Unit - IV W

UNIT IV Molecular Rearrangements The atoms or groups within a molecule move from one atom to another, thus forming
structural isomer of the compound called a rearrangement molecule. The molecular rearrangement may be defined as the reaction which involves reshuffling of the sequence of the atoms to form a new structure. Types of molecular rearrangement There are two types of molecular rearrangement. They are, 1. Intermolecular rearrangement 2. Intramolecular rearrangement 1. Intermolecular rearrangement In any rearrangement the migrating group actually becomes free even for a small fraction of time is called intermolecular rearrangement. In such reactions the migration group gets completely detached from the molecule during the rearrangement and then it may go to the migration terminus of the other site of the molecule. 2. Intramolecular rearrangement In any rearrangement the migrating group remains attached to the molecule in one or the otherway throughout the process of rearrangement is called intramolecular rearrangement. Anionotropy In a molecular rearrangement if the shifting atom or group is an anion the rearrangement is known as anionotropy. Cationotropy
Department of Chemistry Sri Sarada Niketan College of Arts & Science for Women Kanavaipudur.
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In a molecular rearrangement if the shifting atom or group is a cation the rearrangement is known as cationotropy. Pinacol-pinacolone Rearrangement Conversion of pinacol (tetramethyl dihydroxy ethane) into pinacolone (trimethyl acetone) in the presence of an acid is known as pinacol-pinacolone rearrangement. It is an example of 1,2-shift.
The migrating group may be alkyl or aryl. Mechanism 1. A proton is added to one of the hydroxy groups. 2. The protonated hydroxy group is lost as water water producing a carbonium ion. 3. The migrating group (alkyl group) migrates. 4. A proton is lost we get the final product.
In the case of unsymmetrical pinacols:
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Explanation Since OH group is removed as water any polar effect in the molecule which weakens one C-O bond more than the other will fecilitate the release of that OH group. In the above example the phenyl group has a powerful conjugative effect whereas the methyl group has only a weak inductive effect.
Therefore the OH group lost should be the one on the phenyl side and consequently it will be the methyl group that migrates. Mechanism
Beckmann Rearrangement
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Conversion of aromatic ketoximes to an acid amide on treatment with reagents such as phosphorous pentachloride, sulphuric acid, polyphosphoric acid etc., is known as Beckmann rearrangement. This is also an example of 1,2-shift.
Mechanism 1. A proton is added to the hydroxy group of the oxime. Intermediate (I) is formed. 2. The protonated hydroxy group is lost as water, producing an intermediate (II) analogous to carbonium ion. 3. The migrating group Ar, migrates resulting in the carbonium ion (III). 4. The carbonium ion adds water yielding the oxonium cation (IV). 5. The oxonium cation loses a proton and forms an enol derivative of the amide (V). 6. The enol V is unstable and ketonises spontaneously giving the final product, the amide (VI).
Benzidine Rearrangement
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Conversion of hydrazobenzene into benzidine and other related products in the presence of acid is known as benzidine rearrangement.
The other products that may be produced along with benzidine are,
Mechanism 1. The rearrangement is intramolecular. Two protons are added to hydrazobenzene. We get the deprotonated species (I). 2. The link between the singly charged nitrogen atoms in (I) starts to break in such a way that the electron pair is shifted towards one of the nitrogen atoms. A new bond begins to form between the para-position of the benzene nuclei. An unstable intermediate compound (II) is formed. 3. Finally two protons are eliminated in a fast step resulting benzidine.
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Hofmann Rearrangement Conversion of an amide into a primary amine with one carbon atom less by means of bromine (or chlorine) and alkali is known as Hofmann rearrangement. Since the product contains one carbon atom less than the parent amide this reaction is also known as Hofmann degradation. This is an example of 1,2-shift.
Mechanism 1. The amide is brominated to give the bromamide. 2. A proton is eliminated from the bromamide and forms the anion (I). 3. Br- from (I) is lost so that the nitrogen atom is left with a sextet of electrons. 4. Now the migrating group R migrates from carbon to nitrogen resulting in the formation of isocyanate. 5. The isocyanate is finally hydrolysed to give the amine. This arrangement is intramolecular.
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Curtius Rearrangement Conversion of acid azide into N-alkyl substituted urethane when boiled with an alcohol is known as curtius rearrangement. It is an example of 1,2-shift.
Mechanism 1. The azide first loses a molecule of nitrogen giving (I) which contains a nitrogen atom with sextet of electrons. 2. Now the migrating group R migrates from carbon to nitrogen resulting in the formation of isocyanate. 3. The isocyanate finally reacts with the alcohol giving the N-alkyl substituted urethane. This is also intramolecular rearrangement.
Lossen Rearrangement Hydroxamic acids undergo rearrangement to form isocyanates either on treatment with bases or sometimes thermally, in a reaction known as Lossen rearrangement. The isocyanate may be further converted into an amine.
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Mechanism 1. Abstraction of the proton from the nitrogen atom of the hydroxamic acid derivative. 2. The elimination of the hydroxyl group forming the intermediate (I). 3. The migration of the R with its bonded electrons to form isocyanate. 4. Hydrolysis of isocyanate produces primary amine.
Schmidt Rearrangement Carboxylic acids on treatment with hydrazoic acid and dil.sulphuric acid give amines. This reaction takes place on warming the mixture. It is known as Schmidt rearrangement.
Similarly aldehydes and ketones react to give the corresponding compounds.
Mechanism
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1. In the presence of sulphuric acid, the carboxylic acid undergoes dissociation to form the stable acyl ion (I). 2. This ion reacts with one molecule of hydrazoic acid to form the intermediate (II). 3. One molecule ofnitrogen and H+ is eliminated from the intermediate to form the compound (III). 4. Rearrangement takes place in (III) so as to form the isocyanate which on hydrolysis yields a primary amine.
Benzilic Rearrangement The conversion of benzil into benzilic acid by heating with ethanolic potassium hydroxide is known as benzilic rearrangement.
Mechanism 1. The hydroxide ion is added in a fast reversible step to benzil. 2. The phenyl group along with the bonded pair of electrons migrates in a slow step. 3. A proton is transferred and we get the product.
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Fries Rearrangement Phenolic esters on heating with aluminium trichloride (Lewis acid) give o- and p-acyl phenol. This is known as Fries rearrangement.
Mechanism 1. Exact mechanism is still not clearly understood. There is evidence of both intermolecular and intramolecular reaction mechanisms. It is therefore suggested that both mechanisms are operating simultaneously. 2. At first, AlCl3 complexes with the oxygen of the phenoxy group from which the acylium ion is generated. 3. The acylium ion then attacks the benzene ring and gives the product. Department of Chemistry Sri Sarada Niketan College of Arts & Science for Women Kanavaipudur.
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Cope Rearrangement When 1,5-dienes are heated, they isomerize in a rearrangement is known as Cope rearrangement.
Mechanism Cope rearrangement is a concerted step intramolecular process involving a six-membered cyclic transition state (II).
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Note 1. When 1,5-diene is symmetrical this rearrangement gives a product identical with the starting material.
2. When the diene is not symmetrical, for example 3-methyl-1,5-hexadiene gives 1-methyl-1,5hexadiene in this rearrangement.
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Unit - IV W

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Unit - IV W

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UNIT IV Molecular Rearrangements The atoms or groups within a molecule move from one atom to another, thus forming

In the case of unsymmetrical pinacols:

Similarly aldehydes and ketones react to give the corresponding compounds.

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