October 2015 1446892103 20

National Conference on Recent innovations in Applied Sciences and Humanities’ NCASH-2015 Volume : 4 | Issue : 10 | Special Issue Oct- 2015
2015 • ISSN No 2277 - 8179
Chemistry
KEYWORDS: acylation, pyrrole, acetic
Vapor phase acylation of pyrrole over ferrites anhydride, 2-acetylpyrrole, ferrites.
Department of Chemistry, Guru Jambheshwar University of Science and Tech-

Naseeb Singh
nology, Hisar (Haryana) 125001, India.

Pawan siwach

R. K. Gupta
ABSTRACT e vapor phase acylation of pyrrole was carried out over different ferrites NiFe2O4(NSF-1) ,CrFe2O4(NSF-2),
CoFe2O4(NSF-3),Ni0.5Co0.5Fe2O4(NSF-4),Ni0.5Cr0.5Fe2O4(NSF-5),Cr0.5Co0.5Fe2O4(NSF-6) and Ni0.33Co0.33Cr0.33 Fe2O4
(NSF-7) in a fixed bed reactor at atmospheric pressure using acetic anhydride as an acylating agent. e catalytic activity of the ferrite catalysts
was dependent on the reaction temperature, WHSV and molar ratio. e activity of the catalysts varied with the acidity of the ferrite systems
tested. e yields of 2-acetylpyrrole were 99.096% and selectivity is 99.95 % found under the optimized condition. On NSF-4 under optimized
conditions, Ni2+/Co2+ionic distribution in the spinel lattice influences the acidic-basic properties.
Introduction .e other products formed in negligible amounts on optimized con-

Many organic compounds are synthesized by Friedel–Crafts dition (molar ratio 1:4, WHSV 0.4h-1 and temperature 673 K). e
acylation using homogeneous catalysts like AlCl3, FeCl3, etc. e syn- Ni2+/Co2+ ionic distribution in the spinel lattice of catalyst NSF-4 plays
thesis of organic intermediates is an important area in fine chemical important role for high yield and selectivity.
industry [1-9]. e major drawbacks of these homogeneous catalysts
are that they are corrosive expensive and non-regenerable. So the Variation of weight hour space velocity (WHSV)
problematic homogeneous catalysts replaced by heterogeneous
solid catalysts such as sulphate-ion doped metal oxides, silica-
alumina and zeolites have been investigated. In recent years ferrites
are used as catalysts for the synthesis of many organic compounds
because of their high thermal stability, reusability, easy separation
and eco-friendly nature. Friedel–Crafts acylation of pyrrole is by far
the most popular method for the synthesis of acetyl-pyrroles, which
are key pharmaceutical intermediates, especially for 2-acetylpyrrole
[10-11]. e known processes for the acylation of pyrrole involve
homogeneous acid catalysts and heterogeneous zeolites. e study
reported that acylation of pyrrole gives 2-actylepyrrole formation as
the major product [12-15]. e 2-actylepyrrole is used in producing
aroma of several fruits, used in flavors for tobacco and roasted foods.
e present study was done on ferrites. e ferrites are tested for
Fig. 2. Variation of weight hour space velocity (WHSV).
pyrrole acylation and we have observed high yields and selectivity of
2-actyle pyrrole with negligible side products.
e effect of WHSV on acylation of pyrrole was studied over (NSF-4)
catalyst at a temperature of 673K, at 1:4 molar ratio of pyrrole to ace-
Results and Discussion
tic anhydride and WHSV (0.2, 0.4, 0.6 and 0.8 h-1). e results are
Effect of variation of catalyst on acylation activity
shown in fig.2. Pyrrole conversion increased as the WHSV increased
from 0.2 to 0.4 h-1 and decreased thereafter. e high contact time
causes charring over active sites, hence decreasing the pyrrole con-
version. Below 0.4 h-1 WHSV pyrrole conversion was decreased due to
the low contact time of feed and the catalyst.
Variation of feed with respect to molar ratio

As seen from the results in fig.3., the molar ratio of pyrrole : acetic
anhydride varied from 1:2 to 1:8 and the vapor phase acylation of
pyrrole was carried out over NSF-4 at temperature 673 K and WHSV
0.4 h -1 . Pyrrole conversion and selectivity of 2-actyle-pyrrole
increased with increase in the pyrrole-to-acetic anhydride molar
ratio, reaching a maximum at 1:4. At higher molar ratio, the selectiv-
ity and conversion of 2-actylepyrrole was reduced. is was probably
Fig. 1. Effect of variation of catalyst on acylation activity. due to the unavailability of active sites for pyrrole over the catalyst
surface, because of competition between pyrrole and acetic anhy-
From the data in Fig. 1, all the tested ferrites are found to be active cat- dride adsorption.
alysts for pyrrole acylation with acetic anhydride under optimized
conditions. e maximum yields of acylated products obtained was
99.096% of 2-actyle pyrrole with selectivity 99.95% on NSF-4 catalyst
Research Paper IJSR - INTERNATIONAL JOURNAL OF SCIENTIFIC RESEARCH 57

Volume : 4 | Issue : 10 | Special Issue Oct- 2015 • ISSN No 2277 - 8179 National Conference on Recent innovations in Applied Sciences and Humanities’ NCASH-2015
Fig.5. Effect of time on stream

Fig.3. Variation of feed with respect to mole ratio.
Conclusions
Effect of temperature on acylation A catalytic activity experiment reveals that strong and medium
An effect of temperature on acylation of pyrrole acetic anhydride was acidic sites are suitable for the acylation of pyrrole. e catalytic
studied over (NSF-4) in the temperature range 573-723 K, WHSV activity of the system was dependent on the reaction parameters. e
0.4h-1 and molar ratio 1:4; the results are shown in fig.4. erefore the vapor phase acylation of pyrrole occurred more on NSF-4. e high
investigation of acylation of pyrrole was restricted to only 673 K, yield and selectivity depends on Ni2+/ Co2+ ionic distribution on spinel
where the yield of 2-actyle-pyrrole is high in comparison to the values lattice of ferrite. e maximum yield of acylated product obtained
reported in literature in each acylation reaction. It was also found was 99.096 % of 2-actylepyrrole with 99.95% selectivity, over NSF-4 fer-
that the decrease in the yield of the acylated product at higher tem- rite and acylating agent is acetic anhydride, at molar ratio 1:4, WHSV
peratures is due to the charring of some reactants. ese observa- 0.4 h-1 and temperature 673K. Time on stream conversions was gradu-
tions draw our attention to conclude that the strong and medium ally decreasing, observed for the period of 10h.
acidic sites favor vapor phase acylation of pyrrole.
Fig.4. Effect of temperature on acylation.
Effect of time on stream (TOS)

e reaction was carried out for 10 h on all the catalysts. e best
results are given by catalyst NSF-4 on optimized conditions i.e. molar
ratio 4, WHSV 0.4 h-1 and temperature 673K. e results are depicted
in fig. 5. e continue decrease of catalytic activity has been observed.
e conversion with time on stream decreased gradually but selectiv-
ity is not affected very much. is may be due to coke induced selec-
tivity or may be absence of by-products.
REFERENCE [1] F. Richard, H. Carreyre and G. Perot, J. Catal. 159 1996, 159 , 427. | [2] Y.V. Subba Rao, S.J. Kulkarni, M. Subrahmanyam and A.V. Rama Rao, J. Chem.
Soc. Chem. Commun. 1993, 1456. | [3] A. Corma, Appl. Catal. 1989, 49, 109. | [4] C. Gauthier, B. Chiche, A. Finiels and P. Geneste, J. Mol. Catal. 1987, 42, 229. |
[5] E.A. Gunnewegh, S. Gopie and H. van Bekkum, J. Mol. Catal. 1996, 106, 151. | [6] K. Garre and D. Akporiaye, J. Mol. Catal. 1996, 109, 177. | [7] B. Chiche, A. Finiels and P. Geneste, Appl. Catal.
1987, 30, 365. | [8] G. Perot and M. Guisnet, J. Mol. Catal. 1990, 61, 173. | [9] C. Gauthier, B. Chiche, A. Finiels and P. Geneste, J. Mol. Catal. 1989, 50, 219. | [10] T. Fujisawa, K. Kondo, K. Sakai, US
Patent. 4 266 067 (1981) | [11] H. Goda, M. Kawamura, K. Kato, M. Sato, US Patent. 4 792 612 (1988) | [12] S.J. Kulkarni, Stud. Surf. Sci. Catal. 1998, 113, 151. | [13] W.F. Hölderich, M. Hesse and F.
Navmann, Angew. Chem. 1988, 27, 226. | [14] I.V. Kozhevnikov, Catal. Rev. Sci. Eng. 1995, 37, 311. | [15] T. Yamaguchi, Appl. Catal. 1991, 61, 1.
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National Conference on Recent innovations in Applied Sciences and Humanities’ NCASH-2015 Volume : 4 | Issue : 10 | Special Issue Oct- 2015

2015 • ISSN No 2277 - 8179

Department of Chemistry, Guru Jambheshwar University of Science and Tech-

Department of Chemistry, Guru Jambheshwar University of Science and Tech-

Department of Chemistry, Guru Jambheshwar University of Science and Tech-

Introduction .e other products formed in negligible amounts on optimized con-

Variation of feed with respect to molar ratio

Research Paper IJSR - INTERNATIONAL JOURNAL OF SCIENTIFIC RESEARCH 57

Fig.5. Eﬀect of time on stream

Fig.4. Eﬀect of temperature on acylation.

Eﬀect of time on stream (TOS)

58 IJSR - INTERNATIONAL JOURNAL OF SCIENTIFIC RESEARCH Research Paper

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