QUICK REVISION FOR NAMED REACTIONS

PHARMACEUTICAL ORGANIC CHEMISTRY

[Link] Name of the Starting Reagents used or reaction Final product

Reaction material conditions
1 Acyloin Carboxylic Metallic sodium with aprotic α hydroxy
condensation acid esters solvents (Ether, benzene, ketones.
toluene,xylene free from ( acyloin)
oxygen) Refluxation
2 Aldol condensation Aldehydes Warming with dilute or mild β hydroxy
having α base (The reaction not aldehydes
hydrogens favourable for ketones) (aldols)
(same If reaction is conducted in the Aldehyde+
aldehydes) presence of strong alkali alcohol
repeated condensation and
dehydration results in the
formation of resins.
3 Crossed Aldol Aldehydes Warming with dilute or mild Crossed adducts.
condensation having α base (The reaction can also
hydrogens or taken place with aldehyde and
no α hydrogen ketone)
(different
aldehydes)
4 Baeyer Villiger Ketones Treatment with peracids such as Esters
rearrangement In case of peracetic acid,perbenzoic
cyclic ketones acid,per trifluoroacetic acidand
they will be permono sulphuric acid etc
converted to (commonly used solvents are
lactones. glaceal acetic acid and
chloroform)
5 Beckmann Ketoximes Acid catalyzed conversion N- substituted
Rearrangement (acidic reagents used are amides
H2SO4,SOCl2,SO3,P2O5,PCl5,
C6H5SO2Cl etc)
6 Benzilic Acid Ketones Strong bases Sodium salt of
rearrangement Ex: Benzil the compound
containing
carbonylgroup
(Ex: Sodium salt
of Benzilic acid)
7 Birch reduction Aromatic Reduction with sodium, Un conjugated
rings like potassium or lithium in liquid dienes.
benzene ammonia or amine in the
presence of alcohol
8 Cannizaro reaction Aldehydes Self oxidation reduction Salts of
without α reaction in the presence of aldehydes used
hydrogens strong bases Ex: Sodium salt
Ex: Aromatic Reaction can occur between as sodium
aldehydes, same aldehydes and different benzoate
formaldehyde,t aldehydes
ri alkyl
acetaldehydes
and
heterocyclic
aldehydes etc.

9 Claisen Esters having Self condensation in the β keto esters.

condensation α hydrogen presence of strong bases
10 Claisen Aryl allyl Heating at 2000c o- allyl
rearrangement ethers [Link] ortho
is occupied para
product will
form
11 Claisen – Schmidt Aromatic In the preseof strong bases α,β unsaturated
reaction aldehydes aldehydes,
react with ketones and
aliphatic esters.
aldehydes or
ketones (some
timesaromatic
aldehydes with
with ester
also)
12 Clemmensen Carbonyl Reduction with amalgamated Methylene groups
reduction groups of zinc and concHCl containing
aldehydes and compounds
ketones Ex: Ethyl benzene
Ex:
acetophenone
13 Curtius reaction & Acyl azides Decomposition in an inert Isocyanates.
Curtius solvent (Ex: chloroform (The conversion
rearrangement benzene etc) gentle heat is of acyl azides to
required isocyanates
involves curtius
rearrangement
while curtius
reaction involves
the conversion of
acids to amines
,urethanes and
substituted urea
via curtius
rearramgement.
14 Dieckmann Intramolecular With bases such as sodium, Cyclic β ketone
reaction claisen sodium ethoxide, sodium derivatives.
condensation in hydride etc.
dibasic acid
esters
15 Diel’s alder Alkene + Reaction is initiated Adduct of six
reaction conjugated diene thermally or by lewis acid membered ring
(1,4 addition) catalyst with or without using
the solvents.
16 Dienone phenol When 4,4 dialkyl cyclohexadienone is treated with acid, it is
rearrangement converted to phenol with migration of one of the alkyl group to the
adjacent carbon. This is known as Dienone phenol rearrangement.
The dienone is dissolved in acetic anhydride and treated with
catalytic amount of sulphuric acid. The product on hydrolysis gives
phenol.
17 Favorskii α haloketones Alkoxide ions Esters with
rearrangement Alkali hydroxides or amines rearranged
in place of metal alkoxides carbon skeletons
give acids or amides are formed
respectively.
18 Friedel crafts Alkylation and Presence of metalhalides Alkylated or
reaction acylation of (lewis acid as catalyst usually acylated
aromatic aluminium chloride. aromatic
compounds with compounds.
alkylhalides,acid
halides or
anhydrides
19 Fries Phenolic esters Heating with aluminium tri Ortho and para
rearrangement chloride ( Lewis acid) acyl phenols.
20 Hell volhard Aliphatic Small amount of Red Mono α
zelinsky reaction carboxylic acids phosphorus halogenated
with bromine or acids.
chlorine ( but not
iodine and
fluorine)
21 Hofmann Amide Reacts with alkaline Primary amine
rearrangement or hypohalite ( NaOH solution
Hofmann +Br2 or Cl2)
bromamide
reaction
22 Houben-Hoesch Polyhydroxy phenols, phenolic ethers and some reactive hetrocyclic
reaction compounds (eg: pyrrole) undergo acylation with nitrile and
hydrochloric acid in the presence of a lewis acid. This particular
Friedel crafts acylation with nitriles is called Houben Hoesch reaction
23 Knoevenagel Aldehydes and ketones Condensation with α, β
reaction compounds having unsaturated
active methylene compounds.
group Ex: Malonic
ester)in the presence
of basic
catalyst(pyridine or
piperidine)
24 Mannich reaction Any compound containing Formaldehyde and Amino methyl
active hydrogen ammonia or primary or substituted
or secondary amines amino methyl
usually as their derivatives
hydrochlorides( Hcl
being used as
catalyst)
25 Meerwein The reaction involves reduction of aldehydes or ketones to alcohols by
ponndorf verley treatment with aluminium isopropoxide in excess of isopropyl alcohol.
reaction The reaction is reversible. (The reverse reaction called Oppenauer
oxidation is employed for the oxidation of alcohols using aluminium t-
butoxide as catalyst in the presence of excess ketone.)
26 Michael reaction The base catalysed addition of compounds having active methylene
group (or relatively acidic hydrogens) to an activated olefinic bond of
the type –C=C-Z (Z= electron withdrawing) is classified as Michael
reaction.
Compounds having active methylene groups are donors, which
include malonic ester; cyanoacetic ester acetoacetic ester aliphatic
nitro compounds sulphones indenes etc.
Compounds having an activated olefinic bond are called acceptors,
which include aldehydes,ketones,nitriles,esters of α,β unsaturated
acids.

27 Oppenauer Oxidation of secondary Different bases Ketone of the

oxidation alcohol with a ketone alcohol.( This
reaction is
reverse of
Meerwein
ponndorf
verley
reaction)
28 Perkins reaction Condensation between In the presence of α, β
aromatic aldehydes and sodium or potassium unsaturated
aliphatic acid anhydrides salt of the aromatic acids
(Vinylogs, heterocyclic corresponding to the
aldehydes and even pthalic anhydride
anhydride also gives the The acid anhydride
reaction used should have
atleast two α
hydrogens.
29 Pinacol 1,2 diols Acid catalyzed Ketones or
pinacolone rearrangement aldehydes
rearrangement
30 Reformatsky Treatment of reactive In the presence of a β hydroxy
reaction organic halide eg: α Zinc metal and esters
haloester or its vinylog with subsequent hydrolysis
a carbonyl compound
31 Reimer tiemann Formylation of phenols Warm heating at 600c Orthho and
reaction with chloroform in alkaline (The method is para isomers
solution appliclable for (Hydroxy
phenols and some benzaldehydes)
heterocyclic
compounds)
32 Sandmeyer This reaction involves the conversion of aromatic primary amines in to
reaction an aryl diazonium salt byb treatment with nitrous acid (HCl+ NaNO 2)
at 0-50c. Subsequent decomposition of the diazonium salt by heating
with cuprous chloride or bromide in the presence of an excess amount
of corresponding halogen acid gives aryl chloride or bromide. The
overall reaction is thus the replacement of the amino group of the
aromatic amine by halogens.
33 Schmidt reaction Carboxylic acids and In the presence of Amines
hydrazoic acid sulphuric acid
34 Sommelet Sommelet reaction involves the oxidation of choromethyl group to an
reaction aldehyde group by the use of hexamethylenetetramine and subsequent
hydrolysis in acidic medium. The reaction is successful with benzylic
halide.
35 Stobbe Aldehydes and ketones In the presence of Salts of α, β
condensation condense with esters of bases such as unsaturated
succinic acid C2H5ONa.Me3COK half esters.
or NaH
36 Stork enamine Enamines on treatment with α alkylated
reaction (Vinyl amines which are reactive alkylhalides ketones.
α,β unsaturated amines are and subsequent
called enamines) hydrolysis
37 Ullmann reaction Ullmann coupling reaction involves the condensation of aryl halides in
the presence of finely divided copper or copper bronze at an elevated
temperature (100-3500c) to yield di aryl derivatives. Thus iodobenzene
in nitro benzene when heated in the presence of copper powder gives
di phenyl in 80% yield. Alternatively the reactants may be heated in a
sealed tube.
38 Vilsmeier hack Vilsmeier hack reaction involves a convenient method for the
reaction formylation of aromatic rings. The method is however applicable to
active aromatic substrates such as amines and phenols. Aromatic
hydrocarbons and heterocyclics more reactive than benzene can also
be formylated. The reagent used for formylation is N-phenyl-N methyl
formanilide which is prepared from N-methyl aniline, formic acid and
phosphorus oxy chloride. Cobalt chloride may be substituted for
phosphorus oxy chloride.
 39 Wittig Phosphonium salt Reacted with strong bases such as Removes halo
reaction C6H5Li,BuLi,NaNH2,NaH,C2H5ONa acid to give
etc the reagent
methylene
Triphenyl
phosphorane
40 Wolff kishner Carbonyl group of In the presence of strong bases such Methylene
reduction aldehyde and ketone as C2H5Ona or NaOH groups are the
+ hydrazones or products.
semicarbazones or
azines
41 Wolff α diazoketones Treatment with solid silver oxide Ketene.
rearrangement

Prepared by
Dr. [Link] Babu
Associate Professor
[Link] Reddy College of pharmacy
Mehdipatnam Hyderabad