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08/14/2015
Chapter 8
8.1
A substitution reaction occurs when leaving group is replaced with
nucleophile.
Elimination reaction a proton from the beta position is removed
together with the leaving group forming a double bond. RXN is called beta
elimination or 1,2-elimination and can be accomplished with any good
leaving group.
When leaving group is halide reaction is dehydrohalogenation
Water is dehydration
Product of elimination reaction possesses a C=C double bond called an
alkene
8.2
Naming alkenes
1. Identify parent, longest chain that includes pi bond. Suffix ene to
indicated C=C double bond.
2. When numbering, pi bond should receive lowest number position.
3. ID substituents
4. Assign locant to substituent.
5. Arrange substitutents alphabetically
Page 347 simple alkene names
8.4
Double bond comprised of sigma bond and pi bond.
In a stepwise process the leaving group leaves then the base abstracts a
proton.
8.7
Many elimination reactions exhibit second-order kinetics with rate equation
that has following form:
Rate = k[substrate][base]
Rate is linearly dependent on concentrations of 2 different compounds
(substrate and base).
Bimolecular elimination reactions are called E2 reactions. E = elimination 2
= bimolecular
Rate of an SN2 process with a tertiary substrate is so slow can be assumed
that the substrate is inert under such reaction conditions.
Tertiary substrates undergo E2 reactions quite rapidly.
A substitution reaction occurs when the reagent functions as a nucleophile
and attacks an electrophilic position
An elimination reaction occurs when the reagent functions as a base and
abstracts a proton
With tertiary substrate, steric hindrance prevents the reagent fron function
as nucleophile at an appreciable rate, but reagent can still function as base
without encountering much steric hindrance
Tertiary substrates react readily in E2 reactions even more than primary
substrates
In energy diagram of E2 process, focus transition state.
3rd substrate, both R groups are alkyl groups
1st substrate both R groups are H atoms.
8.10
compare 2 core step of E1 with 2 core step of SN1.
Sn1 have up to 3 addl step
E1 only up to 2 addl step
-proton transfer before first core step
-carbocation rearrangement in between 2 core steps
proton transfer req at beginning of E1. Necessary when leaving group is OH.
Must be protonated, so acid is needed. Page 377
e1 mechanism involve formation of carbocation intermediate via hydride
shift or methyl shift. Page 378. Rearrangement occur between 2 core step of
e1 mechanism.
E1 can have many steps
-have atleast 2 core step (loss of leaving group & proton transfer) and addl
2 step 1. Before 2 core stop possible proton transfer 2. Inbetween 2 core
step possible carbocation rearrangement
page 379 picture mechanisms.
Number of humo in energy diagram of e1 always = number of step in
mechanism. Steps range from 2-4.
Case where carbocation rearrangement possible, products obtained from
rearrangement and w.o rearrangement.
8.11