REARRANGEMENTS

Some ions or neutral molecules which are produced in chemical reactions may stabilize themselves by rearranging their atoms of
radicals or bonds within the ions or molecule is known as rearrangement.
* It always takes place to obtain more stable ions or molecule.
* It takes place in ions or in molecules when they have specific conditions to rearrange themselves. Therefore each and every
molecule or ion may not undergo rearrangement.
* It does not take place for similar or less stable product.

 HOFFMANN REARRANGEMENR
 WAGNER MERRWEIN REARRANGEMENT
 PINACOL- PINACOLONE REARRANGEMENT
 WOLFF REARRANGEMENT
 BECKMANN REARRANGEMENT
 FAVORSKII REARRANGEMENT
 HOFFMANN REARRANGEMENT
* It converts only Primary amide (R-CO-NH2) into Primary amine (R-NH2) because both H and H have to remove in steps 1 and 3 respectively.
* The reagents are Br2 and NaOH.
* It is carbon to nitrogen atom rearrangement.
* N-bromoamide anion (R-CO-NH¯-Br ) undergoes rearrangement.
R-CO-NH2 + Br2 + 4NaOH → R-NH2 + 2NaBr + Na2CO 3 + 2H2O

Mechanism of reaction
1. R-CO-NH-H + NaOH → R-CO-NH¯ + H2O + Na+ 2. R-
CO-NH¯ + Br-Br → R-CO-NH-Br (N-bromoamide) + Br -
3. R-CO-NH-Br + NaOH→ R-CO-N¯Br (N-bromoimide anion) + H2O + Na+
4. N-bromoimide anion undergoes rearrangement (rearrangement of R group from carbonyl carbon to nitrogen) to give Isocynate (R-N=C=O).

5. R-N=C=O + HOH → R-NH-COOH.

6. R-NH-COOH + NaOH → R-NH-COONa + H2O.
7. R-NH-COONa + NaOH → Na2CO 3 + R-NH2.
____________________________________________________________________________________________________________________
Total of all 7 steps: R-CO-NH2 + Br2 + 4NaOH → R-NH2 + 2NaBr + Na2CO 3 + 2H2O
 WAGNER MERRWEIN REARRANGEMENT

* It takes place in carbocation's (when carbon carries positive charge) only.

* Only methyl group (CH 3) which attached on carbon atom just next to C+ can be rearranged. For example CH 3 groups of ( I ) can
be rearranged but CH 3 groups of ( II ) can not be rearranged.

* Order of stability of carbocations is 3ᵒ ˃ 2ᵒ ˃ 1ᵒ

* Rearrangement of methyl group takes place only to get more stable carbocation. For example in ( I ) methyl can be rearranged
because ( I ) is primary carbocation and the carbocation ( III ) obtained after rearrangement is tertiary.

* WMR does not take place for decreasing order of stability. For example ( III ) can not produce ( I ) by WMR.
* The most stable carbocation gives the final or the major product
* WMR generally involved the following reactions:
1- Dehydration of alcohol.
2- SN reaction of alkyl halide.
3- Addition reaction of alkene.
1- Dehydration of alcohol: Acid forms carbocation which rearranges itself into more stable carbocation which eliminates H + to
give alkene.
(CH 3)2CH-CH 2-OH + H + → (CH 3)2CH-CH 2-OH 2+ → (CH 3)2CH-CH 2+ + H 2O
(1ᵒ carbocation) WMR CH 3-CH +-CH 2-CH 3 → CH 3-CH=CH-CH 3 + H +
(2ᵒ carbocation) ( alkene)

2- SN reaction of alkyl halide: Alkyl halide gives carbocation which stabilizes itself by WMR into more stable carbocation and
carbocation thus obtained combines with incoming nucleophile to give product.

(CH 3)3C-CH 2-Cl → (CH 3)3C-CH 2+ + Cl- (leaving nucleophile)

(alkyl halide) (1ᵒ carbocation)
WMR
(CH 3)2CH +-CH 2CH 3 + OH - (incoming nucleophile) → (CH 3)2CH (OH)-CH 2CH 3
(3ᵒ carbocation) (alcohol)

3-Addition reaction of alkene: (CH 3)2C=CH 2 + HCl → major product ?

* First of all add positive part of the molecule (H +) into both carbon atoms to obtain possible carbocations
(CH 3)2C=CH 2 + H + → (CH 3)2CH-CH 2+ and (CH 3)2C+-CH 3

(I) ( II )
* ( I ) is 1ᵒ carbocation and ( II ) is 3ᵒ carbocation. Therefore ( II ) is more stable and will be used for addition of negative part of
the molecule (Cl-) to give major product.
(CH 3)2C+-CH 3 + Cl- → (CH 3)2C(Cl)-CH 3
 PINACOL- PINACOLONE REARRANGEMENT

* Pinacol is Di-tertiary-1,2-diol ( It contains two OH groups on adjacent carbon atoms and both the carbon atoms to which OH
groups are attached are structurally tertiary in arrangement).
* Pinacol may be symmetrical and unsymmetrical. Symmetrical Pinacol divides itself into two similar halves ( I ) and
unsymmetrical Pinacol divides itself into two dis-similar halves ( II ).

* When a Pinacol (either symmetrical or unsymmetrical) is treated with acid (H +) it undergoes chemical reaction and
rearrangement to give a ketone. This ketone is known as Pinacolone. Pinacol + H + → Ketone (Pinacolone)
Mechanism of reaction or rearrangement
It can be divided into two categories:
1- For symmetrical Pinaol
2- For unsymmetrical Pinacol
1- For Symmetrical Pinacol:

1. Since Pinacol is symmetrical therefore any one of the OH can be protonated which by removal of water may produce
carbocation
2- Produced carbocation is tertiary and highly stable due to +I.E of alkyl groups but it can stabilize it further by taking methyl
group from the carbon atom containing OH group and to produce carbocation with OH group (resonance stabilized).

3- The carbocation obtained in step-2 takes lone pair of electron of oxygen atom to give Pinacolone (ketone) with recovery of H +
ion.

2- For Unsymmetrical Pinacol:

1- Both of the OH groups have to be protonated to obtain possible carbocations ( I and II)
(CH3 )2 C(OH)-(OH)C(C 6 H5 )2 + H+ → (CH3 )2 C +-(OH)C(C 6 H5 )2 or (CH3 )2 C(OH)-+C(C 6 H5 )2
(I ) ( II )
2- To stabilize ( I ) into C + ----- type carbocation we have to move phenyl group (C 6 H5 ) from C to C and we will obtain C + -----OH carbocation ( III ) having one C 6 H5
group and to stabilize ( II ) into C + -----OH type carbocation we have to move methyl group (CH3 ) from C to C and we will obtain C + -----OH carbocation ( IV ) having
one CH3 group.

3- In structure III to stabilize the positive charge of carbon atom by resonance there is a competition in between lone pair of
electron of oxygen atom and pi-bond of benzene ring therefore structure-III can not be completely stabilized by resonance and it is
not favorable to give final Pinacolone. In structure-IV there is no competition of resonance stabilization so it is easily stabilized by
resonance to give Pinacolone.

Q.
 WOLFF REARRANGEMENT

* It is rearrangement of α-dizoketone ( R-CO-CHN 2) to ketene ( R-CH=C=O) intermediate.

* It is actually rearrangement of R group from carbonyl carbon to carbon atom of diazomethyl.

* α-dizoketone may prepared by reacting R-CO-Cl and Diazomethane (CH 2N 2) and R-CO-Cl may obtain by reacting R-CO-OH with HCl.

R-CO-OH + HCl → R-CO-Cl + H 2O

R-CO-OH + H + → R-CO-OH 2+ + Cl- → R-CO-Cl + H 2O

R-CO-Cl + CH 2N 2 → R-CO-CHN 2 (α-dizoketone ) + HCl

* Molecule of α-dizoketone is electrically neutral because carbon atom carries negative charge and nitrogen atom carries positive
charge. R -C O -C H N N

Mechanism of rearrangement

* This rearrangement is catalyzed by heat of light or Ag+ ion.

* By rearrangement Ketene (R-CH=C=O) is obtained with elimination of nitrogen molecule (N 2 or N≡N ).
 Ketene (R-CH=C=O)
Ketene obtained by Wolff rearrangement is very important intermediate and can be used to prepare the following compounds
* Homologous products:
Treatment of ketene with H 2O, ROH and NH 3 may produce homologous (compound with difference of CH 2 is known as
homologous member) carboxylic acid, ester and amide respectively.

R-COOH + HCl → R-CO-Cl + CH 2N 2 → R-CO-CHN 2 → R-CH=C=O + H 2O → R-CH 2-COOH (homologous acid)

(actual molecule) (α-dizoketone) (ketene) + ROH → R-CH 2-COOR (homologous ester)

+ NH 3 → R-CH 2-CO-NH 2 (homologous amide)

O R
* 2+2 Cyclo addition product:
R-CH=C=O + H 2C=CH 2 →

* Ring contracted product:

If α-diazoketone is cyclic Wolff rearrangement results in a ring contracted product
 BECKMANN REARRANGEMENT

* It takes place in acid-catalyzed conversion of an oxime into an N-substituted amide.

* It is actually migration of R1 (which is trans to OH) group from carbonyl carbon atom to nitrogen atom.

* Oxime can be prepared by reacting ketone (R1R2C=O) with hydroxylamine (H2N-OH).

R1R2C=O + H2N-OH → R1R2C=N-OH (oxime) + H2O.

* Molecule of oxime is stereo-specific in nature due to presence of lone pair of electron of nitrogen atom in Sp2
hybridized orbital.

* Due to stereo specificity of the oxime when it undergoes acid catalyzed reaction only migration of R1 which is trans to
OH takes place.
 Mechanism of reaction

Step-1: Protonation of OH group of oxime takes place

Step-2: Removal of water molecule from the nitrogen atom and migration of R1 to the nitrogen atom with formation of carbocation.

Step-3: Hydration of carbocation.

Step-4: Removal of H + ion leaving OH group on carbon atom.
Step-5: Tautomerism takes place to give finally N-substituted amide.
 FAVORSKII REARRANGEMENT
* It takes place in base induced conversion of α-halo-ketone into carboxylic acid molecule.
CH3-CO-CH2-Cl + OH- → CH3-CH2-COOH + Cl-
(α-halo-ketone) (Carboxylic acid)
* It is basically carbanion ion (carbon atom contains negative charge) rearrangement.
* α-halo-ketone can be obtained from symmetrical or unsymmetrical ketones and therefore it may be symmetrical or unsymmetrical.
CH3-CO-CH3 + Cl2 → CH3-CO-CH2-Cl + HCl
(symmetrical ketone) (symmetrical α-halo-ketone)
C 6H5-CH3-CO-CH3 + Cl2 → C 6H5-CH3-CO-CH2-Cl + HCl
(un-symmetrical ketone) (un-symmetrical α-halo-ketone)
Mechanism of reaction or rearrangement
Mechanism can be divided into three categories:
1- Favorskii rearrangement of symmetrical α-halo ketone. 2- Favorskii rearrangement
of un-symmetrical α-halo ketone. 3- 3-Favorskii rearrangement of cyclic α-halo ketone.
1- Favorskii rearrangement of symmetrical α-halo ketone:
CH3-CO-CH2-Cl + OH- → CH3-CH2-COOH + Cl-
* OH- ion eliminates H atom from α-carbon (which does not has halogen) to give enolate (carbon with negative charge) and H2O.
* Enolate makes bond with α-carbon (which has halogen) to give cyclo-propanone with removal of Cl- ion. This step is known as 1,3 dehydohalogenation.
* OH- ion attacks on carbonyl carbon of cyclo-propanone.
* Ring opening takes place and two enolates were obtained by following pathway (I) and (II).
* Since both enolates formed by pathway (I) and (II) are same therefore single carboxylic acid was obtained by taking H+ from H2 O.

2- Favorskii rearrangement of un-symmetrical α-halo ketone:

C6H 5-CH 3-CO-CH 2-Cl + OH - → C6H 5-CH 3-CH 2-COOH + C6H 5-CH(COOH)CH 3

(major) (minor)
* In the last step of the mechanism two different enolates (I) and (II) will be obtained

* Enolate (I) due to having aromatic ring (C6H 5) is resonance stabilized and more stable than elolate (I).

* The major carboxylic acid will be obtained when elolate (I) will take H + from H 2O.
3-Favorskii rearrangement of cyclic α-halo ketone:

* Cyclic α-haloketone by Favoraskii rearrangement produce ring-contracted carboxylic acids.

Mechanism of reaction