Topics in Catalysis Vol. 29, Nos.

3–4, June 2004 (Ó 2004) 145

Insight into green phase transfer catalysis

G.D. Yadav*
Department of Chemical Engineering, University Institute of Chemical Technology (UICT),
University of Mumbai, Matunga, Mumbai – 400019, India

There is a need to develop green, clean and smart chemical technologies. Waste reduction through clever strategies and catalysis
are at the heart of green chemistry. In the case of over 600 industrial phase transfer catalyzed (PTC) processes in several industries,
mostly practised as liquid–liquid PTC, the catalyst is not recovered and disposed as a waste. Liquid–liquid PTC can be replaced by
solid–liquid (S–L), liquid–liquid–liquid (L–L–L), solid (catalyst)–liquid–liquid, solid–liquid–omega liquid, gas–liquid–solid (G–L–S)
and capsule membrane PTC to recover and reuse the catalyst and also to enhance selectivity, thereby advocating the realm of green
PTC. Use of microwaves and ultrasound will also help in increasing rates. MILL–PTC and MISL–PTC are attractive techniques to
enhance rate and selectivities under mild input of microwave irradiation (MI). In cascade-engineered PTC, several steps are
combined in a reactor using the same catalyst and solvent, if used at all, without separation, or with partial replenishment of the
reactants for all the steps to get substantial waste minimization. This paper provides a new insight into PTC for some reactions of
industrial importance.
KEY WORDS: phase transfer catalysis (PTC); green chemistry; waste minimization; solid–liquid (S–L); liquid–liquid–liquid (L–L–
L); solid (catalyst)–liquid–liquid; solid–liquid–omega liquid; gas–liquid–solid (G–L–S) and capsule membrane PTC; microwave
irradiation.

1. Introduction minimization and environmental protection’’. The ori-

1.1. Green chemistry – a historical perspective
Green chemistry has become a catchy title for all
practitioners and learners alike [1,2]. Chemists and
chemical engineers, as also biotechnologists and material
scientists, are engaged in developing green, clean and
smart technologies. It would not be perhaps a coincidence
that green chemistry hinges on a dozen clean principles.
Why a dozen? One is tempted to contrast the ‘‘Clean
Dozen’’ against the off-beat movie ‘‘Dirty Dozen’’.
Waste minimization, whether of material or energy or
both, is a pivotal theme in green chemistry since totally
waste-free processes may not be realized in practice.
Typical waste reduction strategies involve the end-of-pipe
solutions to treat waste. It makes sense to reduce waste at
the source rather than using expensive post-treatment
technologies. Thus, any modification of a given process
or development of a new process, which results in savings
of raw material or energy or both, reduces waste and
lessens the burden on environment, reduces hazard and
increases profitability, fits into the ambit of green
chemistry and also sustainable development.
Not many would appreciate that green chemistry is
not a new concept as it is made to believe, but it is the
proverbial old wine in a new bottle. The genesis of
chemical engineering as a separate discipline in Man-
chester, England and at MIT, USA during the 1880s was
indeed based on the green chemistry buzzwords, ‘‘waste
*E-mail: gdyadav@udct.org; gdyadav@hotmail.com; gdyadav@yahoo.com
gin of green chemistry can be traced to the Solvay
process invented in 1811 for the manufacture of soda
ash from NaCI and CaCO3. By 1873, the Solvay process
had displaced in toto the old polluting LeBlanc process
using CaCO3 and Na2SO4, which was practised since
1787, wherein Na2SO4 was produced from NaCl and
H2SO4. The nagging problems of disposition of CaSO4
were never satisfactorily solved, and huge quantities of
leftover calcium sulphate still exist in Europe. However,
partially as a result of the first anti-chemical pollution
legislation (The Alkali Act of Great Britain of 1857), the
industry started absorbing HCl gas in water in tall
contactors and sold it as a valuable byproduct. George
Davis, who is credited as being the father of chemical
engineering was a visionary Alkali Inspector of England
who had inspected the Lead-Chamber, Le Blanc, and
Solvay processing plants to monitor pollution levels in
accordance with the Alkali Works Act of 1863. The
revolution in engineering design and operation paved
the way for a new branch of engineering, aptly named
Chemical Engineering, that was a symbiosis of both
applied chemistry and traditional engineering. The
Solvay process, the first practised example of green
chemistry, showed the prowess of recycle and reuse of
ammonia, which does not appear anywhere in the
stoichiometry but is central to the success of that
technology. The second best example of green chemistry
is the Haber’s ammonia synthesis (1907) that hinged on
catalysis, recycle and energy efficiency and by 1913 it
added to the might of Germany during World War I.
Incidentally this technology is considered as the greatest

1022-5528/04/0600–0145/0 Ó 2004 Plenum Publishing Corporation

146 G.D. Yadav/Green phase transfer catalysis
contribution of the chemical industry to society during
the 20th century. In today’s context, the historical
perspective leads us to the much talked about dozen
principles of green chemistry that are in the hub of
research [1,2]: (1) pollution prevention; (2) atom econ-
omy; (3) less hazardous chemical syntheses; (4) design-
ing safer chemicals; (5) safer solvents and auxiliaries; (6)
design for energy efficiency; (7) use of renewable
feedstocks; (8) reduction of derivatives and waste; (9)
catalysis; (10) designing chemicals easy to degrade; (11)
real-time analysis for pollution prevention; (12) inher-
ently safer chemistry for accident prevention.
If chemistry and chemical engineering have to regain
the lost glamour and prestige, putting the green chem-
istry principles into industrial practice would be most
desirable. Heterogeneous catalysis, bio-catalysis, sol-
ventless synthesis, use of microwaves and ultrasound,
etc. have demonstrated how atom economical processes
are also the most cost-effective. If waste cannot be
reduced, then end-of-pipe solution as a regulatory
approach has been practised in industry with a view
that the technology is perfect and only the effluent
should be treated. Although total waste cannot be
eliminated, there are other approaches to waste mini-
mization at source [3]. Since most of the published work
in green chemistry is about solid catalysts, it is intended
to cover the ubiquitous phase transfer catalysis (PTC),
in perspective, to practice it as a green science.
1.2. Process intensification of multiphase reactions
The importance of mass transfer with chemical reac-
tion, in multiphase processes, which are ubiquitous in
a gamut of process industries, in influencing the selec-
tivity, although well illustrated [4] was not appreciated
Figure 1. New approaches in development of green chemistry and engineering in multiphase reactions.
in practice in fine chemical industry until recently [5,6].
It is a common practice in process industries to conduct
reactions in homogeneous media using exotic solvents,
to overcome mass transfer effects, notwithstanding the
environmental and safety aspects. Figure 1 depicts how
the rates of homogenous or heterogeneous reactions and
selectivity of the desired products can be enhanced or
intensified, under otherwise similar conditions. Addition
of inert phase (A), different forms of energy (E),
catalysis (C) and synergism of A, E and C are listed as
possible ways. Of these approaches, E and C are much
talked about in the literature. Improvements in multi-
phase reactor design will further boost the green aspects.
Instead of conducting reactions in homogeneous media,
it may be desirable to convert the reaction into a
multiphase system and achieve the same objective most
economically. Indeed deliberate addition of mass trans-
fer resistance changes selectivity and makes the process
green. The existence of multiple phases need not be
integral to the process and instead one may deliberately
impose an additional phase to realize several benefits
like use of cheaper chemicals, adoption of milder
condition, avoidance of filtration from toxic mixtures
and avoidance of exothermic conditions. For instance,
one may introduce a second inert phase in a homoge-
nous reaction medium and the second phase can be a
liquid or solid. In a biphasic system, it can be demon-
strated that a third phase can be added to intensify
reaction rates. If a solid is added, then the particle size of
the solid can be so chosen as to increase the reaction
rate. Indeed in gas–liquid reactions, particle size (dp)
smaller than the diffusion-film thickness (dL ) of the
liquid film next to gas–liquid interface leads to enhanced
reaction rates under a certain set of conditions; for
instance, absorption of carbon dioxide in Ca(OH)2
 G.D. Yadav/Green phase transfer catalysis 147

slurries [7], and absorption of chlorine in NaOH or
Ca(OH)2 slurries coupled with desorption of hypochlo-
rous acid gas [8,9]. Indeed this is an excellent example of
green chemistry since pure hypochlorous acid can be
absorbed in NaOH or Ca(OH)2 slurries to produce
chloride-free stable hypo solution and the process
becomes 100% atom economical. The added inert
particles, in general, could be a porous or non-porous
medium. Enormous possibilities exist and some of these
have been explored in our laboratory in the context of
heterogeneous and homogeneous catalysis.
1.3. Phase transfer catalysis
In many cases, it is useful to convert homogenous
liquid-phase reactions into a biphasic system and still
maintain very high rates as exemplified by PTC. Since
reaction rates are enhanced by orders of magnitude
including less expensive solvents (if any), milder condi-
tions and better selectivities, small reactor volumes are
needed and hence PTC meets one of the criteria of green
chemistry. But still there are larger issues to be
addressed, to make PTC greener. A majority of PTC
reactions are conducted under liquid–liquid (L–L)
conditions wherein the organic phase is normally the
reaction phase with associated transfer of aqueous phase
reagent as an ion pair with the phase transfer catalyst
such as quaternary ammonium and phosphonium salts,
crown ethers, cryptands, polyethylene glycols, etc.
Table 1 gives some salient features of different catalysts
[10 –12]. A few are practised as solid (reactant) – liquid
(organic) PTC. Solid–liquid (S–L) PTC works on the
same principle as L–L PTC either through homogeneous
solubilization or heterogeneous solubilization. PTC is a
very popular technique due to several advantages
associated with it such as: (i) ease of conducting
reactions under milder/safer reaction conditions, (ii)
increased rates of very slow reactions, (iii) high yield and
selectivity, (iv) reduction/elimination of solvent, (v) use
of alternative raw materials thus reducing cost of
chemicals, (vi) frequently simplified separation of prod-
ucts, and (vii) simplicity of process and equipment.
2. Green phase transfer catalysis
Phase transfer catalysis has been applied to over 600
industrial processes in a variety of industries such as
intermediates, dyestuffs, agrochemicals, perfumes,
flavours, pharmaceuticals and polymers involving a
business of US $12 billion [10 –12]. Several phases can
co-exist in PTC as given in figure 2 and some of these fit
into the domain of green chemistry, which will be
elaborated in this paper. PTC has been quite successful
for C, N, O and S alkylation in fine chemical industries,
apart from dehydrohalogenations. The effluent-treat-
ment problems associated with soluble PTC requiring
large quantity of water to wash the organic phase has
hampered exploitation of PTC in many other bulk
industries. Thus the applications of PTC are practically
confined to the synthesis of low-volume and high-cost
specialty, agro and pharmaceutical chemicals. The main
drawback of L–L PTC from the environmental perspec-
tive is that the homogeneous catalyst is normally not
recovered and reused. The bulk cost of catalyst ranges
from US$ 2 to 400 per kg, with crown ethers being the
most expensive and hence catalyst recovery or reuse is
most desirable. The separation of phase-transfer cata-
lysts from the reaction mixture can be achieved by
extraction, distillation and adsorption. Extraction needs
an additional solvent that has to be distilled off to
recover the catalyst. Distillation becomes feasible only if
the catalyst has a lower boiling point than the reactants,
products and the solvents. Otherwise, distillation is an
energy-intensive process to recover catalysts from dilute
solutions. In the case of adsorption, the catalyst has to

Table 1
Salient attributes of phase transfer catalysts [10–12]

Catalyst Cost Stability and Activity Use and recovery of catalyst

Ammonium salts Cheap Moderately stable under basic conditions and Widely used: Recovery is relatively difficult
up to 100 °C, decomposition by Hofmann
elimination under basic conditions.
Moderately active
Phosphonium salts Costlier than Thermally more stable than ammonium Widely used: Recovery is relatively difficult
Ammonium salts salts, although less stable under basic
conditions
Crown ethers Expensive Stable and highly active catalysts both under Often used: Recovery is difficult and poses
basic conditions and at higher temperatures environmental problems due to their toxicity
even up to 150–200 °C
Cryptands Expensive Stable and highly reactive except in the Used sometimes: high costs and toxicity but
presence of strong acids high reactivity
Polyethylene Very cheap More stable than quaternary ammonium salts Often used: can be used when larger quantities
glycols (PEG) but lower reactivity of catalyst cause no problems: relatively easy
to recover
148 G.D. Yadav/Green phase transfer catalysis

Phase Transfer Catalysis

I - Quat. N, P, As, S salts

Waste II - Crown ethers, aza crowns,
Minimization
cryptands
III - Polyethylene glycols
IV - Cyclodextrins

Bi-Phase
Multi-Phase Reactions
Reactions

S-L-S
L-S(cat)-L L-L(cat)-L L-L-S-L G-L-S L -L S-L
S(react)-L(ω-aq)-L

Only one L phase

Polymer Inorganic Capsule Normal Inverse Interfacial

particle solid membrane
supported supported

Aq.-wet Normal Inverse

(hydrophilic)
Homogeneous Heterogeneous
solubilization solubilization
Org.-wet
(hydrophobic

Four regimes
Intermediate- of operation
wet

Figure 2. Classification of PTC reactions. (The solid boxes suggest that the maximum studied reactions are biphasic.)

be eluted using a solvent. Since the quantities of the
catalyst used are small, they do not contribute much to
the expensive product cost. The catalyst is usually not
recovered but removed by washing the organic phase
with copious quantities of water which is disposed to the
effluent treatment plant as an end-of-pipe approach of
pollution prevention. The water-washing reduces the
overall yield of the product. Although milder reaction
conditions and use of cheap solvents in L–L PTC
improve the economics, PTC need to be practised from
the green chemistry perspective such as solventless
synthesis and catalyst reuse. Although total waste-free
chemical processes are not realizable in practice, the
concept of eco-efficiency is useful for optimizing chem-
ical processes with the aim of minimizing risk, resource
depletion, and waste generation. PTC is a mature
discipline but several intricacies of PTC in reactions of
industrial importance are not understood or properly
modelled. For instance, the effect of nature and number
of phases in the intensification of rates and selectivities
has not been investigated in detail. This paper provides a
new insight on PTC with reference to some reactions of
industrial importance and green chemistry. With refer-
ence to figure 2, the PTC strategies, which have
potential for waste minimization and green chemistry,
are as follows.
 G.D. Yadav/Green phase transfer catalysis
1. Solid–liquid PTC
2. Solid–liquid (x)–liquid (org) PTC
3. Microwave-irradiated solid–liquid (MISL) and
liquid–liquid (MILL) PTC
4. Solid–liquid–liquid PTC (‘‘triphase catalysis’’)
5. Solid–solid–liquid PTC
6. Gas–liquid–solid PTC (also known as G–L PTC)
7. Capsule membrane PTC
8. Liquid–liquid–liquid PTC
9. Cascade-engineered PTC
10. Selectivity-engineered PTC
2.1. Solid–liquid PTC
The high rate of reaction exhibited by L–L PTC
reactions in comparison with conventional homogeneous
reactions in hydroxylic solvents results from the presence
of weakly solvated and highly reactive ion pairs in
organic media. A certain amount of water of hydration is
co-extracted with the ion pair migrating from the
aqueous phase to the organic phase. This can sometimes
interfere and fully suppress a reaction or lead it to by-
product formation. L–L PTC is disadvantageous for
systems where the presence of water can lead to side
reactions such as hydrolysis. For instance, with allylic
and benzylic halides, under certain conditions, hydrolysis
may compete unfavourably with substitution when
aqueous cyanides are used. In such cases, the conversion
of L–L PTC into S–L PTC proves to be advantageous
from the view point of not only suppression of side
reactions but also the intensification of rates due to
increase in particle surface area and mass transfer rates
by orders of magnitude in comparison to those available
Figure 3. Comparison of S–L PTC mechanisms (heterogeneous solubilization can be represented by porous or non-porous solids with constant
or shrinking core particles).
149
in L–L dispersion. While L–L PTC involves heteroge-
neous reaction between two reagents located in an
aqueous, and an organic phase, S–L PTC involves
reaction of an anionic reagent in a solid phase (usually
a salt) with a reactant located in a continuous organic
phase. Two popular approaches have been used to model
these reactions, namely, homogeneous solubilization
model of Yadav and Sharma [13] and heterogeneous
solubilization model of Naik and Doraiswamy [17]
(figure 3). The particles could be partially soluble leading
to homogeneous solubilization (figure 4) has been found
to account for many S–L PTC reactions where a solid is
also generated as a co-product. S–L PTC became popular
due to the spectacular enhancement in rates in the
presence of crown ethers for which the concept of naked
ions was proposed. The inorganic substrate would fit
smugly into the cavity of the crown ether and thus get
into the organic phase for reaction. Tertiary amines,
quaternary ammonium salts, crown ethers and polyeth-
ylene glycols are some of the commonly used S–L PT
catalysts. Waste reduction, a major theme in green
chemistry, is achieved in S–L PTC due to the fact that
the aqueous phase promoted side reactions are totally
suppressed and the selectivity is enhanced by order of
magnitude in comparison with the L–L PTC. Besides, the
catalyst is located entirely in the organic phase thereby
increasing the concentration of the ion pair with the
reagent. In many S–L reactions the co-product is also a
solid, which can be easily filtered off the organic mass and
only thereby reducing large quantities of aqueous waste.
From a commercial point of view, S–L PTC is
advantageous since a variety of benign organic solvents,
if required at all, can be used to influence the kinetics
150 G.D. Yadav/Green phase transfer catalysis

Figure 4. Typical S–L PTC under homogeneous solubilization. (a) Regime 1: very slow reaction. The reaction occurs in the bulk organic phase as
a homogeneous reaction. Mass transfer effects are unimportant, (b) Regime 2: slow reaction. The reaction occurs in the bulk organic phase. No
free concentration of ion pairs exists in the bulk organic phase, (c) Regime 3: fast reaction. Diffusion of [Q+Y]org and its reaction with RX are
steps in parallel, and the reaction occurs in the organic liquid film next to the S–L interface, (d) Regime 4: instantaneous reaction. The reaction
between [Q*Y]org and RX is so fast that they cannot coexist in the organic phase. [Q*Yl0rg diffuses from the L–L interface, and RX diffuses from
the bulk organic phase into the organic liquid film and react at a plane T from the interface. No free [Q+Y)]org exists beyond distance X and no
free RX exists beyond distance (d0
k) toward the interface. Note that for simplicity other ion pairs are not shown.

and separation of valuable products is often made very
simple. Solventless synthesis is one common theme in
green chemistry and thus solid–liquid reactions with
practical reaction rates in the absence of a solvent are
most desirable on industrial scale. S–L PTC can be
made solventless by using the liquid product itself as a
solvent, which reduces separation costs and also avoids
contamination of the product by a foreign solvent.
Yadav and Sharma [13] developed this idea for benzyl
esters wherein the rates were 4-fold higher under
otherwise similar conditions and complete conversion
to esters was obtained and the product filtered from the
co-product salt. They proposed the first mechanistic and
kinetic model of S–L PTC.
Nitroanisoles are important precursors in the organic
process industry and are made from chloronitrobenzenes
by using sodium hydroxide and methanol under L–L
PTC, which requires reflux temperatures, leading to loss
in selectivity due to formation of p-nitrophenol. Synthe-
sis of p-nitroanisole was carried out from p-chloronitro-
benzene (PCNB) and solid sodium methoxide by using
tetrabutylammonium bromide as a catalyst under S–L
PTC as opposed to the standard L–L PTC system. The
advantages of the S–L PTC are that the reaction is
conducted at room temperature with 100% conversion
and 100% selectivity. The kinetics and mechanism are
also established for this reaction. The methoxylation of
o-chloronitrobenzene (OCNB) was also studied. The rate
of methoxylation of PCNB was much greater than that
of OCNB at 30 °C. m-Chloronitrobenzene does not react
with sodium methoxide under otherwise similar condi-
tions [14].
 G.D. Yadav/Green phase transfer catalysis
The advantages of S–L PTC in waste reduction are
also illustrated in the preparation of o-nitrodiphenyl
ether, a valuable intermediate in pharmaceuticals, which
is traditionally prepared by reacting aqueous sodium
phenoxide with o-chloronitrobenzene in toluene in the
presence of cuprous chloride or in refluxing chloroben-
zene with copper powder as catalyst. This process is
highly exothermic and the reaction sometimes gets out
of control. A 100% selective and cheaper process to
synthesize o-nitrodiphenyl ether using a S–L PTC is
reported [15]. The S–L PTC reaction of p-chloronitro-
benzene with 2,4-dichlorophenol was carried out in
presence of a base to produce nitrofen to get 100%
selectivity [16].
2.2. Solid–liquid (x)–liquid (org) PTC
In some S–L PTC reactions, the major problems are
the difficulty in the formation of the reactive ion pair
at the solid surface and poor efficiency of catalyst
regeneration in an anhydrous system. The addition of a
third water phase in trace amounts leads to form the
so-called omega (x) phase in S–L PTC and it catapults
the rates greatly wherein the crystal lattice is broken
and is freely available to exchange the anion to form
Figure 5. General mechanism for S–L (x)–L PTC cyanide displacement reaction in presence of x-phase.
151
the quaternary ion pair. The amount of water, catalyst
structure and amount, speed of agitation, temperature
and nature of organic phase play a pivotal role. Most
of the models of the S–L PTC including that of Yadav
and Sharma [13] have assumed a very fast anion
exchange in the homogeneous solubilization of the
nucleophile thereby leading to a typical pseudo first-
order kinetics. p-Chlorophenyl acetonitrile is a very
significantly used intermediate serving as precursor to
many pharmaceutical and agrochemical products. In
the cyanide displacement on p-chlorobenzyl chloride
under S–L (x)–L conditions, it was observed that
the experimental results could not be explained by the
simple homogeneous solubilization model. Even the
heterogeneous solubilization models of Naik and
Doraiswamy [17] were found to be inadequate and
therefore a totally new approach was called for. As the
reaction proceeds, the process converts itself from
S(reagent)–Lð xÞ–L(org) into Lð xÞ–L(org) PTC system.
Unlike in L–L PTC, in S–L PTC the co-catalyst does
not contribute to enhancement in reaction rates. In
fact, the so-called S(reagent)–Lð xÞ–L(org) PTC turns out
to be Lð xÞ–L(org) PTC reaction where the x-phase is
saturated with the nucleophile which is better trans-
ferred to the organic phase for reaction with the
ORGANIC PHASE
152 G.D. Yadav/Green phase transfer catalysis
substrate than the solid particle in dissolved state in
normal L–L PTC (figure 5). The kinetic model could
take into account the role of different parameters and
indeed, the mass transfer effects could also be
accounted for. The novelties of synthesis of a-isopro-
pyl-p-chlorophenyl acetonitrile, which is an important
intermediate in the synthesis of a pyrethroid insecticide
named fenvalerate, from p-chlorophenyl acetonitrile
and isopropyl bromide under S(reagent)–Lð xÞ-L(org) PTC
have also been explained recently [19]. The role of a
limited amount of water is found to be very important
in enhancing the rate of a S–L PTC reaction. Once
again there is no need of using a solvent and one of
reactants or products can be employed in excess to
convert the limiting reactant and thus waste is
minimized [18,19].
2.3. Microwave-irradiated liquid–liquid (MILL) and
solid–liquid (MISL) PTC
Microwave (MW)-irradiated reactions have been
studied by a number of researchers. Three types of
solvent-free systems have been coupled with MW: (i)
reactions between reacting species, requiring at least one
polar molecule as liquid–liquid and solid–liquid systems.
(ii) Reactions between supported reagents in dry media
by supporting compounds inorganic oxides on silica,
alumina and clays. The S–L PTC mechanism involves
exchange of solid nucleophile (Y)) with the leaving
group X) of Q+X). If the ion pair Q+Y) is a polar
species, it can undergo microwave activation which will
result in the enhancement of the reaction rate. The
reactions that are amenable to MW S–L PTC are
esterifications, etherifications, phenolic polyethers,
N-alkylations, C-alkylations of active methylenes, aldol
condensations, ester saponifications, transesterifications,
isomerizations, b-eliminations, dealkylation of aromatic
ethers, etc. Use of MW S–L PTC renders faster
reactions and cleaner processes since the synthesis is
solvent-free, economical, selective, safer and easy to
manipulate [20]. Several aromatic ethers have been
prepared by Yadav and Bisht [21–23] using the
microwave irradiated solid–liquid (MISL) and liquid–
liquid (MILL) PTC with a meagre power input of 40 W
leading to faster reactions when compared to conven-
tional/classical heating. The enhancement factor defined
as the ratio of the initial rate under microwave irradi-
ation to that under conventional heating is in the range
of 1.6–9 for MILL–PTC [21] and 5.3–30 for MISL–PTC
[22], with 100% selectivity of the ether. The partitioning
of the catalyst in the organic phase is not affected in the
case of MW irradiated systems than in the conventional
heating and enhancement in rates is realized due to
higher entropy since rates of PTC reactions are propor-
tional to catalyst concentration in the organic phase. It
is possible to determine both rate constants and
equilibrium constants form the same set of data [21–23].
2.4. Solid–liquid–liquid PTC
S–L–L PTC which was erroneously named as ‘‘tri-
phase catalysis’’ as a sequel to PTC involves the use of a
supported catalyst with two immiscible liquid-phase
reagents [22]. Polymer-supported ammonium salts,
phosphonium salts, macrocyclic polyethers, polar sol-
vent residues and/or poly(ethylene glycols) are effective
and reusable phase transfer catalysts. A majority of work
is reported with quaternary salts supported on polymeric
supports preferably polystyrene-based matrix cross
linked divinylbenzene (DVB). Typically in L–L–S PTC,
the organic phase and the solid catalyst are dispersed in
the continuous aqueous phase. This technique possesses
several advantages such as easy recovery from reaction
mixture by filtration, potential use in continuous flow
reactors and recycling of catalyst. The disadvantages of
L–L–S PTC are higher initial cost of preparation and
lower catalytic activity due to diffusion limitations. The
polymer-supported catalysts are generally prepared by
two methods, namely, chemical modifications of cross-
linked polymer supports, and copolymerization of
functional monomers with cross-linkers. The catalysts
prepared by the second method have chemically pure
structures, although the synthesis of the monomers with
catalytic moieties is rather difficult and the active sites
bound to the monomer unit near the cross-linker unit in
the solid phase may have decreased catalytic activity.
Organic polymer supports are prepared by copolymer-
ization of vinyl monomers such as styrene, alkyl meth-
acrylate or vinyl pyridine with crosslinkers such as
divinylbenzene (DVB) or ethylene dimethacrylate [10].
Inorganic supports such as silica gel, alumina and clay
are also used as supports for L–L–S PTC [24,25]. The
most popular supports are microporous (gel) polystyrene
resins, minimally cross-linked with DVB (1–4%) or
macroporous (macro-reticular) supports, highly cross-
linked with more than 10% DVB. The microporous
resins have low specific surface areas and the polymeric
chains shrink in a dry state or poor solvents. The resins,
however, swell well in good solvents to extend the
polymeric chains. The macroporous resins have high
specific surface areas and hardly swell in any solvent. In
order to overcome the diffusion limitations, spacer
chains are provided on the support and this technique
leads to enhanced activity. Therefore, the overall rate in
L–L–S PTC is determined by one or more of the
following rate controlling processes (i) mass transfer of
reactants (substrate and reagent), (ii) intra-particle
diffusion of reactants, and (iii) the intrinsic rate at the
active site.
The wetting nature of support matters a great deal in
L–L–S PTC [26]. The microporous resins have low
specific surface areas and the polymeric chains shrink in
a dry state or poor solvents. A macroporous polymer
possessing high porosity which swells considerably
would be a better choice as support for the PTC. The
 G.D. Yadav/Green phase transfer catalysis
Figure 6. Some of S–L–L PTC mechanisms.
degree of crosslinking with DVB should be low in
polystyrene-based supports in order to have high poros-
ity and hence swelling. A detailed schematic representa-
tion of S–L–L PTC is shown in figure 6 with two typical
cases amongst 16 different mechanisms [26].
The microporous polymer matrix swells both in
presence of water and organic phase, when contacted
independently. In the presence of two immiscible liquid
phases, the polymer will uptake preferentially the
wetting fluid depending on the surface properties of
the polymer. In general, the wettability of the support
governs the controlling mechanism. If the porous
support is mixed wet, i.e. when it imbibes both aqueous
and organic phases due to capillary action, it would be
most desirable because the aqueous and organic phases
which contain the reactants, must be in the close vicinity
of the bound, Q+. On the contrary, when the support is
strongly wetted by one of the liquid phases, either water
or the organic phase, the other phase must diffuse into
the pores filled by the strongly wetted liquid. Thus, the
diffusion of that reactant, in the pores plays a very
dominant role and thus solubility becomes important. In
the latter case, the reactant couples with the quaternary
153
salt to generate the product. If the support is strongly
wetted by water, then the nucleophile in the form of
metal salt, M+Y), will undergo ion exchange and the
catalyst bound on the matrix will be in the ~Q+Y) form.
The substrate, RX from the organic phase must be first
solubilized in the aqueous phase and should diffuse to
the sites to react with the ion pair, Q+Y). If, on the
contrary, the support is wetted by the organic phase, all
the pores will be filled by the organic phase. Thus, the
substrate and the polymer bound catalyst have the same
species X), the leaving group. The aqueous phase
containing the nucleophile (Y)), must diffuse through
the organic phase to the site for ion-exchange with
Q+X) to yield Q+Y) and a facile reaction will take
place with the substrate RX already present over there.
In the case of a support which does not have a
preferential wettability to any liquid phase, it will
imbibe both the phases if it comes in contact with them.
The pores will contain both the phases and thus, some
network of pores will contain aqueous phase and some
organic phase and at some places one of them will be
dispersed into the other phase. Overall the phase
transfer catalysis will work by three different mecha-
nisms. In a majority of cases, the catalytic sites on the
exterior surface of the resin particle take part in the
reaction since the extent of porosity does not influence
the overall activity [26,27]. To overcome diffusion
barriers spacer arms are used in the polymer matrix
onto which the PTC is mounted. A 5-fold increase in the
rates is reported by using spacer arms which dangle
across the interface of aqueous and organic phase inside
the porous polymer thereby enhancing the rate of
reaction [27]. In the case of immobilized PT catalysts
used in L–L dispersions, the rates of reactions are slower
due to intra-particle diffusion limitations by 2–4 orders
of magnitude vis-à-vis those observed in L–L PTC.
Indeed, the intra-particle diffusion of one of reactants
which does not wet the catalyst surface is most crucial in
these reactions and use of an appropriate temperature or
a suitable solvent may be needed to enhance the rates.
Moreover, the most efficient large molecular weight
catalysts are not effective when immobilized and that
only a few phase transfer agents can be anchored to the
solid phase. Both organic and inorganic supports have
been used to support PTC [27–29]. Increasing the length
of the chains, which anchor the catalysts to polymer
matrix, helps in increasing the rate of S–L–L PTC [27].
An example of converting waste into useful products
is given by Yadav and Haladvanekar [28]. Benzene is
exhaustively chlorinated under UV light to produce
benzenehexachloride (BHC) containing a thermody-
namic mixture of several isomers such as a; b; c; d; e;
etc. of which the c isomer is the yesteryears popular
pesticide Lindane (c-BHC) which is about 14%. Thus
there is no atom economy. In the past, the 86% other
isomers, which are environmentally deleterious, were just
dumped as landfill. However, it is possible to use these
154 G.D. Yadav/Green phase transfer catalysis
isomers to get useful trichlorobenzenes by dehydrochlo-
rination under PTC conditions. Dehydrochlorination of
benzene hexachloride to 1,2,4-trichlorobenzenes (88%
yield) was successfully carried out in L–L–S PTC using
polymer-supported tri-n-butyl amine which forms a
quaternary salt.
The macroporous resins have high specific surface
areas and hardly swell in any solvent. In order to
overcome the diffusion limitations, spacer chains are
provided on the support and this technique leads to
enhanced activity. Inorganic supports such as silica gel
or alumina and clays are also used as supports for L–L–S
PTC. The inorganic supports have high surface areas and
should be more useful than organic supports. Silica,
alumina and polymers are unstable in strong acidic and
alkaline media and have low physical strength. In
comparison, clays are cheap, have high physical strength
and possess relatively high resistance towards alkali
treatment. Many alkylation reactions are mediated by
hydroxyl ions and conducted under strong alkaline
conditions with PTC. Thus supporting the phase transfer
catalyst on clays would offer certain advantages, which
appear to be distinctly different due to the fact that clays
are inorganic oxide surfaces with much higher surface
area and bulk density (figure 7). Polymer-supported
PTC have bulk densities which lie between the aqueous
and organic phases and the mechanistic aspects include
this fact. In the case of clays, the catalyst will be in the
continuous phase, and the type of dispersed phase and
the reactant within it would have a pronounced effect on
the yields. Synthesis of benzoic anhydride from sodium
benzoate and benzoyl chloride has been achieved at
30 °C with clay-supported quaternary ammonium salts
[25]. The selectivity to the product was 100% and the
catalyst was reusable without loss in activity. The clay-
supported catalyst was found to be more active than
polymer-supported catalysts. This is a classic case of
change in wettability of the support favoring quick
exchange of anions and clay surface was wetted by
aqueous phase with organic phase as continuous phase,
and aqueous phase as dispersed phase in the reactor.
Figure 7. S–L–L PTC: clay-supported mechanism.
2.5. Solid–solid–liquid PTC
Since S–L–L PTC reactions are slower by orders of
magnitude, much efforts were expended on the intensifi-
cation of these polymer supported reactions. The activity
of some commercial catalysts such as benzyltrimethylam-
monium ion exchange resins has been reported to be
insignificant because of its preferential water wettability
which prevents any accessibility of active site by the
substrate. The S–L PTC reactions enhance rates of
reactions by several fold over corresponding L–L PTC
and thus a marriage between S–L–L and S–L PTC was
conceivable leading to solid–solid–liquid (S–S–L) PTC,
wherein the catalyst and one of the reagents would be
solids and the other liquid could be the reagent or reagent
in a solvent. SN2 type of reactions involving base-
catalysed alkylations, and oxidation of secondary alco-
hols have been carried out by using a non-polar solvent
with inorganic solid reagents based on polymer-sup-
ported quaternary ammonium and phosphonium salts
[30]. The product can be simply filtered and recovered by
distilling the solvent off. S–S–L PTC is found to be better
than S–L–L PTC. Once again the enhancement in rates
and reduction of waste is obvious in this technique.
2.6. Gas–liquid–solid PTC
Gas–liquid phase transfer catalysis (G–L PTC), again
a misnomer for G–L–S PTC, involves the use of phase
transfer catalysts in gas–liquid–solid systems, where the
organic substrate is in gaseous form and is passed over a
bed consisting of the inorganic reagent (or some other
solid reagent/co-catalyst in solid form or an inert
inorganic support), which is coated with a phase transfer
catalyst in its molten state. Although, strictly, this is a
gas–liquid–solid triphase system, it has traditionally
been referred to as G–L PTC. The advantages of G–L–S
PTC include ease of adaptation to continuous flow
operation, absence of organic solvents since the organic
substrate is present in gaseous form, ease of recovery of
the phase transfer catalyst as it is directly loaded onto
the solid bed, and better selectivity for some reactions in
comparison with L–L PTC [31]. Phosphonium salts,
crown ethers and polyethylene glycols are the preferred
catalysts used to carry out a variety of reactions under
G–L PTC. The mechanisms of G–L PTC reactions differ
from the traditional mechanisms for L–L and S–L PTC.
A variety of mechanisms have been proposed for G–L
PTC since different types of reactions are involved.
However, it is clear that the gaseous reactant has to
diffuse through the molten liquid film of the phase
transfer catalyst, with reaction occurring simultaneously
between the diffusing species and the catalyst. When the
molten thermally stable phase transfer catalyst is sup-
ported on an inert matrix, the solid phase functions
strictly as a support for the catalyst. Separation of the
catalyst from the reaction mixture is easier in this case.
Reaction is diffusion controlled and excess catalyst does
 G.D. Yadav/Green phase transfer catalysis 155

not affect the conversion above a certain value as a result only enable easy recovery of both aqueous and organic
of congestion of pores and reduction of surface area. phases after the reaction without any problems of
The use of fixed bed reactors becomes feasible. However, emulsification, but also ensure that the catalyst does not
only a few cases have been reported about its utility. contaminate the product in the organic phase. The
interface between the two liquid phases resides in the
2.7. Capsule membrane PTC spongy layer of the capsule, wherein the catalyst is
anchored and it leads to easy accessibility of the catalyst
The reduction in reaction rates in S–L–L PTC due to
to ion pairs with nucleophile and leaving group. The
intra-particle diffusion can be overcome by providing
exact location of the interface inside the thin layer of
easy accessibility to the catalytic sites. The normal
the membrane will depend on its pore size distribution,
approach will be smaller particle and larger pore sizes.
the external pressure exerted by the outside phase in the
The high speeds used to overcome external mass transfer
agitated mixture, and also the wettability nature. If the
resistance lead to particle attrition and loss of catalysts
reaction mechanism is SN2 type, there should be an
during filtration. These problems are solved by using the
exchange of ions via the catalyst on spacer chains or
capsule membrane phase transfer catalysis (CMPTC) in
anchors, which are dangling across the aqueous and
which quaternary ammonium and phosphonium salts of
organic phases. Whether the substrate and the nucleo-
acryloyl monomers are supported/grafted onto a large,
phile reside inside the capsule itself is of no consequence
ultrathin nylon capsule membrane, accelerating reac-
for the mechanism because the locale of the reaction
tions between substrates in the inner organic phase and
would be at the interface in the spongy layer of the
water-soluble anions in the outer phase (figure 8)
capsule. Besides, the anchors have a limited scope to
CMPTC offers the following advantages: (i) high
diffuse across the interface. If there is any mass transfer
reactivity as a result of the onium salts attached as long
limitation on this exchange process, it would perhaps be
graft–polymer chains; (ii) there is no induction period
more pronounced for the case wherein the organic phase
for the reaction caused by swelling of supports; and (iii)
is located inside the capsule. The concept of inverse
easy separation of the catalyst and the inner organic
CMPTC was also developed for these reactions.
phase from the outer aqueous phase.
CMPTC was found to give maximum rates due to easy
Yadav and Mehta [32] have carried out a detailed
accessibility of the phase transfer agent to both aqueous
theoretical and experimental analysis of the CMPTC
and organic phase reagents.
alkaline hydrolysis of benzyl chloride to benzyl alcohol,
with 100% selectivity and without any dibenzyl ether
formation, which is normally encountered in L–L PTC. 2.8. Liquid–liquid–liquid PTC
The oxidation of benzyl chloride to benzaldehyde with
When a phase transfer catalyst has limited solubility in
oxidizing agents such as potassium dichromate and
both the aqueous and organic phases, a third immiscible
hydrogen peroxide by using capsule membrane phase
liquid phase can be formed in the middle. Its formation
transfer catalysis has also been investigated [32–34].
and stability depend on the phase equilibria–hydrophilic
CMPTC can be operated as a fixed bed reactor. The
and lipophilic balance, density difference and tempera-
CMPTC principles can be exploited in membrane
ture. In liquid–liquid–liquid phase transfer catalysis
reactors, with the phase transfer catalyst immobilized
(L–L–L PTC), most of the reactions occur in the third
on the membrane surface with aqueous and organic
liquid phase with both aqueous and organic reactants
phases on either side of the membrane. This would not
transferring to this phase for reaction [35–44]. Three
types of mechanisms can prevail:(a) Type I–the reaction
in the organic phase (L–L PTC), (b) Type II—the
Q+X- reaction at the interphase between an organic phase and
an aqueous phase or in the bulk aqueous phase (L–L
Y-Q+ inverse PTC), (c) Type III—the reaction in the third
Q+X- Bulk aq. phase
phase (figure 9) This third phase should become the main
M+ Y- X-
Q+X- reaction phase to intensify the rates of reaction and to
Y-Q+ Inner org improve the selectivity of the desired product, apart from
Q X phase
+ -
Q+X-
+ -
the economical and environmental benefit. L–L–L PTC
Q Y + RX -
YQ
+
Q+X- + M+Y- is very attractive in reactions of industrial relevance [36–
X-Q+ = +X- +RY
Q

Q+X- 42]. The catalyst-rich third phase can be recycled

X-Q+ repeatedly and also the aqueous phase can also be reused
+
QX QY
- + -
Q+Y-
Q X-
+
Aq. phase film
a few times to reduce waste. The overall enhancement
-
XQ + +
QY - leads to less reactor volume and better quality control.
Q+Y- Q+X- The L–L PTC reaction of PCNB with sodium
methoxide/ethoxide to synthesize p-nitroanisole (PNA)
Figure 8. Capsule membrane PTC. and p-nitrophenetole (PNP) is dangerous and is
156 G.D. Yadav/Green phase transfer catalysis
Figure 9. Liquid–liquid–liquid PTC.
inefficient. Instead use of sodium hydroxide and meth-
anol or ethanol, with tetrabutylammonium bromide
(TBAB) as catalyst were chosen as the L–L–L PTC
systems to get 100% yield of the products [38]. The
catalyst is reused and the rates are higher by order of
magnitude. The use of n-butanol and NaOH in place of
sodium butoxide as the butoxylating agent with PCNB
is also very effective under L–L–L PTC. Reaction of
PCNB with 2,4-dichlorophenol was carried out in
presence of a base under L–L–L PTC to get 100%
yields of a useful herbicide nitrofen [16]. Etherification
reaction between benzyl chloride and sodium phenate to
yield 100% benzyl phenyl ether, which is also used
industry as intermediate, solvent, heat transfer fluid and
perfume was also enhanced under L–L–L PTC [41].
2.9. Cascade-engineered PTC
In pharmaceutical, dyestuff, agrochemical and fra-
grance industries, multi-step as well as multiphase
reactions are very common and the amount of waste
generated ranges from 50–100 kg/kg product. No atom
economy is realized with respect to the raw materials
and separation of products is many times cumbersome
or difficult adding to the cost of processing. Instead of
conducting several multi-step reactions, with intermit-
tent separation and purification, it becomes advisable to
carry out reactions in a single reactor by choosing the
appropriate reaction conditions, with different modes of
operation. In the case of PTC, optimum use of catalyst
and solvent can be made for several reactions before its
being discarded. It would reduce the cost of the catalyst
per kilogram of the product and also reduce the huge
amount of waste which is generated. This concept forms
the basis of ‘‘cascade-engineered phase transfer cataly-
sis’’ (CEPTC) [3] which has been pursued for the phase
transfer catalyzed conditions by performing various
synthetic steps in the same reactor thereby minimizing
both by-product formation and separation stages and
concurrently making optimum use of the catalyst and
the solvent [42]. In certain multi-step synthesis, the
nature of the catalyst is the same and it is advisable to
use the same catalyst without separation under optimum
set of conditions. If the catalyst is homogeneous, it is
used at least in two to three consecutive steps without
separation and if it is heterogeneous, it could be used
repeatedly. It is also possible to have a combination of
L–L, S–L, S–L (x)–L, S (cat)–L–L and L–L–L PTC
depending on the type of reaction (figure 10) Thus,
F
E
P
A+B
+Cat
ETP
ETP
ETP
(a) Reaction and product separation at each stage
E F
P
A+B
Cat CEPTC
ETP
(b) Same catalyst and solvent in several stages
without separation of products at each stage
Figure 10. Cascade-engineered PTC.
 G.D. Yadav/Green phase transfer catalysis 157

Figure 11. Benzyl chloride reactions for CEPTC and SEPTC processes.

waste can be minimized and economic viability of the
process could be achieved elegantly through cascade
engineering. The principle of cascade engineering as
applied to PTC, could be used advantageously for
reactions of industrial importance.
Benzyl chloride is an excellent reagent to explore the
advantages of cascade engineered PTC. Benzyl chloride
leads to very important products by converting L–L
PTC into S–L and L–system. The various industrially
important products are benzyl alcohol (by hydrolysis),
dibenzyl ether (by hydrolysis), phenylacetonitrile (nitrile
substitution), benzyl esters (esterification), phenylacetic
acid (hydrolysis of phenylacetonitrile) which are all PTC
catalysed reactions (figure 11) [42]. The reactions were
studied independently as well as in cascade system. The
cascade reaction system itself is novel where from one
starting material a variety of products are obtained by
changing the parameters.
Phenylacetonitrile is used as an intermediate in the
preparation of many compounds (figure 12). It can be

Figure 12. Cascade engineered PIC reactions: possible products starting from chloronitrobenzene with varying mole ratios of reactants.
158 G.D. Yadav/Green phase transfer catalysis
used for C-alkylation of any group (introducing an extra
carbon group in the molecule). It is used in the pharma-
ceutical industry, for the preparation of pentapiperdine,
idoxifen (non-steroidal antiestrogen), oxelodine, pheno-
peridine and dyclonine. Even the higher acetonitriles,
namely, benzyl phenylacetonitrile and dibenzyl phenyl-
acetonitrile also can be used for this purpose [40].
Fenvalerate is synthesised by a multistep process
comprising of several PT catalyzed reaction steps. The
most widely reported method involves the phase transfer
catalysed cyanide displacement of p-chlorobenzyl chlo-
ride (p-CBC), to give p-chlorophenyl acetonitrile
(p-CBCN) as the first step. The second step involves
the reaction of p-CBCN with isopropyl halide under
alkaline conditions again catalyzed by a phase transfer
agent. The product can be hydrolyzed to the corre-
sponding acid once again under phase transfer catalyzed
conditions and further subjected to a series of reactions
to produce fenvalerate (figure 13). The first three steps
of the fenvalerate process can be elegantly combined to
carry out a single pot reaction. Both the cyanide
displacement and C-alkylation steps in the sequence
are amenable to L–L PTC. However, the selectivity of
the process is greatly influenced by the hydrolysis
reaction taking place during C-alkylation under alkaline
conditions. In this regard, S–L PTC can prove to be very
Figure 13. First three stages of fenvalerate synthesis using CEPTC. The last stage is also a PTC process [39].
beneficial since it suppresses hydrolysis. Thus, cyanide
displacement and C-alkylation steps could be studied
both under L–L and S–L PTC conditions. A further
strategy would be to distill off the unreacted alkyl halide
from the reactor and retain the reaction mixture along
with the catalyst and carry out the alkaline hydrolysis of
the product to the corresponding acid. This step ought
to be carried under L–L PTC conditions [19,42].
A preliminary strategy for the CEPTC under S–L (x)–
L conditions involves the cyanide displacement of
p-chlorobenzyl chloride using solid sodium cyanide in
the x-phase, which is a small quantity of water in a S–L
reaction mixture, and a PT catalyst in an organic solvent
followed by addition of a solid alkali and isopropyl
halide to the reaction mixture without separation of the
intermediate and without any further addition of catalyst
or solvent. In the cyanide displacement reaction,
although quantitative conversion can be obtained by
using higher concentration of NaCN, it is desirable to
use it in a stoichiometrically deficient quantity (<1–5%)
to avoid cyanide disposal problems. This leaves some
unconverted p-chlorobenzyl chloride in the reaction
mixture which can interfere with the C-alkylation of
the product p-chlorophenyl acetonitrile. It is therefore
necessary to convert the residual p-chlorobenzyl chloride
before commencing the alkylation reaction. Considering
 G.D. Yadav/Green phase transfer catalysis 159

these complexities, the following three-step reaction the PT catalyst as is seen from the study of various
strategy was adopted for the CEPTC scheme (figure 11). parameters.

I. Cyanide displacement on p-chlorobenzyl chloride
to form p-chlorophenyl acetonitrile.
II. Conversion of unreacted p-chlorobenzyl chloride.
III. Alkylation of p-chlorophenyl acetonitrile with iso-
propyl bromide under alkaline conditions.
Since the system was based on the chemistry of
synthesis of fenvalerate, the desired product of CEPTC
would be a-isopropyl-p-chlorophenyl acetonitrile.
Although various other industrially significant products
were obtained during CEPTC synthesis, total selectivity
to the desired product can be achieved by employing the
following optimum conditions (table 2):
 Equimolar quantities of NaCN can be used in step
I, which would ensure total conversion of p-CBC
and hence formation of two products of step II,
namely, a-(p-chlorobenzyl)-p-chlorophenyl aceto-
nitrile and p,p0 -dichlorodibenzyl ether can be totally
avoided.
 Conducting the CEPTC reaction in an autoclave
under inert atmosphere at elevated temperatures
would not only improve conversions but also elimi-
nate the product resulting from oxidative decyana-
tion i.e. p-chlorobenzoic acid-methylethyl ester.
 The formation of di-alkylated product, a,a0 -diiso-
propyl-p-chlorophenyl acetonitrile can be avoided
by using appropriate quantities of the reactants and
Varying the reaction conditions could alter the yield
of various products formed during the process. Opti-
mum use of the PT catalyst and the solvent is ensured to
make the process green and cost effective. The same
solvent and catalyst was used in all the three S–L–(x)–L
steps of CEPTC, thereby improving the economics of
the process as well as the separation stages are avoided,
thus minimising the waste. CEPTC thus proves its basic
fundamental of ‘‘cost and waste minimization’’.
2.10. Selectivity-engineered PTC
In order to study selectivity engineering with phase
transfer catalysis, chlorobenzenes could be used as the
starting materials. Both the chloro and nitro groups
could be manipulated to obtain a variety of products, all
having commercial values. The sulphide reduction of
chloronitrobenzenes could lead to chloroanilines, amin-
ophenols, aminothiophenols or substituted diphenyl
sulphides or polysulphides or mixture thereof in the
presence of Na2S under alkaline condition using a
suitable PTC. The PTC could be used under L-L, S–L,
L–L–L and L–L–S (catalyst) and depending on the type
of the system used, the product selectivity could be
varied [44,45]. Chloronitrobenzenes could be hydrolysed
to form nitrophenols, which may give dinitrophenyle-
thers by combining with either chloronitrobenzene or

Table 2
Control reaction for CEPTC-all S–L (x)–L PTC processes [39]

Parameter Stepl S–L (x)–L Step II S–L (x)–L Step III S–L (x)–L Final reaction mixture

Time* 0 2h 2.25 h 6.25 h

Speed of agitation 1000 rpm 1000 rpm 1000 rpm
Tetrabutylammonium bromide 0.002 mol – – 0.002 mol
Toluene 25 cm3 – – 25 cm3
Water (for x-phase) 1 cm3 1 cm3 1.049 cm3 1.218 cm3
p-chlorobenzyl chloride 0.025 mol 0.005 mol – –
Sodium cyanide 0.02 mol – – –
p-chlorophenyl acetonitrile – 0.02 mol 0.01825 mol 0.01076 mol
Potassium hydroxide – 0.02 mol 0.0173 mol 0.0102 mol
Potassium chloride – 0.0134 mol 0.0134 mol
Sodium chloride – 0.02 mol 0.02 mol
Potassium bromide – – – 0.001945 mol
p,p0 -dichlorodibenzyl ether (inert, – – 0.002275 mol 0.002275 mol
product of step II)
a-(p-chlorobenzyl)-p-chlorophenyl – 0.00045 mol 0.00045 mol
acetonitrile (inert, product of step II)
Isopropyl bromide – – 0.04 mol 0.0236 mol
a-isopropyl-p-chlorophenyl acetonitrile – – – 0.00553 mol
(desired product)
a; a0 -diisopropyl-p-chlorophenyl acetonitrile – – – –
p-chlorobenzoic acid-methylethyl Ester – – – 0.001945 mol
Temperature 90 °C 90 °C 60 °C
Reaction time for each step 2h 15 min 4h

*Time of commencing each step from t = 0.

160 G.D. Yadav/Green phase transfer catalysis
another molecule of nitrophenol. Nitrophenols and the
corresponding ethers are important intermediates in
organic process industry. Chloronitrobenzene could be
reduced to form chloroaniline which could further yield
aminothiophenol, if sodium sulphide or bisulphide is
used as the reducing agent. Aminophenol is an impor-
tant chemical used as photographic developer, interme-
diate in the manufacture of sulphur and azo-dyes and in
the dyeing of furs and feathers. Aminothiophenol is
mainly used as corrosion inhibitor in structural steels,
copper and in preparation of many intermediate chem-
icals. During sulphide reduction some other products
are likely to be formed. These are the thioethers or
sulphides, such as dinitrodiphenyl sulphide or polysulp-
hides and diaminodiphenyl sulphide or its polysulp-
hides, from the corresponding thiols. Certain other
combinations are also possible, such as addition of one
aminothiophenol and one nitrothiophenol to yield
aminonitro diphenyl sulphide or polysulphide. These
are useful as corrosion inhibitors.
The hydrolysis of p-chloronitrobenzene with aqueous
sodium hydroxide under L–L PTC yields p-nitrophenol
as the sole product, which is instantly extracted into the
aqueous phase as a sodium salt. No p-p0 -dinitrodiphenyl
ether is formed. When p-nitrophenol is reduced by
aqueous sodium sulphide, it gives p-aminothiophenol as
the only product; no formation of p-aminophenol is
detected, For producing p-aminophenol, the reaction
should be conducted starting from p-nitrophenol or
from p-chloronitorbenzene, which is converted, to
p-nitrophenol insitu under L–L PTC, followed by
neutralisation of the aqueous phase and subsequent
reduction with sodium sulphide under L–L PTC. Both
p-aminophenol and p-aminothiophenol are formed as
sodium salts, which could be separated from the
reaction mixture by dissociation extraction because
their pKa values are different [44]. An interesting
example of selectivity engineering of O-vs. C-alkylation
of p-methoxyphenol with allyl bromide in L-L PTC has
been reported under the influence of interfacial mass
transfer resistance [46].
3. Conclusions
Waste minimization is a theme of green chemistry.
End-of-pipe solution as a regulatory approach has been
adopted by several in industry assuming that the
technology is perfect, economical and only the effluent
should be treated. Phase transfer catalysis is a popular
method having 600 odd industrial practices but with
very little attempts to improve the process from envi-
ronmental perspective. The L–L PTC reactions are
conducted under milder conditions at much faster
reaction rates and improved selectivities to desired
products and are thus by definition waste reduction
processes. The phase transfer catalyst is not recovered
but treated as a waste since the quantities are very small
and do not contribute much to the expensive product.
However, the rates of reactions can be further enhanced
to have less reactor volume and processing times in
batch processes. L–L PTC can be further modified to
convert it into several multiphasic reactions, to recover
and reuse the catalyst and also to enhance selectivity,
under the ambit of green chemistry to make PTC readily
acceptable to industry. The S–L, S–L(x)-L, MISL,
MILL, G–L–S, S–L–L, CMPTC, L–L–L, cascade- and
selectivity-engineered PTC are some modifications of the
traditional processes. Use of microwaves and ultrasound
should be made in consonance with solventless synthesis
as exemplified in MILL–PTC and MISL–PTC. So
combining several steps in a single pot reaction and
using the same catalyst and solvent, without separation
or with partial replenishment of the reactants for all the
steps fits elegantly into the concept of waste minimiza-
tion and it was discussed as CEPTC, which seems
promising to offer additional benefit of enhancing the
selectivity of the desired product through manipulation
of various parameters such as number of phases, catalyst
loading, type of catalyst, stoichiometric ratio of the
starting materials and temperature. In agrochemicals
and pharmaceuticals this approach can be employed
where multi-step synthesis coupled with several separa-
tion stages add to the cost of the product. The selectivity
engineered PTC concept can be applied in a number of
multiproduct industries based on a family of com-
pounds.
Acknowledgment
Thanks are due to the Darbari Seth Chair Professor-
ship Endowment and NMITLI projects from CSIR for
financial support. Gift samples of phase transfer
catalysts as well as research support by M/s Dishman
Pharmaceuticals and Chemicals Ltd, Ahmedabad, India
is gratefully acknowledged.
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