6. Alkenes: Structure and Reactivity

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6. Alkenes Structure and Reactivity

• Based on McMurrys Organic Chemistry, 6th edition

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Alkene - Hydrocarbon With Carbon-Carbon Double
Bond

• Includes many naturally occurring materials
• Flavors, fragrances, vitamins
• Important industrial products
• These are feedstocks for industrial processes

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Alkenes
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6.2 Degree of Unsaturation

• Relates molecular formula to possible structures
• Degree of unsaturation number of multiple bonds
  or rings
• Formula for a saturated acyclic compound is
  CnH2n2
• Each ring or multiple bond replaces 2 H's

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Example C6H10

• Saturated is C6H14
• Therefore 4 H's are missing
• This has two degrees of unsaturation
• Two double bonds?
• or triple bond?
• or two rings
• or ring and double bond

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Other Examples of C6H10
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Degree of Unsaturation With Other Elements

• Organohalogens (X F, Cl, Br, I)
• Halogen replaces hydrogen
• C4H6Br2 and C4H8 have one degree of unsaturation
• Oxygen atoms these don't affect the total count
  of H's

C4H8O3
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Degree of Unsaturation With Other Elements
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If C-N Bonds Are Present

• Nitrogen has three bonds
• So if it connects where H was, it adds a
  connection point, and there an extra H
• Subtract one H for equivalent degree of
  unsaturation in hydrocarbon

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Prob. 6.3 Valium--C16H??ClN2O
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Summary - Degree of Unsaturation

• Count pairs of H's below CnH2n2
• Add number of halogens to number of H's (X
  equivalent to H)
• Don't count oxygens (oxygen does not affect the
  of Hs)
• Subtract N's - they have three connections

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6.3 Naming of Alkenes

• Find longest continuous carbon chain for root of
  the name
• Number carbons in chain so that double bond
  carbons have lowest possible numbers
• Double bond carbons must be numbered
  consecutively

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Alkene Nomenclature longest chain must contain
the CC
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Alkene Nomenclature
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Cycloalkene nomenclature
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Cycloalkene nomenclature
1-methylcyclohexene 3-methylcyclohexene
4-methylcyclohexene
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Problem 6.4 (Page 178)
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Problem 6.6 (Page 178)
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Many Alkenes Are Known by Common Names
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Alkene Group Names
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6.4 Electronic Structure of Alkenes

• Carbon atoms in a double bond are sp2-hybridized
• Three equivalent orbitals at 120º separation in
  plane
• Fourth orbital is an unhybridized p orbital
• Combination of an electron pair in an orbital
  formed by the overlap of two sp2 orbitals of two
  atoms forms ? bond between them

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6.4 Electronic Structure of Alkenes

• Additive interaction (overlap) of p orbitals
  creates a ? bonding orbital
• Subtractive interaction creates a ? anti-bonding
  orbital
• Occupied ? orbital prevents rotation about ?-bond
• Rotation prevented by ? bond - high barrier,
  about 268 kJ/mole in ethylene

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Rotation of ? Bond Is Energetically Costly

• This prevents rotation about a carbon-carbon
  double bond (unlike a carbon-carbon single bond).
• Creates possible geometric isomers (cis/trans)

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6.4 Cis-Trans Isomerism in Alkenes

• The presence of a carbon-carbon double can create
  two possible structures
• cis isomer - two similar groups on same side of
  the double bond
• trans isomer similar groups on opposite sides
• Each carbon must have two different groups for
  these isomers to occur

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Cis, Trans Isomers Require That End Groups Must
Differ in Pairs
X
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6.5 Sequence Rules The E,Z Designation

• Neither compound is clearly cis or trans
• Substituents on C1 are different than those on C2
• We need to define similarity in a precise way
  to distinguish the two stereoisomers
• Cis, trans nomenclature only works for
  disubstituted double bonds

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Develop a System for Comparison of Priority of
Substituents

• Assume a valuation system
• If Br has a higher value than Cl
• If CH3 is higher than H
• Then, in A, the higher value groups are on
  opposite sides
• In B, they are on the same side
• Requires a universally accepted valuation

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Ranking Priorities Cahn-Ingold-Prelog Rules

• Must rank atoms that are connected at comparison
  point
• Higher atomic number gets higher priority

In this case,The higher priority groups are
opposite (E )-1-bromo-1-chloro-propene
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E,Z Stereochemical Nomenclature

• Priority rules of Cahn, Ingold, and Prelog
• Compare where higher priority group is with
  respect to bond and designate as prefix
• E -entgegen, opposite sides
• Z - zusammen, together on the same side

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2-chloro-2-butenes
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Extended Comparison

• If atomic numbers are the same, compare at next
  connection point at same distance
• Compare until something has higher atomic number
• Do not combine always compare

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Dealing With Multiple Bonds

• Substituent is drawn with connections shown and
  no double or triple bonds
• Added atoms are valued with no ligands themselves

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Some Examples
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Practice problem 6.1 p. 183
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Solution
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Problem 6.11, p. 184
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Problem 6.42 (p. 208) E or Z?
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6.6 Alkene Stability

• Cis alkenes are usually less stable than trans
  alkenes

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6.7 Alkene Stability

• Compare heat given off on hydrogenation ?Ho
• Less stable isomer is higher in energy and gives
  off more heat
• tetrasubstituted gt trisubstituted gt disubstituted
  gt monosusbtituted

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Comparing Stabilities of Alkenes

• Evaluate heat given off when CC is converted to
  C-C (catalytic hydrogenation)
• More stable alkene gives off less heat (DH)

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Heats of hydrogenation of butenes
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Equilibration of 2-butenes
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Alkene Stability

• Compare heat given off on hydrogenation ?Ho
• Less stable isomer is higher in energy and gives
  off more heat
• tetrasubstituted gt trisubstituted gt disubstituted
  gt monosusbtituted

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Alkene Stabilities from DHs
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Hyperconjugation

• Electrons in neighboring filled ? orbital
  stabilize vacant antibonding ? orbital net
  positive interaction
• Alkyl groups are more stabilizing than H

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Bond strengths/hybridization effects

• sp3-sp3 bond is weaker than sp3-sp2, sp2-sp2

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Name each which is more stable? Problem 13, p.
188
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6.7 Electrophilic Addition Reactions of Alkenes

• General reaction mechanism electrophilic
  addition
• Attack of electrophile (such as HBr) on ? bond of
  alkene produces carbocation and bromide ion
• Carbocation is itself an electrophile, reacting
  with nucleophilic bromide ion

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Examples
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Writing Organic Reactions

• No established convention shorthand
• Can be formal kinetic expression
• Not necessarily balanced
• Reactants can be before or on arrow
• Solvent, temperature, details, on arrow

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For Example
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Addition of HBr to 2-methylpropene
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Electrophilic Addition Energy Diagram
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Electrophilic Addition for Syntheses

• The reaction is successful with HCl and with HI
  as well as HBr. Note that HI is generated from KI
  and phosphoric acid

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6.8 Orientation of Electrophilic Addition
Markovnikovs Rule

• In an unsymmetrical alkene, HX reagents can add
  in two different ways, but one way may be
  preferred over the other
• If one orientation predominates, the reaction is
  regiospecific
• Markovnikov observed in the 19th century that in
  the addition of HX to alkene, the H attaches to
  the carbon with the most Hs and X attaches to
  the other end (to the one with the most alkyl
  substituents)
• This is Markovnikovs rule

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Example of Markovnikovs Rule

• Addition of HCl to 2-methylpropene is
  regiospecific one product forms where two are
  possible
• If both ends have similar substitution, then the
  reaction is not regiospecific

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Examples
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But
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Practice Problem 6.2 (p. 193)
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Solution
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Practice Problem 6.3 (p. 194)
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Solution
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Problem 6.14 Major products?
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Problem 6.15 Which alkene would you add HX to?
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Stability of Carbocations and Markovnikovs Rule

• More stable carbocation forms faster
• Tertiary cations and associated transition states
  are more stable than primary cations

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Mechanistic Source of Regiospecificity in
Addition Reactions

• If addition involves a carbocation intermediate
• and there are two possible ways to add
• the route producing the more alkyl substituted
  cationic center is lower in energy
• alkyl groups stabilize carbocation

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6.9 Carbocation Structure and Stability

• Carbocations are planar
• The positively charged carbon is surrounded by
  only 6 electrons in three sp2 orbitals
• The fourth orbital on carbon is a vacant p-orbital

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6.10 Carbocation Structure and Stability

• The stability of the carbocation (measured by
  energy needed to form it from R-X) is increased
  by the presence of alkyl substituents
• Therefore stability of carbocations
• 3º gt 2º gt 1º gt CH3

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Heterolytic bond dissociations energies
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Stabilizing Carbocations
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Stabilizing Carbocations
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Problem 6.16 carbocation structure?
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6.10 The Hammond Postulate

• If one carbocation intermediate is more stable
  than another, why is the reaction through the
  more stable one faster?
• The relative stability of the intermediate is
  related to an equilibrium constant (DGº)
• The relative stability of the transition state
  (which describes the size of the rate constant)
  is the activation energy (DG)
• The transition state is transient and cannot be
  examined

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Transition State Structures

• A transition state is the highest energy species
  in a reaction step
• By definition, its structure is not stable enough
  to exist for one vibration
• But the structure controls the rate of reaction
• So we need to be able to guess about its
  properties in an informed way
• We classify them in general ways and look for
  trends in reactivity the conclusions are in the
  Hammond Postulate

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Statement of the Hammond Postulate

• A transition state should be similar to an
  intermediate that is close in energy
• Sequential states on a reaction path that are
  close in energy are likely to be close in
  structure - G. S. Hammond

In a reaction involving a carbocation, the
transition states look like the intermediate
G
carbocation
Reaction
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Competing Reactions and the Hammond Postulate

• Normal Expectation Faster reaction gives more
  stable intermediate
• Intermediate resembles transition state

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Non-Hammond Behavior

• More stable intermediate from slower reaction
• Conclude transition state and intermediate must
  not be similar in this case not common

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Transition State for Alkene Protonation

• Resembles carbocation intermediate
• Close in energy and adjacent on pathway
• Hammond Postulate says they should be similar in
  structure

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Transition State resembles cation
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Energy Diagrams for Markovnikov
Anti-Markovnikov Addition
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6.11 Mechanism of Electrophilic Addition
Rearrangements of Carbocations

• Carbocations undergo structural rearrangements
  following set patterns
• 1,2-H and 1,2-alkyl shifts occur
• Goes to give more stable carbocation
• Can go through less stable ions as intermediates

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Carbocation rearrangements
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Hydride Shifts
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Alkyl (methyl) shifts
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Cholesterol Biosynthesis
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Problem 6.47 What will be the rearranged cations?
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Problem 6.19 mechanism?
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Problem 6.48 mechanism?
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Problem 6.49 mechanism?
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Terpenes
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Terpenes
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Terpene Biosynthesis
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Limonene biosynthesis