有机化学英文件chapter9.pptVIP

Organic Chemistry William H. Brown Christopher S. Foote Brent L. Iverson Nucleophilic Substitution and ?-Elimination Chapter 8 Nucleophilic Substitution Nucleophilic substitution: any reaction in which one nucleophile substitutes for another at a tetravalent carbon Nucleophile: a molecule or ion that donates a pair of electrons to another molecule or ion to form a new covalent bond; a Lewis base Nucleophilic Substitution Some nucleophilic substitution reactions Solvents Protic solvent: a solvent that is a hydrogen bond donor the most common protic solvents contain -OH groups Aprotic solvent: a solvent that cannot serve as a hydrogen bond donor nowhere in the molecule is there a hydrogen bonded to an atom of high electronegativity Dielectric Constant Solvents are classified as polar and nonpolar the most common measure of solvent polarity is dielectric constant Dielectric constant: a measure of a solvent’s ability to insulate opposite charges from one another the greater the value of the dielectric constant of a solvent, the smaller the interaction between ions of opposite charge dissolved in that solvent polar solvent: dielectric constant 15 nonpolar solvent: dielectric constant 15 Protic Solvents Aprotic Solvents Mechanisms Chemists propose two limiting mechanisms for nucleophilic substitution a fundamental difference between them is the timing of bond-breaking and bond-forming steps At one extreme, the two processes take place simultaneously; designated SN2 S = substitution N = nucleophilic 2 = bimolecular (two species are involved in the rate-determining step) Mechanism - SN2 both reactants are involved in the transition state of the rate-determining step Mechanism - SN2 Mechanism - SN1 Bond breaking between carbon and the leaving group is entirely completed before bond forming with the nucleophile begins This mechanism is designated SN1 where S = substitution N = nucleophilic 1 = unimolecular (only one species is involved in the rate-determining ste