Solvent effect ketones

Decomposition late studies on dialkyl peioxydicaibonates ia vaiious solvents leveal diamatic solvent effects that ptimatily lesult fiom the susceptibiUty of peioxydicaibonates to iaduced decompositions. These studies show a decieasiag oidei of stabiUty of peioxydicaibonates ia solvents as follows TCE > saturated hydrocarbons > aromatic hydrocarbons > ketones (29). Decomposition rates are lowest in TCE where radicals are scavenged before they can induce the decomposition of peroxydicarbonate molecules. 

A decisive solvent effect is also observed with other a,/ -epoxy ketones. Specifically, 3jS-hydroxy-16a,17a-epoxypregn-5-en-20-one and its acetate do not react with thiocyanic acid in ether or chloroform. However, the corresponding thiocyanatohydrins are formed by heating an acetic acid solution of the epoxide and potassium thiocyanate. As expected, the ring opening reaction is subject to steric hindrance. For example, 3j6-acetoxy-14f ,15f5-epoxy-5) -card-20(22)-enoIide is inert to thiocyanic acid in chloroform, whereas the 14a,15a-epoxide reacts readily under these conditions.Reactions of 14a,15a-epoxides in the cardenolide series yields isothiocyanatohydrins, e.g., (135), in addition to the normal thiocyanatohydrin, e.g., (134). 

The best way to take advantage of the organic solvent effect without simultaneously diluting the sample is by employing solvent extraction. By this method the element to be analyzed can actually be concentrated and a solution of the element is obtained in essentially pure organic solvent. One of the most commonly used systems involves formation of the metal chelate with ammonium 1-pyrro-lidinecarbodithioate (APDC) and then extracting this into methylisobutyl ketone (MIBK). APDC chelates of many elements form and extract into MIBK from acid solution. 

The Claisen rearrangement is an electrocyclic reaction which converts an allyl vinyl ether into a y,8-unsaturated aldehyde or ketone, via a (3.3) sigmatropic shift. The rate of this reaction can be largely increased in polar solvents. Several works have addressed the study of the reaction mechanism and the electronic structure of the transition state (TS) by examining substituent and solvent effects on the rate of this reaction. 

The activation of various reactions by Lewis acids is now an everyday practice in synthetic organic chemistry. In contrast, solvent effects on Lewis acid catalysed Diels-Alder reactions have received much less attention. A change in the solvent can affect the association step leading to the transition structure. Ab initio calculations on the Diels-Alder reaction of cyclopentadiene and methyl vinyl ketone in aqueous media showed that there is a complex of the reactants which also involves one water molecule119. In an extreme case solvents can even impede catalysis120. The use of inert solvents such as dichloromethane and chloroform for synthetic applications of Lewis acid catalysed Diels-Alder reactions is thus well justified. General solvent effects, in particular those of water, will be discussed in the following section. 

Several animal studies indicate that chloroform interacts with other chemicals within the organism. The lethal and hepatotoxic effects of chloroform were increased by dicophane (DDT) (McLean 1970) and phenobarbital (a long-acting barbiturate) in rats (Ekstrom et al. 1988 McLean 1970 Scholler 1970). Increased hepatotoxic and nephrotoxic effects were observed after interaction with ketonic solvents and ketonic chemicals in rats (Hewitt and Brown 1984 Hewitt et al. 1990) and in mice (Cianflone et al. 1980 Hewitt et al. 1979). The hepatotoxicity of chloroform was also enhanced by co-exposure to carbon tetrachloride in rats (Harris et al. 1982) and by co-exposure to ethanol in mice (Kutob and Plaa 1962). Furthermore, ethanol pretreatment in rats enhanced chloroform-induced hepatotoxicity (Wang et al. 1994) and increased the in vitro metabolism of chloroform (Sato et al. 1981). 

Haloform reaction, 237, 296 Halogenation alkanes, 300, 323 alkenes, 179,186, 313 benzene, 138,316 ketones, 295 Hammett equation, 362 additional parameters, 374, 388, 395 derivation of, 362 deviations from, 375 empirical nature of, 395 implications of, 394 reaction pathway, and, 375 solvent effects and, 388 spectroscopic correlations, 392 standard reaction for, 362, 395 steric effects and, 361, 383 thermodynamic implications of, 394 Hammett plots, 359 change in rate-limiting step and, 383 change in reaction pathway and, 378... 

When the alcohol adduct from the allenylzinc reagent and diisopropyl ketone was treated with 80 mol% of allenylzinc bromide in HMPA, a mixture containing 12% of diisopropyl ketone and 88% of recovered alcohol was obtained after 7 days at ambient temperatures (equation 1). Thus, it may be deduced that the allenylzinc additions are reversible. Presumably, the propargyl adducts are intrinsically favored, but steric interactions between the R1 and R2 substituents in the propargyl product favors an increased proportion of allenyl adducts in a reversible process (see Table 1). HMPA would expectedly facilitate reversal of the addition by decreasing the ion pairing between the alkoxide anion and ZnBr cation of the adducts. This expectation was subsequently confirmed by a study of solvent effects. 

A semiempirical force field is constructed for the calculation of conformational potential energies of unstrained, acyclic, aliphatic aldehydes and ketones, taking solvent effects into consideration. Detailed conformational calculations for fitting and testing the necessary parameters are done. The results are incorporated into a RIS scheme for polylmethyl vinyl ketonels. 

Interesting solvent effects have also been observed189 [Eq. (9.47)]. Product distribution at secondary sites in water is almost statistical, and ketones are the main products. In acetonitrile, the y position is oxidized with the preferential formation of alcohols. 

Incorporation of these heterocycles into poly(dienes) has pronounced effects on polymer solubility. Solubility in oxygenated solvents, especially ketonic solvents, increases whereas solubility in hydrocarbon solvents decreases dramatically. This has led to applications requiring resistance to swelling in oil, gasoline and naphtha. 

Finally, with the analogous substituted butyrophenones, Pitts has reported that no such solvent effect on reactivity is observed in the intramolecular H-atom abstraction process although the absorption spectra of these ketones show pronounced solvent shifts similar to the corresponding benzophenones. 

Cyclic enones participate in several other photochemical reactions. Irradiation of neat cyclopentenone417 or cyclohexenone418 leads to formation of dimers. Eaton has shown that the reaction is quenched by piperylene and that there is a strong polar solvent effect on the ratio of head-to-head and head-to-tail dimers formed.511 Similar solvent effects have been noted for the triplet-state photodimerization of isophorone.512 Head-to-head dimers are favored in polar solvents and in neat ketone, while head-to-tail dimers are favored in nonpolar media. 

The solvent effects observed in the photochemical rearrangements of cross-conjugated dienones suggest that the availability of a proton to an excited state of the ketone may be an important controlling factor. It is interesting to consider the possibility that protonation of an excited state may lie behind the apparent polar reactions. Triplet states are likely to be more polarizable and to be stronger bases than the corresponding... 

The Bayhs-Hillman reaction of optically pure azetidine-2,3-diones [235, 236] with methyl vinyl ketone in the presence of l,4-diazabicyclo[2.2.2]octane (DABCO) in acetonitrile at -20°C for 1 h have been reported to give functionalized allylic alcohols, having the p-lactam scaffold, in good yields (80%) and complete diastereoselectivity [237]. In terms of achieving good yields with a reasonable rate of reaction, 50 mol% of DABCO seemed to be the catalyst amount of choice for this reaction. No significant solvent effect was observed in the overall yield (Scheme 108). 

A remarkable solvent effect on the chemoselectivity was discovered by Agarwala and Bandyopadhyay (Scheme 3.24, B) [114]. When cyclohexene la was oxidized with tBuOOH in the presence of an electronegative substituted iron(III) porphyrin complex in CH2Cl2-MeOH, epoxide 4a was the predominant product (69% yield) in addition to alcohol 2a and ketone 3a as byproducts in 20% and 11% yields,... 

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