Ketone production utilization

Use as Solvent. Toluene is more important as a solvent than either benzene or xylene. Solvent use accounts for ca 14% of the total U.S. toluene demand for chemicals. About two-thirds of the solvent use is in paints and coatings the remainder is in adhesives, inks, pharmaceuticals, and other formulated products utilizing a solvent carrier. Use of toluene as solvent in surface coatings has been declining, primarily because of various environmental and health regulations. It is being replaced by other solvents, such as esters and ketones, and by changing the product formulation to use either fully soHd systems or water-based emulsion systems. 

Numerous linkers have been developed with the aim of immobilizing substrates on a solid support. Commercially available (+)-a-lipoic acid has been employed as a novel, chemically stable linker for the immobilization of ketones. The utility of this thioacetal-based linker in solid-phase synthesis has been demonstrated by the synthesis of several 4-acetylbiphenyls by means of the Suzuki reaction. The products were readily cleaved from the solid support by treatment with [bis(trifluoroacetoxy)iodo]benzene [PhI(OCOCF3)2] [107]. 

This represents probably one of the earliest interests in the chemistry of Ti compounds." Ketones, like cyclohexanone, are easily dimethylated by MeTiCb, Me2 IlCl2 and Me2Zn/riCU- " Depending upon the molecular ratio of Mc2Zn and TiCU, various products (43), (154) and (155) are obtained from cyclohexanone (equation 57), as is reported in Table 1S. The reaction proceeds dirough cationic intermediates various functionalities (e.g. carboxylic acid esters, primary and secondary alkyl halides) are well tolerated. Some problems arise when a,3-unsaturated ketones are utilized, because of the formation of two distinct dimethylated products (equation 58). ... 

As a test reaction to determine the activity of this catalyst, the coupling of 4-nitrobenzaldehyde with methyl vinyl ketone, a paradigmatic example of the Baylis-Hillman reaction, was selected. The major product was the corresponding p-hydroxyketone 110 accompanied by minor amounts of the Michael adduct 111 that appeared at high conversions when an excess of methyl vinyl ketone was utilized (Scheme 3.31). 

As already underlined in the introduction to this book, catalytic homogeneous acylation reactions represent a remarkable improvement in the preparation of aromatic ketones because, in the conventional Lewis-acid-promoted reactions, formation of a stable complex between the ketone product and the catalyst implies that at least a stoichiometric amount of catalyst must be utilized. This drawback prompted a great number of studies aimed at setting up the experimental conditions to make catalytic Friedel-Crafts acylation reactions. Some positive results from fhe homogeneous catalytic Friedel-Crafts acylations are described here, with special attention to crucial economic and environmental advantages such as the recycling of expensive catalysts and the development of solvenf-free and highly selective synthetic processes. 

The Dess-Martin periodinane oxidation utilizes 1,1,1-triacetoxy-1,1 -dihydro-1,2-benziodoxol-3(lH)-one (2) as an oxidant for the conversion of primary and secondary alcohols (1) to their corresponding aldehyde (3) and ketone products, respectively. 

Kayer MA. Disorders of ketone production and utilization. Mol Genet Metab. 2006 87(4) 281-3. 

In contrast to peripheral tissue, which can readily oxidize ketone bodies, the liver is poorly equipped for ketone body utilization. Consequently, whenever the production of ketone bodies in liver exceeds the ability of the peripheral tissue to use them, ketosis takes place [134, 135]. 

Acetone is used to extract fats, oils, waxes, and resins from natural products, to dewax lubricating oils, and to extract certain essential oils. The pharmaceutical industry uses acetone to extract B-vitamin complexes, alkaloids, antibiotics and enzymes. Methyl ethyl ketone is used to dewax lube oil. Methyl isobutyl ketone is used to dewax mineral oil, refine tall oil, and in extractive distillation and separation of isopropyl alcohol from ethyl and butyl alcohols. The extraction and purification of antibiotics and other pharmaceutical products utilize MIBK. Methyl isobutyl ketone is used in the extraction of rosin from pine wood and the extraction of heavy metal ion complexes from water solutions. 

For the preparation of the 2-methylpyrrolo[2,3-b]pyridine derivative, the ten-butyl sarcosine ester derivative,12c(R=r-Bu), was utilized as the tetraester component. Dieclonann cyclizadon of 12c occurred rapidly at room temperature when treated with sodium ethoxide. The resulting anion product was quenched with methyl iodide to afford a mixture of O- and C-methylated products, 15 and 16. The ketonic product 16 was reduced to 17 with sodium borohydride. The resulting alcohol 17, when treated with trifluoroacetic acid at 80, underwent acid catalyzed loss of isobutylene, carbon dioxide, and water to afford the 2-methylpyrrolo[2,3-b]pyridine 18. When this sequence of reactions was run without separating 15 from 16, die trifluoroacedc acid treatment afforded the 3-methoxypyrrolo[2,3-b]pyridine 19 in addition to 18. This result demonstrated that 15 underwent acid-catrdyzed loss of isobutylene and carbon dioxide under these mild reaction conditions. This provided a second method far the synthesis of 3-alkoxy-pyrrolo[2,3-b]pyridines. 

In non-ruminant animals, including Man, the liver is the only organ that adds ketone bodies to the blood since its enzymes are active in ketone body production but inactive in ketone body utilization. This is exactly the reverse of the condition in muscle and other extrahepatic tissues which oxidize ketone bodies but do not produce them. 

Kita and coworkers use potassium bromide to depolymerize iodosobenzene 17 by generating an I—Br bond. Homolytic cleavage of the I—Br bond to generate the iodine-centered radical allows formation of the benzylic radical 18. The authors propose the benzylic radical is trapped by bromine radical to generate a benzylic bromide 19, a known byproduct of the reaction conditions. Conversion to the alcohol and subsequent oxidation yields the aryl ketone 20. While the ketone products are useful themselves, Ochiai utilizes this mechanism, though with a different hyperva-lent iodine reagent, to deprotect benzylic ethers such as 21 to alcohols 2. ... 

An interesting case are the a,/i-unsaturated ketones, which form carbanions, in which the negative charge is delocalized in a 5-centre-6-electron system. Alkylation, however, only occurs at the central, most nucleophilic position. This regioselectivity has been utilized by Woodward (R.B. Woodward, 1957 B.F. Mundy, 1972) in the synthesis of 4-dialkylated steroids. This reaction has been carried out at high temperature in a protic solvent. Therefore it yields the product, which is formed from the most stable anion (thermodynamic control). In conjugated enones a proton adjacent to the carbonyl group, however, is removed much faster than a y-proton. If the same alkylation, therefore, is carried out in an aprotic solvent, which does not catalyze tautomerizations, and if the temperature is kept low, the steroid is mono- or dimethylated at C-2 in comparable yield (L. Nedelec, 1974). 

As a class of compounds, nitriles have broad commercial utility that includes their use as solvents, feedstocks, pharmaceuticals, catalysts, and pesticides. The versatile reactivity of organonitnles arises both from the reactivity of the C=N bond, and from the abiHty of the cyano substituent to activate adjacent bonds, especially C—H bonds. Nitriles can be used to prepare amines, amides, amidines, carboxyHc acids and esters, aldehydes, ketones, large-ring cycHc ketones, imines, heterocycles, orthoesters, and other compounds. Some of the more common transformations involve hydrolysis or alcoholysis to produce amides, acids and esters, and hydrogenation to produce amines, which are intermediates for the production of polyurethanes and polyamides. An extensive review on hydrogenation of nitriles has been recendy pubHshed (10). 

Uses, cx-Aminonitriles may be hydrolyzed to aminoacids, such as is done in producing ethylenediaminetetracetate (EDTA) or nittilotriacetate (NTA). In these cases, formaldehyde is utilized in place of a ketone in the synthesis. The principal use of the ketone-based aminonitriles described above is in the production of azobisnittile radical initiators (see below). AN-64 is also used as an intermediate in the synthesis of the herbicide Bladex. Aminonitriles are also excellent intermediates for the synthesis of substituted hydantoins by reaction with carbon dioxide however, this is not currently commercially practiced. 

Insofar as they are used to purify other products, several processes used in the refinery fall under the classification of dewaxing processes however, such processes must also be classified as wax production processes (2). Most commercial dewaxing processes utilize solvent dilution, chilling to crystallize the wax, and filtration (28). The MEK process (methyl ethyl ketone—toluene solvent) is widely used. Wax crystals are formed by chilling through the walls of scraped surface chillers, and wax is separated from the resultant wax—oil—solvent slurry by using fliUy enclosed rotary vacuum filters. 

An example is the preparation of 18-trideuterio 5a-steroids bearing a side chain at C-17. Labeling of this position with three deuteriums was accomplished by utilizing the Johnson procedure for steroid total synthesis. This synthesis involves, in part, introduction of the 18-angular methyl group by methylation of the D-homo-17a-keto-17-furfurylidene intermediate (243). By substituting d3-methyl iodide in this step, the C/D cis- and ra/J5-18,18,18-d3 labeled ketones [(244) and (245)] are obtained. Conversion of the C/D tra 5-methylation product (245) into 18,18,18-d3-d /-3)8-hydroxy-5a-androstan-17-one (246) provides an intermediate which can be converted into a wide variety of C-18 labeled compounds of high (98%) isotopic... 

No blocking group was utilized in the Schering-Hoffman-La Roche approach instead, advantage was taken of the fact that the 7a-bromo-5a-6-ketone is the thermodynamic product ... 

The reaction of the enamines of cyclic ketones with alkyl isocyanates, acyl isocyanates, phenyl isothiocyanates, and acyl isothiocyanates has also been reported 112). The products are the corresponding carboxamides. The products from the isothiocyanates have been utilized as intermediates in the preparation of various heterocyclic compounds 113). 

The Pictet-Spengler condensation has been of vital importance in the synthesis of numerous P-carboline and isoquinoline compounds in addition to its use in the formation of alkaloid natural products of complex structure. A tandem retro-aldol and Pictet-Spengler sequence was utilized in a concise and enantioselective synthesis of 18-pseudoyohimbone. Amine 49 cyclized under acidic conditions to give the condensation product 50 in good yield. Deprotection of the ketone produced the indole alkaloid 51. 

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