K-10 and KSF clays as green and recyclable heterogeneous catalysts for the Cannizzaro reaction using DABCO under MWI and solvent-free conditions

Article abstract of DOI:10.13005/ojc/320140

Montmorillonite K-10 and KSF clays as recyclable and heterogeneous catalysts are used to catalyze the Cannizzaro reaction by 1,4-diazabicyclo [2.2.2]octane (DABCO) under microwave irradiation (MWI) and solvent-free conditions in excellent yields within seconds. The solid clays applied in the first cycle are recovered and reused in the subsequent reactions.

Full text of DOI:10.13005/ojc/320140

ISSN: 0970-020 X
CODEN: OJCHEG
2016, Vol. 32, No. (1):
Pg. 359-365
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
K-10 and KSF Clays as Green and Recyclable Heterogeneous
Catalysts for the Cannizzaro Reaction Using DABCO under
MWI and Solvent-free Conditions
OMID MARVI* and MARYAM TALAKOUBI
1Department of Chemistry, Payam Noor University, PO Box 19395-3697 Tehran, Iran.
*Corresponding Author E-mail: omid_marvi@pnu.ac.ir
http://dx.doi.org/10.13005/ojc/320140
Received: January 11, 2016; Accepted: February 26, 2016
ABSTRACT
Montmorillonite K-10 and KSF clays as recyclable and heterogeneous catalysts are used
to catalyze the Cannizzaro reaction by 1,4-diazabicyclo[2.2.2]octane (DABCO) under microwave
irradiation (MWI) and solvent-free conditions in excellent yields within seconds. The solid clays
applied in the first cycle are recovered and reused in the subsequent reactions.
Keywords: Cannizzaro; DABCO; MWI ; KSF and K-10 clays
INTRODUCTION
reaction,3b,6gas-phase process,8and Lewis acid
catalysis.9 In a few examples conducted at room
temperature, strong basic media are still required7,10
or yields of the majority of the reactions are rather
low or moderate.9c Despite all of these modifications,
the reaction still requires drastic conditions in most
cases.
The redox disproportionative conversion
of aldehydes into their corresponding alcohols
and carboxylic acids, known as Cannizzaro
reaction1,is one of the oldest processes in synthetic
organic chemistry and is classically conducted at
elevated temperatures using equimolar or excessive
amounts of alkali metal hydroxides or other strong
bases. Such harsh conditions and competitive
formation of undesired side products have been
the main limitations for Cannizzaro reaction in
the past several decades.2Many developments
have been made to the original version of the
reaction in the past several years by means of
microwave irradiation,3ultrasound mediation,4cation
templates,5solid-supported reagents,6solvent-free
conditions,7 crossed Cannizzaro version of the
Natural alumosilicates, such as zeolites and
clays, are solid acids that could act as an efficient
alternative to liquid acids. Natural and modified
clays have attracted attention due to their extremely
versatile properties and high potential in green
chemistry. Though the physicochemical properties
of the clays are similar their BET surface areas differ.
K-10 Has a higher surface area (about 250 m2 /g1)
compared to that of KSF (10 m2/g1).11

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MARVI & TALAKOUBI, Orient. J. Chem., Vol. 32(1), 359-365 (2016)
The combined use of montmorillonites The mechanism of this reaction is well
and microwave irradiation (MWI) showed rate known and is described as below (Scheme 2).
enhancements, high yields and short reaction times. Here, we only emphasize minor differences and
In addition, the use of solvent- free conditions with advantages that are due to the use of solid catalysis.
heterogeneous media under microwave irradiation is As this reaction is carried out in a solvent-free, open
a useful alternative and has received considerable reaction system, the key step is the adsorption
attention due to its greater efficiency from economic of the carbonyl compound on the surface of the
as well as ecological points of view.12
catalyst.Montmorillonite is considered to be a mixed
Brønsted-Lewis solid acid. The majority of the acid
Recently, use of nonmetallic reagents is an centers are of Lewis acid type.17The adsorption
area of growing interest because of environmental occurs when the electron rich carbonyl oxygen
regulations. Among the various organic bases,1,4- interacts with a surface Lewis acid center, and it is
diazabicyclo[2,2,2]octane (DABCO) has been of rather chemical than physical nature. This Lewis
employed as an efficient organic base to bring about acid–base interaction anchors the aldehyde and
various organic transformations.13-15
initiates strong electrophilic character on the carbonyl
In continuation of ongoing investigations carbon, resulting in a surface-bound intermediate of
exploring the use of montmorillonites as solid carbocationic nature.
supports in the synthesis and reactivity of organic
compounds using microwave irradiation,16this
work reports a simple, green and environmentally
acceptable microwave promoted the Cannizzaro
ExpERIMENTAL
Chemicals were purchased from Aldrich
reaction by DABCO over K-10 and KSF clays as and Merck chemical companies and used without
efficient heterogeneous catalysts (Scheme 1). The further purification.Montmorillonite KSF clay, surface
solid clays can be recovered later and reused in the area 15 10 m2/g, chemical composition (average
subsequent reactions. Details of recyclability of the value): SiO2 (54.0%), Al2O3 (17.0%), Fe2O3 (5.2%),
recovered clays have been shown in the Table 1.
CaO (1.5%), MgO (2.5%), Na2O (0.4%), K2O (1.5%)
and montmorillonite K10 clay,surface area:(200 10)
Results summarized in the Table indicate m2/g, chemical composition (average value): SiO2
the scope and generality of the reaction with respect (73.0%), Al2O3 (14.0%), Fe2O3 (2.7%), CaO (0.2%),
to the various benzaldehydes. The nature of the MgO (1.1%), Na2O (0.6%), K2O (1.9%) were
substituents on the aromatic ring of benzaldehyde purchased from Fluka chemical company. Melting
has different influences.The presence of the electron points were measured on an Electro thermal 9100
1
withdrawing groups such as nitro and fluorine which apparatus. H NMR and 13CNMR spectra were
increase the polarity of the carbonyl group inductively, recorded by a FTNMR BRUKER DRX 500 Avence
1
give high yields of products as well as the short spectrometer (500 MHz for H NMR and 125 MHz
reaction time compared to the electron donating for 13C NMR).Chemical shifts were measured in
groups like methyl and methoxy. On the other hand, ppm from TMS. DMSO-d6 was used as solvent as
the percentage of the products obtained by the well as the internal standard. Physical and spectral
K-10 clay is more than those prepared by the KSF data of the synthesized compounds are given in the
clay. This observation can be attributed to the more Supplementary material to this paper. Microwave
surface area in K-10.
irradiations were realized with a Synthewave 402®
Scheme 1: Solvent-free Cannizzaro reaction by DABCO on KSF and K-10 clays and MWI.

MARVI & TALAKOUBI, Orient. J. Chem., Vol. 32(1), 359-365 (2016)
361
Table 1:The yields and reaction times for the solvent-free Cannizzaro
reaction by DABCO on KSF and K-10 clays under MWI
Entry
Aldehyde
Acida
Yield (%)b
K10/KSF
Time (s)
1
95(91)/92(89)
30
2
3
4
94(92)/92(88)
96(93)/94(90)
98(94)/94(89)
30
15
20
5
98(96)/95(90)
15
6
7
8
91(88)/90(85)
97(94)/94(90)
94(90)/91(86)
40
20
30
9
88(84)/87(82)
95(92)/92(86)
40
30
10
11
12
96(85)/91(87)
96(93)/94(90)
15
20
a All the benzoic acid derivatives are well known compounds (literature and/ or commercial sources).
b Yields are based on isolated acids. Yield of alcohols was almost the same as acid in each case. Yields indicated in the
parenthesis correspond to those reactions which the recovered clays were used. The fresh solid clay portion applied in the first
cycle was filtered off at the end of reaction, washed with methanol (2×30 mL) and dried at 120 °C under the reduced pressure
to be reused in the subsequent reaction.

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MARVI & TALAKOUBI, Orient. J. Chem., Vol. 32(1), 359-365 (2016)
(Prolabo, France) single mode focused microwave (d, 1JC–F = 254.2 Hz), 132.47 (d, 3JC–F = 9.6 Hz), 125.54
reactor.18
(d, 4JC–F = 3.4 Hz), 115.63 (d, 2JC–F = 22.35 Hz).
General procedure
3-Nitrobenzoic acid (entry 4)
In a 50 mL beaker, aldehyde (1 mmol)
m.p.140-143 °C;1H NMR (500MHz, DMSO-
was roughly mixed with 1 g montmorillonite. After 2 d6, d/ ppm): 8.11 (s, 1H), 8.02 (d,J= 7.7 Hz, 1H), 7.98
min of mechanical stirring, DABCO (10 mmol) was (d, J= 7.8 Hz, 1H), 7.65 (d,J= 7.8 Hz, 1H), 7.59 (t, J
added and then mixture was submitted into a single =7.7 Hz, 1H) ppm. 13CNMR (125MHz, DMSO-d6, d/
mode focused microwave reactor with continuous ppm):174.21(COOH), 137.57 (CNO2), 131.96 (C4),
rotation for the time described in Table 1 (optimized 131.29 (CCOOH), 129.76 (C6), 129.98 (C3), 128.28
time) at 40 °C. After completing the reaction (TLC), (C5) ppm.
water (30 mL) was added to the mixture ,the product
was washed by CH2Cl2 (2×10 mL), clay was filtered, 4-Nitrobenzoic acid (entry 5)
and the solvent was evaporated to give the alcohol
m.p. 239-243 °C; 1H NMR (500MHz,
component. To obtain the acid component, the DMSO-d6, d/ ppm): 8.12 (2H, d, J = 8.1 Hz, aromatic),
filtrate was acidified, extracted with CH2Cl2, and 7.65 (2H, d, J = 8.1 Hz, aromatic);13C NMR (125MHz,
dried over magnesium sulphate. Then the solvent DMSO-d6, d/ppm): 169.21 (COOH), 141.13 (CNO2),
was evaporated to givethe acid component.The 131.54 (C2), 129.18 (CCOOH), 128.34 (C3).
solid clay portion was washed with methanol and
dried at 120 °C under a reduced pressure to be 4-Methylbenzoic acid (entry 6)
reused in the subsequent reactions which showed
the gradual decrease in the activity (Table 1). The d6, d/ ppm): 8.18 (2H, d, J = 8.2 Hz, aromatic), 7.23
filtrate was dried over MgSO4, the organic solvent (2H, d, J = 8.5 Hz, aromatic), 2.54 (3H, s, CH3); 13
m.p.181-184 °C;1H NMR (500MHz, DMSO-
C
was evaporated, and aryl alcohol was obtained. NMR (125MHz, DMSO-d6, d/ppm): 175.13 (COOH),
Isolated products were characterized by melting 152.95 (CCH3), 134.36 (C2), 123.47 (CCOOH),
1
points, HNMR and 13C NMR spectrometric data 121.56 (CCOCH3), 31.92 (CH3) .
and were compared with the literature and/or with
authentic samples.
4-Nitrobenzoic acid (entry 7)
m.p.142-145 °C;1H NMR (500MHz, DMSO-
Spectroscopic and analytical data
Benzoic acid (entry 1)
d6, d/ ppm): 8.12 (1H, d, J = 8.0 Hz, CHCCOOH),
7.49–7.41 (2H, m, aromatic) 7.39–7.22 (1H,
m.p.120-121 °C;1H NMR (500MHz, DMSO- m, CNO2CH); 13CNMR (125MHz, DMSO-d6, d/
d6, d/ ppm): 8.15 (2H, dd, J = 8.1, 1.3 Hz, ortho), ppm):176.59(COOH), 142.83(CNO2), 135.48(C4),
7.49 (2H, t, J = 7.2 Hz, meta), 7.38 (1H, t, J = 8.1 132.77 (CCOOH), 131.91 (C6), 129.18 (C3), 127.86
Hz, para); 13C NMR (125MHz, DMSO-d6, d/ ppm): (C5).
172.54 (COOH), 134.76 (C4), 133.42 (C2), 131.26
(C1), 129.77 (C3).
3-Chlorobenzoic acid (entry 8)
m.p.151-155 °C;1H NMR (500MHz, DMSO-
d6, d/ ppm): 8.09 (s, 1H), 7.93 (d,J= 7.8 Hz, 1H), 7.96
4-Bromobenzoic acid (entry 2)
m.p.151-152 °C;1H NMR(500MHz, DMSO- (d, J= 7.8 Hz, 1H), 7.59 (d,J= 7.9 Hz, 1H), 7.43 (t,
d6, d/ ppm): 7.91 (2H, d, J = 8.2 Hz, aromatic), J =7.7 Hz, 1H) ppm. 13CNMR (125MHz, DMSO-d6,
7.48(2H, d, J = 8.4 Hz, aromatic);13C NMR (125MHz, d/ppm):173.45(COOH), 135.21(CCl), 131.96 (C4),
DMSO-d6, d/ppm): 167.54 (COOH), 131.09 (C2), 130.48 (CCOOH), 129.94 (C6),129.73 (C3), 128.62
130.49 (C3), 129.65 (CCOOH), 127.43(CBr).
(C5) ppm.
4-Fluorobenzoic acid(entry 3)
4-Methoxybenzoic acid (entry 9)
m.p. 184-186 °C;1H NMR(500MHz, DMSO-
m.p.181-183 °C;1H NMR(500MHz, DMSO-
d6, d/ ppm): 8.19 (2H, t, 3J H–H = 7.8 Hz, aromatic), d6, d/ ppm): 8.02 (2H, d, J = 8.5 Hz, aromatic), 7.11
2
7.11 (2H, d, JH–H = 8.2 Hz, aromatic); 13C NMR (2H, d, J = 8.6 Hz, aromatic), 3.78 (3H, s, CH3); 13
C
(125MHz, DMSO-d6, d/ppm):171.12 (COOH), 167.15 NMR (125MHz, DMSO-d6, d/ppm): 171.55 (COOH),

MARVI & TALAKOUBI, Orient. J. Chem., Vol. 32(1), 359-365 (2016)
363
Scheme 2: possible mechanism for Cannizzaro reactionby DABCO over clay under MWI.
163.67 (COCH3), 133.72 (C2), 121.54 (CCOOH),
114.57 (CCOCH3), 55.38 (CH3) .
2-Chlorobenzoic acid (entry 12)
m.p. 238-240 °C;1H NMR(500MHz, DMSO-
d6, d/ ppm): 8.08 (2H, d, J = 8.2 Hz, aromatic), 7.54
(2H, d, J = 8.3 Hz, aromatic); 13C NMR (125MHz,
DMSO-d6, d/ppm): 168.08 (COOH), 138.57(CCl),
130.49(C2), 128.65(CCOOH), 127.81(C3).
4-Chlorobenzoic acid(entry 10)
m.p. 139-142 °C; 1H NMR (500MHz,
DMSO-d6, d/ ppm): 8.07 (1H, d, J = 8.2 Hz,
CHCCOOH), 7.42–7.38 (2H, m, aromatic) 7.35–7.29
(1H, m, CClCH); 13CNMR (125MHz, DMSO-d6, d/
ppm):172.21(COOH), 135.93(CCl), 133.59(C4),
132.28 (CCOOH), 131.75 (C6), 128.43 (C3), 126.81
(C5).
In conclusion, a simple and efficient
procedure for the clay catalyzed Cannizzaro reaction
in the presence of 1,4-diazabicyclo[2.2.2]octane
(DABCO)under MW irradiation and solvent-free
conditions was established. This present method is
superior since it is eco-friendly, advantageous over
previously described methods in yield, requires no
special apparatus, there is simplicity of operation,
and is non-hazardous, simple and convenient.
In addition, the simple experimental and product
isolation procedures combined with the easy
recovery and reuse of these worthwhile natural clays
play an important role in development of the clean
and environmentally friendly strategy in this new and
benign method.
2-Fluorobenzoic acid (entry 11)
m.p. 123-124 °C; 1H NMR(500MHz,
DMSO-d6, d/ ppm): 8.09 (1H, d, J= 8.0 Hz ,
CHCCOOH) , 7.55 (1H, m, CFCH), 7.28–7.19 (2H,
m, aromatic);13CNMR (125MHz, DMSO-d6, d/ppm):
170.12(COOH), 163.65 (d, 1JC–F = 261.2 Hz), 134.72
(d, 3JC–F = 9.4 Hz), 131.67(C6), 124.38 (d, 3JC–F = 2.5
Hz), 117.53 (d, 2JC–F = 10.28 Hz), 117.12 (d, 2JC–F
=
21.98 Hz).

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364
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