Alkylation aromatic ketone

A ketimine can also be alkylated by the same process.140 In situ generation of a ketimine from the aromatic ketone 114 and benzylamine provides an efficient catalytic process with Wilkinson catalyst (Scheme 35). The alkylated aromatic ketone 115 is obtained in good yield. Better reactivity and selectivity are obtained with ketimine... 

Several examples have appeared of diversion of the normal photochemistry of ortho-alkyl aromatic ketones due to apparent interception of the intermediate biradical by an unsaturated group present elsewhere in the molecule.Thus the vinyl aryl ketones (376) are converted to (377) in reasonable yields upon irradiation with ultra-violet light,while irradiation of the ortho-alkynyl acetophenone (378) in methanol yields diastereomers of (379)The latter reaction is thought to proceed by coupling of the initially formed ketyl radical onto the alkyne to give a carbene (380). The photochemistry of the jS-diketone (381) gives a mixture of the benzocyclobutenol (382) and the tetralone (383), and the proportions depend on the identity of the R-substituent in (381). The formation of (383) can be rationalised in terms of interception of the ketyl radical in the initially formed 1,4-biradical by the remote carbonyl group. 

As noted in the introduction to this chapter, the photochemistry of the ortho-nitrobenzyl group parallels that of ortho-alkyl aromatic ketones in that in the excited state a hydrogen atom can migrate from the benzylic position to an oxygen atom of the nitro group. This reaction has now been studied by time resolved... 

Hydroxy, alkoxy, and amino aldehydes can, like phenols and aromatic amines, be halogenated under mild conditions. The possibility of loss of the aldehyde group has already been mentioned (page 163), and so will be (page 194) the competition between nuclear and side-chain halogenation in substituted alkyl-aromatic ketones. 

Table 26.26 Asymmetric reduction of representative alkyl aromatic ketones with K-glucoride in THF at -78 °C [7]...

The reagent K-xylide also reduces alkyl aromatic ketones smoothly and in high yields. (Eqs. 26.31,26.32 Table 26.30) [1]. 

Claisen-Schmidt reaction. Aromatic aldehydes condense with aliphatic or mixed alkyl-aryl ketones in the presence of aqueous alkali to form ap-unsaturated ketones ... 

Lithiated indoles can be alkylated with primary or allylic halides and they react with aldehydes and ketones by addition to give hydroxyalkyl derivatives. Table 10.1 gives some examples of such reactions. Entry 13 is an example of a reaction with ethylene oxide which introduces a 2-(2-hydroxyethyl) substituent. Entries 14 and 15 illustrate cases of addition to aromatic ketones in which dehydration occurs during the course of the reaction. It is likely that this process occurs through intramolecular transfer of the phenylsulfonyl group. 

Contaminants and by-products which are usually present in 2- and 4-aminophenol made by catalytic reduction can be reduced or even removed completely by a variety of procedures. These include treatment with 2-propanol (74), with aUphatic, cycloaUphatic, or aromatic ketones (75), with aromatic amines (76), with toluene or low mass alkyl acetates (77), or with phosphoric acid, hydroxyacetic acid, hydroxypropionic acid, or citric acid (78). In addition, purity may be enhanced by extraction with methylene chloride, chloroform (79), or nitrobenzene (80). 

Ketones and alcohols are frequently used as alkylating agents Ketones often condense with two molecules of an aromatic compound through an alcohol intermediate [79, 20, 21] T,r,I -Trifluoroacetophenone and aniline afford 1,1 bis(4-ammophenyl) 1 phenyl 2,2,2-trifluoroethane [27] (equation 14)... 

The most important method for the synthesis of aromatic ketones 3 is the Friedel-Crafts acylation. An aromatic substrate 1 is treated with an acyl chloride 2 in the presence of a Lewis-acid catalyst, to yield an acylated aromatic compound. Closely related reactions are methods for the formylation, as well as an alkylation procedure for aromatic compounds, which is also named after Friedel and Crafts. 

Acylation (Sections 16.3,21.4) The introduction of an acyl group, —COR, onto a molecule. For example, acylation of an alcohol yields an ester, acylation of an amine yields an amide, and acylation of an aromatic ring yields an alkyl aryl ketone. 

This procedure illustrates a general method for preparing aromatic hydrocarbons by the tandem alkylation-reduction of aromatic ketones and aldehydes.2 Additional examples are given in Table I. 

ALCOHOL represents a convenient method of converting allyl alcohol to 2-substituted 1-propanols, while a one-pot reaction sequence of alkylation (alkyl lithium) and reduction (lithium—liquid ammonia) provides excellent yields of AROMATIC HYDROCARBONS FROM AROMATIC KETONES AND ALDEHYDES. 

The isolated double bonds in the dihydro product are much less easily reduced than the conjugated ring, so the reduction stops at the dihydro stage. Alkyl and alkoxy aromatics, phenols, and benzoate anions are the most useful reactants for Birch reduction. In aromatic ketones and nitro compounds, the substituents are reduced in preference to the Dissoiving-Memi... 

Parathion is very slightly soluble in water (20 parts per million), but is completely miscible in many organic solvents including esters, alcohols, ketones, ethers, aromatic and alkylated aromatic hydrocarbons, and animal and vegetable oils. It is practically insoluble in such paraffinic hydrocarbons as petroleum ether, kerosene, and refined spray oils (about 2%) unless a mutual solvent is used (1). 

Acid and base extractions from this material have been shown to form spontaneous structures in solution termed coercevates that could easily form the basis for protypical membranes (more of this in Chapter 9). Hydrocarbons with chain lengths C15-C30 (both straight and branched chains) and of course PAHs, predominantly pyrene and fluoranthrene, polar hydrocarbons such as aromatic ketones, alkyl and aryl ketones, nitrogen and sulphur heterocycles and most intriguingly purine and pyrimidine analogues have all been observed from this rich carbonaceous cocktail of compounds. Why ... 

The 0/7/fo-alkylation of aromatic ketones with olefins can also be achieved by using the rhodium bis-olefin complex [C5Me5Rh(C2H3SiMe3)2] 2, as shown in Equation (9).7 This reaction is applied to a series of olefins (allyltrimethyl-silane, 1-pentene, norbornene, 2,2 -dimethyl-3-butene, cyclopentene, and vinyl ethyl ether) and aromatic ketones (benzophenone, 4,4 -dimethoxybenzophenone, 3,3 -bis(trifluoromethyl)benzophenone, dibenzosuberone, acetophenone, />-chloroacetophenone, and />-(trifluoromethyl)acetophenone). 

Nitrogen functionality also assists the alkylation of ortho-Cr-H bonds of aromatics, as shown in Equations (10)—(12). In the case of aromatic imines, Ru3(GO)i2 exhibits a high catalytic activity.8-10 This reaction gives the alkylation product together with the alkenylation product in the reaction with triethoxyvinylsilane. Rhodium catalysts show the same activity to give the alkylation product.11,12,12a For example, the Rh(i)-catalyzed reaction of the imine of aromatic ketones with methyl acrylate... 

Under the above-described conditions, esters are nnaffected and aliphatic ketones are barely rednced. In the presence of zinc iodide, however, aliphatic ketones, as well as aldehydes and aromatic ketones, are converted into methyl ethers in high yields. If alcohols other than methanol are nsed, the corresponding alkyl ethers are obtained. 

Like aldehyde, the ketone function provides sufficient activation on an aromatic ring for the nucleophiUc substitution. Reduction of the carbonyl group after incorporation of the F-fluoride ion yields F-alkyl aromatics [177]. This methodology using F for trimethylammonium exchange, then reduction of the carbonyl compound, have proved to be useful for the synthesis of a [2- F]fluo-rophenol at high specific activity [141] (Scheme 39). 

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