PHASE TRANSFER CATALYST

The phase transfer catalysts are ionic substances, ussually quaternary ammonium salts,
where the cationic is lipophillic(highly), in general used in catalysis or accelerating the
reaction between water insoluble organic compounds and water soluble reactants.

Criteria to use phase transfer catalysts is:

i) Influence of solvents: solvents should be aprotic, and immiscible with water to avoid
strong interactions with an ion pairs .
ii) Influence of cation: the larger the number of carbon chain around the central N atom in
the PTC , the better is the lipophilicity of the catalyst.
Ex: N(CH3 )4+ Cl- is a poor catalyst as compared to N(Bu)4+ cl- .
iii) Salt effects: addition of salt increases the extraction co efficient many times thus
increases rate of reaction.
Types of phase transfer catalyst: PTC used are quaternary onium salts. However in practice only
limited number of ammonium and phosphorium salts are widely used. Normally used are:
1. Aliquat 336 : N+ CH3 (C8 H17 )3 Cl- ( methyl trioctyl ammonium chloride)
2. Benzyl trimethyl ammonium chloride(TMBA)
3. Benzyl triethyl ammonium chloride(TEBA)
4. Cetyl tributyl ammonium chloride
5. Cetyl tri methyl ammonium chloride
6. tetra-n-pentyl ammonium chloride
7. Benzyl tri butyl ammonium chloride
8. Benzyl tri phenyl phosphonium iodide.

Mechanism of action of PTC:

 The conditions for PTC is to use two phase system.
 The organic substance is dissolved in a water insoluble organic solvent such as hydrocarbon
or a halogenated hydrocarbon
 Now the PTC is added , the alkyl groups of PTC are sufficiently larrge enough to confer
solubility in the organoc phase , the PTC carries nucleophile from aquoeus phase to organic
phase as a result the reaction proceeds satisfactorily in good yields.
 _ 4
_
Organic + +
phase Q CN + RCl RCN + Q Cl

1 2
+ _ + _ 3 + _ + _
Aqueous +
phase
Q CN + Na Cl Na CN Q Cl
Preparation of phase transfer catalyst
1. Quaternary salts: it is most widely use method for preparation of quaternary ammonium, phosphonium
and arsonium salts by alkylation of tertiary amines, phosphines or arsines.

R3 N + R’X R3 R’N+ X –
METHOD:
A Mixture of stoichiometric amounts of amine , phosphine or arsine and the apporpriate alkyl bromide or
iodide or methane sulfonate is warmed at 50-100 c for few hours or 2-3 days.

2. Exchange of anions on the quaternary salts: in this it is achieved by shaking the solution of the
quaternary salt In methylene chloride with an excess of aqueos solution of an inorganic salt of the
desired anion.
Ex : conversion of bromide to chloride
R4 N+ Br- + NaCl R4 N+ Cl- + NaBr

3. Silver oxide method: it is method to prepare the quaternary salt in the hydroxide form either by mixing
the quaternary PTC with the silver oxide. Then the hydroxide salt with the appropriate acid leads to PTC.
R4 N+ X- + Ag2 o R4 N+ OH- + Ag X
APPLICATIONS OF PTC IN ORGANIC SYNTHESIS:
1. Synthesis of nitriles from alkyl halides: To synthesize nitriles from alkyl halides needs lot of
conditions like stirring and heating for long time. It can be overcomed by addition of small
quantity of PTC.
PTC
R X + NaCN RCN + NaX
2. Synthesis of benzoyl cynaide from benzoyl chloride: carboxylic acid chlorides on reaction with
aq. Solution of sodium cynaide in presence of Bu 4 N+ X- gives the corresponding benzoyl
cynaides with good yields.
Bu4 N+ X-
C6 H5 CO Cl + NaCN C 6 H5 CO CN + Na Cl
3. Synthesis of azides from alkyl halides:
4. Syntheis of sulphonates from alkyl halides:

RCl + Na2 SO3 R SO3 Na + Na Cl

5. Synthesis of aryl ethers :
Ar OH + RX Ar OR + HX
6. Elimination reactions :Dehydrogenation :

R CH – CH2 R’ RCH=CHR’
Br
ADVANTAGES OF PTC :
1. Do not requires vigorous conditions and the reactions are fast.
2. Do not require expensive aprotic solvents.
3. Do not require high temperatures , reactions usually occurs at low
temperature.
4. There is no need of anhydrous conditions since water is used as the
one of the phase.
5. Many reactions which require strong base like alkoxide, sodamide ,
sodium hydroxide etc can be proceed with even by OH- as it
becomes strongly nucleophillic in the presence of PTC.
6. The reactions which otherwise proceed can be made to proceed in
the good yields.
7. modifications of selectivity and modification of product ratio is
possible.
8. Higher yields through the suppression of side reactions is possible
by use of PTC.