Name Reactions (Part - 1)

1. Sabatier - Sander’s Reaction :

Hydrogenation of alkene take place in presence of nickel.
Ni/H 2
R-CH=CH2  
 R–CH2–CH3
With Hydrogenation syn addition

2. Wurtz’s Reaction : -
In case of wurtz’s reaction alkyl halide reacts with sodium in presence of dry ether to give
alkane.
Reaction : -
Dry
R–Cl + 2Na + Cl –R 
Ether
 R–R + 2NaCl

Golden Points : -
 This reaction undergo both radical and ionic mechanism.
 This disproportionation take palce in reaction.
 3o alkyl halide undergo disproportionation.
 Order of reactivity of halides.
R–I > R–Br > R–Cl > R–F
 Order of reactivity of alkyl halides.
1o > 2o > 3o
Dry
Ex. CH3–Cl + 2Na + Cl–CH3 
Ether
 CH3–CH3 + 2NaCl

Ex. Br Cl + Na 


3. Frankland Reaction : -
In this reaction alkyl halides reactes with Zn in presence of dry ether to give higher alkane.
It is an extension of Wurtz reaction for the preparation of higher alkanes.
Reaction : -
Dry
R–X + Zn + R–X 
Ether
 R–R + ZnX2
Dry
Ex. 2CH3–I + Zn 
Ether
 CH3–CH3 + ZnI2

4. Kolbe’s Electrolysis : -
In Kolbe’s electrolysis potassium or sodium salt of carboxylic acids is electrolysed in aqous
medium and give higher alkane.
Reaction : -
R  R  2CO 2  H 2  2KOH
Electrolysis
R–COO- Na+ + R–COO- Na+ + 2H2O   
At anode
 
At cathode

Electrolysis
Ex. 2CH3 –COO–Na+ + 2H2O   CH3–CH3 + 2CO2 + H2 + 2NaOH
KES
Ex. COOK + H2O   + 2CO2 + H2 + 2KOH
KOOC
CH 2  COO  K  CH 2
Ex. | KES
+ 2H2O   || + 2CO2 + H2 + 2KOH
CH 2  COO  K  CH 2

CHCOONa CH
Ex. || + 2H2O KES
 ||| + 2CO2 + H2 + 2NaOH
CHCOONa CH
Golden Points : -
 Fumaric and malic acid they are having same products but they are geometrical isomers.
Fumaric acid is trans while malic acid is cis.
[Page No : 02]
 Name Reactions (Part - 1)

 A mixture of sodium acetate and sodium propionate would give ethane, propane and n-
butane.
 Salts of 3o acids give ester as major product.
 Alkyl groups in the  -position decrease the yield of alkanes. The yield of alkanes are
increased by using dimethyl formamide as solvent.
By using Wurzt’s, Frankland and Kolbe’s be can not prepar methane (CH4)
Wurzt’s, Frankland and Kolbe’s reactions gives good results for alkanes having even number
of carbon atoms or symmetric alkanes.

5. Corey House Synthesis Reaction:-

This synthesis involves the reaction between alkyl halide and lithium dialkyl copper in
presence of dry ether.
Reaction :-
Li CuI R 'Cl
R–X   RLi  R2CuI   R–R’
R2CuLi 
 Gilmann’s Reagent
CH3–X + (CH3CH2)2 CuLi   CH3CH2CH3 + CH3CH2Cu + LiX
 It is good method for the prepration of alkanes having odd number of carbon atoms.
 1o & 2o alkyl halides good yield of alkanes
 R–X should not be 3o-alkyl halide.

6. Decarboxylation of Carboxylic Acid :-

This reaction carried out by heating sodium salt of fatty acid with soda line. The carboxylic
acid under this condition decarboxylates to give an alkane containing one carbon atom less
than original molecule.
Reaction :-
Soda lime
RCOONa + NaOH 
(CaO  NaOH )
 RH + Na2CO3


nC (n–1)C
Soda lime
Ex. CH3COONa + 
(CaO  NaOH )
 CH4 + Na2CO3


NaOD
Ex.CH3COONa +  CaO
 CH3–D + Na2CO3
 Monobasic acids are stable and must be decarboxylated under very vigorous conditions.
 Decarboxylation occurs readily with compounds having electron withdrawing groups.

7. Grignard Reagent (RMgX)

It reacts with active hydrogen to give alkane (active hydrogen means hydrogen directly bonded
with more electronigetive atoms.
Reaction:-
CH3MgCl + H2O 
 CH4 + MgOHCl
D 2O
Ex. CH3–Mg–Br   CH3–D

8. Hydrolysis of Carbide:-
Reaction:-
Be2C + H2O 
 Be(OH)2 + CH4
Al4C3 + H2O  Al(OH)3 + CH4
Methane (CH4 ) can be prepared from decarboxyletion, grignard reagent and hydrolysis of
carbides.

[Page No : 03]
 Name Reactions (Part - 1)

10. Clemmensen’s Reduction:-

Aldehydes and ketones on treatment with Zn-Hg and Conc. HCl give alkane.
Reaction:-
Zn  Hg/conc.HCl
O   CH2
Zn  Hg/conc.HCl
Ex. CH3CHO   CH3. CH3 + H2O
Zn  Hg/conc.HCl
Ex. CH3COCH3   CH3CH2CH3 + H2O

Zn  Hg/conc.HCl
Ex.  
Cl
OH
 It is electrode based reaction.
 Conc. HCl is preferable due to dil. HCl can not perform complete reaction.
 Ketones are more reactive than aldehydes due to ketones form more stable carbocation.
 This methode is not good for carbonyl compound having acid sensitive groups like –OH, –
SH, C=C, C  C etc.

11. Wolff-Kishner Reduction:-

Aldehydes and ketones on treatment with NH2–NH2/KOH or strong base to give alkanes.
Reaction:-
1 1
R R H
2 N  NH 2
O + (HHydrazine)
R  KOH R H
2 2

O
H 2 N  NH 2
Ex. ( Hydrazine)
 KOH

 This method is not good for carbonyl compounds with base sensitive groups like NH3+,
COOH etc.
12. Witting Reaction :-
Conversion of aldehydes and ketones into alkenes.
Reagent:- Phosphorus ylide
R R
O + Ph P=CH 
 CH2 + Ph P=O
3 2 3
R' R'

Ex. O + Ph3P=CH2 
 CH2 + Ph3P=O

 i  Ph 3P
  CHCH3 + Ph3P=O
Ex. CH3–CH2–Br +  ii RLi
 iiicyclohexenone

13. Oxymerusation-Demercuration :-
Alkenes react with mercuric actate followed by water & sodium bro-hydride give alcohol.
Alkanes react with mercuric actate followed by water give aldehydes and ketones.
Reaction:-

[Page No : 04]
 Name Reactions (Part - 1)

 i Hg  OAc  /H O
CH3-CH=CH2 
 ii  NaBH 4  CH 3  CH  OH
2 2

|
CH 3

Hg(OAC)2 /CH3OH
Ex.   OCH3

It follow MKW rule and anti adition take place

Put –OH group on more crowed carbon atom
No carbocation is formed and no rearrengement is possible
O
||
Hg(OAC)2 /H 2O
RC  CH 
R  C  CH 3

O
C CH
Ex. Hg(OAC)2 /H 2O
 CH3

Only acetylene give aldehyde remaining alkynes give ketone as major product.
Put C=O on more crowed carbon atom.

14. Hydroboration :-
Alkenes on hydroboration give less substituted alcohol as major product.
Reaction:-
CH 3 CH 3
|  i BH 3 /THF |

 ii  H 2O2 /OH 

R  CH  CH  CH 2 R  CH  CH 2  CH 2OH

 3
i BH /THF
Ex. 
 ii  H O /OH 

2 2
OH
It followes anti markownivs rule.
Syn addition take place
Reaction:-2
Alkynes on hydroboration give aldehydes and ketones as major product.
 3
i BH /THF
RC  CH 
 ii  H 2O2 /OH 
 RCH2CHO

 3
i BH /THF O
Ex. 
 ii  H O /OH 

2 2

Put C=O less steric carbon.

Terminal alkynes give aldehydes.
Internal alkynes give ketones.

15. Friedal-Craft akylation :-

Benzine in presence of lewis acid on tritment with alkyl halide produce alkyl benzene.
Reaction:-
R
AlCl3 /BX3 /FeX 3 /ZnX 2
+ R–X  + AlX3 + HCl

CH2CH3
AlCl3
Ex. + CH3CH2Cl 


[Page No : 05]
 Name Reactions (Part - 1)

CH2CH2CH3 CH(CH3)2
AlCl3 (Cumene)
Ex. + CH3CH2CH2Cl   +
(Minor) (Major)
Long carbon chain is not possible on benzene ring with this reaction. Due to rearrengement
of carbocation branching take place on ring.
Poly alkylation takes place with Fredal-Craft akylation.

16. Friedal-Craft Acylation:

Benzine on treatment with acid halides or acid anhydrides in presence of lewice acid produce
aromatic ketones.
O
O
+ || AlX 3
  R
R CX
(Acid halide)

O
O O
Ex. + || || AlCl3
  CH3
CH 3  C  O  C  CH 3

O
O
Ex. + || AlCl3
  Et
CH 3  CH 2  C  Cl

No rearrengement is possible in this reaction.

Acylium ion is electrophile
Phenol and Aniline dont give friedal of alkylation and acylation.
Benzine ring with strong electron with withdrawing groups does not undergo both friedal
craft alkylation and acylation.
17. Gattermann-Koch reaction:-
Benzene on treatment with carbon monoxide and HCl under pressure in presence of
anhydrous AlCl3 and a little cuprous chloride gives benzaldehyde.
Reaction:-
Anhydride AlCl3
C6H6 + CO + HCl  C6H5CHO + HCl
 
 C HO  AlCl 4
CO + HCl + AlCl3   Electrophile 

The electrophile C HO is generated as follows

18. Gettemann aldehyde reaction:-

In presence of catalyst anhydrous AlCl3 benzene reacts wit HCN and HCl to form an aldimine
which on hydrolysis yields benzaldehyde.
Reaction:-
Anhyd. AlCl3
C6H6 + HCN + HCl  
 C6H5CH=NH + HCl

Ex. C 6 H 5CH  NH  H 2O  HCl   C6 H 5CHO  NH 4Cl
Aldimine Dil.


The electrophile C H  NH is generated as follows
 
 C H  NH  Al Cl 4
HCN  HCl  AlCl3 
[Page No : 06]
 Name Reactions (Part - 1)

19. Etard’s Reaction:-

Chromyl chloride is a weak oxidising agent. It react with toluene in CCl4/CS2/ether solution
give a precipitate which on treatment with water produces benzaldehyde.
Reaction:-
CCl 4
C 6H 5CH 3  2Cr2O 2Cl 2   C6 H 5CH 3 .2CrO2Cl2 
3H 2O
C6H5CHO + 4HCl + 2H2CrO4
Addition complex  Hydrolysis 
20. Sandmeyer Reaction:-
The Cl , Br and CN nucleophiles can easily be introduced in the benzene ring of benzene diazonium salt in the
presence of Cu(I) ion. This reaction is called Sandmeyer reaction.
Reaction:-

CuCl/HCl
ArCl + N2
CuBr/HBr
ArN 2X ArBr + N2
CuCN/KCN ArCN + N
2

21. Gatterman Reaction

Chlorine or bromine can be introduced in the benzene ring by treating the benzene diazonium salt solution with
corresponding halogen acid in the presence of copper powder. This is referred as Gatterman reaction.
Reaction:-
Cu/HCl
ArCl + N2 + CuX
ArN2X Cu/HBr ArBr + N2 + CuX

22. Balz-Schiemann Reaction

When arenediazonium chloride is treated with fluoroboric acid, arene diazonium fluoroborate is precipitated
which on heating decomposes to yield aryl fluoride.
Reaction:-
 
Ar N 2 Cl   HBF4 
 Ar  N 2 BrF4 
Heat
 Ar  F  BF3  N 2
23. Finkelstein Reaction
Alkyl iodides are often prepared by the reaction of alkyl chlorides/ bromides with NaI in dry acetone. This
reaction is known as Finkelstein reaction.
Reaction:-
R  X  NaI 
 R  I  NaX
(X=Cl, Br)
This reaction in forward direction can be favoured by precipitating NaX formed in dry acetone (according to Le
Chatelier’s principle)
24. Swarts Reaction
Heating an alkyl chloride/bromide in the presence of a metallic fluoride such as AgF, Hg2F2, CoF2 or SbF3 gives alkyl
fluorides. The reaction is termed as Swarts reaction.
Reaction:-
H 3C  X  AgF 
 H 3C  F  AgX
(X= Cl, Br)
Finkelstein Reaction and Swarts Reaction are known as halogen exchange reaction.
25. Hunsdiecker Or Borodine-Hunsdiecker Reaction:-
Silver salts of carboxylic acids in CCl4 solution are decomposed by Cl2 or Br2 giving alkyl halides.
Reaction:-
CCl4
RCOOAg + Br2   RBr + AgBr + CO2

[Page No : 07]
 Name Reactions (Part - 1)

CCl4
Ex. C2H5COOAg + Cl2   C2H5Cl + AgCl + CO2
The yield of alkyl halides is 1o > 2o > 3o.
Cl2 gives poor yields while Br2 gives better yields.
Iodine forms esters with silver salts, which is known as Birnbaum-Simonini reaction.
Ex. 2COOAg + I2 
 RCOOR + CO2 + 2AgI 

26. Wurtz-Fittig Reaction

A mixture of an alkyl halide and aryl halide gives an alkylarene when treated with sodium in dry ether and is called
Wurtz-Fittig reaction.
Reaction:-
X R
Ether
+ Na + RX   + NaX

27. Fittig Reaction

Aryl halides also give analogous compounds when treated with sodium in dry ether, in which two aryl groups are
joined together. It is called Fittig reaction.
X
Ether
2 + Na   + 2NaX

28. Dakin Reaction:-

This reaction is characteristic of o- and p-hydroxy aldehyde or o- and p-amino aldehyde with alkaline H2O2 ,
followed by hydrolysis to give o- or p-dihydroxy benzene or o- or p-aminophenol.
Reaction:-
CHO ONa OH
H 2O 2  NaOH H 3O 

 

OH ONa OH
CHO ONa OH

H 2O2  NaOH 
H 3O
Ex.    
OH ONa OH
29. Elbs Persulphate Oxidation:-
In this reaction, monohydric phenols are oxidised to dihydric phenols by alkaline potassium persulphate (K2S2O8).
Hydroxylation normally occurs at p-position, but if this is blocked, then in the o-position.
Reaction:-
K 2S2O8 
HO 
 NaOH
O OSO 3K 
H 3O
 HO OH

30. Reimer-Tiemann Reaction:-

Phenols for aromatic compounds containing EDG when refluxed with CHCl3 and alkali yield o- and p-
hydroxybenzaldehyde. The ortho product is the predominant product. It is an electrophilic substitution (SE) on
PhO– ion. The electrophile is dichlorocarbene (:CCl2) which contains a C with only six electrons.
OH
ONa
OH CHCl2 ONa
CHCl3  aq.NaOH NaOH CHO H
      CHO
(Minor) +
Intermediate p-hydroxybenzaldehyde

[Page No : 08]
 Name Reactions (Part - 1)

OH
CHO
(Major)

Salicylaldehyde
31. Extention to Reimer-Tiemann Reaction:-

OH OH
COOH
OH

+ CCl4 + KOH 
 +
Salicyclic COOH
Acid p-hydroxybenzoic acid

32. Kolbe-Schmitt Reaction:-

Phenol when heated at (390-410 K) under pressure with CO2 and alkali gives salicylic acid after acidification in
addition to some amount of p-isomer.

ONa OH OH
COONa COOH

390 410K HCl

+ O=C=O 
6 atm
 
Sodium Sodium Salicyclic
Phenoxide salicylate Acid
If the temperature is increased to above 430 K or potassium phenoxide is used instead of sodium phenoxide, then p-
isomer is the main product.
33. Rosenmund Reduction
Acyl chloride (acid chloride) is hydrogenated over catalyst, palladium on barium sulphate. This reaction is called
Rosenmund reduction.
O O
Cl H
H2

Pd  BaSO4

benzoyl chloride benzaldehyde

Me
CHO
Cl  H2
 H
Ex. Me Pd  BaSO4 S H
( Lindlar 's catalyst )
O (Z) or cis -pent-3-enal

Lindlar catalyst also reduces  C  C  bond to (C=C) bon in syn-adition.

BaSO4 prevents the aldehyde from being further reduced to alcohols and acts as a poison to the Pd catalyst.
Ketones canot be prepared by this method.
34. Stephen reaction
Nitriles are reduced to corresponding imine with stannous chloride in the presence of hydrochloric acid, which
on hydrolysis give corresponding aldehyde. This reaction is called Stephen reaction.

H 3O
RCN  SnCl 2  HCl 
 RCH  NH   R  CHO
It does not reduce (C=C) or  C  C  bond.
Ketones canot be prepared by this method.
35. Aldol reaction:-
Aldehydes and ketones having at least one  -hydrogen undergo a reaction in the presence of dilute alkali as
catalyst to form  -hydroxy aldehydes (aldol) or  -hydroxy ketones (ketol), respectively. This is known as Aldol

[Page No : 09]
 Name Reactions (Part - 1)

reaction. The name aldol is derived from the names of the two functional groups, aldehyde and alcohol, present
in the products.
I. Aldol condensation:-
The aldol and ketol readily lose water to give ,  -unsaturated carbonyl compounds which are aldol condensation
products and the reaction is called Aldol condensation.


2 CH 3  CHO 
dil.NaOH
 CH 3  CH  CH 2  CHO 

 H 2O
 CH 3  CH  CH  CHO
Ethanal But  2  enal
|
OH
3 Hydroxybutanal
( Aldol)

CH 3 CH 3
| |

Ba (OH )2
2CH 3  CO  CH 3   CH 3  C  CH 2 CO  CH 3 
 H 2O
 CH 3  C  CH  CO  CH 3
|
OH
Papanone (Ketol) 4  Methylpent  3  en  2  one
4  Hydroxy  4  (Aldol Condensation product)
methylpen tan  2  one

II. Cross aldol condensation:

When aldol condensation is carried out between two different aldehydes and / or ketones, it is called cross aldol
condensation. If both of them contain ±-hydrogen atoms, it gives a mixture of four products.
NaOH
Me  CHO  Et  CHO 
 CH 3  CH  CH  CHO  CH 3 CH 2  CH  C  CHO
|
CH 3
III. Intramolecular Aldol Condensation Via cyclisation:-
When a dialdehyde or a keto aldehyde or a diketone is reacted with weak base, it undergoes intramolecular aldol
condensation to give five or six or sometimes larger number of rings.

2 Me
3 O 1
4 Me
2 1 Me
7
5
Me 8 
O
O 6 OH
  -Unsaturated ketone
 H2O
Ota-2,7-dione (1-Acetyl-2-methyl
(Diketone) cyclopent-1-ene)

The step involving C–C bond formation is promoted by lectron withdrawing group on carbonyl carbon.
This reaction is bimolecular and second order reaction.
The dehydration of aldol in basic medium proceed through E1cb elimination. If a stereogenic double bond is formed
by E1Cb elimination the major product is trans- or an E-isomer of  -unsaturated carbonyl compounds.
Acid catalyzed aldol condensation is often useful when reactants or products are unstable to alkali.
36. Cannizzaro reaction:
Aldehydes which do not have an  -hydrogen atom, undergo self oxidation and reduction (disproportionation)
reaction on treatment with concentrated alkali. In this reaction, one molecule of the aldehyde is reduced to alcohol
while another is oxidised to carboxylic acid salt.
O
H H
2 O 
Conc.KOH
 H3C–OH + OK
H potassium f ormate

[Page No : 010]
 Name Reactions (Part - 1)

COONa
Conc.NaOH
2 CHO  CH2OH +
sodium benzoate
Hydride ion transfer take place.
It is disproportionation reaction.
Me O
N CH , CCl3CHO Does not undergo cannizzaro reaction, Eventhough they have  -Hydrogen atoms.
Me
At low concentration of base this reaction is biomolecular with third-order kinetics .
At higher concentration of base this reaction is biomolecular with fourth-order kinetics.
Crossed-Cannizzaro Reaction:-
When two different aldehydes lacking  -H atom are reacted in the presence of a strong base, they undergo redox
reaction to give a molecule of alcohol and salt of an acid.

OH 
HCH=O + PhCH=O   HCOO  PhCH 2 OH
I II
More reactive Less reactive
than (II) than (I)
37. Tischenko reaction :-
All aldehydes can be made to undergo Cannizzaro reaction by treatment with aluminium ethoxide. Under these
condition the acid and alcohol are combined as ester and this is known as Tischenko reaction.
 2 5 3
C H O Al
2CH3CHO   CH3COO2H5

 2 5 3C H O Al
2CH3CH2CHO   CH3CH2COOCH2CH2CH3

This is a two steps reaction.
(i) Redox reaction followed by ester formation.
(ii) Thus this reaction is extension of Cannizzaro reaction.
38. Reformatsky Reaction:-
Reaction between carbonyl compound with  -bromo esters in presence of zonc to give  -hydroxy acids or ,  -
unsaturated acids is known as Roformatsky reaction.
OZnBr
C6H 5CH CH COOC H
2 2 5 
H 2 /OH
C6H5CHO + Zn + BrCH2COOC2H5 
  
(Intermediate)

OH
| 
 C6 H 5 CH  CHCOOH
 H2O
C6 H 5  CH  CH 2 COOH Cinnamic acid

39. Perkin Reaction:-

The condensation reaction between aromatic aldehyde and an aliphatic anhydride containing two  -H atom in the
presence of sodium salt of same aliphatic acid to give ,  -unsaturated acid is known as Perkin reaction.

CH 3COONa
C6 H 5CHO  H 2CHCOOCOCH 3 
 H 2O
C6 H 5CH  CHCOOCOCH 3 
 C6 H 5CH  CHCOOH
Acetic anhydride Cinnamic acid

+ CH3COOH
Only  -H atoms of anhydrides are involved in reaction.
The carbanion is derived from acid anhydride and not from the salt.
High temperatures are required because a weak base is used with a weakly acidic reagent.
40. Knoevenagel Reaction:-
Reaction between benzaldehyde and any reactive methylene compound, e.g., malonic acid, malonic esters, acetoacetic
ester, in the presence of a base to give  -unsaturated compound is known as Knoevenagel reaction.

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 Name Reactions (Part - 1)

COOH Piperidine COOH 

C6H5CHO + H2C or
 C6H5CH C   C6H5CH=CHCOOH
COOH OC 2 H 5 COOH  CO2

41. Benzoin Condensation:-

When benzaldehyde is refluxed with aq. alcoholic KCN solution to give benzoin (  -Hydroxy Ketone), the process
is called benzoin condensation.

O O OH O
|| || | ||
aq.alc.
C6H 5  CH  HC  C6 H 5 
KCN
 6 5 Benzoin  C6 H 5
C H  CH  C

Cyanide is a very specific catalyst for benzoin condensation because it is a very weak base and a very good
nucleophile.
42. Beckmann Rearrangement:-
Oximes of carbonyl compound undergo a rearrangement in the presence of mineral acids (H2SO4) or HCl or
H3PO4) or Lewis acids (PCl5, PhSO2Cl, SbCl5, POCl3, ArSO3H) to give substituted amides which on hydrolysis
gives carboxylic acid and amines.
O
R'
R R
R N
O + H2NOH 
 N OH H
 H
R' R' Oxime
Substituted amide
This rearrengement is an example of nitrogen deficient.
In this rearrengement anti-eliminetion takes place
i.e., the group which is anti to the (OH) group migrates from C to N atom.
The function of the acidic reagent is to convert the (OH)to a better leaving group.
43. Beyer-Villiger Oxidation:-
Ketone on treatment with peracid followed by hydrolysis gives acid and alcohol.
O
Peracid H
|| 
C6 H 5COOOH
 RCOOR   ROH + RCOOH
R CR
e–- withdrawing group in peracid facilitates the reaction.
Strong e–-donating group migrates.
44. Meerwein-Ponndorf-Verley reduction:-
Reduction with aluminium isopropoxide in excess of isopropyl alcohol is called Meerwein-Ponndorf Verley (MPV)
reduction. It is a selective reduction which reduces C=O to CHOH but does not reduce groups like – NO2. n

O
O R ||
 (CH ) CHO  Al
C OH + CH  C  CH
+ 2[H] 
3 2 3

R R' in(CH ) CHOH
3 2
R' H 3 3

45. Pinacol-Pinacolone rearrangement:-

Two molecules of ketones undergo reduction in the presence of Mg/Hg to form pinacol. Upon treatment with
mineral acids, pinacol is converted into pinacolone. this transformation involves dehydration and rearrangement
called pinacol-pinacolone rearrangement.

CH 3CH 3
CH3 CH3 | |
H3C CH 3  C  C  CH 3
H3C CH3 | |
2 O  Mg/Hg HOH
  + Mg(OH)2
H3C  Benzene as solvent  O O OH OH
Mg 2,3 Dimethylbu tan e  2,3diol
 Pinacol 

46. Hell-Volhard-Zelinsky (HVZ )reaction.

Carboxylic acids having an ±-hydrogen are halogenated at the ±-position on treatment with chlorine or bromine in
the presence of small amount of red phosphorus to give ±-halocarboxylic acids. The reaction is known as Hell-

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 Name Reactions (Part - 1)

Volhard-Zelinsky reaction.
X 2 /Re d phosphorus
R–CH2–COOH  H 2O
 R  CH  COOH
|
X
X  Cl, Br
 halocarboxylic acid

47. Base-catalysed Transesterification:- (JEE Mains)

The reaction occurs between the ester and R” O–. alkoxide ion) in the solvent R”OH.
R”O– is a better nucleophile than R”OH and attacks at the (C=O) group to give a tetrahedral intermediate which
loses R’O– to give a new ester, but the loss of R”O– would give the original ester.

O O
O
R + O-R" R OR"
R OR" + R'O
*OR' OR' -OR' *
48. Claisen Ester Condensation:- (JEE Mains)
In Claisen ester condensation, two molecules of an ester containing  -H atom condense together in the presence
of a base such as NaOMe or NaOEt to give a molecule of  -keto ester and a molecule of alcohol.
O O
NaOEt
H3 C C OEt + H–CH2
–COOEt 
EtOH
 H3 C C CH 2COOEt + EtOH
49. Intramolecular Claisen Ester Condensation:- (JEE Mains)
Diester containing  -H atom with base (NaH with catalytic amount of EtOH used as the basic catalyst and not
NaOEt/EtOH) undergoes an intramolecular condensation to give cyclic  -keto esters.

O
2 C OEt
5 O 3
4
6 OEt 1
1 NaH/EtOH 4
3 OEt  O 5
2 O
2-Carbethyoxy cyclopentanone
50. Favorski Rearrangement:- (JEE Mains)
 -Haloketones gives carboxylic acid when treated with base. This reaction is known as farorski rearrengement.
O
|| NaOH
 
C 6 H 5  C H 2  C  C H 2  Cl H  /H 2O C6H5–CH2–CH2–COOH
 

O
Br NaOH

H  /H O
 COOH
2

51. Arndt-Eistert reaction:- (JEE Mains)

This reaction is a method for converting an acid RCOOH to a homologous series, R–CH2COOH, in which Woff
rearrangement is the key step. In this reaction, R–COCl from R–COOH is converted to R–CH 2COOH by
diazomethane via formation of  -diazoketone.
PCl5 CH 2 N 2 Slow Ag2O/HOH
R  COOH 
or SOCl 2
 R  COCl   RCOCHN 2   R  CH  C  O   RCH 2COOH
Diazoketone

 i SOCl2
R  COOH 
 ii CH2 N2 R  CH 2COOR '
 iii Ag 2O/R 'OH

O
||
 i SOCl2
R  COOH 
 ii CH 2 N2
 R  CH 2  C  NHR '
 iii  Ag2 O/ R ' NH 2

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 Name Reactions (Part - 1)

52. Baeyer-Villiger Oxidation:-

Aliphatic ketones undergo oxidation with Caro’s acid (per monosulphuric acid, H2SO5) or per benzoic acid
(C6H5CO3H) or m-chloro perbenzoic acid (CPBA) or per acetic acid (CH3CO3H) or CF3CO3H, etc., to form esters
or their hydrolysed products.
O O
|| ||
CF3CO3H
R  C  R ' 
 Per acid   R  C O R'
In case of unsymmetrical ketones, the preference of insertion of oxygen atom between carbonyl carbon and alkyl
group in decreasing order is as follows:
C6H5 > 3o alkyl > 2o alkyl > 1o alkyl > CH3
O O
|| ||
CF3CO 3H
C 6H 5  C  CH 3 
 Per acid   CH 3  C  O  C6 H 5

O O
O CH3
O O
m CPBA
CH 3   CH3 +
Major Minor
53. Hofmann Bromamide Rearrangement or Degration Reaction:-
Amides on reaction with Br2 or Cl2 in alkali give 1o amine with one C atom less than the parent amide. This is
known as Hofmann bromamide rearrangement or degradation reaction.
RCONH 2  Br2  4KOH 
 RNH 2  2KBr  K 2 CO3  2H 2O
The overal reaction involves the elimination of (CO) as CO32– ion.
It involves intramolecular rearrangement in which alkyl or aryl group migrates from C to N.
Slow and rate-determining step (R.D.S.) is the formation of isocyanate from acylnitrene.
..
The intermediate species formed is acylnitrene (RCO N :) .
54. Lossen Rearrangement Reaction:-
Hydroxamic acid in basic medium rearranges to give alkyl isocyanate via acylnitrene formation, which on hydrolysis
gives 1o amine.

O O
O H ||
|| | || .. Slow H 2O
  R.D.S
  R–N=C=O   CO2 + RNH2
R  C  N  OH OH 
 R  C  N  OH 
 OH R  C  N :
Acylnitrene Alkyl isocyanate
55. Curtius rearrangement Reaction:-
Acid azides on heating in non-polar solvent (benzene) give alkyl isocyanate via acylnitrene formation, which on
hydrolysis gives 1o amine.
O
O O ||
|| || .. Slow H 2O
NaN 3
R  C  Cl   R  C  N 3 
R.D.S
 R  C  N :   R–N=C=O   CO2 + RNH2
 N2

Acylnitrene Alkyl isocyanate

56. Claisen-Schmidt rearrangement Reaction:-
Carboxylic acid on reaction with hydrazoic acid in the presence of acid (H2SO4) gives acid azide which on heating
gives alkyl isocyanate followed by hydrolysis to give 1o amine.

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 Name Reactions (Part - 1)

O O O
|| || ||
NH 3 
.. Slow H 2O
R  C  OH 
H 2SO 4
 R  C  N 3 
 N2
R.D.S
 R  C  N :   R–N=C=O   CO2 + RNH2
 H2 O

Acylnitrene Alkyl isocyanate

57. Carbylamine reaction:- (isocyanide test)
Aliphatic and aromatic primary amines on heating with chloroform and ethanolic potassium hydroxide form isocyanides
or carbylamines which are foul smelling substances. This reaction is known as carbylamines reaction or isocyanide
test.
Heat
R–NH2 + CHCl2 + 3KOH   R–NC + 3KCl + 3H2O
Note: Secondary and tertiary amines do not show this reaction and is used as a test for primary amines.

58. Hinsberg’s Test

Benzenesulphonyl chloride (C6H5SO2Cl), which is also known as Hinsberg’s reagent, reacts with primary and
secondary amines to form sulphonamides.
(a) The reaction of benzenesulphonyl chloride with primary amine yields N-ethylbenzenesulphonyl amide. The
hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the presence of strong electron withdrawing
sulphonyl group. Hence, it is soluble in alkali.

O
O S NH Et
S Cl + H2N–C2H5 
 O + HCl
O N -ethylbenzenesulphonamide
(b) In the reaction with secondary amine, N,N-diethyl- benzenesulphonamide is formed. Since N, Ndiethylbenzene
sulphonamide does not contain any hydrogen atom attached to nitrogen atom, it is not acidic and hence insoluble in
alkali.
O
O H3C S N C2H 5
S Cl + H2N–(C2H5)2 
 O C2H5 + HCl
O N,N-diethyl-4-methylbenzenesulphonamide
(c) Tertiary amines do not react with benzenesulphonyl chloride.
Note: This test is used for the distinction of primary, secondary and tertiary amines and also for the separation of a
mixture of amines. However, these days benzenesulphonyl chloride is replaced by p-toluenesulphonyl chloride.

59. Gabriel phthalimide synthesis:-

Gabriel synthesis is used for the preparation of pure primary amines. Phthalimide on treatment with ethanolic
potassium hydroxide forms potassium salt of phthalimide which on heating with alkyl halide followed by alkaline
hydrolysis produces the corresponding primary amine.

O
O O
N-R
NH KOH NK RX
    O
O O N-AlkylPhthalimide

O O
ONa
N-R NaOH(aq.)
 R  NH 2
 ONa (1o amine)
O O
Note: Aromatic primary amines cannot be prepared by this method because aryl halides do not undergo nucleophilic
substitution with the anion formed by phthalimide.
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 Name Reactions (Part - 1)

60. Coupling Reactions:-

Benzene diazonium chloride reacts with phenol in which the phenol molecule at its para position is coupled with the
diazonium salt to form p-hydroxyazobenzene. This type of reaction is known as coupling reaction.

N NCl + H OH 
OH N N OH + Cl– + H2O
Similarly the reaction of diazonium salt with aniline yields p-aminoazobenzene.

N NCl + H NH2 
OH N N NH2 + Cl– + H2O
61. Conversion of Aldopentose to Aldohexose:-

O
CN COOH C
HC CN HP C
O HCN CHOH  CHOH 
H C OH HO C H H3C + CHOH
(CHOH)3 + (CHOH)2  O (CHOH) O
(CHOH)3 (CHOH)3   (CHOH)2  2
CH2OH CHOH HC 
CH2OH CH2OH  HC
Aldopentose CH2OH CHOH
Pair of C-2 epimer cyanohydrin CH2OH
Glyconic
Stephen's reduction Acid CH2OH
SnCl2 + HCl/H3O+
-Lactone is also f ormed. Lactone
HC O Mixture is reduced without separation
HC O
CHOH Na/Hg
CHOH + C-2
(CHOH)3 CO2
Epimer
(CHOH)3 Ph=3-5
CH2OH
CH2OH
(Aldohexose)
(Aldohexose)

62. Conversion of Aldohexose to Aldopentose:-

a. (Ruff degradation) Oxidative decarboxylation):-

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