Ketones amination

Typical nonsieve, polar adsorbents are siUca gel and activated alumina. Kquilihrium data have been pubUshed on many systems (11—16,46,47). The order of affinity for various chemical species is saturated hydrocarbons < aromatic hydrocarbons = halogenated hydrocarbons < ethers = esters = ketones < amines = alcohols < carboxylic acids. In general, the selectivities are parallel to those obtained by the use of selective polar solvents in hydrocarbon systems, even the magnitudes are similar. Consequendy, the commercial use of these adsorbents must compete with solvent-extraction techniques. 

Modem commercial wet-acid purification processes (see Fig. 4) are based on solvents such as C to Cg alcohols, ethers, ketones, amines, and phosphate esters (10—12). Organic-phase extraction of phosphoric acid is accompHshed in one or more extraction columns or, less frequently, in a series of countercurrent mixer—settlers. Generally, 60—75% of the feed acid P2 s content is extracted into the organic phase as H PO. The residual phosphoric acid phase (raffinate), containing 25—40% of the original P2O5 value, is typically used for fertilizer manufacture such as triple superphosphate. For this reason, wet-acid purification units are almost always located within or next to fertilizer complexes. 

Resin cured butyl (HR) Acids Lyes Strong alkahes Strong phosphoric acid Dilute mineral acids Ketones Amines Water Fats and fatty acids Petroleum oils Chlorinated hydrocarbons Liquids with dissolved chlorine Mineral oil Oxygen rich demin. water Strong oxidants... 

Sodium (metal). Used as a fine wire or as chips, for more completely drying ethers, saturated hydrocarbons and aromatic hydrocarbons which have been partially dried (for example with calcium chloride or magnesium sulfate). Unsuitable for acids, alcohols, alkyl halides, aldehydes, ketones, amines and esters. Reacts violently if water is present and can cause a fire with highly flammable liquids. 

Amines Ketone-amines Acetone-diphenylainine and acetone-aniline (I) Yes Main use in rubber compounds for good heat aging. 

Visible light systems comprising a photoreducible dye molecule e.g. 87)293 or an a-diketone e.g. 85)2% and an amine have also been described. The mechanism of radical production is probably similar to that described for the ketone amine systems described above (i.e. electron transfer from the amine to the photoexcited dye molecule and subsequent proton transfer). Ideally, the dye molecule is reduced to a colorless byproduct. 

The reaction with bromine is very rapid and is easily carried out at room temperature, although the reaction is reversible under some conditions. In the case of bromine, an alkene-Br2 complex has been detected in at least one case. Bromine is often used as a test, qualitative or quantitative, for unsaturation. The vast majority of double bonds can be successfully brominated. Even when aldehyde, ketone, amine, so on functions are present in the molecule, they do not interfere, since the reaction with double bonds is faster. 

Reactions were carried out in liquid phase in a well-stirred (1000 rpm) high-pressure reactor (Parr Instruments, 300 mL) at 30 bar and 150°C with 370 mg catalyst for two hours, unless otherwise specified. The feed consisted of the amine with slight excess of ketone at ketone/amine-group molar ratio of 1.6 while maintaining a reaction volume of about 150 mL. In a typical experiment, 576 mmol of aniline is mixed with 920 mmol of cyclohexanone and 370 mg of BS2 catalyst in the 300 mL reactor. The reactor is closed and then pressure-tested to 50 psi above operating pressure to ensure that the system is leak proof Once pressure-tested, the headspace is replaced... 

Scheme 4.9 gives some examples of the use of boranes in syntheses of alcohols, aldehydes, ketones, amines, and halides. Entry 1 demonstrates both the regioselec-tivity and stereospecificity of hydroboration, resulting in the formation of trans-2-methylcyclohexanol. Entry 2 illustrates the facial selectivity, with the borane adding anti to the endo methyl group. 

The solubility of most metals is much higher when they exist as organometallic complexes.4445 Naturally occurring chemicals that can partially complex with metal compounds and increase the solubility of the metal include aliphatic acids, aromatic acids, alcohols, aldehydes, ketones, amines, aromatic hydrocarbons, esters, ethers, and phenols. Several complexation processes, including chelation and hydration, can occur in the deep-well environment. 

The wheel-and-axle design as source for host-guest compounds was originally proposed by Toda and Hart in 1981 for hosts containing hydroxyl functions 481 (see Ch. 3, Sect. 2.1 of Vol. 140). The l,l,6,6-tetraphenylhexa-2,4-diyne-l,6-diol (24) provides a representative compound. It forms 1 2 crystalline inclusion complexes with a large number of small guest molecules, including a variety of ketones, amines, amides and a sulfoxide 48). 

Aldehyde/Ketone Amine Conditions Product(s) and Yield(s) (%)... 

Many volatile organic compounds (hydrocarbons, alcohols, aldehydes, acids, esters, ketones, amines, etc.) have been identified in marine systems [ 156,157]. These volatile materials may have an important role in the cycling of organic... 

Reductive amination aldehyde or ketone => amine (amine or ammonia, H2, Rh)... 

Dubois and co-workers (119,410-415) characterized alkyl (R) substituent effects in simple and sterically congested alkanes, alkenes, carboxylic acid derivatives, ketones, amines, alcohols, and so on by the use of topological parameters XR ... 

The a-cleavage in molecular ions of ketones, amines, ethers and similar functionalized compounds yields specific cleavage products of high importance for structure elucidation. Analogous behavior is observed in the mass spectra of phenylal-kanes. [49]... 

The original synthesis of duloxetine (3) is relatively straightforward, involving a four-step sequence from readily available 2-acetylthiophene 30 (Scheme 14.7). Understandably, the main synthetic challenge stems from the presence of a chiral center, because duloxetine (3) is marketed as the (5)-enantiomer as shown. Thus, a Mannich reaction between 30 and dimethylamine generated ketone amine 31, which was then reduced to provide intermediate racemic alcohol amine 32. The desired optically active (5)-alcohol 32a was accessed via resolution of racemate 32 with (5)-(+)-mandelic acid, which provided the necessary substrate for etherihcation with 1-fluoronaphthalene to afford optically active amine 33. Finally, A -demethylation with 2,2,2-trichloroethyl chloroformate and cleavage of the intermediate carbamate with zinc powder and formic acid led to the desired target duloxetine (3). 

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