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V = k x [RX] x [-OH]
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Reaction Kinetics
The study of rates of reactions is called kinetics Rates decrease as concentrations decrease but the rate constant does not Rate units: [concentration]/time such as L/(mol x s) The rate law is a result of the mechanism The order of a reaction is sum of the exponents of the concentrations in the rate law the example is second order
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SN2 Process
The reaction involves a transition state in which both reactants are together
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The carbon atom in (a) bromomethane is readily accessible resulting in a fast SN2 reaction. The carbon atoms in (b) bromoethane (primary), (c) 2-bromopropane (secondary), and (d) 2-bromo-2-methylpropane (tertiary) are successively more hindered, resulting in successively slower SN2 18 reactions.
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The Nucleophile
Neutral or negatively charged Lewis base Reaction increases coordination at nucleophile Neutral nucleophile acquires positive charge Anionic nucleophile becomes neutral
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Stable anions that are weak bases are usually excellent leaving groups and can delocalize charge
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Alkyl fluorides, alcohols, ethers, and amines do not typically undergo SN2 reactions.
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The Solvent
Protic solvents that can donate hydrogen bonds (OH or NH) slow down SN2 reactions by solvation by associating with reactants nucleophile Energy is required to break interactions between reactant and solvent Polar aprotic solvents (no NH, OH, SH) form weaker interactions with substrate and permit faster reaction by raising the ground-state energy
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V = k[RX]
Rate-Limiting Step
The overall rate of a reaction is controlled by the rate of the limiting/(slower) step The rate depends on the concentration of the species and the rate constant of the step The highest energy transition state point on the diagram is that for the rate determining step (which is not always the highest barrier) V = k[RX]
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The planar intermediate leads to loss of chirality A free carbocation is achiral Product is racemic or has some inversion
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SN1 in Reality
Carbocation is biased to react on side opposite leaving group Suggests reaction occurs with carbocation loosely associated with leaving group during nucleophilic addition Alternative that SN2 is also occurring is unlikely
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Nucleophiles in SN1
Since nucleophilic addition occurs after formation of carbocation, reaction rate is not normally affected by nature or concentration of nucleophile
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Solvent in SN1
Stabilizing carbocation also stabilizes associated transition state and controls rate Solvent effects in the SN1 reaction are due largely to stabilization or destabilization of the transition state
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SN1 and SN2 reactions are well known in biological chemistry Unlike what happens in the laboratory, substrate in biological substitutions is often organodiphosphate rather than an alkyl halide
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E1
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E2 reaction
Concerted mechanisms require specific geometric arrangement IN ORDER FOR orbital of the bonds being broken can overlap with those being formed and the electron can flow smoothly from one bond to another Geometric arrangement for SN2 is back- side attack E2 occur with periplanar geometry (H, X, and C=C lie in the same plane)
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E2
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E1cB
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Geometry of Elimination E2
Syn-periplanar geometry the H and the X are on the same side (eclipsed, high energy) Anti periplanar geometry the H and the X are on opposite side (staggered, low energy) Anti coplanar (theta=180 degree) or antiperiplanar arrangement is most commonly seen in E2 Antiperiplanar preferred because allows orbital overlap and minimizes steric interactions
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E2 Stereochemistry
Overlap of the developing orbital in the transition state requires periplanar geometry, anti arrangement
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Predicting Product
E2 is stereospecific Meso-1,2-dibromo-1,2-diphenylethane with base gives cis 1,2-diphenyl. None isomeric Z alkene formed, because it requires syn periplanar, higher energy RR or SS 1,2-dibromo-1,2-diphenylethane gives trans 1,2-diphenyl
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Comparing E1 and E2
Strong base is needed for E2 but not for E1 E2 is stereospecifc, E1 is not E1 gives Zaitsev orientation
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E1cB Reaction
Takes place through a carbanion intermediate
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