CH 15 CONJUGATED DIENES

- the class of compounds & the related molecular systems which will be discussed in this chapter
have in common the following structural feature:

- a set of adjacent sp2-hybridized carbon atoms whose interacting p atomic orbitals create a
delocalized pi (π) electron system

- these delocalized π electron systems lend themselves to the unique stability & reactivity exhibited
by the molecules which possess them

CLASSIFICATION & STRUCTURE –

- conjugated dienes contain two carbon-carbon double bonds separated by one carbon-carbon
single bond:
FG = C C C C
conjugated diene

- other types of dienes are possible, of course:

C C (C)n C C n>1 C C C

isolated diene cummulated diene

- other conjugated alkene systems (trienes, tetraenes,....polyenes) characterize numerous

molecules of significant biological and theoretical interest

EX ‘s

Benzene β-Carotene
( a cyclic conjugated triene) (a conjugated polyene)

Nomenclature –

- conjugated dienes are named using IUPAC rules for alkenes; the general form is:

alka-diene
Cl Cl
EX ‘s 5
1 4

2 3
(E
E)-hexa-1,3-diene 5,5-dichlorocyclopenta-1,3-diene
PREPARATION OF CONJUGATED DIENES –
- conjugated dienes are best prepared by dehydrohalogenation of allylic halides (whose preparation
is discussed later)

B
C C C C C C C C + HX
X H
allyl halide conjugated diene

X = Cl, Br, I, .... B = OH , OR , NH2 ,...... (in E2 solvent)

- the elimination reaction is regiospecific; the orientation of the second double bond is dictated by
conjugation to the first double bond

EX. Br

OH

DMF

STABILITY OF CONJUGATED DIENES –

- recall that the relative stability of an alkene can be determined by measuring enthalpy or heat of
hydrogenation (∆HH o) of the double bond
2

H2 ∆HH2o = -
C C C C kcal/mol
M
H H
alkene alkane

- by comparing heat of hydrogenation values for alkenes & dienes which produce the same alkane
upon reduction, the following correlation can be assumed:

as ∆HH2o9 C=C Stability 8

- in this manner, the relative stabilities of dienes can be determined:

 Compound Structural Formula Heat of Hydrogenation, ∆HH2o

alkene C C ~30 kcal/mol

isolated diene C C (C)n C C ~60 kcal/mol

conjugated diene C C C C ~54 kcal/mol

cummulated diene C C C ~70 kcal/mol

- it can be seen that a conjugated diene is more stable than an isolated diene by approximately 6
kcal/mol (a cummulated diene is much less stable than either diene)

Rationale –

- each carbon in the conjugated diene uses sp2 hybrid orbitals (sp2 HO’s) to construct its sigma
bond framework

- each carbon, therefore, has a p atomic orbital (p AO) remaining which can house one of the four
pi (π) electrons (from the two double bonds)

- the four p AO’s can align parallel & overlap so that there is double bond character between all four
carbons (including the second & third carbons)

- this creates resonance stabilization through delocalization of the four π electrons through the four
parallel p AO’s

EX.

Resonance stabilization through delocalization in butadiene

ELECTROPHILIC ADDITION TO CONJUGATED DIENES –
- reaction of a conjugated diene with one equivalent of an electrophilic reagent results in the
formation of two regioisomeric addition products:

1 2 3 4 1 2 3 4 1 2 3 4
C C C C + E Nu C C C C + C C C C
conjugated diene electrophilic E Nu E Nu
reagent 1,2-adduct 1,4-adduct

E Nu = HX, X2, H2O, .....

EX.
Cl Cl
Cl2
+

Cl Cl

1,2-adduct 1,4-adduct

- the reaction outcomes (1,2-addition & 1,4-addition) are rationalized by the existence of a certain
critical intermediates:

Allylic Carbocations –

- these resonance-stabilized intermediates are another example of delocalized π electron systems:

C C C C C C C C C

Resonance Contributors, RC's Resonance Hybrid, RH

- allylic carbocations are crucial intermediates in many other organic chemical transformations

- allylic carbocations are more stable than their corresponding alkyl counterparts:

Carbocation Stability Ranking:

3o allylic > 3o . 2o allylic > 2o . 1o allylic > 1o

R R R R H H
C C C > R C ~ C C C > R C ~ C C C > R C
R R H H H H
o
3o allylic R 3o R 2o allylic R 2o R 1o allylic R 1 R
Mechanism –

Kinetic vs Thermodynamic Control in Electrophilic Addition to Conjugated Dienes –

- the virtual “preference” for 1,2-addition versus 1,4-addition varies with temperature :

1 2 3 4 1 2 3 4 1 2 3 4
C C C C + E Nu C C C C + C C C C
E Nu E Nu

1,2-adduct 1,4-adduct

Low T major minor

High T minor major

- furthermore, heating the 1,2-adduct converts it to the 1,4-adduct:

1 2 3 4
∆
1 2 3 4
C C C C C C C C
E Nu E Nu

1,2-adduct 1,4-adduct

EX. Cl Cl
HCl
+

H H

1,2-adduct 1,4-adduct

T = - 80 oC 80 % 20%

T = +40 oC 15 % 85%
- this temperature-dependent product predominance can be explained by a general phenomenon
which applies to many reactions:

Kinetic Control –

- conditions characterized by low temperatures

- equilibrium has not yet been achieved & reaction processes are primarily irreversible

- the faster formed (kinetic) product is favored & will predominate

- the faster formed product ensues from the more stable intermediate

EX. the more stable allylic carbocation (RC I) leads to the major product ± the 1,2-adduct

More stable intermediate ......leads to major product

1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4
C C C C > C C C C C C C C C C C C
E E E E Nu
RC I RC II 1,2-adduct
RC I
(more stable R ) (major)

Thermodynamic Control –

- conditions characterized by high temperatures

- equilibrium has been achieved & reaction processes are primarily reversible

- the more stable (thermodynamic) product is favored & will predominate

- the more stable alkene product is the one with the more substituted double bond

EX. the more stable (more substituted) alkene is the major product ± the 1,4-adduct

More stable alkene has the more substituted C C & forms the major product

1 2 3 4 1 2 3 4
C C C C > C C C C
E Nu E Nu

1,4-adduct 1,2-adduct
Major
(more substituted; more stable)
 Reaction-Energy Profile - Kinetic vs Thermodynamic Control in Addition of HBr to 1,3-butadiene

ALLYLIC FREE RADICAL HALOGENATION –

- like allylic carbocations, other allylic reactive intermediates (i.e. radicals & carbanions) are
resonance stabilized by π electron delocalization

- this creates a reactive site at the allylic carbon in alkenes, where for example, free radical
substitution can take place:

allylic C - a reactive site

C C C H

allylic H - can be removed/substituted

- thus, at low concentrations, halogens will substitute at the carbon next to the double bond of an
alkene rather than add to the double bond itself:

@ low [X2], substitute here

X2 C C C H X2
hi conc lo conc

C C C H C C C X
@ high [X2], add here
X X
addition substitution
- allylic halogenation is analogous to the free radical alkane halogenation discussed previously

∆
C C C H + X2(g) C C C X + HX
or hν
alkene allylic halide

X = Cl, Br (usually gas phase; low concentration)

- as with electrophilic addition to conjugated dienes, reaction outcomes in allylic halogenation are
dictated by key intermediates:

Allylic Free Radicals –

- these resonance-stabilized intermediates account for the specific orientation of the substitution
(at the allylic carbon) as well as for the formation of multiple allyl halide products

C C C C C C C C C

Resonance Contributors, RC's Resonance Hybrid, RH

- the product predominance is (as before) temperature-dependent and is consistent with the
dictates of kinetic control (more stable intermediate favored at low T) or thermodynamic control
(more stable product favored at high T)

Mechanism –
 EX. Cl

+ Cl2(g) hν
+ + HCl
low conc 0 oC
Cl

Major

N-Bromosuccinimide, NBS –

- a reagent which provides the required low concentration of bromine for allylic halogenation
without the inconvenience and difficulties associated with a gas phase reaction

∆
C C C H + NBS C C C Br + HBr
or hν
alkene allylic bromide
O

NBS = N-bromosuccinimide, N Br

- NBS reacts with hydrogen bromide (initially from impurities & then from the reaction itself) to
generate a low, constant concentration of bromine
O O

N Br + H Br N H + Br Br

low, constant
O O concentration
NBS succinimide

- the bromine molecule is then cleaved (by heat or light) to bromine atoms & the mechanism
proceeds as described above for gas-phase generated halogens

EX.
Br
NBS
CH2 CH CH2CH3 CH2 CH CH CH3 + Br CH2 CH CH CH3 + H Br
o
77 C
Major
THE DIELS-ALDER REACTION–
- a 1,4-addition to a conjugated diene of the two carbons of an alkene’s double bond:

C C
C C ∆ C C
+
C C C C
C C

diene dienophile cycloadduct

- the Diels-Alder reaction is a member of two larger classes of reactions:

Pericyclic Reactions % concerted processes characterized by transition states composed of

closed loops of interacting p atomic orbitals

Cycloaddition Reactions % pericyclic reactions which form a ring, the size of which depends on
the number of carbons (& π electrons) in the reactants

- hence, the Diels-Alder reaction is a [4+2] cycloaddition reaction (many others exist)

- the Diels-Alder reaction is the most popular & useful cycloaddition reaction, capable of producing
a myriad range of substituted cyclic compounds in excellent yield with minimal effort

Mechanism –

- a concerted process in which two π bonds are transformed to two σ bonds & one π bond is
relocated, producing a six-membered ring
new σ
new π
C C C
C C C C C C
C C C C C C
C C C
new σ
diene dienophile transition state cycloadduct
4πe 2πe loop of parallel p AO 's 6-membered ring

Stereochemistry –

- because it is a concerted process, [4+2] cycloaddition is a stereospecific reaction

- the stereochemical configuration of both the diene & the dienophile will be conserved in the
product

- thus, if the diene or dienophile has a cis configuration, then the cycloadduct will be cis

- conversely, if the diene or dienophile has a trans configuration, then the cycloadduct will be trans
Conformation –

- the required conformation for the reacting diene is the less stable “cisoid” conformer:

C C
C C
does not react reacts
C C
C C

"transoid" "cisoid"
more stable less stable

- cis,cis -dienes with large, bulky groups on the 1 & 4 positions cannot adopt the cisoid
conformation (steric hindrance) & are rendered unreactive

Electron Demand –

- for best results, the diene should be electron “rich” (substituted with electron donating groups)
& the dienophile should be electron “poor” (substituted with electron withdrawing groups)

- because alkyne carbons are already electron deficient, acetylenic dienophiles are very effective

- it has been found that electron “poor” dienes react with electron “rich” dienophiles and such
“reverse electron demand” Diels-Alder reactions give good yields as well

EX. electron demand

CN CN
+ ∆

e rich e poor

EX. acetylenic dienophile

CO2CH3
CO2CH3
∆
+
CO2CH3
CO2CH3

EX ‘s stereospecific towards dienophile

CN CN CN CN
∆ & ∆
+ +
CN CN NC CN
cis cis trans trans
EX ‘s stereospecific towards diene

O O O O
∆ ∆
+ O O & + O O

O O O O
trans, trans cis trans, cis
or trans
or
out, out out, in

Endo Rule –

- cyclic dienes produce bicyclic cycloadducts upon Diels-Alder cycloaddition

- the bicycle has an exo (top) face & an endo (bottom) face relative to the bridgehead

- the dienophile ‘s substituent(s) prefer endo positions (transition state stabilization)

- the endo product predominates in a bicyclic cycloadduct

An
∆ or An Endo
An +
Exo

cyclic diene dienophile Endo (predominates)

A = C, N, O, .... bicyclic cycloadduct

n = 1 or 2

EX ‘s endo product

CN CN
∆
+ or
CN CN CN
CN
cis
cis & e ndo

∆
+ or
CO2CH3
CO2CH3
CO2CH3
endo
EX ‘s use in synthesis

∆
+
CHO
CHO

COOH COOH
Synthesize:
FROM & Dienes

COOH COOH