromia-alumina catalyst (24), or parallel formation of ethyl-, methylethyl-, and vinylethylbenzene from diethylbenzene on faujasite (89a). 

Phoronediozonide (Sym-Diisopropylideneacetone-ozonide). C j 407, light green syrup, very expl, self-flammable on standing in air. Was prepd by Harries Turk by passing ozone thru a well cooled chloroformic soln of phorone [2,4-dimethyl-heptadien-(2,5)-on-(4)], (CH3)2C CH.CO,CH C(CH3)2, followed by vacuum removal of chlf at 20°... 

Phorone (Di iso p ropy lidene acetone, 2,6-dimethyl-2,5-heptadien-4-one). 

Dimethyl peroxide Diethyl peroxide Di-t-butyl-di-peroxyphthalate Difuroyl peroxide Dibenzoyl peroxide Dimeric ethylidene peroxide Dimeric acetone peroxide Dimeric cyclohexanone peroxide Diozonide of phorone Dimethyl ketone peroxide Ethyl hydroperoxide Ethylene ozonide Hydroxymethyl methyl peroxide Hydroxymethyl hydroperoxide 1-Hydroxyethyl ethyl peroxide 1 -Hydroperoxy-1 -acetoxycyclodecan-6-one Isopropyl percarbonate Isopropyl hydroperoxide Methyl ethyl ketone peroxide Methyl hydroperoxide Methyl ethyl peroxide Monoperoxy succinic acid Nonanoyl peroxide (75% hydrocarbon solution) 1-Naphthoyl peroxide Oxalic acid ester of t-butyl hydroperoxide Ozonide of maleic anhydride Phenylhydrazone hydroperoxide Polymeric butadiene peroxide Polymeric isoprene peroxide Polymeric dimethylbutadiene peroxide Polymeric peroxides of methacrylic acid esters and styrene... 

Figure 1. Influence of T1O2 content of LT-aerogels on relative proportion of Si-O-Ti connectivities R = [Si-0-Ti]/(Si-0-Si], mean pore diameter, and initial rate (to) of a-iso-phorone ep>oxidation with t-butyl hydroperoxide at 60 C. Data taken from ref. [18].

The solid base catalysed aldol condensation of acetone was performed over a CsOH/Si02 catalyst using a H2 carrier gas. The products observed were diacetone alcohol, mesityl oxide, phorone, iso-phorone and the hydrogenated product, methyl isobutyl ketone. Deuterium tracer experiments were performed to gain an insight into the reaction mechanism. A mechanism is proposed. 

The reaction mechanism is shown in Figure 4 and is adapted from work by Fiego et al. [9] on the acid catalysed condensation of acetone by basic molecular sieves. The scheme has been modified to include the hydrogenation of mesityl oxide to MIBK. The scheme begins with the self-condensation of acetone to form diacetone alcohol as the primary product. The dehydration of DAA forms mesityl oxide, which undergoes addition of an addition acetone to form phorone that then can cyclise, via a 1,6-Michael addition to produce isophorone. Alternatively, the mesityl oxide can hydrogenate to form MIBK. 

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