Ketones production

Figure C2.3.9. Product distribution of dissymmetrical ketone photolysis as influenced by cefyltrimethylammonium chloride (CTAC) micelles. The initial ketone, A(CO)B is photolysed to lose the carbonyl group and to produce tliree products, AA, AB and BB. These data are for benzyl (A) 4-methylbenzyl (B) ketone. Product AA is 1,2-diphenylethane, product BB is 1,2-ditolylethane and product AB is l-phenyl-2-tolyl-ethane. At low CTAC concentration, in the absence of micelles, a random distribution of products is obtained. In the presence of micelles, however, the AB product is heavily favoured. Adapted with pennission from 1571.

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

N-Acylation is readily carried out by reaction of the alkaU metal salts with the appropriate acid chloride. C-Acylation of pyrroles carrying negative substituents occurs in the presence of Friedel-Crafts catalysts. Pyrrole and alkylpyrroles can be acylated noncatalyticaHy with an acid chloride or an acid anhydride. The formation of trichloromethyl 2-pyrryl ketone [35302-72-8] (20, R = CCI3) is a particularly useful procedure because the ketonic product can be readily converted to the corresponding pyrrolecarboxyUc acid or ester by treatment with aqueous base or alcohoHc base, respectively (31). 

Eq. (4e)] is not reduced by metal-ammonia solutions so that the existence of this equilibrium cannot lead to further reduction of the saturated ketonic product only protonation on carbon can result in further reduction (see page 39). 

The reaction of androst-4-ene-3,17-dione with DDQ in refluxing benzene or dioxane leads to the A -3-ketone as the major product, although small amounts of A -3-ketone and A -3-ketone are also produced. The latter arises from the A -3-ketone, since the A -3-ketone is not dehydrogenated further under the usual reaction conditions. A -3-Ketone production is more favored in benzene than it is in dioxane substituents at C-6 can also influence this selectivity. A recent thorough investigation of the mechanism of dehydrogenation of 3-ketones under neutral and acidic condi-... 

When ethyl trifluoroacetylacetate is treated with an allylic alkoxide, tran-sesterification is followed by ester enolate Claisen rearrangement m a process that on decarboxylation yields stereospecifically the tnfluoromethyl ketone product [22] (equation 19)... 

The reactions of dichlorocarbene with morpholine and piperidine enamines derived from cyclopentanone and cyclohexanone have been reported to lead to ring expanded and a-chloromethylene ketone products (355,356). Similarly a-chloro-a, -unsaturated aldehydes were obtained from aldehyde derived enamines (357). Synthesis of aminocyclopropanes (353,359) could be realized by the addition of diphenyldiazomethane (360) and the methylene iodide-zinc reagent to enamines (367). 

From the outset, the further O acylation of the initial ketonic products was recognized. Detailed studies have been made of the benzoylation of morpholinoeyclohexene (379-382) and of the effect of the amine moiety of cyclohexanone derived enamines on the ratio of produets (iS5) obtained from acylations. 

Electrochemical reduction of oxazolinium salts 36 gives the anions 37, which add efficiently to alkyl halides or, in the presence of McsSiCl, to methyl acrylate, methyl vinyl ketone, and acrylonitrile. Simple acid hydrolysis then gives the ketone products 38 and 39, and this method is quite general since the starting salts are readily prepared from carboxylic acids, R C02H (87TL4411). 

The cyanobenzylpiperidine 94 acts as an effective benzoyl anion equivalent for addition to alkynes. As shown, the initial adduct 95 is readily cleaved with copper sulfate to give the ketone product 96 (93LA375). 

Friedel-Crafts acylation reactions usually involve the interaction of an aromatic compound with an acyl halide or anhydride in the presence of a catalyst, to form a carbon-carbon bond [74, 75]. As the product of an acylation reaction is less reactive than its starting material, monoacylation usually occurs. The catalyst in the reaction is not a true catalyst, as it is often (but not always) required in stoichiometric quantities. For Friedel-Crafts acylation reactions in chloroaluminate(III) ionic liquids or molten salts, the ketone product of an acylation reaction forms a strong complex with the ionic liquid, and separation of the product from the ionic liquid can be extremely difficult. The products are usually isolated by quenching the ionic liquid in water. Current research is moving towards finding genuine catalysts for this reaction, some of which are described in this section. 

The Friedel-Crafts acylation reaction has also been performed in iron(III) chloride ionic liquids, by Seddon and co-workers [96]. An example is the acetylation of benzene (Scheme 5.1-66). Ionic liquids of the type [EMIM]Cl/FeCl3 (0.50 < X(FeCl3) < 0.62) are good acylation catalysts, with the added benefit that the ketone product of the reaction can be separated from the ionic liquid by solvent extraction, provided that X(FeCl3) is in the range 0.51-0.55. 

The enol undergoes tautomerization to give the final ketone product. 

Although analogous to the direct coupling reaction, the catalytic cycle for the carbonylative coupling reaction is distinguished by an insertion of carbon monoxide into the C-Pd bond of complex A (see A—>B, Scheme 31). The transmetalation step-then gives trans complex C which isomerizes to the cis complex D. The ketone product E is revealed after reductive elimination. 

Amidine a-Halo ketone Product Isolated Yields Lit. Yields... 

Further insight into the P-borylation reaction of a,P-enones (Scheme 2.32) showed that the reaction can be carried out in THF, and the catalyst generated in situ from CuCl (5 mol%), the imidazolium salt (5 mol%), and NaO Bu (10 mol%), to form the [Cu(O Bu) (NHC)] as the catalysis initiating species. In this case, stable boron enolate products are formed which need to be hydrolysed by methanol to the ketone products [114]. 

Lead tetraacetate can effect oxidation of carbonyl groups, leading to formation of a-acetoxy ketones,215 but the yields are seldom high. Boron trifluoride can be used to catalyze these oxidations. It is presumed to function by catalyzing the formation of the enol, which is thought to be the reactive species.216 With unsymmetrical ketones, products from oxidation at both a-methylene groups are found.217... 

In contrast to the report by Srinivasan<33) no ketone product was isolated/34 ... 

These results prompted us to investigate the reactions of tetrafluoro-benzyne with other alkoxybenzenes 114> not only in order to attempt to explore mechanistic features more closely, but also because we envisaged that the ketonic products would undergo interesting reactions. 

A recyclable system for the directed rhodium-catalyzed hydroacylation of olefins was reported using a homogeneous phenol and 4,4 -dipyridyl solvent system at 150 °C. High yields were obtained even after eight cycles and the ketone product was obtained after decantation (Equation (132)).115... 

---