Acetone other routes

Other Rea.ctlons, The anhydride of neopentanoic acid, neopentanoyl anhydride [1538-75-6] can be made by the reaction of neopentanoic acid with acetic anhydride (25). The reaction of neopentanoic acid with acetone using various catalysts, such as titanium dioxide (26) or 2irconium oxide (27), gives 3,3-dimethyl-2-butanone [75-97-8] commonly referred to as pinacolone. Other routes to pinacolone include the reaction of pivaloyl chloride [3282-30-2] with Grignard reagents (28) and the condensation of neopentanoic acid with acetic acid using a rare-earth oxide catalyst (29). Amides of neopentanoic acid can be prepared direcdy from the acid, from the acid chloride, or from esters, using primary or secondary amines. 

Cumene processes are currently the major source for phenol and coproduct acetone. Chapter 8 notes other routes for producing acetone. 

There are several other routes to acetone of minor importance air oxidation of IPA reaction between IPAand acrolein for the production of allyl alcohol, with acetone as the by-product vapor phase oxidation of butane coproduction when IPA is oxidized yielding acetone and H2O2, hydrogen peroxide, the principal ingredient of bleach and by-product production from the manufacture of methyl ethyl ketone. 

Thioxo-1,2,4-dithiazolidines can be obtained from thioxo-l,2,4-thiadiazolidines by Dimroth rearrangement (Scheme 47) or reversibly by addition and elimination of acetone (Scheme 22). 1,2,4-Dithiazole type products are also obtained from thiocarbonyl isothiocyanates (154) by reaction with CI2 <84CHEC-I(6)897>, PhMgBr, Sj, or CS2. Other routes include reactions of carbonyl isothiocyanates and thiocarbonyl isocyanates with P4S10 or Sg <84Chec-I(6)897> and sulfonyl isocyanates with dialkyl thioketenes. Phenylisothiocyanate heated with N,C-disubstituted oxaziridines affords 3,5-diimino-l,2,4-dithiazolidines (226, 227). Other miscellaneous syntheses of 1,2,4-dithiazoline derivatives include cyclization of A7-thioacyl hexafluoroacetonimine to 5,5-bis(trifluoromethyl)-... 

Other routes are by condensation of an aniline with acetone or with acrolein or glycerol in presense of a dehydrating agent followed by oxidation... 

The competitiveness of the oxidation of isobutene compared to the conventional acetone cyanohydrin route (Equation 33) is not only related to its performance and better environmental standards but has to contend with the demands of other users for isobutene, particularly for MTBE and ETBE production. In fact the predominant methacrylic acid process is still the hydrolysis of acetone cyanohydrin however, the change of mood on the use of MTBE in gasoline blends in the USA, could signal a future shift of isobutene availability making it a more attractive feedstock for methacrylic acid production. 

Note that by-products can have a major influence on the economics of a chemical process. Phenol manufacture provides a striking example of this. The original route, the benzenesulphonic acid route, has become obsolete because demand for its by-product sodium sulphite (2.2 tonnes/1 tonne phenol) has dried up. Its recovery and disposal will therefore be an additional charge on the process, thus increasing the cost of the phenol. In contrast the cumene route owes its economic advantage over all the other routes to the strong demand for the by-product acetone (0.6 tonnes/1 tonne phenol). The sale of this therefore reduces the net cost of the phenol. 

It will be noted that the cumene process is based only on materials derived from petroleum in contrast to many other routes there is no substantial requirement of heavy inorganic chemicals. The economics of the process are bound up with the value of the co-product, acetone. The first cumene-phenol plant came on stream in 1952 and since this time the cumene process has become increasingly dominant. 

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