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Subject Chemistry

Paper No and Title Paper-9, Organic Chemistry-III (Reaction Mechanism-2)

Module No and Title Module-25, Mechanism and orientation in Pyrolytic

elimination.
Module Tag CHE_P9_M25

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.
____________________________________________________________________________________________________

TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
3. Mechanism of pyrolytic eliminations
3.1 The pyrolytic Ei elimination mechanism
3.2 Free radical pyrolytic elimination mechanism
4. Scope and synthetic importance of pyrolytic eliminations
4.1 Ester pyrolysis
4.2 Chugaev elimination of Xanthates and Thionocarbonates
4.3 The Cope Elimination of tert-amineoxides
4.4 Sulfoxides containing substrates
4.5 Selenoxide pyrolysis
5. Summary

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.
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1. Learning Outcomes
After studying this module, you shall be able to

• Know what is meant by pyrolytic elimination

• Learn about the type of substrates which undergo pyrolytic eliminations
• Acquaint yourself with its mechanism and stereochemical aspects
• Distinguish between various types of pyrolytic eliminations
• Analyze the pyrolytic eliminations of acyclic and alicyclic systems

2. Introduction

The term pyrolytic elimination literally means an elimination reaction occurring in the organic
substrate due to the application of heat (Greek word pyr meaning fire). Pyrolytic eliminations do
not require any additional reagent or solvent to occur, and mostly carried out in the gaseous phase
though can be performed in inert solvents. Thus, these type of eliminations are different from
other types of eliminations (E1,E2 or E1cB) as all other types of elimination reactions require an
added base (external base or solvent) to proceed. These thermal elimination reactions of
molecules can also be termed as pyrolytic Ei (Elimination internal) reactions.
Carboxylic esters, xanthates, amine oxides, sulfoxides and selenoxides are some
substrates which commonly undergo pyrolytic eliminations. For example, ethyl acrylate on
heating at 590 oC leads to the formation of acrylic acid and ethylene.

Based on the position of the leaving group, these may be α-eliminations, β-eliminations or
1,3/1,n-eliminations, among these the β-pyrolytic eliminations are the most common.

• α-eliminations involve elimination of two leaving groups connected to the same carbon
and encountered where the more common β-elimination is not possible. For example

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.
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• β-eliminations occur when two groups are lost from adjacent carbons and as mentioned,
constitute most of the pyrolytic eliminations with a typical Ei mechanism. These will be
discussed in detail in the following sections.
• 1,3 and 1,n- pyrolytic eliminations may also take place. For example,

The other type of pyrolytic elimination reaction involves free radicals, for example in polyhalides
and primary monohalides. Free radical eliminations involve the normal sequence for radical
reactions, namely: initiation, propagation and termination steps and are frequent at 600-900 oC
temperatures.

3. Mechanism and stereochemical aspects of pyrolytic eliminations

3.1 The pyrolytic Ei elimination mechanism

The pyrolytic eliminations occur most commonly via the Ei mechanism involving a cyclic
transition state, which may comprise of four-, five- or six-membered transition states. It is a
concerted mechanism, and is almost exclusively a syn elimination (the hydrogen atom and the
leaving group depart from the same side of the resulting double bond). (see 4.1) Evidences for
this mechanism are:

1. First order reaction kinetics.

2. No reaction intermediate has been isolated, suggesting it to be a concerted mechanism.
3. Free radical inhibitors show no effect on the reaction (no free radical mechanism
involved).
4. Moreover, these eliminations show a negative entropy of activation which advocates that
the transition state has a more restricted geometry (consequences of a cyclic transition
state).
5. Exclusive syn elimination as demonstrated experimentally in various substrates with the
use of radio-labelling techniques. For example, the pyrolysis of the erythro and threo
isomers of 1-acetoxy-2-deutero-1,2-diphenylethane gave in each case trans-stilbene but,
the stilbene from the erythro compound retained all the deuterium while the threo
compound lost all of it. This must be due to syn elimination of hydrogen or the deuterium
atom and the acetoxy group and preferred conformations (as shown) for syn elimination

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.
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are those in which the phenyl groups are as far removed as possible from each other
which explains the experimental results.

3.1.1 Aspects of pyrolytic Ei eliminations in acyclic systems

For acyclic systems, pyrolytic Ei eliminations that involve a four-or five-membered cyclic
transition state, there is an obligation that all the atoms are co-planar. However, this constraint
does not apply for the six-membered cyclic transition state. If two or more syn periplanar
arrangements are available, the one with least crowding is preferred, as seen in the preceding
discussion for 1-acetoxy-2-deutero-1,2-diphenylethane. Similarly, pyrolysis of 2-butyl acetate
affords a mixture of 1-butene, cis-2-butene, and trans-2-butene, with the trans/cis ratio around 2
(since there is less steric interaction between the two methyl groups in the transition state leading
to the trans-alkene).

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.
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3.1.2 Aspects of pyrolytic Ei eliminations in alicyclic systems

In alicyclic systems, additional restrictions are imposed by the conformations of the leaving
groups and the obligation to form the cyclic intermediate. This point is made clearer by the
example of ethyl-2-acetoxycyclohexanecarboxylate in which the leaving group is axial. The
double bond in the direction of carbethoxyl group does not form even though it would be
conjugated, since there is no equatorial hydrogen on that side. However, in the case of its
diastereomer in which the leaving group is equatorial and the hydrogen at the carbethoxyl group
is axial, can adopt the necessary cyclic transition state that leads to the conjugated alkene.

Thus, we can generalize these observations as:

1. When leaving group is axial, it cannot attain a cyclic transition state with a neighbouring
axial hydrogen.
2. When the leaving group is equatorial, it can form the cyclic transition state with either an
equatorial (trans-relationship) or axial (cis-relationship) with a hydrogen atom at adjacent
carbon as can be seen in the following example of methylcyclohexyl xanthate.

3.2 Free radical pyrolytic elimination mechanism

Free radical elimination is found in polyhalides and primary monohalides. The steps are similar to
any free radical reaction, i.e. there is an initiation step, followed by several propagation steps, and
then finally there are termination steps. A schematic representation of the free radical elimination
mechanism is as shown in figure-1.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.
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Fig. 1: Free radical pyrolytic elimination

The  main  result  of  the  free  radical  pyrolytic  elimination  (excluding  other  
complexities)  can  be  summed  up  as:  

 
The  initiation  step  is  the  thermally  induced  homolytic  cleavage  of  the  C−X  bond  to  
give  two  free  radicals.  The  pyrolytic  cleavage  of  C-­‐X  bonds  is  favoured  at  600-­‐900  oC  
temperatures  and  the  stability  of  the  resulting  free  radicals  also  plays  a  vital  role  for  
the  initiation  step.  
 
Propagation  reactions  can  follow  many  paths.  Often  pyrolysis  takes  place  in  several  
stages  and  the  product  that  forms  through  a  previous  free  radical  cycle  may  get  
pyrolysed  and  each  resulting  fragment  can  propagate  to  another  product  depending  
upon  the  pyrolysis  time,  gas  pressure  and  temperatures  employed.  Generally,  
intramolecular  reactions  like  β-­‐scissions  and  back-­‐biting  (isomerizations)  are  
common.  For  example,  butyl  radical  may  undergo  a  scission  process  resulting  in  
ethyl  radical  and  ethylene.  

 
Sometimes,  many  complex  reactions  may  occur  including  aromatization,  depending  
upon  the  substrate  and  may  contribute  to  the  complexity  of  the  pyrolysed  product.  

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.
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For  example,

The  termination  step  also  depends  upon  the  pyrolysis  parameters  and  kinetics  of  
the  reaction  and  which  in  turn  contributes  to  the  complexity  of  the  final  product.  
Occasionally,  such  free  radical  eliminations  can  be  followed  by  rearrangements  such  
as  in  the  case  of  9,9-­‐dimethylfluorene.  

 
 

4. Scope and synthetic importance of pyrolytic eliminations

Pyrolytic eliminations occur in a variety of substrates containing appropriate leaving groups and
are important from a synthetic perspective. However, in some cases, the use of high temperatures
may pose a challenge but nevertheless, these elimination reactions especially the Cope
elimination, Chugaev reaction and selenoxide pyrolyses provide a significant route to obtain
alkenes. The important substrates undergoing pyrolytic eliminations are discussed in detail in the
following sections.

4.1 Ester Pyrolysis

The pyrolysis of esters is usually affected at high temperatures (300-500 oC).

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.
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It can be carried out by simple heating, if the boiling point of the ester is high enough or else is
carried out by passing the vapour through a heated tube. Moreover, since these reactions do not
necessarily require any solvent or base, hence, these reactions are clean to perform and isolation
of product is simplified (in cases when a single product is formed). Further, when a sensitive or
reactive substrate is present, the lack of any added acidic or basic reagents is an additional
advantage. A case in point is, diacetate(I) gives 1,2-dimethylene cyclohexene which otherwise
difficult to prepare. It tends to aromatize to o-xylene.

The high temperatures required for pyrolyses of carboxylic esters has limited their synthetic
usefulness. When pyrolysing long-chain fatty acid esters such as cetyl palmitate which generates
palmitic acid and hexadecane, higher temperatures may lead to pyrolysis of the sensitive long
hydrocarbon chain generating complex by-products and may lead to formation of char.

4.2 Chugaev elimination of Xanthates and Thionocarbonates

The Russian chemist Lev Aleksandrovich Chugaev (1899) discovered a way to eliminate water
from alcohols to produce alkenes via the formation of an intermediate xanthate and this
methodology came to be known as Chugaev reaction.

Since these related thiocarbonates or xanthates eliminate at temperatures in the region of 150–
250oC, this reaction is of immense synthetic potential than ester pyrolysis as further
decomposition of the alkene product(s) can often be avoided. However, on the flip side,
separation of the alkene from sulfur-containing by-products can sometimes be troublesome.

Xanthate salts are easily produced by the reaction of an alcohol with sodium or potassium
hydroxide and carbon disulfide, and on treatment with iodomethane, it is transformed into a
xanthate.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.
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At about 150-200 °C, the alkene is formed by a syn-elimination through a 6-membered cyclic
transition state. The side product decomposes to carbonyl sulfide (OCS) and methanethiol.

Eliminations using acyclic xanthates give primarily the E-alkene product, although significant
amount of the Z-isomer is also formed and the regioselectivity is often poor and depends upon the
specific substrate being pyrolysed.

4.3 The Cope Elimination of tert-amineoxides

The Cope elimination, developed by Arthur C. Cope, is an elimination reaction of the N-oxide of
a tertiary amine to form an alkene and a hydroxylamine at milder reaction temperatures (100-200
o
C). This reaction provides an alternative to Hofmann elimination of the quaternary ammonium
salts. The N-oxide can be easily prepared in situ from tertiary amines with an oxidant such as m-
CPBA or H2O2. The mild conditions of the Cope elimination, as exemplified by the synthesis of
1,4-pentadiene, permits the generation of a new alkene bond, without eventual rearrangement into
conjugation with other unsaturated systems.

The Cope elimination is also a syn-elimination and involves a five-membered cyclic transition
state which must be planar (syn-coplanarity). The amine oxide (leaving group) itself acts as a
base. The net reaction is 1,2-elimination.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.
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The sterically demanding amine-oxide reacts preferentially with the more easily accessible
hydrogens, and often gives good selectivity favoring the less-substituted alkene. Thus, Cope
elimination is regioselective. and for simple alkenes, the reaction follows the Hofmann Rule.

The following structures exemplify the stereochemical requirement for reaching a five-membered
cyclic transition state and the influence of sterically demanding groups for some cyclic
compounds. Thus, heating dimethylmenthylamine oxide gave a mixture of 2- and 3-menthene,
whereas the isomeric neomenthylamine oxide gave only 2-menthene.

Another remarkable difference between Cope elimination and ester or xanthate pyrolysis is
exemplified by the example of 1-methyl-cyclohexyl derivatives as shown. Cope elimination
results in the exclusive formation of methylenecyclohexane which is attributed to the formation
of a five-membered cyclic transition state that allows preferential abstraction of a hydrogen atom
from the methyl group, whereas with the more flexible six-membered transition state of the ester
CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)
Module-25, Mechanism and orientation in Pyrolytic elimination.
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or xanthate pyrolyses, hydrogen atom abstraction is also possible from the cyclohexyl ring.
However, with larger, more-flexible rings, the cycloalkene is the major product from the amine
oxides or the esters.

The Cope Elimination is extremely sensitive to solvent effects, and a 106-fold rate increase can be
obtained going from protic to aprotic solvents arising from hydrogen bonding between the amine
oxide and the solvent. Within aprotic solvents, decreasing polarity significantly increases the
reaction rate.

4.4 Sulfoxide containing substrates

Sulphur and selenium belong to the same group (periodic table) and show valences from 2 to 6.
An organic sulphide is oxidized to sulphoxides and to some extent sulphones. sodium periodate
and hydrogen peroxide are commonly employed for sulphide-sulphone reaction.
Sulphoxides containing β-hydrogen undergo syn-elimination on heating to give an olefin. Of
particular importance is the use of diphenyl disulphide to prepare phenyl alkyl sulphide from
compounds containing activated C-H bond.

Oxidation of the sulphide, followed by heating of the sulphone introduces a double bond. The
reaction involves a 5-membered T.S. as in other cases.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.
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In this reaction, CH3SSCH3 requires a temperature of 110°C while PhSSPH requires 50-60°C.
The overall reaction consisting of a carbonyl compound, alkyl phenyl sulphide, surphoxide and
finally pyrolysis leads α, β - unsaturated carbonyl compounds. This method has same advantages
over other methods.

4.5 Pyrolysis of selenoxide

It was discovered that for superior results can be obtained using alkyl phenyl selenoxides in place
of sulphoxides. The merits of the method are:

I) It is a very mild method. The selenoxide elimination occurrs even at room temperature or
below. Sometimes elimination taking place during oxidation step itself.
II) The selenoxide need not be isolated
III) The elimination is Syn-elimination reaction.
IV) It involves a 5-membered cyclic T.S.
V) Good yields and wide scope.
VI) Alkyl Phenyl selenides (First Step) are accessible by a variety of method.

The following example illustrates these aspects.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.
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The end compound is α-methylene lactone and generation of such structural unit is not easy.

5. Summary

• Pyrolytic eliminations are different from other types of elimination (E1, E2 or E1cB) and
do not require any added reagent (base or acid) but require the application of heat.
• Pyrolytic reactions often occur in the gas phase, without the addition of another reagent.
• These may be α-eliminations, β-eliminations or 1,3/1,n-eliminations, though the β-
pyrolytic eliminations are the most common.
• These are exclusively syn-eliminations that undergo the Ei (Elimination internal)
mechanism involving a cyclic transition state, which may comprise of four-, five- or six-
membered transition states.
• In those versions of the Ei mechanism that involve a four- or five-membered cyclic
transition state, there is a requirement that all the atoms are co-planar.
• The other type of pyrolytic elimination reactions involves free radicals, for example in
polyhalides and primary monohalides. Free radical eliminations involve the normal
sequence for radical reactions, namely: initiation, propagation and termination steps and
are frequent at 600-900 oC temperatures.
• Carboxylic esters, xanthates, tert-amine oxides, sulfoxides and selenoxides are some
substrates which commonly undergo pyrolytic syn-eliminations (Ei mechanism).
• Of the various substrates for pyrolytic eliminations, selenoxide pyrolysis provides the
most milder conditions and is often carried-out in a one-pot reaction sequence (no need to
isolate the selenoxide) to produce the C=C in good yields.
• These pyrolytic eliminations are important from a synthetic perspective and these
methods have been used for the synthesis of natural products and compounds of
pharmaceutical significance.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-25, Mechanism and orientation in Pyrolytic elimination.