International Review of Chemical Engineering (I.RE.CH.E.), Vol. 4, N. 6
ISSN 2035-1755
November 2012
Special Section on 4th CEAM 2012 - Virtual Forum
A Facile Solvent-Free Skraup Cyclization Reaction
for Synthesis of 2, 2, 4-trimethyl-1, 2-dihydroquinoline
Ganapati D. Yadav, Rahul P. Kumbhar, Saumydeep Helder
Abstract – An optimized and efficient process has been found to synthesize 2, 2, 4-Trimethyl-1, 2dihydroquinoline from an acid- catalyzed Skraup Cyclization of acetone and aniline. Polyhedral
oligomeric silsesquioxane functionalized with sulfonic acid group [POSS-SO3H] used as an acid
catalyst, synthesized by self-assembly of silane precursor was used. Different characterization of
POSS-SO3H using TPD, SEM, XRD, TGA and FT-IR was carried out. The comparative study of
the effect of reaction parameters such as speed of agitation, mole ratio, catalyst loading and
temperature was analyzed to obtain maximum conversion. Copyright © 2012 Praise Worthy Prize
S.r.l. - All rights reserved.
Keywords: Solid Acid Catalyst, POSS, Skraup Cyclization, 2, 2, 4-Trimethyl-1, 2Dihydroquinoline, Langmuir-Hinshelwood-Hougen-Watson Mechanism
years due to its widespread availability and enhanced
biological activity [2]-[4]. Many derivatives of 2,2,4trisubstituted-1,2-dihydroquinolines are known to exhibit
a wide range of pharmacological properties such as
bactericidal[5], anti-diabetic[6], anti-inflammatory[7],
anti-malarial[8], lipid per-oxidation inhibitors[9],
progesterone-agonists[10]
and
antagonists[11].
Furthermore, the utility of 2, 2, 4-trimethyl-1, 2dihydroquinolines as antioxidants for rubber and polyolefins, feed additives, dyes, and pharmaceuticals is also
well-recognized [12]-[19]. Its polymeric form i.e. Rubber
Anti-oxidant RD is mainly used for natural rubber and
chloroprene rubber etc. It has stronger restrained effect to
the metallic catalysis and oxidation. It has a longer-time
remaining of protective effect, because it has a higher
molecular weight and has little diffusive loss [20].
Silica [21] is commonly used as a catalyst support
since it can withstand extensive 3D network structures.
One class of silicones is silsesquioxanes [22] i.e.
silicones with a Si: O ratio of 1:1.5. These structures are
called polyhedral oligomeric silsesquioxanes or POSS
with a general formula of [RSiO1.5]n (see Fig. 1).
Polyhedral oligomeric silsesquioxanes (POSS) are
thermally robust cages consisting of a silicon–oxygen
core framework possessing alkyl functionality on the
periphery [22]-[29]; they are used for the development of
high performance materials in medical, aerospace, and
commercial applications [30]. POSS molecules can be
functionally tuned, are easily synthesized with inherent
functionality, are discreetly nano-sized, and are often
commercially available.
In this system, POSS crystals have been effectively
synthesized by the process of self-assembly.
Functionalization of POSS [31]-[35] was carried out so
as to impregnate acidic sites, and was then characterized
by
several
techniques
including
Temperature
Nomenclature
A
B
C
CA
CB
CC
Cs
Ct
CW
Ea
K
k
K’
KA
KB
KC
KW
M
rA
W
w
X
Acetone
Aniline
2, 2, 4-Trimethyl-1, 2-dihydroquinoline
Concentration of acetone (mol/cm3)
Concentration of aniline (mol/cm3)
Concentration of 2, 2, 4-Trimethyl-1, 2dihydroquinoline (mol/cm3)
Concentration of vacant sites (mol/ g catalyst)
Total concentration of sites (mol/ g catalyst)
Concentration of water (mol/cm3)
Activation energy (kcal/mol)
Forward rate constant for cyclization reaction
Effective rate constant for cyclization reaction
Backward rate constant for cyclization reaction
Adsorption equilibrium constant for A
Adsorption equilibrium constant for B
Adsorption equilibrium constant for C
Adsorption equilibrium constant for W
Molar ratio of acetone to aniline
Rate of reaction w. r. t. A (mol/cm3 min g
catalyst)
Water
Catalyst loading (g/cm3)
Fractional conversion
I.
Introduction
The increasing chemical pollution in the recent
decades has escalated the demand for extensive and
effective implementation of green chemistry. Catalysis
plays a pivotal role in green chemistry and waste
minimization [1]. The synthesis of dihydroquinolines and
their derivatives have been the focus of prolonged
interest among organic and medicinal chemists for many
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597
Ganapati D. Yadav, Rahul P. Kumbhar, Saumydeep Helder
Programmable Desorption (TPD), X-Ray Diffraction
(XRD),
Fourier
Transform
Infrared
(FT-IR)
Spectroscopy, Thermo Gravimetric Analysis (TGA) and
Scanning Electron Microscopy (SEM).
II.2.
II.2.1. Synthesis of mercaptopropyl polyhedral
oligomeric silsesquioxane (POSS-SH)
Silane precursor (3-mercaptopropyl trimethoxy silane)
was hydrolyzed using aqueous ammonia solution which
performs as a catalyst, in the presence of ethanol as
solvent. The reaction mixture was stirred at room
temperature (30oC) for 48 h [23]. Initially, the reaction
concoction was transparent indicating complete
dissolution of silane monomers. After 2 hours of the
reaction as the hydrolysis and condensation reaction
proceeded, the mixture became opaque indicating the
formation of colloidal particles. The product started to
precipitate from the suspension in duration of stirring.
Finally, the reaction concoction with almost clear
supernatant was obtained after 48 hour. The precipitate
obtained was filtered, washed and dried in an oven for 4
h at 60oC.
Fig. 1. Basic structure of POSS, R-hydrogen/alkyl/alkylene/aryl/arylene
Among the most general approaches for the synthesis
of such dihydroquinolines is Skraup cyclization which
involves the heating a mixture of nitro-ethane, aniline,
and glycerol with concentrated sulfuric acid [36].
Doebner and Von Miller modified this procedure by
using an alpha and beta unsaturated ketone with an
aromatic amine by heating in the presence of acid
catalyst or iodine [37]. Over the last century, a number of
other methods have been made to improve the yields and
reproducibility of Skraup cyclization involving a variety
of catalysts [38]. However, in spite of the potential
utility, some of these methods suffer from drawbacks
including the use of unavailable and costly reagents,
higher temperature, longer reaction times, lower yields
and the use of hazardous solvents. Another important
issue is that most of these procedures involve either
conventional heating or microwave-irradiation
On studying the various solvent-free reactions, [39][45], we would like to put forward a POSS-SO3H acidcatalysed reaction for the synthesis of 2, 2, 4trisubstituted-1,
2-dihydroquinolines
at
different
temperature under solvent-free conditions. It involves the
formation of a self-aldol condensation product which
attacks aniline to form the desired quinoline. In this
study, the reaction kinetics of POSS-SO3H catalyzed
Skraup cyclization reaction (Fig. 1) of aniline with
propan-2-one has been examined to synthesize 2, 2, 4trimethyll-1, 2 di-hydroquinoline.
II.
II.2.2. Oxidation of POSS-SH to sulfonic acid POSS
(POSS-SO3H)
Excess amount of 30% hydrogen peroxide solution,
required for complete oxidation were added to the
precipitate with methanol as solvent, stirred in a
magnetic stirrer for 4 h [46]-[50]. The final product was
filter out using methanol solvent and dried. In order to
ensure that all the sulfonic groups were protonated, the
solid was suspended in a 10 wt% H2SO4 (~100 ml)
solution for 1 h. The solid was then filtered off and
washed with water and it was then dried in an oven for 4
at 60oC.
II.3.
Catalyst Characterization
For characterization of catalyst, the Fourier Transform
Infrared (FT-IR) Spectroscopy was done on Perkin Elmer
Spectrum GX, in the scan range of 4000 cm-1 and 600
cm-1. XRD was obtained by a Rigaku Miniflex X-Ray
Diffractometer and was used to confirm the crystalline
structure. Thermal stability was determined by DSCTGA using a Perkin Elmer Pyris Diamond TG/DTA. The
surface morphology was studied by using JEOL JSM
6380LA analytical Scanning Electron Microscopy (SEM)
and elemental analysis was done by using Energy
Dispersive X-ray Spectroscopy (EDXS) (JEOL JSM
6380LA Analytical scanning Microscope). To determine
the acidic/basic character, Temperature Programmable
Desorption (TPD) was done on a Micromeritics 2920
TPD/TPR Analyzer
Experimental
II.1.
Catalyst Preparation
Materials
II.4.
3-mercaptoproyl trimethoxy silane (3-MPTS)
precursor were obtained from Fluka, USA; sulfuric acid,
hydrogen peroxide, methanol, ethanol, aniline, acetone ,
toluene, n-dodecane, aqueous ammonia solution, were
obtained from M/s. S. D. Fine Chemicals, Mumbai, India
and use of analytical grade.
Reaction Procedure
The reaction as depicted in the scheme 1 was carried
out at different reaction conditions in a laboratory
autoclave. The reaction parameters were optimized to
determine the optimum speed of agitation, molar ratio of
reactants, catalyst loading and temperature.
Copyright © 2012 Praise Worthy Prize S.r.l. - All rights reserved
International Review of Chemical Engineering, Vol. 4, N. 6
Special Section on 4th CEAM 2012 - Virtual Forum
598
Ganapatii D. Yadav, Raahul P. Kumbh
har, Saumydeeep Helder
II.5.
all the MPTMS--functionalizeed materials. The sampless
with
hout pore direecting agent shhowed no refl
flection peaks,,
indiicating (see Fig.
F
3) no loong range ord
dering of thee
messopores in theese materials bby the templaate-free route..
Thiss is in contraast to functionnalized SBA-- 15 samples,,
which have onee intense peaak and two weak peaks,,
m
withh
indeexed to diffraactions, charaacteristic of materials
ordeered hexagonnal arrays of one dimensiional channell
stru
ucture [61].
Metthod of Analyssis
The analyysis was carrieed out by GC
C (Chemito model
m
1000, FID detector)
d
usinng a BPX50 capillary collumn
(0.22 mm ×330 m). The product
p
conforrmation was done
d
by using GC
C–MS (QP20010 GCMS, Shimadzu reestek,
phase: Rtxwaax, length 30 m,
m 0.25 mm I.D., 0.25 µm).
IIII. Resultt and Discu
ussion
I
III.1.
Catalysst Characterizzation
III.1.1. Fourier Traansform Infrarred (FT-IR)
S
Spectroscopy
Qualitativve identificatiion of the organic
o
functiional
groups in the materialls was perfoormed by FTIR
F
spectroscopyy. IR spectraa of the silanne monomer and
silane-based cubic crystals, two peaks at 2942 and 2927
2
cm-1 are obseerved (see Figg. 2), which can
c be assigneed to
C–H stretchhing vibrationns from proppyl and methhoxy
groups in thee silane monom
mer, respectivvely.
Fig. 3. XRD result
r
after functioonalization (POS
SS-SO3H)
XRD
X
pattern showed sharrp crystalline peaks at 2θθ
=10
0° and 25°, which
w
are in close agreem
ment with thee
literrature resultss for POSS structures [6
62]-[65] Thee
resu
ulting crystallline and am
morphous ph
hases in thee
syntthesize mateerials are deenoted as su
ulfonic acid-funcctionalized paartially crystaalline POSS material
m
[66]..
Thee X-ray powdder pattern of POSS show
ws two mainn
charracteristic difffraction peakks at 10o and 25o (2θ), thee
peak
ks at 10o (2θ),, is for the sizee of POSS mo
olecule.
Fig. 2. FT-IR spectra before (P
POSS-SH) and affter functionalizattion
(PO
OSS-SO3H)
III.1.3. Thhermo Gravimetric Analysiss (TGA)
For merrcaptopropyl-ttrimethoxysilaane-based cubic
c
crystals, thee asymmetric Si–O–Si strretching vibraation
bands were observed att 1128 cm-1 [51]-[53]. For a
work structuree, the Si–O–S
Si absorption peak
random netw
usually appears around 1050 to 1000 cm-1. More
M
evidence forr the cage strructure of cubbic crystals iss the
existence off a symmetricc Si–O–Si strretching vibraation
peak at 551 cm-1, which is
i the characteeristic feature of a
double ring from the cagge structure [51]. In addiition,
peaks at 693 cm-1 and 8433 cm-1 can bee assigned to Si–C
S
stretching vibrational
v
annd Si–(CH2)3 rocking moodes,
respectively [51]-[53]. Thhe spectrum clearly
c
showss the
symmetric sttretching’s off Si–O–Si peak at 770–1100
cm-1 which correspondss to the silssesquioxane cage
structure [544]-[59]. The small
s
peak at 2942 cm-1 caan be
attributed to the [(C–H)]] deformationn mode [60]. The
i assigned too the
wide and strrong band at 3450 cm-1 is
OH deformattion due to H2O.
Thermo
T
Gravim
metric Analyssis (TGA) rev
vealed that thee
cataalyst was theermally stablee up to a teemperature off
250oC, and the overlay of thhe plots befo
ore and afterr
funcctionalization indicates (seee Fig. 4) thee addition off
oxy
ygen atoms due to a reductioon in the therm
mal stability.
Itt is reasonable to concludde that the crrystallinity off
pseu
udo cubic pow
wders is slighttly lower than
n that of cubicc
crysstals [65]-[666]. The TGA
A curve for the sphericall
partticles from thee sol–gel proccess shows a quite
q
differentt
deco
omposition beehavior. The ssublimed cubic crystals lostt
their cubic morphhologies resultting in amorphous powder-like materials.
III.1.4. Scanning Eleectron Microsccopy (SEM)
and Ennergy Dispersiive X-Ray Speectroscopy
(ED
DXS)
Scanning
S
Elecctron Microsscopy (SEM) divulge thee
SEM
M images of sulfonic aacid functionalized POSS
S
materials, presennce of regular cubic shaped
d crystals afterr
funcctionalization,, whereas before fun
nctionalizationn
glob
bular aggregattes were preseent (see Figs. 5).
5
I
III.1.2.
X-rayy Diffraction (XRD)
(X
Powder X-ray
X
diffractioon analyses were
w
performeed on
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599
Ganapati D. Yadav, Rahul P. Kumbhar, Saumydeep Helder
were related to non acid-functionalized material. See Fig.
6(b), show NH3-TPD profile of POSS-SO3H, which is
functionalized material and two desorption peaks were
observed. The desorption peaks at 140oC –200oC
represent increase in the acid strength.
Fig. 4. XRD result after functionalization (POSS-SO3H)
(a)
Figs. 5. SEM images before (a) and after functionalization (b) of POSS
EDXS was done to confirm composition of sulphur,
silicon and oxygen in synthesized catalyst. Table I shows
sulfur (S), Silicon (Si) and Oxygen (O) contents in the
sulfonic acid-functionalized POSS samples obtained
from elemental analysis. The amount of S, Si and O
present in the un-functionalized POSS samples was
relatively low as compared to functionalized POSS
(b)
Figs. 6. TPD analysis of POSS before (a) and after functionalization (b)
TABLE I
ELEMENTAL COMPOSITION
III.1.6. Application of Catalyst for Skraup Cyclization
Reaction
Composition%
Element
Before functionalization
Our catalyst is acidic nature so we choose the reaction
as depicted below (see Scheme 1) was carried out at
different reaction conditions in a laboratory autoclave.
The reaction parameters were optimized to determine the
optimum speed of agitation, molar ratio of reactants,
catalyst loading and temperature
After functionalization
O
21.47
48.45
Si
45.66
35.63
S
32.87
15.92
III.1.5. Temperature Programmed Desorption (TPD)
CH3
Temperature Programmable Desorption (NH3-TPD)
performed on the catalyst divulges it to be acidic as
depicted by the adsorption of ammonia gas as well as the
distribution of surface and strength of acid sites. See Fig.
6(a), show NH3-TPD profile of POSS-SH, which is not
functionalized material and two desorption peaks were
observed. The peak at temperature lower than 100oC was
attributed to the physically adsorbed NH3 [67]-[68], and
other one desorption peaks in the range of 170oC –200oC
O
NH2
+
2 H C
3
CH3
∆ = 140°C to 170°C
N
H
Acid Catalyst
aniline
propan-2-one
CH3
CH3
2,2,4 trimethyl 1,2 dihydroquinoline
Scheme 1. Skraup Cyclization reaction
Parameters, Temperatures were varied from 140oC to
170oC, rotation speeds from 800 rpm to 1400 rpm, molar
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Ganapati D. Yadav, Rahul P. Kumbhar, Saumydeep Helder
ratio was varied from 1:3 to 1:9 and catalyst loading was
varied from 0.01 g/cm3 to 0.03 g/cm3.
external mass transfer resistance. Greater the agitation
speed, lesser will be the resistance due to external mass
transfer and hence it will not be the rate-determining step
in the reaction. The effect of the speed of agitation (see
Fig. 7) was studied by varying from 800 to 1400 rpm,
under analogous reaction conditions. The conversion of
aniline, the limiting reactant, at different intervals of time
is shown in Fig. 7.
It was observed that the conversion of aniline was
practically the same beyond 1000 rpm, which ensure that
external mass-transfer effects did not persuade the
reaction rate. To be on secure region, all further
experiments were conducted at 1000 rpm.
III.2. Proposed Reaction Mechanism
Both the alcohol and acid get adsorbed on the catalyst
sites and the reaction proceeds though cyclization
reaction of aniline and acetone as shown in plausible
mechanism (see Scheme 2).
III.3. Kinetic Study
III.3.1. Effect of Speed of Agitation
The speed of agitation determines the relative effect of
Scheme 2. Plausible cyclization reaction mechanism
III.3.2. Development of Mechanistic Model and Kinetics
of the Reaction
.
(1)
This step is assumed to be fast; hence it is taken to be
at equilibrium. Therefore, we have:
In the absence of both external mass transfer and
intraparticle diffusion resistances, it is possible to
develop a kinetic model. It is assumed that 2naphthol (A)
and dimethyl carbonate (B) adsorb on catalytic site, so
we propose the Langmuir-Hinshelwood-Hougen-Watson
(LHHW) Model for the reaction mechanism. Scheme 2
depicts the catalytic cycle. This model has been found to
work well for initial rate data for reactions carried out on
solid acid catalysts where surface adsorption and
desorption are weak [69]-[75].
The steps involved in the mechanism are:
1. Adsorption of Aniline (A) on a vacant acidic site (S)
(2)
.
2. Adsorption of Acetone (B) on a vacant acidic site (S)
.
(3)
This step is assumed to be fast; hence it is taken to be
at equilibrium. Therefore, we have:
.
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(4)
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Ganapati D. Yadav, Rahul P. Kumbhar, Saumydeep Helder
100
90
(12)
.
or:
Conversion (%))
80
Now, we have:
60
(13)
.
70
50
.
40
30
.
(14)
From the equations of adsorption of both the reactants
we have:
20
10
0
(15)
0 10 20 30 40 50 60 70 80 90 100
Time (min)
800 rpm
1000 rpm
1200 rpm
1400 rpm
(16)
The number of available active sites changes during
the progression of the reaction. So, we can relate amount
of catalyst in terms of total catalytic sites only. Thus, we
have:
Fig. 7. Aniline: Acetone (1:5), n-decane 2 µl, Temperature 160°C,
Catalyst loading 0.03 g/cm3
3. Surface reaction of A.S with B.S in the vicinity of the
site leading to formation of the intermediate I which
reacts with another adsorbed species AS
.
.
.
.
.
.
.
.
(5)
.
.
.
.
.
.
.
.
(17)
(18)
(6)
(19)
The steps involving the surface reactions are assumed
to be the rate determining step for the overall reaction
and initially we assume these reactions to be irreversible.
Also, by steady state approximation, we assume the
rate of change of concentration of intermediate I as zero.
Therefore, we have:
.
.
.
Hence:
(20)
(7)
(8)
Substituting the expression for Cs into that for the rate
equation:
If step 6 is assumed to be rate determining, the all
other steps are in quasi-equilibrium.
(21)
.
4. Desorption of products from catalyst site
.
/
/
(22)
(9)
(10)
When adsorption and desorption constants are small,
the LHHW model converts itself into a power law model:
Again, these steps are assumed to be fast, and thus we
have:
(11)
.
(23)
.
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This implies:
100
(24)
90
80
Conversion (%)
Since the total number of sites is proportional to the
catalyst loading, :
(25)
We can define an effective rate constant
:
(26)
,
70
60
50
40
30
20
10
Now, due to very high mole ratio 1:7 (Aniline:
Acetone), we can safely assume that concentration of
acetone (CB) remains constant. When all adsorption
equilibrium constants are very small, and for CB0>>CA0,
hence, effective rate constant k can be defined as:
0
0 10 20 30 40 50 60 70 80 90 100
0.01 g/cc
Time (min)
0.02 g/cc
0.03 g/cc
(27)
,
Fig. 8. Speed of agitation = 1000 rpm, Aniline: Acetone (1:5), n-decane
2 µl, Temperature 160°C
Therefore it is a pseudo first order reaction.
Let A be the fractional conversion of the limiting
reagent A. Then:
This conversion increases with increasing catalyst
loading, which can be attributed to the proportional
increase in the number of active sites available.
However, beyond loading of 0.02 g/cm3, there was not
any significant increase in the conversion observed.
(28)
(29)
III.3.4. Effect of Mole Ratio(Aniline:Acetone)
Under solvent-less conditions, the effect of mole ratio
of aniline to acetone was studied from 1:3 to 1:9. The
catalyst loading was kept at 0.02g/cm3 and speed of
agitation at 1000 rpm. The most suitable mole ratio was
found to be 1:7 with aniline as the limiting reagent as
shown in Figure 9.
(30)
By integrating the above equation:
(31)
100
90
We get:
ln
Conversion (%)
80
(32)
Hence, if it follows the LHHW model (see Fig. 11),
the graph of –ln(1-XA) versus t should give a straight line.
Fig. 11 represents the aforementioned quantities for
different temperatures.
70
60
50
40
30
20
III.3.3. Effect of Catalyst Loading
10
In the absence of external mass transfer resistance, the
rate of reaction is directly proportional to catalyst loading
based on the entire liquid phase volume, which is due to
the proportional increase in the number of active sites.
Further reactions were carried out with 0.024 g/cm3
catalyst loading. The catalyst loading was varied over a
range of 0.01 – 0.03 g/cm3 under similar reaction
conditions (see Fig. 8 ).
0
0 10 20 30 40 50 60 70 80 90 100
1:03
Time (min)
1:05
1:07
1:09
Fig. 9. Speed of agitation = 1000 rpm, n-decane 2 µl, Catalyst loading
0.02 g/cm3, Temperature 160°C
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As the concentration of acetone increases, the number
of available sites for adsorption of aniline decreases, and
there is not any considerable increase in conversion and
yield above a mole ratio of 1:7
3
2,5
y = 0,09x
R² = 0,986
2
y = 0.076x
R² = 0.994
1,5
y = 0.057x
R² = 0.992
III.3.5. Effect of Temperature
ln (1-X)
The effect of temperature (see Fig. 10) was studied at
four different temperatures in the range 140–170oC under
similar reaction conditions as shown in Fig 10. For a
specific conversion of aniline, the reaction rate increases
with temperature rise.
Therefore, it was found that the conversion increased
significantly with increase in temperature. There was
marginal increase in conversion at 170oC to that of
160oC; this would suggest a kinetically controlled
mechanism. Hence the optimum temperature was
determined to be 160oC.
1
y = 0.036x
R² = 0.985
0,5
0
0
10
III.3.6. Arrhenius Plot
In order to determine the energy of activation, ln(k) is
plotted against the inverse of temperature in accordance
with Arrhenius’ Law:
20
30
Time (min)
140 Deg C
150 Deg C
160 Deg C
170 Deg C
40
50
Fig. 11. Validation of LHHW model
(33)
-2,25
(34)
y = -5582,x + 10,25
R² = 0,964
100
90
-2,75
ln k
80
70
Conversion (%)
60
-3,25
50
40
30
-3,75
0,0022
20
10
0,0023
0,0024
0,0025
1/T (K-1)
0
0 10 20 30 40 50 60 70 80 90 100
Fig. 12. Arrhenius plot
Time (min)
III.3.7. Stability of Catalyst
140 Deg C
160 Deg C
150 Deg C
170 Deg C
The reusability of the catalyst was studied, after
completion of reaction the catalyst was recovered and
washed with methanol for two to three times by refluxing
the used catalyst in ethanol for 30 min in order to remove
any adsorbed materials, like product, remaining reactants
from within the pores. It was separated and dried at 373
K overnight. This process was repeated for every reuse
of catalyst. The little loss in conversion after second
reuse was found due to the adsorption of molecule on the
Fig. 10. Speed of agitation = 1000 rpm, n-decane 2 µl, Catalyst loading
0.02 g/cm3, Aniline: Acetone (1:7)
An Arrhenius plot was used to estimate the apparent
activation energy of the reaction (Fig. 12). The apparent
activation energy was computed to be 11.054 kcal/mol,
which indicates intrinsically kinetically controlled
reaction.
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604
Ganapati D. Yadav, Rahul P. Kumbhar, Saumydeep Helder
catalyst surface. Recyclability of catalyst was studied for
three cycles. About 80–85% catalysts were recovered at
the end of the reaction. Out of the total recovered catalyst
from previous batch, 70% catalyst used for next reaction
with 30% fresh catalyst so as to make desired quantity of
standard batch. The catalyst could be reused with some
decrease in conversion (see Table II) for three cycles
after fresh use. Thus, POSS-SO3H was proved to be
superior catalyst for cyclization reaction.
[5]
[6]
[7]
[8]
[9]
TABLE II
CATALYST REUSABILITY STUDIES
\
Conversion
Fresh
94
1st reuse
86
nd
2 reuse
81
3rd reuse
76
IV.
[10]
[11]
[12]
Conclusion
2,2,4- Trimethyl-1,2-dihydroquinoline has been
successfully synthesized by the Skraup Cyclization
reaction of aniline and acetone carried out with a new
acid catalyst, POSS-SO3H, in solvent free conditions
with very high conversions at a relatively shorter time
period, with various characterization of catalyst like
TPD, TGA, SEM, XRD and FT-IR spectroscopy. The
effects of various parameters on the rates of the reactions
were discussed. A pseudo first order rate equation for the
reaction mechanism was successfully developed. The
apparent activation energy 11.054 kcal/mol was
estimated, as value of the activation energy authorize that
the reaction is intrinsically kinetically controlled.
[13]
[14]
[15]
[16]
[17]
[18]
Acknowledgements
[19]
GDY acknowledges support for personal chairs from
the Darbari Seth Professor Endowment and R. T. Mody
Distinguished Professor Endowment, and J. C. Bose
National Fellowship from Department of Science and
Technology, Government of India. RPK acknowledges
the Department of Atomic Energy (DAE), Government
of India for awarding the Research Fellowship. SH
acknowledge the Indian Academy of Sciences (IASc) for
awarding the summer trainee fellowship.
[20]
[21]
[22]
[23]
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244 (2003) 341–357
Life Member, Indian Society for Surface Science and Technology
Life Member, Membrane Society of India
Life Member, UDCT Alumni Association
Life Member, National Society of the Friends of Trees
Life Patron, Marathi Vidnyan Parishad
Member, Organizing Committee: 3rd International Workshop on
Crystallization, Filtration and Drying, February 2008
Current Catalysis, Bentham Science Publishers, 2011-on
www.ictmumbai.edu.in
gdyadav@yahoo.com
E-mails:
gd.yadav@ictmumbai.edu.in
Rahul P. Kumbhar
Born on 10th May, 1984, in district Sangli, after
completion of B E. (Chem.) from MAE, Pune,
India, having two years of experience as Process
Engineer in company, now pursuing Integrated
Ph. D. from Institute of Chemical Technology,
Matunga, Mumbai, India under the guidance of
Prof. G. D. Yadav.
Main research interests – Catalysis, nanomaterials synthesis and
characterization, application towards chemical reactions like
cyclization, esterification, etc.
E-mail:
gdyrahul@rediffmail.com
Web site: www.ictmumbai.edu.in
Saumyadeep Halder
Summer Trainee, Institute of Chemical
Technology, Matunga, Mumbai, India under the
guidance of Prof. G. D. Yadav.
Pursuing B. Tech from National Institute of
Technology, Tiruchirappalli
Main
research
interests
–
Catalysis,
Isomerization Unit and Catalytic Reforming
Authors’ information
Department of Chemical Engineering,
Institute of Chemical Technology,
Matunga, Mumbai-400019 India.
Unit.
E-mail:
sdhalder92@gmail.com
Ganapati D. Yadav
14th September, 1952, born in Arjunwada district
in Kolhapur city, after completion postgraduation study moved in UDCT, Mumbai,
India, completed B. Chem. Eng., M Chem Engg,
followed by PhD under the guidance of Prof. M.
M. Sharma, now Vice Chancellor & R.T. Mody
Distinguished Professor, J. C. Bose National
Fellow (DST-Govt of India), Institute of Chemical Technology,
Matunga, Mumbai. Adjunct professor RMIT University, Australia.
Fundamental and applied aspects of green, clean and benign processes
in chemical and allied industries such as bulk, intermediate,
pharmaceuticals, fine chemicals, perfume and flavour and inorganics,
new catalytic materials, phase transfer catalysis, nanoscience and
nanotechnology, bio-catalysis, modeling and simulation, biocatalysis in
non-aqueous media, synergism of chemical catalysis with microwaves
and ultrasound, cascade engineered catalysis, renewable materials as
feedstock for value added chemicals, biorefinery. He has made
outstanding and extensive contributions to Green Chemistry &
Technology, Catalysis Science & Engineering and Biotechnology. He
has propounded the selectivity engineering principles including new
theories with direct applications to industrial processes. He reported the
first solid with highest superacidity (UDCaT-5), provided first ever
interpretation of inversion in reaction rates and selectivities of Friedel
Crafts alkylations, and novelties of tri-liquid phase transfer catalysis.
His phenomenal productivity is reflected in 61 patents, 262 papers, 63
Ph Ds, 68 Masters, 3800 citations with h index of 34 and is decorated
with fellowships of prestigious academies and awards.:
Jagdish Chandra Bose National Fellowship, Department of Science and
Technology, Govt. of India
Fellowship of TWAS, The Academy of Sciences for the Developing
World
Fellow, Institution of Chemical Engineers, UK and Chartered Engineer,
Life Fellow, Maharashtra Academy of Sciences
Life Fellow, Indian Institute of Chemical Engineers
Life Fellow, Indian Chemical Society
Member, American Chemical Society
Life Member, Catalysis Society of India
Copyright © 2012 Praise Worthy Prize S.r.l. - All rights reserved
International Review of Chemical Engineering, Vol. 4, N. 6
Special Section on 4th CEAM 2012 - Virtual Forum
607