2,4-Pentanediones

Nonanedione, another 1,3-difunctional target molecule, may be obtained from the reaction of hexanoyl chloride with acetonide anion (disconnection 1). The 2,4-dioxo substitution pattern, however, is already present in inexpensive, symmetrical acetylacetone (2,4-pentanedione). Disconnection 2 would therefore offer a tempting alternative. A problem arises because of the acidity of protons at C-3 of acetylacetone. This, however, would probably not be a serious obstacle if one produces the dianion with strong base, since the strongly basic terminal carbanion would be a much more reactive nucleophile than the central one (K.G. Hampton, 1973 see p. 9f.). 

Ethyl-cf-chloroacetoacetate gives 5-carbethoxy-4-methyl-2-thiazole thiol (387), while 3-chloro-2,4-pentanedione affords the 2-mercapto-4-methyl-5-thiazolylmethylketone in good yield (74%) (387). 

Both of these features are apparent m the structure of the enol of 2 4 pentanedione shown in Figure 18 2... 

Learning By Model mg contains molecu lar models of the enolates of acetone and 2 4 pentanedione Compare the two with respect to the dis tribution of negative charge... 

By far the most popular commercial ketone peroxide is methyl ethyl ketone peroxide [1338-23-4]. Smaller quantities of ketone peroxides such as methyl isobutyl ketone peroxide [28056-59-9] cyclohexanone peroxide [12262-58-7] and 2,4-pentanedione peroxide [37187-22-7] are used commercially (47). 

Ketones with labile hydrogen atoms undergo enol acetylation on reaction with ketene. Strong acid catalysis is required. If acetone is used, isoptopenyl acetate [108-22-5] (10) is formed (82—85). Isopropenyl acetate is the starting material for the production of 2,4-pentanedione (acetylacetone) [123-54-6] (11). 

Penta.nedione, 2,4-Pentanedione [123-54-6] (acetylacetone) is the lowest member of the aUphatic 1,3-diketones and is a colorless Hquid with a mild ketone-like odor. It is completely miscible with organic solvents other physical properties ate shown in Table 1. 

The industrial precursor to 2,4-pentanedione is isopropenyl acetate, produced from acetone and ketene (307,308). The diketone is formed by the high temperature isomerization of isopropenyl acetate over a metal catalyst (309—311). 

Pentanedione can also be produced by the condensation of acetone with ethyl acetate (312—317), or by the condensation of ethyl acetoacetate and ketene (318—321). Other methods are known (322,323). 

Pentanedione is widely used in extraction processes for the separation and purification of metals because of its abiUty to form covalent metal chelates. It is also used as an intermediate in the production of heterocycHc substances and dyes, as a fuel additive (324), and in metal plating and resin modification. 

The toxicity of 2,4-pentanedione is shown in Tables 3 and 11 to be similar to mesityl oxide, and greater than most other 1,2- or 1,4-diketones or monoketones. Inhalation of low levels of 2,4-pentanedione can cause nausea, eye contact can induce stinging, and recurrent exposure to high concentrations (300—400 ppm) can adversely affect the central nervous system and immune system (325). 

Ligand-Modified Rhodium Process. The triphenylphosphine-modified rhodium oxo process, termed the LP Oxo process, is the industry standard for the hydroformylation of ethylene and propylene as of this writing (ca 1995). It employs a triphenylphosphine [603-35-0] (TPP) (1) modified rhodium catalyst. The process operates at low (0.7—3 MPa (100—450 psi)) pressures and low (80—120°C) temperatures. Suitable sources of rhodium are the alkanoate, 2,4-pentanedionate, or nitrate. A low (60—80 kPa (8.7—11.6 psi)) CO partial pressure and high (10—12%) TPP concentration are critical to obtaining a high (eg, 10 1) normal-to-branched aldehyde ratio. The process, first commercialized in 1976 by Union Carbide Corporation in Ponce, Puerto Rico, has been ficensed worldwide by Union Carbide Corporation and Davy Process Technology. 

The di(hydroxyaLkyl) peroxide (2) from cyclohexanone is a soHd which is produced commercially. The di(hydroxyaLkyl) peroxide (2) from 2,4-pentanedione (11, n = 1 X = OH) is a water-soluble soHd which is also produced commercially (see Table 5). Both these peroxides are used for curing cobalt-promoted unsaturated polyester resins. Because these peroxides are susceptible to promoted decomposition with cobalt, they must exist in solution as equihbrium mixtures with hydroperoxide stmctures (122,149). 

---