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Pyrolytic Elimination

The document discusses pyrolytic elimination, a thermal elimination reaction that occurs without the need for additional reagents or solvents, primarily in the gaseous phase. It details the mechanisms of pyrolytic eliminations, including the Chugaev and Cope eliminations, highlighting their concerted nature and regioselectivity according to Hofmann's rule. The Chugaev reaction specifically involves the formation of xanthates and their subsequent pyrolysis to yield alkenes through a stereospecific syn-elimination process.

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68 views

Pyrolytic Elimination

The document discusses pyrolytic elimination, a thermal elimination reaction that occurs without the need for additional reagents or solvents, primarily in the gaseous phase. It details the mechanisms of pyrolytic eliminations, including the Chugaev and Cope eliminations, highlighting their concerted nature and regioselectivity according to Hofmann's rule. The Chugaev reaction specifically involves the formation of xanthates and their subsequent pyrolysis to yield alkenes through a stereospecific syn-elimination process.

Uploaded by

zdhother82
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Pyrolytic

Elimination
Submitted By: Bisma Shafaqat (roll no 24), Era Noor
(roll no 25), Faiqa Noor (roll no 27)
Group no: 6
Subject: Organic Chemistry
Lahore College For Women University.
Table Of Content
1. Introduction
2. Mechanism of pyrolytic eliminations
2.1 The pyrolytic Ei elimination mechanism
2.2 Chugaev elimination of Xanthates
2.3 Cope Elimination
Introduction
• The term pyrolytic elimination literally means an elimination reaction
occurring in the organic substrate due to the application of heat.
• Pyr is a Greek word 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.
• 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.
• These thermal elimination reactions of molecules can also be termed as
pyrolytic Ei (Elimination internal) reactions.
• Carboxylic esters, xanthates, amine oxides, sulfoxides are some substrate
which commonly undergo pyrolytic eliminations.
Mechanism and stereochemical
aspects

1. First order reaction kinetics.


2. No reaction intermediate has been isolated,
suggesting it to be a concerted mechanism.
 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.
Follows Hoffman’s rule
• The Hofmann rule states that the major product in Hofmann eliminations and
other similar elimination reactions is the less stable alkene (or the alkene
featuring a lesser substituted double bond). This rule is used to predict the
regio selectivity of some elimination reactions.
• Regioselectivity: The position of substituent around double bond.
Chugaev Reaction
• The Chugaev elimination is a chemical reaction
that involves the elimination of water from alcohols to
produce alkenes. The intermediate is a xanthate.
• Steps:
1. Xanthate Formation:
An alcohol reacts with carbon disulfide (CS₂) in the presence of a base (like
sodium hydroxide or sodium hydride) to form a xanthate salt.
2. Xanthate Alkylation:
The xanthate salt is then alkylated, typically with methyl iodide (CH₃I), to
form a xanthate ester.
• 3.. Pyrolysis and Elimination:
Heating the xanthate ester leads to the pyrolysis and a syn-elimination reaction,
resulting in the formation of an alkene and byproducts like carbonyl sulfide (COS)
and methanethiol (CH₃SH).
4. Syn-Elimination:
The elimination is stereospecific, meaning the hydrogen and xanthate oxygen are
eliminated from the same side of the molecule.
5. Chugaev's Rule:
The Chugaev reaction is known for proceeding via an intramolecular cis-elimination
without the rearrangement of the carbon skeleton
Cope Elimination
Reference
• Wang, Z., Comprehensive Organic Name Reactions and
Reagents, John Wiley & Sons, Inc.,2010
• Laue T.,Plagens A.,Named Organic Reactions, Second
edition, John Wiley & Sons, Ltd, 2005

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