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Article history: Clays and modified clays are used to catalyze various types of organic reactions such as addition, Michael
Received 20 May 2010 addition, carbene addition and insertion, hydrogenation, allylation, alkylation, acylation, pericyclic reactions,
Received in revised form 17 October 2010 condensation reactions, aldol formation, imine synthesis, diazotization reactions, synthesis of heterocycles,
Accepted 19 October 2010
esterification reactions, rearrangement/isomerization reactions, cyclization reactions, oxidation of alcohols,
Available online 6 October 2010
dehydrogenation, epoxidation and several more. Clays function as Brønsted and/or Lewis acids, or as bases.
Keywords:
Clays with combined acidic and basic properties have been developed by simple procedures of modification.
Clay mineral Such clays are employed to catalyze a sequence of acid and base-catalyzed reactions in one pot. Good
Activated bentonite enantioselectivity and stereoselectivity are achieved using chiral organic compounds and chiral complexes
Montmorillonite intercalated between clay layers. Examples from recent literature are described here.
Saponite © 2010 Elsevier B.V. All rights reserved.
Organic synthesis
Heterogeneous catalyst
0169-1317/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2010.09.016
G. Nagendrappa / Applied Clay Science 53 (2011) 106–138 107
noted that the literature covered is essentially from articles in interlamellar space of the catalyst and is helped by its Lewis acid
mainstream journals published between 2000 and 2010, with a few character. This modified Hosomi–Sakurai reaction is environment
exceptions; the patent literature is completely omitted. As a result the friendly and delivers protected homoallylic ethers due to six membered
review is not exhaustive; some aspects and several types of reactions are pericyclic transition state of ene reaction (Scheme 3).
left out for various reasons. The reaction with aliphatic aldehydes and ketones was successful
in some cases, which are given below, with yields of the homoallylic
2. Addition reactions ether products mentioned in the parentheses.
Scheme 4. Allylation of ketones and aldehydes using potassium salts of allyl- and crotyltrifluoroborates.
predominantly more than the other. The K10 catalyzed reactions are dehydration and oxidation in the final step to deliver quinolines in good
better stereoregulated with the diastereomeric ratio being greater than in to excellent yields (De Paolis et al., 2009) (Scheme 5). The reaction is
the case of BF3.OEt2 catalyzed reactions. carried out under solvent-free condition and with the assistance of
Montmorillonite K10 clay catalyzes the addition of aniline deriva- microwave radiation.
tives to cinnamaldehyde in a Michael fashion as the first step of a A three-component reaction of enaminones, β-ketoesters/1,3-
domino process involving cyclization in the second step followed by diketones and ammonium acetate takes place under the catalytic
An Iranian natural bentonite modified by N-alkylated 1,4- proposed mechanism is a bit elaborate; the interested reader may
diazabicyclo[2,2,2]octane quaternary salt was found to act as a good refer to the original paper).
catalyst in triphase reactions consisting of the solid catalyst and the Dithiocarbamic acid A adds to arylideneoxazalones B to form the
aqueous and organic phases (Ghiaci et al., 2005). When a mixture of Michael adducts C which undergo cyclization to 1,3-thiazinan
cyclooctene, the catalyst, chloroform and an aqueous solution of derivatives D. The reactions are carried out by microwave irradiation
sodium hydroxide was refluxed, dichlorocarbene was generated, of the reactants adsorbed on montmorillonite K10, basic and neutral
which added to the cyclooctene present in the reaction mixture, alumina, and silica gel. The best yields (76–91%) were obtained in the
forming dichlorobicyclo[6.1.0]nonane as the product in almost shortest reaction times from the reactions performed on K10 clay.
quantitative yield (Scheme 12). Reactions carried out on other solid catalysts were inferior. Micro-
The triphase systems (water-petroleum ether-catalyst) with water wave irradiation without using the adsorbent K10 clay was found to
soluble nucleophiles work well for nucleophilic substitution reactions be ineffective, demonstrating the significant role of clay for the
also (Scheme 13). success of the reactions (Siddiqui et al., 2010) (Scheme 15).
Triazenes have been synthesized (Scheme 14) by adding p-
aminobenzene-1-sulfonyl azide or amide to a cold mixture of sodium 3. Condensation reactions
nitrite and acid-treated clay (K10, bentonite, or kaolin), followed by a
cyclic secondary amine, which adds to the diazo intermediate formed Carbon–carbon bond forming reactions are of primary importance in
in the previous step (Dabbagh et al., 2007). The yields are moderate in organic synthesis. Among the numerous procedures developed for this
all the cases and are similar to the yields obtained using HZSM-5 and purpose aldolization/aldol condensation occupies an important posi-
sulfated zirconia. The mechanism does not involve formation of the tion. The aldol reaction is catalyzed by acids as well as bases. A base is the
conventional diazonium salt intermediate. Instead it consists of initial preferred catalyst to obtain aldol. Because of the importance of these
interaction of nitrite with protonated silicate of clay followed by a reactions attention is being paid to develop environment friendly
series of nucleophilic addition and elimination processes. (The procedures using heterogeneous clay catalysts.
Hydrotalcites (HT) as solid base catalysts have been successfully
used in bringing about the aldol reactions. For example, Roelofs et al.
(2000) have reported the self condensation of acetone (1) to give
aldol 2 and cross condensation of acetone with citral (3) on modified
hydrotalcite catalysts at 0 °C (Scheme 16). The catalyst shows high
activity and a small amount (5%) of it is enough to effect the aldol
formation. The cross aldol (4) is formed with very high selectivity.
These reactions are 100% atom economic and are examples for good
“green” procedures.
Scheme 12. Addition of dichlorocarbene in triphase system. Acetaldehyde (5) condenses with heptanal (6) in the presence of
hydrotalcite-type catalysts to give cross condensation product none-
nal (7) in ethanol at 100 °C (Tichit et al., 2003) (Scheme 17). If the
Brønsted base strength is increased due to a higher proportion of MgO
or hydrated sites, the reaction takes a different course through the
intermediate α-anion of heptanal (10) to give 8 and 9.
In an interesting study an acid-layered clay was combined with a
basic layered clay to bring about sequential acid and base-catalyzed
reactions in one pot. Motokura et al. (2005) mixed Ti4+ intercalated
Scheme 13. Nucleophilic substitution in triphase system. montmorillonite with surface tunable basic hydrotalcites. The acid-
Scheme 18. Sequential multiple reactions using combined acid and basic layered clay.
Scheme 23. Reaction using coexisting acidic and basic sites in tandem.
Scheme 30. Coumarin-3-carboxylic acids from malonic acid and salicylic aldehydes.
116 G. Nagendrappa / Applied Clay Science 53 (2011) 106–138
stereochemical outcome and product yields on Diels–Alder reaction produced oligomeric and polymeric products rather than [4+2] addition
carried out in ionic liquid, 1-hexyl-3-methylimidazolium (HMI) products. p-Chloro and p-nitrobenzaldehyde gave very poor yields of the
tetrafluoroborate. The results with other supports like silica or corresponding dihydropyrans as compared to o-chloro- and o-
alumina or without support in the same medium were not good. nitrobenzaldehyde.
Microwave irradiation was also not as good as K10 clay. With K10 clay Chiba et al. (1999) have generated in situ the highly reactive o-
as catalyst the yields were as high as 99% and endo:exo ratio was 93:7. quinomethanes from o-hydroxybenzyl alcohols at room temperature
The reaction took just 30 min at room temperature (Scheme 36). The using wet monmorillonite K10 and lithium perchlorate in nitrometh-
same medium after work up was reused four times without much loss ane. The presence of air is necessary. The quinomethanes formed add
in yields. instantly to olefins to give benzodihydropyrans (Scheme 38).
Several clay catalyzed hetero-Diels Alder reactions have been reported Methylene cyclopropanes function as dienophiles in their aza-
in the last few years. Dintzner et al. (2007) found that the carbonyl group Diels–Alder addition reaction with ethyl (arylimino)acetates under
of benzaldehyde and its derivatives adds to 2,3-dimethyl-1,3-butadiene the catalytic influence of montmorillonite K10 in dichloroethane at
under the influence of montmorillonite K10 clay in carbon tetrachloride at room temperature to produce tetrahydroquinolines. The K10 clay
25 °C to form dihydropyrans. The clay was preheated to 250 °C which performs as good as triflic acid in catalyzing these reactions (Zhu et al.,
enabled the collapse of the interior structure of clay by extrusion of water 2009b) (Scheme 39).
leading to a decrease in Brønsted acidity but an increase in Lewis acidity Two of the authors of this group, Shao and Shi (2003) had reported
that is responsible for the catalytic activity of the clay, suggest the authors. similar aza-Diels–Alder reactions of methylene cyclopropanes with
Based on the fact that benzaldehydes with ortho-substituents having lone Schiff bases. In this case they had employed monmorillonite KSF clay
pair electrons give far better yields of dihydropyran products, the authors or scandium triflate as catalyst (Scheme 40). The Schiff bases were
propose a clay metal ion coordinated transition state that favours the produced in situ by the reaction of aryl aldehydes and aryl amines
reaction (Scheme 37). The less substituted dienes (e.g., isoprene) employed directly in the 3-phase reaction.
Scheme 32. Isobezofuranones from phthaldehydic acid and ketones without solvent.
G. Nagendrappa / Applied Clay Science 53 (2011) 106–138 117
Aryl amines add to endocyclic enecarbonates resulting in the latter moderate to good yields varying from 42–81% depending on the
undergoing ring opening to give aralkyl imines under the influence of substituents (Scheme 43). The hetero-Diels–Alder reaction proceeds
montmorillonite KSF clay in THF at room temperature. The imines so by a multistep process in which the acetylene adds to the Schiff base
formed are highly reactive and undergo rapid aza-Diels–Alder formed by the condensation of the amine and the aldehyde. Slightly
reaction with a second molecule of the endocyclic enecarbonate better yields were obtained in oxygen atmosphere instead of open air.
present to finally give hexahydro-1H-pyrrolo(3,2-c) quinoline deri- The research group also found that, among some twenty different
vatives (Yadav et al., 2004a) (Scheme 41). solid supports, the HClO4 treated montmorillonite worked the best in
The same group of workers had previously reported (Yadav et al., terms of yields, reaction time, work up procedure, etc.
2002) similar reaction of aryl amines with dihydrofuran and Cyclopentadiene and furan undergo Diels–Alder addition at room
dihydropyran to produce furano- and pyrano-quinolines (Scheme 42). temperature with trans-2-methylene-1,3-dithiolane-1,3-dioxide in
A similar mechanistic pathway is proposed for this reaction also. the presence of Fe3+-doped montmorillonite K10 combined with
Guchhait et al. (2009) have reported a multicomponent Povarov 2,6-di-tert-butyl-4-methylphenol (butylated hydroxytoluene, BHT) to
reaction involving aromatic amine, aromatic aldehyde and terminal give the product in a overall yield of 64% (Gültekin, 2004)
acetylene. The three compounds were allowed to react in the (Scheme 44).
presence of perchloric acid-treated montmorillonite clay at 70 °C in Aldimines generated in situ from aliphatic aldehydes and p-
open air. Substituted quinolines were obtained as products in anisidine add to Danishefsky diene in the presence of montmorillonite
K10 in aqueous or aqueous acetonitrile medium to produce 2-alkyl- particularly as oils, fats and waxes. They are a major component of all
2,3-dihydro-4-pyridones in excellent yields (Akiyama et al., 2002) living organisms. They have numerous applications in industries and as
(Scheme 45). foods and fuels, for which esters obtained from both natural as well as
Montmorillonite K10, filtrol-24, bentonite and pyrophillite clays synthetic sources are employed. There are several ester forming
were used as catalysts to bring about Diels–Alder addition of 1,4- reactions available, such as (i) reaction of alcohols or phenols with
naphthoquinone and N-phenylmaleimide to 4,6-bis(4-methoxyphenyl)- carboxylic acids, carboxylic acid anhydrides or acyl halides, (ii) addition
and 4-(4-methoxyphenyl)-6-methylpyran-2(H)-ones under a dry state of carboxylic acids to olefins, (iii) addition of alcohols to ketenes,
adsorbed condition. Filtrol-24 performed the best under this condition. (iv) substitution of alkyl halides/tosylates with carboxylates, (v) Baeyer–
Further, when montmorillonite K10 and bentonite were modified Villiger oxidation of ketones, etc. The most common and expedient
by impregnating with AlCl3, ZnCl2 and FeCl3 using their aqueous or method is the acid-catalyzed reaction of a carboxylic acid with an
nonaqueous solution (PhNO2 for AlCl3, MeCN for ZnCl2 and FeCl3), alcohol, called esterification, which is usually carried out in homoge-
followed by washing with water and drying, the resulting modified K10 neous media. Though several Brønsted acids are used as catalysts for this,
and bentonite catalysts performed as well as filtrol-24. Among the doped the most convenient and commonly used one is concentrated sulfuric
catalysts FeCl3-containing ones worked the best (Kamath et al., 2000) acid. The disadvantages of using this acid, like corrosion problems,
(Scheme 46). handling difficulties, waste disposal hassles, environmental hazards etc.
are well known. This opens up a good opportunity for acid clays to
5. Esterification reactions replace the hazardous mineral acid in ester forming processes, and a
substantial amount of research activity is going on in this area.
Esters, which are normally understood to be alkyl or aryl carbox- Clays available commercially or occurring naturally, including
ylates, are an important class of naturally occurring compounds, those found in the geographical region of the researchers, have been
Scheme 36. Diels–Alder reaction in ionic liquid. K10 is the best catalyst. Scheme 37. Hetero-Diels–Alder reaction of benzaldehyde with dimethylbutadiene.
G. Nagendrappa / Applied Clay Science 53 (2011) 106–138 119
Scheme 38. o-Quinomethanes from o-hydroxybenzyl alcohols and their D–A addition.
found to work well with or without suitable modifications. The most 2 h reaction time). They also discovered that the supporting K10 clay is
successful esterification catalysts have been the montmorillonites, essential for the reaction, since InCl3 alone was not effective as catalyst.
normally those that possess high Brønsted acidity. Some selected The yield of benzyl benzoate was only 11% after 1 h of reaction at 50 °C
examples from recent literature are described here. between benzyl alcohol and benzoyl chloride with InCl3 as catalyst,
Kaolin, montmorillonite K10 and KSF supported with transition while with equivalent amount of InCl3/K10 as catalyst the ester yield
metal chlorides, InCl3, GaCl3, FeCl3, and ZnCl2 were employed to was 96%. The authors further found that the InCl3/K10 catalyst was
esterify tert-butanol with acetic anhydride to tert-butyl acetate with almost as effective in its fifth time reuse as in the beginning.
more than 98% selectivity. The K10 clay was found to be the best Srinivas and Das (2003) have demonstrated that ferric chloride
support and K10 supported InCl3was the best catalyst followed by supported on montmorillonite K10 clay (Fe3+/K10) is an efficient
GaCl3/K10, FeCl3/K10 and ZnCl2/K10, in that order. A noteworthy esterification catalyst. The catalyst is highly selective in esterifying
feature was the low activity of the catalysts for the dehydration of tert- both saturated and unsaturated aliphatic carboxylic acids, while the
butanol below 50 °C (Choudhary et al., 2001a) (Scheme 47). aromatic acids are unreactive, as demonstrated by using mixtures of
In a later study employing the InCl3/K10 catalyst Choudhary et al. aromatic and aliphatic acids. The yields of esters are high and the
(2004) reported the preparation of thirteen esters by the reaction of catalyst is reusable. The catalyst is shown to be useful also in the
benzyl alcohol, phenol, 4-nitrophenol, 1-naphthol and 2-naphthol with preparation of amides of aliphatic carboxylic acids with aliphatic as
benzoyl chloride, acetyl chloride and n-butyryl chloride. The reaction well as aromatic amines, but ineffective in the preparation of the
gave high yields of esters (up to 98%) under mild conditions (50 °C, 0.2– amides of aromatic acids with aromatic amines (Scheme 48).
Some Brazilian natural clays (smectite, atapulgite and vermicu- Vijayakumar et al. (2004, 2005a,b) have shown that acid activated
lite), without pretreatment or activation, have been demonstrated by Indian bentonite is a good catalyst, in some cases better than zeolites,
Silva et al. (2004) to act as good catalysts for transesterification of for the preparation of aryl and alkyl esters of fourteen different
ethyl acetoacetate and ethyl bezoylacetate by six carbohydrate- aromatic and aliphatic carboxylic acids. Particularly, the yields of aryl
acetonides. Refluxing a mixture of the reactants and the catalyst in esters of long chain fatty acids are very impressive, which were more
toluene for ~48 h produced the acetonide esters in good yields by than 90%, are very impressive. Results of a part of their work are
replacing the ethyl group of the β-keto esters. The reaction mixture on depicted in Scheme 50.
cooling to room temperature was stirred (~24 h) with bezylamine to Earlier Kantam et al. (2002) observed that Fe3+-impregnated
produce β-benzyl enamino esters (Scheme 49). montmorillonite clay catalyzed the esterification of various aliphatic
acids, including the long chain fatty acids, aromatic acids, and α,β-
unsaturated mono- and dicarboxylic acids with alcohols, under mild
reaction conditions. The yields were obtained in the range of good to
excellent.
In three reports Reddy et al. (2004, 2005a,b) describe their study
on the esterification of monocarboxylic and dicarboxylic acids with
phenols and alcohols including ethylene glycol. They found that Al3+
exchanged montmorillonite GK-129 was the best catalyst compared
with the same clay exchanged with divalent and other trivalent metal
cations. It is better than the similarly treated montmorillonite K10 or
Indian bentonite. Its performance is comparable to the results Scheme 48. Ferric chloride supported on K10 for esterification.
obtained using zeolite H-β or p-toluene sulfonic acid catalyst. They
discuss various experimental conditions such as temperature,
reaction time, solvents, catalyst preparation, etc., that give the best Methyl mandelate, used in flavouring and perfumery, has been
results, as well as the catalyst's performance in its reuse. Their results prepared by esterification of mandelic acid with methyl alcohool in
are consolidated in Scheme 51. Reddy et al. (2007) have carried out the presence of montmorillonite K10 supported dodecatungstopho-
esterification of succinic acid with iso-butyl alcohol to di-iso-butyl sphoric acid (DTP/K10) and its cesium salt (Cs-DTP/K10) (Yadav and
succinate in connection with the evaluation of surface activity of Mn+- Bhagat, 2005) (Scheme 52). The Cs-DTP/K10 catalyst was found to be
montmorillonite clay catalysts, where Mn+ = Al3+, Fe3+, Cr3+, Zn2+, better than K10 and other solid catalysts like S-ZrO2. The catalyst was
Ni2+, Cu2+ and H+. The reactions performed on Al3+-mont and H+- shown to be recyclable. Using the same catalyst (Cs-DTP/K10 clay)
mont gave the best yields (96% and 97%), Fe3+-mont and Cr3+-mont Yadav and George (2008) have carried out the esterification of
gave good yields (74% and 51%), while the other Mn+-mont catalysts benzoic acid with phenol to phenyl benzoate which then undergoes
gave poor yields (23–27%). The results were rationalized based on Fries rearrangement to give 2- and 4-hydroxybenzophenones. The
various properties of catalysts due to exchanged ions. selectivity of the products depended on a number of experimental
As noted in the section on condensation reactions, Motokura et al. parameters.
(2005) have esterified cyanoacetic acid with methanol to methyl The esterification strategy was used by Mittal (2007) to increase
cyanoacetate over the combined Ti4+-mont, HT catalyst (Section 3, the basal plane spacing in clays in order to achieve shear induced
Scheme 18). exfoliation. This was accomplished by modifying the clay platelets with
Scheme 45. Alkyldihydropyridones from Danishefsky diene and aldimines formed in situ.
quaternary ammonium ions carrying hydroxyalkyl groups, which were catalytic activity of different batches of commercially available K10
then reacted with long chain fatty acids (Scheme 53). The paper reports montmorillonite clays. They have found that acid treatment improves
various aspects of catalyst modification and resulting properties. the activity of the clay and suggest that esterification is suitable for
Wallis et al. (2007) have employed the esterification of maleic determining the degree of clay delamination. They suggest that loss of
anhydride with p-cresol, along with a transacetalization reaction, layer stacking and increase in available exchange sites for protonation
diacetylation of bezaldehyde with acetic anhydride and tetrahydro- are responsible for clay activity enhancement. They compare this with
pyranylation of ethanol (Scheme 54), to assess and improve the an earlier observation by Reddy et al. (2005a) who had observed
dramatic improvement in the catalytic activity of K10 montmorillon- p-Hydroxybenzoic acid esters, with the sobriquet parabens, find
ite clay with much reduced specific surface area on acid treatment. application in cosmetic, pharmaceutical and food industries. Hazarika
Thermally activated Nigerian Ukpor kaolinite clay and Udi clay et al. (2007) have prepared the methyl, ethyl and n-propyl p-hydroxy
were shown to be good catalysts for the preparation of n-propyl benzoates by refluxing the mixtures of the aromatic acid and
acetate (Igbokwe et al., 2008). Various experimental parameters were appropriate alcohol on montmorillonite K10 clay for 10–15 h, and
measured to obtain the best yield of the ester. obtained the esters in 81–90% yields (Scheme 56). The acid-treated
Esterification of long chain fatty acids, stearic, oleic and palmitic clay gave slightly better yields (~2% more).
acid, with short chain alcohols, methanol, ethanol, 1-propanol, 1- Acetic acid reacts efficiently with 2-methoxyethanol in the
butanol and 2-butanol has been carried out using a series of presence of clay catalyst treated with sulfuric acid and aluminium
montmorillonite based clay catalysts, KSF/0, KP10, K10 (Neji et al., salts and calcined at 313–633 K, to give methoxyethyl acetate. Both
2009) (Scheme 55). The product esters are meant to be used as Lewis acid and Brønsted acid sites are active in catalyzing the
biodiesel. A variety of reaction conditions were investigated. KSF/0, esterification process (Wang and Li, 2000) (Scheme 57).
which had the lowest pH value, was found to be the best catalyst. The The waxy stearyl stearate ester was synthesized by reacting stearic
yields in the case of primary alcohols were almost quantitative, but in acid with stearyl alcohol on montmorillonite clay under solvent-free
the case of 2-butanol the ester was obtained in only 40% yield. The condition. The temperature was strictly maintained at 170 °C
catalyst was recycled twice without significant loss in its activity. throughout the bulk of the reaction mixture in the pilot scale reactor
by using microwave irradiation. The pure ester is obtained in 95%
yield on filtering off the solid catalyst. The use of microwave radiation
reduces the reaction time by a factor of 20–30 times compared to the
time required by the reaction done in conventional reactor (Esveld
et al., 2000) (Scheme 58).
chemicals, and several others. It is an electrophilic substitution reaction indeed catalysts, they are not really used in catalytic quantities, but in
of usually aromatic and heteroaromatic compounds by alkyl or acyl much larger amounts. This obviously poses serious problems of
groups catalyzed by a number of Lewis and Brønsted acids under handling, recovery and disposal of the waste products. In this respect,
homogeneous or heterogeneous conditions. Alkyl halides, alcohols, Friedel–Crafts reactions are an antithesis of Green chemistry principles.
sulfonates and olefins are used as alkylating agents, and acyl halides or This has provided challenging opportunity to explore alternative
acid anhydrides are generally used for acylation. The most commonly catalytic procedures. Thus reusable, environmentally benign solid acid
used catalysts are AlCl3, ZnCl2, SnCl4, BF3, FeCl3, SbCl5, H2SO4, H3PO4, etc., catalysts including clays are being explored for these reactions. Clays
mostly under homogeneous conditions. Though these Lewis acids are and modified clays have been used successfully as catalysts for bringing
about Friedel–Crafts alkylation and acylation.
Cyclopentyl and cyclohexyl derivatives of benzene, toluene, o-
and p-xylene, mesitylene and anisole have been prepared in 85–95%
yield by refluxing a solution of the respective aromatic substrate
with cyclopentanol or cyclohexanol in 1,2-dichloroethane on Fe3+-
montmorillonite with 10 mol% of TsOH or MsOH as cocatalyst
(Chaudary et al., 2002) (Scheme 59). The suggested mechanism
involves the formation of sulfonate ester of the alcohol as intermediate
which alkylates the arene selectively. In the absence of the cocatalyst
TsOH or MsOH, the reaction with cyclopentanol produces only a minor
amount of the expected alkylated product (~30%), while the major
product is dicyclopentyl ether (~60%). The reaction does not take place
Scheme 55. Esters for using as biodiesel. in the absence of Fe3+–montmorillonite.
An interesting case of Fe–Mg–hydrotalcite anionic clay being used
for the Friedel–Crafts alkylation has been described by Choudhary
et al. (2005a) (Scheme 60). They have benzylated anisole, mesitylene,
p-xylene, toluene and naphthalene with high degree of conversions,
using benzyl choride. They observed that calcining increases the
activity of the catalyst, and that the higher the calcining temperature
the more active the catalyst is. They attribute this to dehydration at
200 °C, formation of metal oxides on calcining at 500 °C and higher
temperatures up to 800 °C. They also found that the used catalyst is
Scheme 56. Preparation of p-hydroxybenzoic acid esters. more active than the one used for the initial reaction. This observation
is explained as due to a possible formation of Lewis acid sites resulting
from the reaction of HCl liberated in the benzylation process.
In–Mg hydrotalcite anionic clay is found to function in a similar
manner (Choudhary et al., 2005b). Ga–Mg–hydrotalcite anionic clay
was used earlier for benzylation and benzoylation of benzene
Scheme 57. Preparation of methoxyethyl acetate. (Choudhary et al., 2001b).
Benzene has been alkylated with propylene to cumene on Al3+- the presence of montmorillonite K10 clay-POCl3 under microwave
exchanged synthetic Zn-saponite with 99% conversion (Scheme 61), irradiation. The effect of this catalyst was comparable to the silica
compared to just 0.3% conversion when the same reaction was gel-POCl3 catalyzed reaction (Devi, 2006).
performed using commercial solid phosphoric acid (SPA), (Vogels A number of other clay-based catalytic systems have been
et al., 2005). developed by several groups of researchers for bezylation reactions.
To introduce an isopropyl group on xylenes, isopropyl alcohol is The reactions are conducted in liquid phase or solvent-free conditions
used by Yadav and Kamble (2009). They have obtained dimethylcu- with or without microwave irradiation. Studies were directed to find
menes by reacting xylenes with isopropyl alcohol in an autoclave in the right experimental conditions to obtain the best results by
the presence of cesium substituted dodecatungstophosphoric acid preparing the most active catalyst.
supported on K10 as catalyst (Scheme 62). The Cs-DTP/K10 was the Ga/AlClx-grafted montmorillonite-K10 was found to be an efficient
most active among the five catalysts studied, including K10, DTP/K10, catalyst for benzylation as well as benzoylation of benzene, substituted
sulfated zirconia and filtrol-24. Various aspects of catalytic activity benzenes and naphthalene, using benzyl chloride and benzoyl chloride
and kinetics of reactions are considered. Selectivity for mono- respectively. The catalyst is highly active, and as such benzoylation
isopropyl products is very high, with the byproducts, diisopropylated occurs even if a strong electron withdrawing group like NO2 is present
xylenes, diisopropyl ether and propylene being formed in small on benzene ring (Choudhary and Jha, 2008) (Scheme 65).
amounts. Clay catalyists obtained from Pakistani clay minerals were found
Cs-DTP/K10 has been used fruitfully in several other Friedel–Crafts to be useful in benzylation of toluene, naphthalene, anthracene,
type reactions. For example, 1,3-dibenzyloxybenzene has been quinoline, 8-hydroxyquinoline and pyridine (Ehsan et al., 2006).
acetylated to 3,5-dibenzyloxyacetophenone with acetic anhydride as
shown in Scheme 63 (Yadav and Badure, 2008).
Phenol has been benzoylated by benzoic acid to 4-hydroxybenzo-
phenone via the formation of phenyl benzoate as intermediate
which underwent Fries rearrangement, a variant of Friedel–Crafts
acylation (Yadav and George, 2008) (Scheme 64). Cs-DTP/K10 has
been found to be a good catalyst for benzoylation of p-xylene to
2,5-dimethylbezophenone (Yadav et al., 2003). Similar results were
obtained when resorcinol was treated with phenylacetic acid in
Scheme 61. Al3+-exchanged synthetic Zn-saponite for alkylation of benzene. Scheme 62. Alkylation of xylenes using Cs-DTP/K10.
126 G. Nagendrappa / Applied Clay Science 53 (2011) 106–138
compounds under microwave irradiation and solvent-free condition Singh et al. (2002) synthesized three sesquiterpenes, elvirol,
(Devi and Ganguly, 2008). The yields are good and comparable to or curcuphenol and sesquichemaenol by Friedel–Crafts alkylation of
better than the yields obtained from reactions using similarly treated appropriate cresols using suitable alkylating agents. The reaction was
silica gel catalyst (Scheme 69). brought about by heating the reaction mixtures in presence of
montmorillonite K10 as catalyst. The targeted sesquiterpenes were
formed in major amounts accompanied by minor quantities of
isomeric compounds (Scheme 70).
Zhang et al. (2008) have prepared a number of dihydrocoumarin
derivatives by a microwave-assisted reaction of cinnamoyl chloride
with phenol and its several derivatives using montmorillonite K10 as
catalyst in chlorobenzene as solvent (Scheme 71). The reaction
proceeds by initial formation of phenyl ester of cinnamic acid
Scheme 67. Chloroacetylation of alkylbenzenes. followed by alkylation-cyclization of the ester to give the observed
found that Al3+ pillared montmorillonite clay shows the highest pillared clay is the best catalyst for the conversion of 1-butene to trans-
conversion rate and reasonable selectivity (Scheme 80). 2-butene and cis-2-butene accompanied by small amounts of cracking
Hydroisomerization of n-heptane to isoheptane was carried out by products (Scheme 82).
Vogels et al. (2005) on synthetic Co-, Mg- and Co/Mg-saponites. They Nucleophilic substitution at allylic position (SN1' or SN2' type)
relate the isomerization to the Lewis acidity of the catalyst (Scheme 81). with isomerization of double bond has been observed by Shanmugam
Moronta et al. (2008) have studied the isomerization of 1-butene and Vaithiyanathan (2008) on K10 clay under neat conditions in the
over natural smectite clay (STx-1, USA) ion-exchanged with Al3+, Fe3+ case of the derivatives of oxindole 71 (Scheme 83). The products
or pillared with Al and Fe polyoxocations. The results show that Al- (72a–c) were further used for construction of spirolactone ring (not
8. Oxidation reactions clay mainly catalyzes the trimerisation of aldehydes to trialkyl 1,3,5-
trioxanes, which is a temperature dependent equilibrium reaction
In this section oxidation reactions that are brought about by a few with trimer-to-aldehyde ratio of 3.9:1 attained at −20 °C. However,
different types of oxidizing reagents in the presence of clay catalysts are when KSF clay is used, oxidation to carboxylic acid takes place under
reviewed. The reactions described include oxidation of aldehydes to aerobic conditions. Only aliphatic aldehydes undergo oxidation, but
carboxylic acids, alcohols to carbonyl compounds, epoxidation, Baeyer– not the aromatic or the unsaturated aliphatic aldehydes.
Villiger oxidation, oxidation and dehydrogenation of hydrocarbons. The common procedures for the oxidation of alcohols to ketones or
An interesting difference between montmorillonite K10 and aldehydes make use of compounds of transition metals, such as
montmorillonite KSF in their interaction with aldehydes has been chromium, manganese, vanadium, etc., which are toxic. It is desirable
observed by Dintzner et al. (2010) (Scheme 91). For example, the K10 to reduce their use or replace them by oxidants that are less hazardous
to health and environment. Many clay-based oxidizing agents that fulfill nitrate and acetoacetate added catalysts give higher yields of products.
this Green chemistry condition have been developed. Eftekhari-Sis et al. The oxidation takes place by a free radical mechanism.
(2007) reported the oxidation of alcohols to aldehydes and ketones Cyclohexanone undergoes Baeyer–Villiger oxidation to ε-caprolactam
using hydrogen peroxide as oxidizing agent in the presence of lithium by hydrogen peroxide in the presence of Brazilian kaolinite interca-
chloride supported on montmorillonite K10. The proposed mechanism lated with a porphyrin derivative, [meso-tetrakis(pentafluorophenyl)
involves the formation of lithium hypochlorite, which is the active porphyrin]-iron(II), Fe(TPFPP). The porphyrin moiety is introduced
oxidizing agent (Scheme 92). between the clay layers after expanding and functionalizing the
Hydrogen peroxide or iodosylbenzene epoxidizes cyclooctene to interlayer space by pretreatment of the clay. The authors (Bizaia et al.,
cyclooctene epoxide and cyclohexane to cyclohexanone in the presence 2009) claim that this is the first example of a porphyrin-in-clay
of modified natural saponite clay (Scheme 93). The modification catalyzed Baeyer–Villiger reaction. In the presence of the same catalyst
procedure involves first, the intercalation of the clay with aluminium iodosylbenzene brings about the epoxidation of cyclooctene and
polycation, followed by calcination at 500 °C to get alumina pillared clay oxidation of cylcohexane to cyclohexanone (Scheme 94). The catalyst
and then impregnation with nickel nitrate or chloride or acetoacetate was reused up to five times without significant diminution in the
(Mata et al., 2009). The amount of nickel loaded may be varied. The yields of products.
Scheme 90. Arylhydrazine addition to cyclic enol ethers and enol lactones to form indoles.
G. Nagendrappa / Applied Clay Science 53 (2011) 106–138 135
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Acknowledgements
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