Western ketone

Table 5. United States, East Asia, and Western Europe Methyl Ethyl Ketone Production ...

In the initial thiocyanate-complex Hquid—Hquid extraction process (42,43), the thiocyanate complexes of hafnium and zirconium were extracted with ether from a dilute sulfuric acid solution of zirconium and hafnium to obtain hafnium. This process was modified in 1949—1950 by an Oak Ridge team and is stiH used in the United States. A solution of thiocyanic acid in methyl isobutyl ketone (MIBK) is used to extract hafnium preferentially from a concentrated zirconium—hafnium oxide chloride solution which also contains thiocyanic acid. The separated metals are recovered by precipitation as basic zirconium sulfate and hydrous hafnium oxide, respectively, and calcined to the oxide (44,45). This process is used by Teledyne Wah Chang Albany Corporation and Western Zirconium Division of Westinghouse, and was used by Carbomndum Metals Company, Reactive Metals Inc., AMAX Specialty Metals, Toyo Zirconium in Japan, and Pechiney Ugine Kuhlmann in France. 

Frontalin (18), the pheromone of the western pine beetle, is an acetal (atom has two single bonds to oxygen). Disconnection reveals diol ketone (19). 

Following their use in the behavioral trials, sub-sets of the experimental females (n = 8) and experimental newly-emerged males (n = 8) were immediately sacrificed with an overdose of brevital sodium and their skin lipids were extracted with hexane overnight (LeMaster and Mason 2002). After removal of the animals, the extracts were returned to Western Oregon University where the methyl ketones composing the female sexual attractiveness pheromone were isolated using column chromatography (described in LeMaster and Mason 2002). 

Red-sided garter snakes from different regions of Manitoba, Canada show signs of isolation by chemical cues. In choice tests, males from a hiber-naculum (overwintering den) in central Manitoba preferred females from their own population to females from western Manitoba. Males from western Manitoba showed no preference. When confronted with experimental trails, males made the same choices. This demonstrated that a chemical factor is involved. Furthermore, the sexual attractiveness pheromone of females, a series of ty-9-cis-unsaturated methyl ketones, varies between the populations. Specifically, the... 

The Bashkirov oxidation (liquid-phase oxidation of n-alkanes or cycloalkanes in the presence of boric acid and hydrolysis) yields the corresponding secondary alcohols [16, 17]. The reaction is used industrially for oxidation of C10 to C18 n-alkanes, providing raw materials for detergents and for oxidation of cyclododecane to cyclo-dodecanol as an intermediate for the production of Nylon 12 (Table 1, entry 8). The process is not of much commercial importance in the western world, however. Oxidation in the absence of boric acids usually leads to mixtures of alcohols, ketones, and carboxylic acids (Table 1, entry 9). 

As another example, let s consider the synthesis of brevicomin, the aggregation pheromone of the Western pine beetle. First, it is necessary to recognize that brevicomin is an acetal and can be disconnected into a diol and a ketone. The diol can be prepared by hydroxylation of an alkene, and the alkene can be prepared by a Wittig reaction ... 

Polcin and Rapson [12] have shown that hydrosulfite predominantly attacks simple quinoid, a,p-unsaturated aldehyde and anthocyanidine structures found in groundwood pulps prepared from western hemlock (Tsuga heterophylla) and eastern spruce (Picea glauca). A few years later, de Vries et al. [13,14] have demonstrated that hydrosulfite can reduce many types of aldehydes and ketones in solution according to the mechanism shown in Figure 13.1. Ketones were found to react sluggishly in water, esters are hydrolyzed, while carboxylic acids and amines are not reduced. 

Most of the methyl ethyl ketone (d ° 0.805t3 mp —819 0, bpt013 = 79.6°Q manufactured worldwide is produced by the dehydrogenation of secondary butanol Smaller quantities me obtained as a by-product of the oxidation of a-butane to acetic add. This is the case in the United States of Celanese in its Pampa, Texas, plant (40,000 t/year) and of Union Carbide in Brownsville, Texas (35,000 t/year). Plants of this type built in Western Europe have been shut down, including the Kooas plant in the Netherlands (20.000 year at Europoort) which was closed in 1979. 

Table 10. U-gives the production, capacities and consumption of methyl ethyl ketone in Western Europe, the United States and Japan in 1984. ...

Naturally Occurring Substances.— Tall oil, obtained as a by-product of pulping conifer wood chips, contains a mixture of fatty and diterpenoid resin acids and neutral compounds. The latter include" pimara-8(14),15-diene-3/S,18-diol, abieta-8,ll,13-triene-15,18-diol, 19-hydroxy-15,16-bisnorlabda-8(17)-en-13-one, 8,13i8-epoxylabd-14-en-6a-ol (6a-hydroxy-13-epimanoyl oxide), and the 9,10-secoabietatriene (41). The latter was also isolated from the bark of the jack pine (Pinus banksiana) and western white pine (P. monticola). A range of 7-monohydroxy, 1,7- and 1,11-dihydroxy-, and 1,7,11-trihydroxy-sandaraco-pimaradienes and their acetates (42) have been obtained" from Zexmenia (Compositae) species. The l,ll-diacetoxy-7-ketone and 6,7-epoxide were also isolated. 

We saw in 47 an opportunity to deploy a triply convergent and enantioselective strategy. The challenge of obtaining the western half of the molecule, which was addressed first, was met with a concise route to racemic tricyclic hydroxy ketone 56 in six short steps [29] from readily available 48 [30]... 

Production of N,N-dimethylaniline in Western Europe in 1985 was around 9,0001. Among the most important compounds based on N,N-dimethylaniline is Michler s ketone, which is used to manufacture triphenylmethane dyes such as Basic Violet 3 (Crystal Violet) or Basic Green 4 (Malachite Green), which is obtainable by reaction with benzaldehyde in a sulfuric acid medium, followed by oxidation. 

Fioroni, G. Fringuelli, R Pizzo, R Vaccaro, L. Epoxidation of a, /3-Unsaturated Ketones in Water. An Environmentally Benign Protocol. Green Chemistry 2003,5,425-428. Experiment developed by Butler, G., and Lampman, G.M., Western Washington University, Bellingham, WA. 

Routledge, V. (2000). The development and application of MS2A reduced ketone resin in painting conservation. Western Association for Art Conservation Newsletter, 22(2), 16-17. 

We can use these choices in some longer sequences. exo-Brevicomin (8.9) is a pheromone from the Western pine beetle. Examining the functionality, we see a carbon attached to two oxygens, that is, an acetal derivative of a ketone. A Wittig reaction was used to bring the two functional groups together (Scheme 8.5). A f/ireo-diol is needed. 

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