The Double Bond as a Substituent

Chapter 10 Conjugation in Alkadienes and Allylic Systems

C C

C+

C C

allylic carbocation

allylic radical

C C C

conjugated diene

Vinylic versus Allylic 10.1 The Allyl Group

H C H C H

H C H
vinylic carbons

C C

allylic carbon

Vinylic versus Allylic

Vinylic versus Allylic

H C H C H
Vinylic hydrogens are attached to vinylic carbons.

H H C C C C H

Allylic hydrogens are attached to allylic carbons.

Vinylic versus Allylic

Vinylic versus Allylic

X C X C X
Vinylic substituents are attached to vinylic carbons.

X X C C C C X

Allylic substituents are attached to allylic carbons.

Allylic Carbocations The fact that a tertiary allylic halide undergoes solvolysis (SN1) faster than a simple tertiary alkyl halide CH3 CH3 H2 C CH C CH3 123 Cl CH3 C CH3 1 Cl

10.2 Allylic Carbocations

C C

relative rates: (ethanolysis, 45C) 45

Allylic Carbocations Provides good evidence for the conclusion that allylic carbocations are more stable than other carbocations CH3 CH3 H2 C CH C+ CH3 CH3 C+ CH3

Stabilization of Allylic Carbocations

Delocalization of electrons in the double bond stabilizes the carbocation. resonance model orbital overlap model

H2C=CH stabilizes C+ better than does CH3 C=CH

Resonance Model

Orbital Overlap Model

CH3 H2 C CH C+ CH3 + H2 C CH3 CH C + CH3 + H2 C CH C

CH3

CH3

Orbital Overlap Model

Orbital Overlap Model

Orbital Overlap Model

10.3 SN1 Reactions of Allylic Halides

Hydrolysis of an Allylic Halide CH3 H2 C CH C CH3 H2 O CH3 H2 C CH C CH3 OH + HOCH2 CH C CH3 (85%) Na2CO3 CH3 H2 C CH Cl

Corollary Experiment CH3 ClCH2 ClCH CH C CH3 H2 O CH3 C CH3 OH + HOCH2 CH C CH3 Na2CO3 CH3

(85%)

(15%)

(15%)

CH3 H2 C CH C CH3 Give the same products because they form the same carbocation. CH3 H2 C CH C+ CH3 + H2 C CH C Cl ClCH and ClCH2 CH C

CH3

(85%) H2 C CH

CH3 C CH3

(15%) OH + HOCH2 CH C

CH3

CH3

CH3

More positive charge on tertiary carbon; therefore more tertiary alcohol in product. CH3 H2 C CH3 CH C+ CH3 CH3 + H2 C CH C CH3 CH3

Allylic SN2 Reactions Allylic halides also undergo SN2 reactions faster than simple primary alkyl halides. 10.4 SN2 Reactions of Allylic Halides H2 C CH 80 relative rates: (I-, acetone) CH2 Cl H3 C CH2 CH2 Cl 1

Allylic SN2 Reactions Two factors: Steric Trigonal carbon smaller than tetrahedral carbon. Two factors: Electronic

Allylic SN2 reactions

Electron delocalization lowers LUMO energy which means lower activation energy.

H2 C

CH 80

CH2 Cl

H3 C

CH2 CH2 Cl 1

H2 C

CH 80

CH2 Cl

H3 C

CH2 CH2 Cl 1

relative rates: (I-, acetone)

relative rates: (I-, acetone)

Allylic Free Radicals are Stabilized by Electron Delocalization 10.5 Allylic Free Radicals

C C C C C

C C

Allylic Free Radicals are Stabilized by Electron Delocalization Spin density is a measure of the unpaired electron distribution in a molecule. Figure 10.2 shows the unpaired electron in allyl radical "divides its time" equally between C-1 and C-3. C-

Allylic Free Radicals are Stabilized by Electron Delocalization

Spin density in allyl radical Figure 10.2

Free Radical Stabilities are Related to Bond-dissociation Energies Bond-

CH3CH2CH2H

410 kJ/mol

CH3CH2CH2 + H CHCH2 + H

10.6 Allylic Halogenation

H2 C

CHCH2H

368 kJ/mol

H2 C

CH bond is weaker in propene because resulting radical (allyl) is more stable than radical (propyl) from propane.

Chlorination of Propene addition ClCH2CHCH3 ClCH H2 C CHCH3 + Cl2 H2 C

Allylic Halogenation

Selective for replacement of allylic hydrogen Free radical mechanism

Cl Allylic radical is intermediate CHCH2Cl + HCl HCl substitution

Hydrogen-atom Abstraction Step Hydrogen-

Hydrogen-atom Abstraction Step Hydrogen-

H C H
410 kJ/mol

H H C C H H
368 kJ/mol

H .. . Cl: .. H
410 kJ/mol

H C C H H .. H : Cl: ..

368 kJ/mol

allylic CH bond weaker than vinylic chlorine atom abstracts allylic H in propagation step

N-Bromosuccinimide Reagent used (instead of Br2) for allylic bromination. O NBr + O (82-87%) (82heat CCl4 O Br + O NH

Limited Scope Allylic halogenation is only used when: all of the allylic hydrogens are equivalent and the resonance forms of allylic radical are equivalent.

Example H Cyclohexene satisfies both requirements. H H

H All allylic hydrogens are equivalent. H H H

Example 2-Butene CH3CH CHCH3 All allylic hydrogens are equivalent.

But CH2 CH3CH

H H

CH3CH

CH

CH

CH2

Both resonance forms are equivalent.

Two resonance forms are not equivalent; gives mixture of isomeric allylic bromides.

Example 2-Butene CH3CH CHCH3 All allylic hydrogens are equivalent.

10.7 Allylic Anions

forms Br CH3CH CH CH2 and Br CH3CH CH CH2

C C

C-

Two resonance forms are not equivalent; gives mixture of isomeric allylic bromides.

Acidity of Propene H3 C CH CH2 pKa ~ 43 H2 C CH CH2 H2 C H3 C CH2 CH3 pKa ~ 62 H2 C CH

Resonance Model

CH2 H2 C

H2 C CH2

CH

CH2

CH2 CH3

CH

Propene is significantly more acidic than propane.

Charge is delocalized to both terminal carbons, stabilizing the conjugate base.

Classification of Dienes

Isolated diene 10.8 Classes of Dienes C Conjugated diene Cumulated diene

Nomenclature

(2E,5E)-2,5-heptadiene (2E ,5E 2,5(2E,4E)-2,4-heptadiene (2E ,4E 2,4C 3,4-heptadiene 3,4-

10.9 Relative Stabilities of Dienes

Heats of Hydrogenation 1,3-pentadiene is 1,326 kJ/mol more stable than 1,4-pentadiene, 1,4but some of this stabilization is because it also contains a more highly substituted double bond.

Heats of Hydrogenation

126 kJ/mol 226 kJ/mol 126 kJ/mol

111 kJ/mol

252 kJ/mol

115 kJ/mol

252 kJ/mol

226 kJ/mol

Heats of Hydrogenation

Heats of Hydrogenation

126 kJ/mol

111 kJ/mol

126 kJ/mol

111 kJ/mol

When terminal double bond is conjugated with other double bond, its heat of hydrogenation is 15 kJ/mol less than when isolated.

This extra 15 kJ/mol is known by several terms: conjugation energy delocalization energy resonance energy

Heats of Hydrogenation Cumulated double bonds have relatively high heats of hydrogenation. H2 C C CH2 + 2H2 CH3CH2CH3 10.10 Bonding in Conjugated Dienes

H = -295 kJ

H2 C

CH2CH3 + H2

CH3CH2CH3 H = -125 kJ

Isolated diene

Isolated diene

1,4-pentadiene 1,4-

bonds are independent of each other.

1,3-pentadiene 1,3-

1,3-pentadiene 1,3-

Conjugated diene

Conjugated diene

Isolated diene

Isolated diene

bonds are independent of each other.

less electron delocalization; less stable

p orbitals overlap to give extended bond encompassing four carbons. Conjugated diene Conjugated diene

more electron delocalization; more stable

Conformations of Dienes H H H H H H H H HH s-cis H H

Conformations of Dienes

s-trans

s-trans

s-cis

s prefix designates conformation around single bond. s prefix is lower case (different from Cahn-IngoldCahn- IngoldPrelog S which designates configuration and is upper case).

Both conformations allow electron delocalization via overlap of p orbitals to give extended system.

s-trans is More Stable Than s-cis s-

Interconversion of conformations requires two bonds to be at right angles to each other and prevents conjugation.

12 kJ/mol

16 kJ/mol

10.11 Bonding in Allenes

12 kJ/mol

Cumulated Dienes

Structure of Allene

C 118.4 118.4 131 pm

Cumulated dienes are less stable than isolated and conjugated dienes. (see Problem 10.10) Linear arrangement of carbons Nonplanar geometry

Bonding in Allene

Bonding in Allene

sp 2

sp

sp 2

Bonding in Allene

Bonding in Allene

Chiral Allenes Allenes of the type shown are chiral A C B A B; X Y Have a chirality axis C C Y X

Chirality Axis

Analogous to difference between: A screw with a right-hand thread and one rightwith a left-hand thread. leftA right-handed helix and a left-handed helix. rightleft-

1,3-Butadiene 1,3590-675C 590- 675 CH3CH2CH2CH3 10.12 Preparation of Dienes chromiachromiaalumina H2 C CHCH + 2H2 CH2

More than 4 billion pounds of 1,3-butadiene 1,3prepared by this method in U.S. each year. Used to prepare synthetic rubber (See "Diene Polymers" box).

Dehydration of Alcohols

Dehydrohalogenation of Alkyl Halides

KHSO4 OH heat Br

KOH heat

major product; 88% yield

major product; 78% yield

Reactions of Dienes

Isolated dienes: double bonds react independently dienes: of one another. Cumulated dienes: specialized topic. Conjugated dienes: reactivity pattern requires us to think of conjugated diene system as a functional group of its own.

10.13 Addition of Hydrogen Halides to Conjugated Dienes

Example: Electrophilic Addition to Conjugated Dienes H + H Proton adds to end of diene system. Carbocation formed is allylic. H H H H H Cl H H

H H H HCl ? ? H H H H H H Cl H

Example:

via: H H

H H X

H +

H H H H H

H H H HCl H H Cl H H H H H

H H H

Protonation of the end of the diene unit gives an allylic carbocation. carbocation.

H + H

H H H H

and: H + H H H H H H Cl H H Cl H H H H H

1,2-Addition versus 1,4-Addition 1,21,4-

1,2-addition of XY 1,2Y

1,4-addition of XY 1,4Y

H + H

H H H H

3-Chlorocyclopentene H H X via + X X Cl H H H H H

HBr Addition to 1,3-Butadiene 1,3H2 C CHCH HBr CH3CHCH Br Electrophilic addition 1,2 and 1,4-addition both observed 1,4Product ratio depends on temperature CH2 + CH3CH CHCH2Br CH2

Rationale 3-Bromo-1-butene (left) is formed faster than Bromo1-bromo-2-butene (right) because allylic carbocations bromoreact with nucleophiles preferentially at the carbon that bears the greater share of positive charge. CH3CHCH CH2 + CH3CH CHCH2Br

Br (formed faster) via: + CH3CHCH + CHCH2

CH2

CH3CH

Rationale 1-Bromo-2-butene is more stable than Bromo3-bromo-1-butene because it has a bromomore highly substituted double bond. +

Rationale The two products equilibrate at 25C. 25 Once equilibrium is established, the more stable isomer predominates. CH3CHCH CH2 CH3CH CHCH2Br

CH3CHCH

CH2

CH3CH

CHCH2Br

Br (formed faster)

(more stable)

Br major product at -80C 80 (formed faster) 1,2 addition product

major product at 25C 25 (more stable) 1,4 addition product

Kinetic Control versus Thermodynamic Control + CH3CHCH Kinetic control: major product is the one formed at the fastest rate. Thermodynamic control: major product is the one that is the most stable. CH2 CH3CH HBr H2 C CHCH CH2 + CHCH2

+ CH3CHCH

CH2

higher activation energy

Example Problem Addition of hydrogen chloride to 2-methyl-1,3-butadiene is a kinetically controlled methyl- 1,3reaction and gives one product in much greater amounts than any isomers. What is this product?

CH3CH

+ CHCH2

CH3CHCH Br

CH2

formed more slowly CH3CH CHCH2Br

HCl

Example Problem Example Problem

Think mechanistically H Cl

HCl

Cl

Kinetically controlled product corresponds to attack by chloride ion at carbon that has the greatest share of positive charge in the carbocation.

+ +
One resonance form is secondary carbocation; other is primary.

One resonance form is tertiary carbocation; other is primary.

Example Problem Think mechanistically H

Example Problem Think mechanistically H

Cl

Cl

More stable carbocation

+
Is attacked by chloride ion at carbon that bears greater share of positive charge.

Cl

Cl major product

One resonance form is tertiary carbocation; other is primary.

One resonance form is tertiary carbocation; other is primary.

Example H2 C 10.14 Halogen Addition to Dienes Gives mixtures of 1,2 and 1,4-addition products 1,4BrCH2CHCH BrCH Br (37%) (63%) CH2 + CHCH Br2 BrCH2CH BrCH CHCH2Br CH2

In General...

10.15 The Diels-Alder Reaction DielsSynthetic method for preparing compounds containing a cyclohexene ring

conjugated alkene diene (dienophile) dienophile)

cyclohexene

via

Mechanistic Features Concerted mechanism Cycloaddition Pericyclic reaction transition state A concerted reaction that proceeds through a cyclic transition state.

Recall the General Reaction...

What Makes a Reactive Dienophile? Dienophile? The most reactive dienophiles have an electron-withdrawing group (EWG) directly electron(EWG) attached to the double bond.

alkene conjugated (dienophile) diene dienophile)

cyclohexene C C

EWG

Typical EWGs C O

The equation as written is somewhat misleading because ethylene is a relatively unreactive dienophile. dienophile.

Example O H2 C CHCH CH2 + H2C 100C 100 O CH via: H3 C CH CH

Example H2 C CHC CH3 benzene O O O CH2 +

O O

benzene via: O CH

100C O 100 O

H3 C O O

(100%)

(100%)

Acetylenic Dienophile O H2 C CHCH CH2 + CH3CH2OCC benzene 100C 100 O COCH2CH3 (98%) COCH2CH3 O O CCOCH2CH3 Diels-Alder Reaction is Stereospecific* Diels*A stereospecific reaction is one in which stereoisomeric starting materials give stereoisomeric products; characterized by terms like syn addition, anti elimination, inversion of configuration, etc. Diels-Alder: syn addition to alkene Dielscis-trans relationship of substituents on alkene cisretained in cyclohexene product

Example C6 H5 H2 C CHCH CH2 + H C C

O COH

Example H H2 C CHCH CH2 + C6 H5 C C

O COH

H C6 H5 COH only product H O only product

C6 H5 H COH H O

O H Cyclic Dienes Yield Bridged Bicyclic Diels-Alder Adducts Diels+ CH3OC O C C H H O COCH3 H COCH3 O COCH3

O COCH3 H is the same as

O COCH3 H H COCH3 O

10.16 The Molecular Orbitals of Ethylene and 1,3-Butadiene 1,3-

COCH3 O

Orbitals and Chemical Reactions

Orbitals and Chemical Reactions

A deeper understanding of chemical reactivity can be gained by focusing on the frontier orbitals of the reactants. Electrons flow from the highest occupied molecular orbital (HOMO) of one reactant to the lowest unoccupied molecular orbital (LUMO) of the other. We can illustrate HOMO-LUMO interactions by HOMOway of the Diels-Alder reaction between Dielsethylene and 1,3-butadiene. 1,3We need only consider only the electrons of ethylene and 1,3-butadiene. We can ignore 1,3the framework of bonds in each molecule.

The MOs of Ethylene Red and blue colors distinguish sign of wave function. Bonding MO is antisymmetric with respect to plane of molecule.

The MOs of Ethylene Antibonding orbital of ethylene; no electrons in this orbital. LUMO

HOMO Bonding orbital of ethylene; two electrons in this orbital. Bonding orbital of ethylene; two electrons in this orbital.

The MOs of 1,3-Butadiene 1,3-

The Two Bonding MOs of 1,3-Butadiene 1,3-

Four p orbitals contribute to the system of 1,31,3butadiene; therefore, there are four molecular orbitals. Two of these orbitals are bonding; two are antibonding. antibonding.

HOMO
4 electrons; 2 in each orbital.

Lowest energy orbital

The Two Antibonding MOs of 1,3-Butadiene 1,3Highest energy orbital 10.17 A Molecular Orbital Analysis of the Diels-Alder Reaction Diels-

LUMO
Both antibonding orbitals are vacant.

MO Analysis of Diels-Alder Reaction Diels-

MO Analysis of Diels-Alder Reaction DielsHOMO of 1,3-butadiene 1,3HOMO of 1,3-butadiene 1,3and LUMO of ethylene are in phase with one another. Allows bond formation between the alkene and the diene. LUMO of ethylene (dienophile) (dienophile)

Since electron-withdrawing groups increase electronthe reactivity of a dienophile, we assume dienophile, electrons flow from the HOMO of the diene to the LUMO of the dienophile. dienophile.

MO Analysis of Diels-Alder Reaction DielsHOMO of 1,3-butadiene 1,3H2 C H2 C

A Forbidden" Reaction CH2 CH2

The dimerization of ethylene to give cyclobutane does not occur under conditions of typical Diels-Alder reactions. Why not? Diels-

LUMO of ethylene (dienophile) (dienophile)

A Forbidden" Reaction H2 C H2 C CH2 CH2 HOMO of one ethylene molecule. LUMO of other ethylene molecule.

HOMO-LUMO HOMOmismatch of two ethylene molecules precludes single-step singleformation of two new bonds.