Ethyl cation, ethylation with

Due to the benzylic p-Tc resonance stabilization the C+-C,pso bond has partial double bond character and the ortho, ortho and meta, meta methine groups syn and anti to the silyl group are non-equivalent. The effect pf the a-silyl group on the positive charge in benzyl cations can be estimated by comparison of the NMR spectroscopic data of the 1 -phenyl-1 -(trimethylsilyl)ethyl cation 1 with those for the 1-phenylethy 1 cation 5 (P) and the cumyl pation 3 (15, 16, 17) (Table 1). 

Alkylimidazolinm tetraflnoroborates are, for example, ionic liquids at room-temperature that can provide an anion to stabilize an intermediate cation-radical with no possibility of nucleophilic attack on it. Ionic liquids have a huge memory effect, and their total friction is greater than that of conventional polar solvents. Thus, the total friction of l-ethyl-3-methylimidazolium hexafluoro-phosphate is about 50 times greater than that of AN (Shim et al. 2007). The solvent effects of ionic liquids on ion-radical ring closures deserve a special investigation. The ring closure reactions can be, in principal, controlled by solvent effects. 

A cation arriving with a nncleophilic anion is another important factor. The nucleophile can attack the substrate in the form of a free ion or an ionic pair. As a rule, lithium salts are less reactive than sodium and potassium salts. Russell and Mndryk (1982) reported several examples of this. The sodium salt of ethyl acetylacetate reacts with 2-nitro-2-chloropropane in DMF yielding ethyl 2-(wo-propylidene) acetylacetate. Under the same conditions, the lithium salt does not react at all. Potassium diethyl phosphite interacts with l-methyl-l-nitro-l-(4-toluylsulfonyl)propane in THF and gives diethyl 1-methyl-l-nitro-l-phosphite. The lithinm salt of the same reactant does not react with the same substrate in the same solvent. 

The effect of an w-silyl group on the positive charge in benzyl cations can be estimated by comparing the NMR spectroscopic data for the 1 -phenyl- 1-trunethylsilylethyl cation 290 with those for the phenyl ethyl cation 78 and the cumyl cation 292 prepared under identical conditions from the corresponding chlorides with Sbl 5. The 1II and 13C NMR data for 78, 290 and 292114 measured under comparable conditions are given in Tables 10 and 11. 

Ab initio DFT calculations were performed using the B3LYP/6-31G(d) hybrid method for the analogous l-p-anisyl-2-SiH3-substituted ethyl cation 324, which is a close model for the experimentally observed cation 323 with alkyl groups at silicon. It has been shown that different alkyl groups at silicon have no significant impact on the electronic stabilization in a-aryl-/l-silyl-substituted carbocations. 

Fig. 4 Elongation of the R3 phosphate ester chain of the cationic PC results in nonlamellar phase formation. Small-angle X-ray diffraction patterns recorded at 20° C show (a) lamellar La (b) cubic Pn3m (c) inverted hexagonal Hn phases formed by dioleoyl cationic PCs with ethyl, hexyl and octadecyl R3 chains, respectively, diCl8 1 -EPC [19], diC18 l-C6PC [20] and diC18 l-C18PC [21]...

Intermolecular addition and addition-cyclization reactions of aminium cation radicals with electron-rich alkenes such as ethyl vinyl ether (EVE) allow an entry into products containing the N—C—C—O moiety of 13-amino ethers 70 or the equivalent of /3-amino aldehydes 71. The mild conditions under which aminium cation radicals are generated from PTOC carbamates makes the reactions described in Scheme 22 possible. In the absence of hydrogen atom donors, the /3-amino ethoxy(2-pyridylthio) acetal 71 was the major product. The mixed acetal can easily be converted... 

Rhenium complexes 22a,b were designed as ditopic receptors for the cooperative complexation of ion pairs [21]. As proved by H NMR titration experiments in CD3CN,the receptors form complexes of 2 1 stoichiometry with alkali metal cations (interaction with both ethyl acetate cavities on the lower rim) and exhibit [16] a positive allosteric effect for iodide complexation compare... 

Phenyl- 1,2-dithiolium cation reacts with acetone and ethyl vinyl ether in the following way (Scheme 4).28... 

With the same methodology, the preparation of 3-phenyl-substituted THFs can be assessed by irradiating ArCl in the presence of a nonterminal alkene. Hence, the photogenerated phenyl cations react with the (E)-3-hexen-l-ol, and this results in the stereoselective formation of traws-2-ethyl-3-aryltetrahydrofuran derivative in good to very good yields (52-88%) [72],... 

The reaction of unsubstituted 2-amino-1,3,4-thiadiazole (131) with 1,3-dicarbonyl compounds is dependent on the nature of the dicarbonyl compound (Scheme 13). Thus, reaction of (131) with pentane-2,4-dione gives the 4,6-dimethyl-2-thiocyanatopyrimidine (132). The formation of (132) may proceed via the cation (132a). With ethyl acetoacetate, however, a mixture of (133) and (134) is formed, (133) also being converted into (134) on heating. 

The Au foil Is quickly dissolved In aqua regia and the Au extracted with ethyl acetate for 1 min. The aqueous phase is then eluted through a Dowex-1 anion resin column (2 zmn diameter, 1 cm long) with 6 M HC1 to complete the removal of Au end other impurities. The dropB. containing the actinide fraction are evaporated and the activity is then eluted through a Dowex-50 resin cation column with 0.4 M soln. of ammonium Q -hydroxy-isobutyrate, which is adjusted to pH 4.0 with HH4OH to separate the various actinide elements from each other, (Mv-Fm-E-Cf)... 

In the gas phase, the reaction of ethyl cations, C2H , with the ambident 2,4-pentanedione (which is 92% enolized at 25 °C in the gas phase) leads predominantly (>95%) to alkylation at the hard oxygen site and not at the soft carbon atom, as predicted by the HSAB concept [662]. Accordingly, the gas-phase alkylation of the enolate ion of cyclohexanone gives only the O- and no C-alkylation product [848], and the gas-phase acylation of acetophenone enolate with trifluoroacetylchloride leads predominantly to the 0-acylation product (0/C ratio = 6.0) [849]. 

Phenolic compounds are generally extracted using various mixtures of water and alcohol. Anthocyanins are traditionally extracted in the flavylium cation form, with methanol-containing hydrochloric acid. For the acylated anthocyanins, it is necessary to replace the hydrochloric acid with a weaker acid, either formic or acetic acid. Lipids, carotenoids, and chlorophyll are removed from the water-alcohol extracts with hexane, chloroform, or petroleum ether. The defatted extracts may be analyzed directly or after a partitioning of the phenolics into ethyl acetate. 

Recently, Chen has synthesized and resolved chiral suberyl carbenium ions and utilized these as catalysts for enantioselective Mukaiyama aldol addition reactions (Eq. (8.22)) [34]. Thus the reaction of the ethyl acetate-derived silyl ketene acetal with benzaldehyde in the presence of 10-20 mol% of catalyst afforded the corresponding adduct in 50% ee. The enantioselectivity of the process proved sensitive to the nature of the cation, consistent with observations previously highlighted by Denmark in related studies [35]. Although at the current level of development the selectivities are modest, the study documents a novel class of metal-free Lewis acidic agents. 

The reaction mechanism proposed by Timberlake and Bridle (1976), suggests that acetaldehyde, in the form of a carbo-cation, reacts with flavanol (tarmin) at position C-6 or C-8 (Figure 1 (1)). This, via several condensation reactions, gives rise to tannin-ethyl-anthocyanin derivatives (Figure 1 (2)) such as malvidin-3-glucoside-ethyl-(epi)catechin and malvidin-3-(6-/7-coumaroyl)-glucoside-ethyl-(epi)catechin. 

There is a scant data on the radical behavior of thianthrene radical cation [58]. As pointed out above, thianthrene radical cation couples with radicals. It shows little reactivity toward oxygen but this may be ascribed to its positive charge which should render it an electrophilic radical. It initiates the polymerization of styrene [59,60], a-methyl styrene [59], and ethyl vinyl ether [59,60],but not that of vinyl pyridine [61], vinyltrimethylsilane [59], methyl acrylate [59, 61], or acrylonitrile [59,61 ]. These results can be explained by cationic rather than radical polymerization. 

In a solution of 1,2-dichloroethane at 60°C, iV-vinylcarbazole has been cationically polymerized with ethyl l-cyano-2-(p-methoxyphenyl)cyclopropane-carboxylate as initiator. The polymers obtained had a bimodal distibution of their molecular weights. It was postulated that the propagation steps of the process proceeded by both free-ion and an ion-pair steps. At low temperatures, low monomer concentrations, higher initiator concentrations, lower conversion, and in more polar solvents, the free-ion propagation was favored [61]. 

Extensive work studying the interaction of poly(N-ethyl-4-vinylpyridinium bromide) (PEVP) and related (partially alkylated) cationic copolymers with anionic lipid membranes has been performed by Yaroslavov, Menger, and Kabanov. In all cases, 4-vinyl pyridine was free radically polymerized and postfunctionalized with alkyl bromides (Figure 17). The initial... 

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