Methylene compounds arenes

Condensation of aryl halides with various active methylene compounds is readily promoted by catalytic action of palladium to give the corresponding arene derivatives containing a functionalized ethyl group [7]. Yamanaka et al. extended this chemistry to haloazoles including oxazoles, thiazoles and imidazoles [8]. Thus, in the presence of Pd(Ph3P)4,2-chlorooxazole was refluxed with phenylsulfonylacetonitrile and NaH to form 4,5-diphenyl-a-phenylsulfonyl-2-oxazoloacetonitrile, which existed predominantly as its enamine tautomer. In a similar fashion, 4-bromooxazole and 5-bromooxazole also were condensed with phenylsulfonylacetonitrile under the same conditions. 

Keywords active methylene compound, LiBr, nitroso arene, Ehrlich-Sachs reaction, microwave irradiation, imine... 

On the other hand, the direct arylation of carbanionic species generated from substrates having relatively acidic hydrogens such as active methylene compounds and ketones can occur (mechanism B) [5,6]. Aryl halides are also capable of coupling directly with appropriately functionalized aromatic substrates and five-membered heteroaromatic compounds as formal carbon nucleophiles via cleavage of their unactivated C-H bonds [5,7-9]. The Fujiwra-Moritani reaction, which is the arylation of alkenes with arenes, is also useful for preparing arylalkenes without employing any halides (mechanism D) [10,11]. 

Calix[n]arenes 1-3 were used as inverse PT catalysts in the alkylation of active methylene compounds with alkyl halides in aqueous NaOH solutions,and in aldol-type eondensation and Michael addition reactions. In the aikylation of phenylacetone with octyl bromide, the IPTC procedure enhanced the alkylation versus hydrolysis and C versus O alkylation selectivities with respect to those observed xmder classical PTC reactions in the presence of tetrabutylammonium bromide (TBAB) or hexadecyltributylammonium bromide (HTPB). Moreover, the aqueous catalyst solution was easily separated from the organic phase eontaining the products, and no organic solvent was required. In the case of the aldol-type condensation of benzaldehyde with indene or acetophenone in aqueous NaOH (Fig. 9), IPTC reaetions eatalyzed by I were compared with those conducted in aqueous micelles in the presence of cetyltrimethylammonium bromide (CTAB) as the sufactant. Although selectivities and yields were similar, the IPTC proeedure avoided the formation of emulsions, thus faciUtating product separation and catalyst recovery. In the light of the results obtained, water-soluble calix[ ]arenes 1-3 were proposed... 

Reaction of rhenium atoms with alkyl-substituted arenes forms dirhenium- l-arylidene compounds (2 2) (Figure 3). The products require insertion, presumably sequential, into two carbon-hydrogen bonds of the alkyl substituent. These reactions seem highly specific and require only the presence of an alkyl-substituted benzene that possesses a CH2 or CH3 substituent. Thus, co-condensation of rhenium atoms with ethylbenzene gives two isomers (see Figure 3) in which the products arise from insertion into the carbon-hydrogen bonds of the methylene or the methyl group. The product distribution in this reaction is in accord with statistical attack at all available sp3 C-H bonds. 

In 1982, /Mert-butyl-cal i x n larenes were studied by Izatt et al. for their capacity to transport cesium from an alkaline medium ([MOH] = 1M) through bulk liquid membranes made of a mixture of diluents able to dissolve these compounds methylene chloride, carbon tetrachloride, and dichloromethane. Experiments were carried out using p-tert-calix[8]arene to measure the rate of cesium transport under conditions of varying source pH. The values of the transport rate, small below a pH of 12, rise rapidly beyond this value, hence confirming that a proton is removed from the ligand in the complexation process. Under such conditions, tetramer, hexamer, and octamer (n = 4, 6, and 8, respectively) display a high selectivity for cesium over the other... 

All types of electrophiles have been used with 2-lithio-l,3-dithiane derivatives, including alkyl halides, sulfonates, sulfates, allylic alcohols, arene-metal complexes, epoxides, aziridines, carbonyl compounds, imines, Michael-acceptors, carbon dioxide, acyl chlorides, esters and lactones, amides, nitriles, isocyanates, disulfides and chlorotrialkylsilanes or stannanes. The final deprotection of the dithioacetal moiety can be carried out by means of different types of reagents in order to regenerate the carbonyl group by heavy metal coordination, alkylation and oxidation184 or it can be reduced to a methylene group with Raney-nickel, sodium or LiAIII4. 

As the methylene protons of the cycloproparenes are formally benzylic, the compounds should be at least as acidic as the corresponding methyl arenes. Simple extended Huckel calculations concur and predict some stabilization of 6 from charge delocalization the cycloproparenyl anion (6) is expected to be accessible. Indeed, treatment of 1 with butyl-lithium at -78 °C provides an organolithium that has been characterized by NMR and shown to be monomeric in solution. Both the H NMR (H(d 1.91, H(2/s) 5.83, H(3/4) 6.13 ppm, respectively) and NMR (C(,) 31.3, C(,a/5a) 149.0, 99.1, C(3/4) 120.4 ppm, respec-... 

However it has been recognised in recent years that macrocyclic products, the calixarenes, (ref.56) also accompany the linear polymers under basic conditions, albeit in low yield but that also they can be formed in low yields in acidic media (ref.57). The four membered parent phenolic member, calix[4]arene was first noted, in alkafine reaction conditions, many yeas ago (ref.58). Although subsequently 4-t-octylphenol was found to give two products (ref.59) at first thought to be stereoisomeric cyclic tetramers, it was shown in later work that 4-t-butyiphenol afforded not only cyclic compounds with methylene, but also dimethylene ether bridges (ref. 60). 

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