Pergamon
Contents
1. Introduction
2. Structure of clay minerals
2.1. Layer structure
2.1.1. Composition and isomorphous substitution
2.2. Smectite group minerals
2.2.1. Montmorillonites
3. Properties of clays
3.1. Ion exchange
3.2. Swelling
3.3. Intercalation and cation-exchange
3.4. Acidity
4. Pillared clays
5. Supported reagents
5.1. Clay-supported reagents
5.1.1. `Clayfen and claycop'
6. Organic reactions in clay media
6.1. Oligomerization reactions
6.2. Dehydration reactions
6.3. Addition reactions
6.4. Isomerization and rearrangement reactions
6.5. Aromatic electrophilic substitution (FriedelCrafts reaction)
6.6. Miscellaneous reactions (DielsAlder, Heck and Suzuki reaction)
7. Basic clays
8. Microwave-accelerated solvent-free organic transformations using clay-supported reagents
8.1. Synthesis of imines and enamines
8.2. Synthesis of imines and enamines using Envirocat EPZGw as a catalyst
8.3. Oxidation of suldes to sulfoxides using clayfen
8.4. Oxidation of alcohols by clayfen
8.5. Oxidation of organic substrates by claycop and hydrogen peroxide
8.6. Solvent-free reductive amination of carbonyl compounds using sodium borohydride on wet clay
8.7. One-pot conversion of aromatic aldehydes to nitriles using hydroxylamineclay
8.8. Cleavage of semicarbazones and phenylhydrazones with ammonium persulfateclay
8.9. Dethioacetalizationregeneration of ketones from thioketones using clay supported nitrate salts
8.10. Nitration of aromatics and selective nitration of styrenes with clayfen and clayan
8.11. Rearrangement reactions (pinacolpinacolone and Beckmann)
8.12. Synthesis of heterocylic compounds
8.12.1. Aziridines and benzimidazoles
8.12.2. Isoav-3-enes and avones
Keywords: clay; clay-supported reagents; organic synthesis; microwave irradiation.
p
Tel.: 11-513-487-2701; fax: 11-513-569-7677; e-mail: varma.rajender@epa.gov
00404020/02/$ - see front matter Published by Elsevier Science Ltd.
PII: S 0040-402 0(01)01216-9
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8.12.3. Quinolones
8.12.4. Bridgehead nitrogen heterocycles-substituted thiazoles
8.12.5. Multi-component reactions (imidazo[1,2-a] annulated pyridines, pyrazine and
pyrimidinesUgi reaction)
9. Conclusions
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1. Introduction
Recent years have witnessed a phenomenal growth in the
use of inorganic solids as reaction media for organic transformations.15 Laszlo even went on to claim that the future
of synthetic organic chemistry rests with heterogeneous
media rather than the currently predominant homogeneous
systems due to certain specic advantages of using solid
surfaces.2a Clay minerals constitute one such medium.2b
Clay minerals occur abundantly in nature and their high
surface area, sorptive and ion-exchange properties have
been exploited for catalytic applications through decades.
Solid clay catalysts6,7 have a broad range of functions
including (a) use as catalytically active agents (usually as
solid acids), (b) as bifunctional or `inert' supports, (c) as
llers to give solid catalysts with required physical properties (e.g. attritionresistance, density, specic heat capacity
etc.).
2. Structure of clay minerals
Clay minerals are made up of layered silicates. They are
crystalline materials of very ne particle size ranging
from 150 to less than 1 micron (colloidal form). There are
two basic building blocks viz. tetrahedral and octahedral
layers, which are common to clay minerals.811
2.1. Layer structure
Tetrahedral layers consist of continuous sheets of silica
tetrahedra linked via three corners to form a hexagonal
mesh and the fourth corner of each tetrahedron (normal to
the plane of the sheet) is shared with octahedra in adjacent
layers. Octahedral layers in clay mineral, on the other hand,
consist of at layers of edge-sharing octahedra, each
formally containing cations at its centre (usually Mg21 or
Al31) and OH2 or O22 at its apices. Octahedral layers may
be trioctahedral or dioctahedral depending on the degree of
occupancy of the octahedral sites.2b
These different classes of clay minerals, namely the 1:1, 2:1,
etc. have a different arrangement of tetrahedral and octahedral layers. Structural units of clays therefore consist of
either
(a) alternating tetrahedral or octahedral sheets (OT or 1:1
structure), e.g. kaolinite group,
(b) a sandwich of one octahedral sheet between two tetrahedral sheets (TOT or 2:1 structure), e.g. smectite clay
minerals of which the most common member is
montmorillonite,
(c) an arrangement in which the three layer TOT units
alternate with a brucite layer (2:1:1 structure), e.g. chlorite.
2.1.1. Composition and isomorphous substitution. Tetrahedral sites in clay minerals are mainly occupied by Si41.
However, isomorphous substitution by Al31 is also
common. In the case of trioctahedral, octahedral sites are
generally occupied by Mg21. Isomorphous substitution by
other divalent cations such as Fe21 or Ni21 or by univalent
cations such as Li1 is common. In the case of dioctahedral
clay minerals, octahedral sites are predominantly occupied
by Al31 and isomorphous substitution by other trivalent
cations like Fe31, Cr31 or divalent cations like Mg21 or
Fe21 are common in 2:1 structures.
2.2. Smectite group minerals
This group of clay minerals has a dioctahedral or trioctahedral 2:1 layer structure, with isomorphous substitution
that leads to a negative layer charge of less than 1.2 per
formula unit. Interlayer spacings vary between ,10 and
and are generally dependent on the nature of the
15 A
exchangeable cation and the relative humidity.
Smectites are divided into four sub-classes depending upon
(a) the type of octahedral layer (dioctahedral or trioctahedral),
(b) the predominant location of layer charge sites (octahedral or tetrahedral).
Montmorillonite and beidellite groups shown below are
dioctahedral smectites with layer charges predominantly
in octahedral and tetrahedral sites, respectively.
Montmorillonite group: (Mx1)ex[(Si8)tet(M(III)42xM(II)x)oct
O20(OH)4]x2
Beidellite group: (Mx1)ex[(Si82xAlx)tetM(III)4octO20(OH)4]x2
where M1 is the exchangeable cation present in the interlayer (e.g. Na1) and M(III) and M(II) are non-exchangeable
octahedrally coordinated trivalent and divalent cations (e.g.
Al31 and Mg21), respectively and the layer charge is
0.5,x,1.2.
Hectorite and saponite groups are trioctahedral smectites
with layer charges predominantly in octahedral and tetrahedral sites, respectively. Their ideal formulae are
Hectorite group: (Mx1)ex[(Si8)tet(M(II)62xM(I)x)octO20(OH)4]x2
Saponite group: (Mx1)ex[(Si82xAlx)tet(M(II)6)octO20(OH)4]x2
M(II) and M(I) are non-exchangeable octahedrally coordinated divalent and univalent cations (e.g. Mg21 and Li1),
respectively and the layer charge is 0.5,x,1.2.
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Scheme 1.
Scheme 5.
Scheme 2.
Triphenylamine readily provides N,N,N 0 ,N 0 -tetraphenylbenzidine.37 The mechanism involves an initial dimerization, followed by a benzidine type rearrangement upon
heating (Scheme 3).
6.2. Dehydration reactions
The intramolecular dehydration of alcohols is efciently
catalyzed by both Al(III) as well as H1-exchanged clays.38
Primary alcohols afford mainly dialkyl ethers with little
alkene production whereas secondary and tertiary alcohols
provide alkenes almost exclusively (Scheme 4).
Scheme 3.
Scheme 4.
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Scheme 6.
Scheme 7.
for the ortho-isomer can be as high as 93% (Cu21 montmorillonite) and as low as 65% (H1 montmorillonite).
Scheme 8.
Scheme 10.
Pillared clays are commonly employed in alkane isomerizations.46 As an example, Fries rearrangement can be used
to prepare alkyl aryl ketones. Clays as well as their various
cation-exchanged forms efciently catalyze the Fries
rearrangement of phenyl as well as naphthyl esters (acetates,
benzoates and sulfonates).47 The nature of the product
depends on the size of the leaving group and is more
pronounced with phenyl esters. Cation-exchanged
montmorillonites are used as effective catalysts for the
facile rearrangement of phenyl toluene-para-sulfonate to
give 2- and 4-hydroxyphenyl-4-tolylsulfones.48 Selectivity
Scheme 9.
1241
Scheme 11.
Scheme 12.
Scheme 13.
1242
Scheme 14.
7. Basic clays
Surface acidity of clays can be reduced substantially by
introducing silylpropylethylenediamine. These modied
clays are weakly basic and can be employed for base-catalyzed reactions such as Knoevenagel condensation.70
Nucleophilic substitution reactions using quaternary ammonium salts-exchanged montmorillonite71 and other claysurfactants composites are also reported.72
The known efciency of surfactant-pillared clays to act as a
dispersed solid phase in a triphasic catalyst system72
prompted us to prepare modied clays by introducing
3-aminopropyl-triethoxysilane and surfactants into the
clay interlayer. We have extended the use of these
organo-clay assemblies in some useful organic transformations. As an example, benzyl cyanides, thiocyanides and
alcohols are easily accessible from the corresponding
Scheme 15.
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Scheme 16.
Scheme 17.
Table 1. Clay-catalyzed synthesis of imines using microwaves
R
C6H5
C6H5
C6H5
C6H5
C6H5
R0
Yield (%)
C6H5
p-HOC6H4
o-HOC6H4
p-Me2NC6H4
p-MeOC6H4
98
95
96
96
97
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Scheme 18.
Table 2. Clay-catalyzed synthesis of enamines using microwaves
Ketone
Cyclohexanone
Cyclohexanone
Cyclohexanone
2-Methylcyclohexanone
Cyclopentanone
Amine
Yield (%)
Time (min)
Morpholine
Piperidine
Pyrrolidine
Pyrrolidine
Piperidine
97
95
95
75
96
8
8
6
12
8
Scheme 19.
Table 3. EPZGw catalyzed synthesis of imines using microwaves
R
Time (min)
Hydrogen
o-Hydroxy
p-Hydroxy
p-Methyl
p-Dimethylamino
p-Methoxy
1.0
1.0
3.0
2.5
3.0
2.5
Yield (%)
97
92
91
90
96
95
Cyclohexanone
Cyclohexanone
Cyclohexanone
Cyclopentanone
Cyclopentanone
Scheme 20.
Ketone
Amine
Yield (%)
Morpholine
Piperidine
Pyrrolidine
Piperidine
Morpholine
96
90
94
93
94
Scheme 21.
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1
2
3
4
5
6
7
8
9
R0
CH2Cl2
MW (solventless)
Time (h)
Yield (%)
Time (s)
Yield (%)
16
12
18
18
20
23
24
11
12
84
83
88
90
72
84
10
78
79
30
R.T.
30
15
60
60
60
R.T.
60
89
86
90
91
75
85
15
81
83
(CH3)2CH
(CH3)2 CH
C4H9
C4H9
C12H25
CH3
C6H5
CH3
C6H5
C6H5
C6H5
C6H5CH2
C6H5CH2
C6H5CH2
Tetrahydrothiophene
Tetrahydrothiopyran4-one
Scheme 22.
Table 6. Oxidation of alcohols by clayfen under microwave irradiation
R
R0
H
C6H5
C6H5
CH2CH3
C6H5CO
C6H5
H
p-CH3C6H4
H
p-CH3OC6H4
p-CH3OC6H4
p-CH3OC6H4CO
H
Tetrahydrofurfuryl
(CH2)5
Time (s)
Yields (%)
15
30
60
15
60
30
30
92
87
93
94
96
94
90
89
Scheme 23.
Table 7. Oxidation of organic substrates by claycop and hydrogen peroxide
R
R0
R 00
Ph
H
COOH
Ph
Ph
COOH
Ph
H
CN
Ph
H
NH2
Ph
H
Br
H
H
p-NO2 Ph
Hydroquinone
Triphenylphosphine
Mole ratio
1:0.8:1
1:0.8:1
1:1.6:2
1:0.8:1
1:0.8:1
1:1.6:2
1:0.8:1
1:0.8:1
Time (s)
Yield (%)
60
90
45
30
30
90
30
15
83
82
80
76
75
69
71
85
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Scheme 24.
Table 8. Reductive amination of carbonyl compounds using K 10 clay supported NaBH4
Entry
Amines
Carbonyl compounds
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Aniline
n-Heptylamine
Tyramine
Aniline
p-Nitroaniline
Aniline
o-Aminophenol
Aniline
p-Aminophenol
Aniline
p-Chloroaniline
Aniline
Aniline
n-Decylamine
3,4-Dimethoxy phenethylamine
Aniline
Benzylamine
Aniline
Benzylamine
Propylamine
Benzylamine
22
23
24
Aniline
Morpholine
Piperidine
Benzaldehyde
Benzaldehyde
Benzaldehyde
Salicylaldehyde
Salicylaldehyde
p-Chlorobenzaldehyde
p-Chlorobenzaldehyde
p-Anisaldehyde
p-Anisaldehyde
p-Nitrobenzaldehyde
3,4-Dimethoxybenzaldehyde
Isobutyraldehyde
2-Ethylbutyraldehyde
2-Ethylbutyraldehyde
Pyrrole-2 carboxyldehyde
Acetophenone
Acetophenone
Cyclohexanone
4-Methylcyclohexanone
Cycloheptanone
1,4-Cyclohexanedione
monoethylene ketal
3-Pentanone
2-Heptanone
2-Heptanone
Timea (min)
Yield (%)
R.T.
R.T.
1.50
R.T.
1.00
0.50
0.75
0.25
0.75
1.25
0.50
1.00
0.75
1.50
1.50
1.50
2.00
1.00
2.00
0.75
1.50
97
94
90
96
88
90
84
93
81
78
91
78
87
86
81
92
66
89
85
79
91
1.00
2.00
2.00
83
81
78
Time for the reduction of in situ generated Schiff's bases in microwave oven; R.T. refers to the reductions at room temperature that are completed on simple
mixing of the Schiff's base with NaBH4 wet clay.
Scheme 25.
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Table 9. Cleavage of semicarbazones and phenylhydrazones with ammonium persulfate and clay using microwave or ultrasonic irradiation
R
R1
R2
Ultrasound
Time (h)
CONH2
CONH2
CONH2
CONH2
CONH2
CONH2
CONH2
CONH2
C6H5
C6H5
CONH2
C6H5
p-ClC6H4
p-OHC6H4
p-MeC6H4
p-OMeC6H4
p-NH2 C6H4
p-OMeC6H4CH2CH2
CH3CH2CH2CH2
C6H5
CH3CH2CH2CH2
Cyclohexyl
Me
Me
Me
Me
Me
Me
Me
Et
Me
Et
0.75
3.00
1.00
3.00
3.00
1.50
3.00
2.50
1.50
1.00
1.50
generated Schiff's base is mixed thoroughly with premoistened and freshly prepared NaBH4 clay and reaction
mixture is irradiated further for 30 s (658C). Upon completion of the reaction, monitored by TLC, the product is
extracted into an organic solvent and the solvent is removed
under reduced pressure to afford the amine derivative.
8.7. One-pot conversion of aromatic aldehydes to nitriles
using hydroxylamineclay
Aldehyde to nitrile conversion is a useful chemical transformation.127130 In most cases, the aldoxime is prepared
rst and then dehydrated using a wide variety of reagents
such as chloramine/base,131 O,N-bis-(triuoroacetyl)hydroxylamine or triuoroacetohydroximic acid,132 triethylamine/
dialkyl hydrogen phosphinates,133 p-chlorophenyl chlorothionoformate/pyridine,134 TiCl4/pyridine,135 and triethylamine/phosphonitrilic chloride.136
The dehydration of an aldoxime generally proceeds at a
much slower rate requiring long reaction times in most of
the conventional methods: e.g. montmorillonite KSF
(1108C, 1319 h)137 or elevated temperatures: e.g. zeolite
(3508C).138 Montmorillonite K 10 clay supported hydroxylamine hydrochloride provides a facile conversion of aldehydes to nitriles (8995%) under solvent-free conditions
upon brief exposure to microwaves (Scheme 25).139
8.8. Cleavage of semicarbazones and phenylhydrazones
with ammonium persulfateclay
Semicarbazones and hydrazones are important derivatives
Scheme 26.
Microwave
Yield (%)
Time (min)
77
90
94
68
88
62
71
79
82
71
69
0.6
1.8
1.0
2.0
0.9
1.0
1.6
1.3
0.5
1.3
0.7
Yield (%)
72
82
85
69
78
65
75
70
71
65
68
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Scheme 27.
Scheme 28.
Scheme 29.
Table 10. Product distribution in solventless nitration of styrenes with
clayfen and clayan
Substrate
Yields (%)
b-Nitrostyrene
Aldehyde
Polymer/others
With clayfen
Styrene
p-Methylstyrene
p-Methoxystyrene
p-Chlorostyrene
68(56)
52(41)
14(14)
52(41)
21(35)
11(24)
09(15)
10(22)
11(09)
37(35)
77(71)
38(37)
With clayan
Styrene
p-Methylstyrene
p-Methoxystyrene
p-Chlorostyrene
59(47)
44(35)
13(12)
49(37)
20(35)
15(26)
12(15)
11(23)
21(18)
41(39)
75(73)
40(40)
Scheme 30.
Bosch et al. have accomplished the Beckmann rearrangement of ketoximes with montmorillonite K 10 clay in `dry'
media in good yields (Scheme 31).180
Scheme 31.
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Scheme 32.
Scheme 33.
Scheme 34.
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Scheme 35.
Scheme 36.
Scheme 37.
Scheme 38.
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Scheme 39.
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83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
139.
140.
141.
142.
143.
144.
145.
146.
147.
148.
149.
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Rajender (Raj) Varma was born in India and obtained his Ph.D. from
Delhi University in 1976. After postdoctoral research at Robert Robinson
Laboratories, University of Liverpool, UK, he was the faculty member at
Baylor College of Medicine, Senior Scientist at Houston Advanced
Research Center and Research Professor at Sam Houston State University
in Texas prior to joining the Clean Processes Branch at National Risk
Management Research Laboratory, US EPA in 1999. He has over 25
years of research experience in management of multi-disciplinary research
programs ranging from natural products chemistry, pulp and paper technology and therapeutics, to development of genosensor technology,
specically the applications and interface of chemical science with biology,
solid state chemistry, bioelectronics, and development of environmentally
friendlier alternatives for synthetic methods using supported reagents,
molten salts, microwaves, ultrasound etc. The primary focus of his research
at EPA is to evaluate novel and safer environmental protocols in industrial
chemistry and its impact in human health and environmental sciences. He
has published over 175 scientic peer-reviewed papers and has been
awarded six US patents. He enjoys reading and jogging.
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