Nucleophilic attack polar solvent effect

Uncatalyzed amidations of acids have been realized under solvent-free conditions and with a very important microwave effect [67 a]. The best results were obtained by use of a slight excess of either amine or acid (1.5 equiv.). The reaction involves thermolysis of the previously formed ammonium salt (acid-base equilibrium) and is promoted by nucleophilic attack of the amine on the carbonyl moiety of the acid and removal of water at high temperature. The large difference in yields (MW > A) might be a consequence of interaction of the polar TS with the electric field (Eq. (15 a) and Tab. 3.6). 

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. 

The khietics of die reactions of 1 -halo-2.4-dinitrobcnzcncs with aliphatic amines have been used to probe solvent effects in mixtures of chloroform or dichloromethane with polar hydrogen-bond acceptors, such as DMSO. In these reactions, nucleophilic attack is rate limiting. Attempts to correlate reactivity with the empirical solvent... 

The better the solvent stabilizes the ions, the more probable that the reaction will follow an SN1 pathway (e.g., in polar protic solvents such as water/acetone). The more highly substituted is the incipient carbenium ion, the more probable that the reaction will follow an SN1 pathway. The more unreactive the nucleophile, the more probable it becomes that a reaction with secondary and tertiary electrophiles will follow an SN1 pathway. A weaker nucleophile is not as effective in the backside attack, since this location is sterically shielded, especially in the case of tertiary substrates. Carbenium ions are planar and therefore less sterically hindered, and are naturally more reactive as electrophiles than the uncharged parent compound. 

Both reactions involve nucleophilic attack of tricoordinated phosphorus on tetrahedral carbon and show all the characteristics of non-polar reactants combining through polar transition states although the solvent effects are sometimes quite modest.— Subsequent studies have demonstrated nucleophilic attack on activated alkenes,Z activated alkynes,Z the carbonyl groupZ-Z and halogen , whilst in the Perkow reaction (eqn. 1) all four possible sites in... 

Recommendations on the synthesis of metal phthalocyanines. It is still difficult to evaluate real reaction mechanisms in each synthetic procedure applied. It is clear that the use of such polar protic solvents as alcohols contributes to higher yields of Pc from PN in the electrosynthesis conditions due to the ease of nucleophilic attack of the generated additional RO-. In the further steps of Pc formation from PN or 1,3-D, a solvent s nature has no significant importance. These data about the importance of, first of all, the initial stage correspond to those reported on UV irradiation [40] of PN solutions, where such a treatment is effective only at the beginning of the process. However, in the case of the use of urea and PA, a solvent must be completely inert (or be close to urea s nature) to carry out the one-step synthesis of metal phthalocyanines, in order to exclude any negative influence on the reaction course. The fact that the yields are almost always higher in the case of direct electrosynthesis could serve as an additional confirmation about the usefulness and necessity of this technique. 

Chemical reactivity is influenced by solvation in different ways. As noted before, the solvent modulates the intrinsic characteristics of the reactants, which are related to polarization of its charge distribution. In addition, the interaction between solute and solvent molecules gives rise to a differential stabilization of reactants, products and transition states. The interaction of solvent molecules can affect both the equilibrium and kinetics of a chemical reaction, especially when there are large differences in the polarities of the reactants, transition state, or products. Classical examples that illustrate this solvent effect are the SN2 reaction, in which water molecules induce large changes in the kinetic and thermodynamic characteristics of the reaction, and the nucleophilic attack of an R-CT group on a carbonyl centre, which is very exothermic and occurs without an activation barrier in the gas phase but is clearly endothermic with a notable activation barrier in aqueous solution [76-79]. 

The exchange reaction of 1-bromonaphthalene with CuCl proceeds effectively in polar solvents, such as DMF or DMSO, at temperatures of 110-150 °C via a second-order mechanism. The reaction is reversible but the equilibrium favors formation of aryl chlorides. The catalysis is inhibited by chloride anion and by pyridine or, particularly, 2,2 -bipyri-dine. The ease of replacement decreased in the order Arl> ArBr> ArCl and the reactivity of the attacking nucleophile decreased in the order CuCl> CuBr> Cul. The exchange reac-... 

We shall conclude this Section with an example of a reaction that undergoes an extreme rate acceleration with an increase in solvent polarity. Thermolysis of a-chlorobenzyl methyl ether in a series of non-nucleophilic, non-HBD solvents shows rate variations up to 10, encompassing a range of 30 kJ/mol (7 kcal/mol) [112], This dramatic solvent effect is best explained by a mechanism involving ionization of the C—Cl bond to form an ion pair, followed by a nucleophilic attack by Cl on CH3 to give an aldehyde and chloromethane cf. Eq. (5-41). 

The mechanism of reaction of amines with tricarbonyl (fluorobenzene) chromium in polar aprotic solvents is especially interesting because the chromium tricarbonyl group exerts a steric effect. Nucleophiles attack the ring from the less hindered side exo to the chromium center to form a-complex 17. Expulsion of fluorine re-... 

Several factors influence whether a reaction will occur by an Sn1 or Sn2 mechanism carbocation stability, steric effects, strength of nucleophile, and the solvent. Tertiary halides tend to react by the SN1 process because they can form the relatively stable tertiary carbocations and because the presence of three large alkyl groups sterically discourages attack by the nucleophile on the carbon-halogen bond. The Sn2 reaction is favored for primary halides because it does not involve a carbocation intermediate (primary carbocations are unstable) and because primary halides do not offer as much steric hindrance to attack by a nucleophile as do the more bulky tertiary halides. Strong nucleophiles favor the Sn2 mechanism and polar solvents promote SN1 reactions. 

Effect of Solvents and Reaction Conditions Synthesis Capabilities Block Copolymers Functional End-Group Polymers Initiation Processes in Anionic Polymerization Initiation by Electron Transfer Initiation by Nucleophilic Attack Mechanism and Kinetics of Homogeneous Anionic Polymerization Polar Media Nonpolar Media... 

The initial step in the mechanism outlined in Scheme 2 is electron transfer quenching of the singlet arene by DCNB. Nucleophilic addition of the amine to the arene cation radical followed by proton and electron transfer steps yields the adduct and regenerates the sensitizer. Adduct formation requires the use of polar solvents, and yields are higher in aqueous vs. dry acetonitrile. Adduct formation is observed in moderately polar solvents (ethers) in the presence, but not in the absence, of an added salt, n-Bu4NBF4. The solvent and salt effects were interpreted as evidence for C-N bond formation via the free arene radical cation, rather than via an ion pair (CRIP or SSRIP), However, Nieminen et ah concluded that nucleophilic attack involves a radical ion pair on the basis of their laser flash photolysis investigation. In addition to this unresolved controversy, the timing of the subsequent proton transfer and electron transfer steps remains to be established. 

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