alkenes properties nomenclature stability addition reactions
TRANSCRIPT
Alkenes
Properties
Nomenclature
Stability
Addition Reactions
Ethylene
Electron Rich -Bond
Cis and Transno rotation about -bond
Elements or Degrees of Unsaturation: -Bond or Ring
Halogens replace Hydrogens
C5H10Cl2 is saturated
ClCl
C6H9Br has 2 degrees of unsaturation
Br
Br
Br
Br
Saturated compounds with Oxygen and Nitrogen
C C
HH
H
H
HH
C2H6
HH
H
C O C
H
HH
C2H6O
N C
H
HHH
C
H
HH
C2H7N
CnH2n+2CnH2n+2O CnH2n+3N
Determine the # elements of Unsaturation
C8H10Br2OC8H18 is saturatedcompound is deficient by 6 "H's"3 degrees of unsaturation
O
BrBrCH2OH
CH3
Br
Br
e.g.
OH Br
Br
Alkene Nomenclature
Cyclic alkenes
Alkyl Groups with -Bonds
CH=CH2
Br
cis 1-bromo-3-vinylcyclohexane
a vinyl group CH2CH=CH2
4-allylcyclopentene
an allyl group(or ethenyl)(or 2-propenyl)
a phenyl group
3-phenyl-1-nonene
Alkylidene GroupsDouble Bonds Fused to Rings
CH2
methylenecyclohexane
CHCH3
ethylidenecyclopentane
Polyenes
Name these Alkenes
cis-trans Isomers
E/Z System
Establish Priority of Substituents on Each sp2
Carbon
What’s My Name?
(Z)-4-ethyl-5-isopropyl-4-nonene
Hi
Hi
Lo
Lo
Priorities with Multiple Bonds
E or Z?
E or Z?
Name These
3,3-dimethyl-1,4-cyclohexadiene 2-butyl-1,5-hexadiene
(E) 1-ethylidene-2-methylcyclopentane3-allylcyclohexene
Hydrogenation Data Helps to Determine Stability
Hhydrogenation of Alkenes
Enthalpy Change Shows Relative Energy of Alkene
Both cis and trans 2-Butene are Hydrogenated to Butane
“E” is More Stable than “Z” by 2.3 KJ/mol
Relative Stabilities of Alkenes
Hyperconjugation bond associates with adjacent C-H bond
C
C
C
mono-substituted disubstituted
C
1-butene trans 2-butene
The Addition Reaction
HBr Addition
Markovnikov’s Rule
The addition of H-X across a double bond results in the more
highly substituted alkyl halide as the major product.
Depicting a Reaction
Addition of HBr or HClMarkovnikov Addition
Markovnikov
Br
C CH
H
HCH3
CH3
HBr
CH3
CH3
C
H
H
C
CH3
CH3C
H
H
Br
C
H
not formed
Regiochemistry Determined by Stability of Intermediate
H-BrBr
H
HBr Br H
3o carbocation
Hyperconjugation
Carbocation Stabilitymore highly substituted, lower energy
3o Carbocation forms Preferentially
What Alkenes are Needed to form Theses Alkyl Halides?
Definitions
• Regioisomers – two constitutional isomers that could result from an addition reaction.
• Regiospecific – only one regiosisomer forms at the expense of the other.
• Regioselective – both regioisomers are formed, but one is formed in preference.
Determine the major product:
a) HCl
b)HBr
c) 2 mol HCl
a) HCl
b)HBr
c) 2 mol HCl
Cl
H
Br
H
Cl ClHH
cis and trans
Rearrangements
CH3
CH3
HCl CH3
CH3
Cl
HH Cl
CH3
CH3
H
methide shiftCH3
CH3
Cl
32o o
Propose a Mechanism
2 Possible pathways to the Carbocation Intermediates
Endo- transition state looks like productExo- transition state looks like Reactant
Hammond’s Postulate
• Related species that are close in energy are close in structure.
• In an endothermic reaction, the transition state is similar to the product in structure and stability.
• In an exothermic reaction, the transition state is similar to the reactant in structure and stability.
• i.e. the structure of the transition state resembles the structure of the most stable species.