A presentation on

Citral using Pericyclic Reactions

Master of Science
School Of Science, GSFC University.
Vadodara

Guided by :
Mr. Gourav Upadhyay

Prepared By:
Thakar Twara Pradipkumar
Semester - III
(20MSC01046) 1
 Table of contents
1. Pericyclic reactions
2. 3, 3-Sigmatropic Rearrangement
2.1 Claisen rearrangement
2.2 Cope rearrangement
3. Synthesis of citral
4. Reactions of citral
5. Applications of citral
6. References

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  1. Pericyclic reactions
 Pericyclic reactions are defined as the reactions that occur by a concerted cyclic shift of electrons.
 This definition states two key points that characterise a pericyclic reaction.
 First point is that reaction is concerted. In concerted reaction, reactant bonds are broken and product
bonds are formed at the same time, without intermediates.
 Second key point in pericyclic reactions involves a cyclic shift of electrons. The word pericyclic means
around the circle. Pericyclic word comes from cyclic shift of electrons. Pericyclic reactions thus are
characterised by a cyclic transition state involving the π bonds.
 The energy of activation of pericyclic reactions is supplied by heat (Thermal Induction), or by UV light
(Photo Induction).
 Pericyclic reactions are stereospecific and it is not uncommon that the two modes of induction yield
products of opposite stereochemistry.
 The three features of any pericyclic reaction are intimately interrelated.
1. Activation: Pericyclic reactions are activated either by thermal energy or by UV light. However, many
reactions that require heat are not initiated by light and vice-versa.
2. The number of π (pi) bonds involved in the reaction.
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3. The stereochemistry of the reaction.
  1.1 Four major types of pericyclic reactions

The first type of reaction is the electrocyclic reaction: A reaction in which a ring is closed (or opened) at the expense of a
conjugated double (or triple bond) bond.

The second type of reaction is the cycloaddition reaction: A reaction in which two or more π electron systems react to form a
ring at the expense of one π bond in each of the reacting partners. In this reaction formation of two new σ (sigma) bonds
takes place which close a ring. Overall there is loss of two π (pi) bonds in reactants and gain of two σ (sigma) bonds in a
product.

The third type of reaction is the sigmatropic rearrangement (or reaction): A reaction in which a σ (sigma) bond formally
migrates from one end to the other end of π (pi) electron system and the net number of π bonds remains the same.

The fourth type of reaction is the group transfer reaction: A reaction in which one or more groups or atoms transfer from
one molecule to another molecule. In this reaction both molecules are joined together by σ (sigma) bond. 4
 Citral or lemonal is a terpenoid with the molecular formula C10H16O.
 Citral is present in the oils of several plants, including lemon myrtle (90-98%).
 The commercial process that involves synthesis of citral has two successive [3, 3]-sigmatropic rearrangements, a
Claisen followed by a Cope.
 BEFORE that it is necessary to understand what is 3-3 sigmatropic rearrangements in detail.

 2. 3, 3-Sigmatropic Rearrangement
 3, 3-Sigmatropic Rearrangement: Very often the migrating sigma-bond is situated between two conjugated pie-
bonds as in Cope and Claisen rearrangements.

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  2.1 Claisen rearrangement
 The original sigmatropic rearrangement occurred when an aryl allyl ether was heated without solvent and an ortho-allyl
phenol resulted. This is the Claisen rearrangement. The first step in this reaction is a pericyclic reaction of a type that you
will learn to call a [3,3]-sigmatropic rearrangement.
 This is a one-step mechanism without ionic intermediates or any charges, just like a cycloaddition. The arrows go round in a
ring. The difference between this and a cycloaddition is that one of the arrows starts on a σ bond instead of on a π bond.

 The Claisen rearrangement is a [3,3]-sigmatropic rearrangement. Count the number of atoms from the old to the new
sigma bond and you will see there are 3 atoms in both directions round the ring. [3,3] sigmatropic rearrangements happen
though a chair-like transition state. If there is a substituent on the saturated carbon next to the oxygen, then trans (E)
geometry is strongly favoured in the product. This a consequence of the chair transition state favouring equatorial
substituents and the concerted nature of pericyclic reactions.
 The second step in the reaction is a simple ionic proton transfer to regenerate aromaticity.

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There are two important general classes of these reactions. The 'all carbon' version is known as the Cope rearrangement,
and an oxygen in the appropriate position changes this to the Claisen rearrangement. There is a series of structural variants
based on these two reactions.
The Claisen rearrangement is the first recorded example of a [3,3]-sigmatropic rearrangement.
The Claisen rearrangement is an exothermic, concerted (bond cleavage and recombination) pericyclic reaction. This type
explained in previous slide in detail.

 The aliphatic Claisen rearrangement

 It was later found that the same sort of reaction occurs without the aromatic ring. This is called either the aliphatic
Claisen rearrangement or the Claisen–Cope rearrangement. Here is the simplest possible example. All these reactions are
called sigmatropic because a σ bond appears to move from one place to another during the reaction. This particular
reaction is called a [3,3]-sigmatropic rearrangement because the new σ bond has a 3,3 relationship to the old σ bond. You
can see this if you number both ends of the old σ bond ‘1’ and count round in both directions to the ends of the new σ
bond in the product. You will find that the ends of the new σ bond both have the number ‘3’.

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 These [3,3]-sigmatropic rearrangements happen through a chair-like transition state, which allows us both to get
the orbitals right and to predict the stereochemistry (if any) of the new double bond. The orbitals look
something like this.

 Note that these do not represent any specific frontier orbitals, they simply show that, in this conformation, the
new σ bond is formed from two p orbitals that point directly at each other and that the two new σ bonds are
formed from orbitals that are already parallel.

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  2.2 Cope rearrangement
 The Cope rearrangement is a [3,3]-sigmatropic rearrangement with only carbon atoms in the ring. In its simplest
version it is not a reaction at all. The starting material and the product are the same.

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In order to construct the transition structure we will require two 3-carbon units: These are the allyl anion (HOMO)
and the allyl cation (LUMO). In fact these are the same orbital, and combining them shows that both components
can react suprafacially in a thermal process. It is reasonable to predict a chair-like transition structure structure.

 Important facts about sigmatropic rearrangements

 Antarafacial processes are very-very rare which occur through small or medium sized ring.
 Distortion of carbon framework impairs coupling with π -bonds, which renders symmetry allowed processes
difficult. Because of it, antarafacial processes are difficult in case of [1, 3]-shifts but not in [1, 7]-shifts.
 Cyclopropane ring can replace π -bond for sigmatropic shift.
 Orbital symmetry rules apply to sigmatropic reactions within ionic species also.
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 3. SYNTHESIS OF CITRAL
STEP 1(Claisen rearrangement)
 ‘Citral’ is a key intermediate in the synthesis of vitamin A, and it is manufactured by a remarkable
process that involves two successive [3,3]-sigmatropic rearrangements, a Claisen followed by a Cope.

 The allyl vinyl ether needed for the Claisen rearrangement is an enol ether of an unsaturated aldehyde
with an unsaturated alcohol.

 The two starting materials are themselves derived from a common precursor, making this a most
efficient process! Heating the enol ether promotes [3,3]-sigmatropic rearrangement propelled by the
formation of a carbonyl group.

 The two starting materials are themselves derived from a common precursor. Heating the enol ether
promotes [3,3]-sigmatropic rearrangement propelled by the formation of a carbonyl group.

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 STEP 2(Cope rearrangement)
 But the product of this rearrangement is now set up for a second [3,3]-sigmatropic rearrangement, so the
product of this rearrangement then undergoes a second [3,3]-sigmatropic Cope rearrangement, this time made
favourable by a shift into conjugation and the formation of two tri-substituted double bonds from two terminal
ones to yield citral as the final product.

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 The first is a Claisen rearrangement which involves an oxygen in the chair-like transition state. The second part
of the single step reaction is a Cope-rearrangement, in which only carbons are involved in the chair-like
transition state. These two reactions happen in succession when the two starting materials are heated together,
and the reaction is driven by formation of a conjugated carbonyl group in the product.

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 4. Reactions of citral
 Reduction of citral, Citral is reduced to either citranellal or nerol/geraniol.
 The H2 catalyst either reduce the double bond or it will reduce the aldehyde to alcohol.

 Synthesis of ionone from citral in which an aldol condensation reaction followed by the rearrangement reaction
 First step is the nucleophillic addition of carbanion of acetone on carbonyl carbon of citral is the base catalysed
reaction.
 The aldol condensation product eliminate water through enolate ion

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 Step 2 the reaction is proceed by acid catalysis where a double bond opens to from the
carbocation
 Arearrangement reaction followed by ring closure then the proton is abstracted from the
molecule by proton acceptor Y to form ionone

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 5. Applications of citral
 Citral is an aroma compound used in perfumery for its citrus effect.
 Citral is used as a flavor and for fortifying lemon oil.
 Citral has strong antimicrobial qualities.
 Citral is used in the synthesis of Vitamin A. ionone and methyl ionone.
 Mask the smell of smoke .
 It is used in perfumes and flavorings and in themanufacture of other chemicals.
 Citral also has a significant role in the production of vitamin A.
 Citral has an effect on some insects. It has amildrepellent action for some species.
 Citral has strong antimicrobial qualities.

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 6. References
1. Molecular orbitals and organic chemical reactions by ian fleming.
2. Organic chemistry by jonathan clayden ,nick greeves, stuart warren 2 nd edition.
3. PERI CYCLIC REACTIONS and organic photochemistry by vinay p. Sharma and rakesh kumar.
4. Essentials of pericyclic and photochemical reactions by biswanath dinda 3 rd edition.
5. Photochemistry and pericyclic reactions by Jagdamba singh and Jaya singh.

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