Volume-3 ~ Issue-4

Abstract: Microwave-assisted efficient and eco-friendly synthesis of bis-, tris(indolyl)methanes and dibis( indolyl)methanes by the reaction of indoles with aldehydes in presence of fruit juice of Citrus limon as catalyst under under solvent-free conditions is reported. The advantages of the protocol are the use of green and inexpensive catalyst, commercially available precursors, simple work-up procedures, high yields and short reaction times.
Keywords: Bis-, tris-, and tetra(indolyl)methanes, Microwave irradiation, Fruit juice of Citrus limon, Green and inexpensive acid catalyst, Eco-friendly

[1] M. Doble, and A. Kumar, "Green chemistry and engineering", Elsevier, 2007.
[2] C. Einhorn, J. Einhorn, and J.L. Luche. "Sonochemistry-The use of ultrasonic waves in synthetic organic chemistry", Synthesis, No.
11, 1989, pp. 787-813.
[3] P.H.H. Hermkens, H.C.J. Ottenheijm, and D.C. Ress, "Solid-phase organic reactions II: A review of the literature Nov 95-Nov 96",
Tetrahedron, Vol. 53, No. 16, 1997, pp. 5643-5678.
[4] L. Perreux, and A. Loupy, "A tentative rationalization of microwave effects in organic synthesis according to the reaction medium,
and mechanistic considerations", Tetrahedron, Vol. 57, No. 45, 2001, pp. 9199-9223.
[5] D. Dallinger, and C.O. Kappe, "Microwave-assistaed synthesis in water as solvent", Chemical. Reviews, Vol. 107, No. 6, 2007, pp.
2563-2591.
[6] M. Hino, and K. Arata, "Synthesis of solid superacid of tungsten oxide supported on zirconia and its catalytic action for reactions of
butane and pentane", Journal of the Chemical Society, Chemical Communications, No. 18, 1988, pp. 1259-1260.
[7] R. J. Sundberg, The chemistry of indoles; Academic press: New York, 1996, p 113.
[8] G. Sivaprasad, P.T. Perumal, V.R. Prabavathy, and N. Mathivanan, "Synthesis and anti-microbial activity of pyrazolylbisindolespromising anti-fungal compounds", Bioorganic & Medicinal Chemistry Letters, Vol. 16, No. 24, 2006, pp. 6302-6305.
[9] R. Bell, S. Carmeli,and N. Sar, "Vibrindole A, a metabolite of the marine bacterium, vibrio parahaemolyticus, isolated from the toxic
mucus of the boxfish ostracion cubicus", Journal of Natural Products, Vol. 57, No. 11, 1994, pp. 1587-1590.
[10] K. Sujatha, P.T. Perumal, D. Muralidharan, and M. Rajendra, "Synthesis, analgesic and anti-inflammatory activities of
bis(indolyl)methanes", Indian Journal of Chemistry, Vol. 48B, No. 2, 2009, pp. 267-272

Abstract: The infra red wave numbers of zirconium chelate of 1,2-naphthoquinone dioxime, were calculated using Gaussian 09 software code, employing RHF / SDD and DFT ( B3LYP ) level and SDD basis set to predict the molecular structure. The fundamental modes are assigned by using animation software. The calculated frequencies are in good agreement with the experimental values. The calculated geometrical parameters are also given. The study is extended to calculate the HOMO-LUMO energy gap, Ionization potential (I), Electron affinity ( A ),Global hardness (η ), chemical potential (μ ) and global electrophilicity( ω ). The calculated HOMO-LUMO energies show the charge transfer occurs in the molecule.
Keywords : 1-2 naphthoquinone dioxime, IR, HF and DFT, Energy gap, Zirconium dioximate

[1] Cukurovali A, Tas E, Ahmedzad M, Synthesis and Metal Complexation of a New Oxime Derivative of 2-Aminothiazole, Synth.
React Inorg. Met Org Nano Met Chem, 27(5), 1997, 639– 646.
[2] Mukherjee S, Patel B A, Bhaduri S, Selective Ethylene Oligomerization with Nickel Oxime Complexes, Organometallics, 28 (10),
2009, 3074–3078.
[3] Ponomareva VV, Dalley NK, Xiaolan K, Gerasimchuk NN, Domasevich KV, Synthesis, spectra and crystal structures of complexes
of ambidentate C6H5C(O)C(NO)CN– ,J Chem Soc Dalton Trans, 1996, 2351-2359.
[4] Milios CJ, Stamatatos TC, Perlepes S P, The coordination chemistry of pyridyl oximes, Polyhedron, 25, 2006, 134-194.
[5] Alzoubi B m, Vidali F, Puchta R, Dücker-Benfer C, Felluga A, Randaccio L, Tauzher G, Van Eldik R., Mechanistic behaviour of
alkylcobaloximes and imino-oxime complexes related to vitamin B(12), Dalton Trans, 7(13), 2009, 2392-2399.
[6] Alper T O, Gazi I, Hasene M, Tuncer H, Nagihan A, A Co(III) complex with a tridentate amineimine- oxime ligand from 1,2,3,4-
tetrahydroquinazoline: synthesis, crystal structure, spectroscopic and thermal characterization , J Coord Chem, 62(6), 2009, 1005–
1014.
[7] Kufelnicki A, Fritsky IO, Sliva TY, Golovaneva IF, Lampeka R D, Stereoselective synthesis of cobalt(III) anionic complexes with
chiral pyruvylaminoacid oximes and metal–ligand interactions in aqueous solution, Polyhedron, 26(12), 2007, 2894-2900.
[8] Gok Y, Kantekin H, The synthesis and characterization of new (E,E)-dioxime and its mono and heteronuclear complexes containing
14-membered tetraaza macrocyclic moiety, Polyhedron, 16(14), 1997, 2413-2420.
[9] V.B. Jadhav, N.R. Gonewar, K.D. Jadhav and R.G. Sarawadekar, Synthesis, spectral and Theoretical investigation on 1-2
naphthoquinone dioxime, Research in Pharmacy 1(3): 01-09, 2011.
[10] A.P. Avdeenko, G.M. Glinyanaya and V.V. Pirozhenko, Russian Journal of Organic Chemistry, 35(10)1480-1487 (1999).

Abstract: An UPLC method has been developed and subsequently validated for the determination of antimigraine drug and its process-related impurities. Separation was achieved with Halo C18, 50x 4.6 mm, 2.7μm column and 1.36 g ofmonobasic potassium phosphate in 1000 mL of water with 2 mL of triethylamine at pH 6.8 using H3PO4, acetonitrile and methanol in the ratio of 55 : 38 : 7 as eluent in isocratic mode. Flow rate was set as 1 mL.min-1UV detection was performed at 225 nm. The method was validated with respect to
specificity, accuracy, precision, linearity, robustness, limit of quantification and limit of detection. The accuracy of the method demonstrated at three levels in the range of 50-150% of the specification limit and the recovery of impurities were found to be in range of 98 to 102%. The detection limits of the process related impurities ranged between 0.16 and 0.24 μgmL-1. The described method is simple, rapid, linear, precise, accurate, robust and stability indicating. The method is useful during process development and quality of bulk manufacturing.
Keywords: Ultra performance liquid chromatography (UPLC), Antimigrainedrugs, Validationand Process related impurities.

[1] Cooper, J. D. H. ;, Muirhead, D. C. ; Taylor, J. E., Determination of Eletriptan in plasma and saliva using automated sequential trace
enrichment of dialyzate and high performance liquid chromatography, Journal of Pharmaceutical and Biomedical Analysis (1999),
21(4), 787-796.
[2] Zecevic, Mira; Jocic, Biljana; Agatonovic-Kustrin, Snezana; Zivanovic, Ljiljana, Validation of an HPLC method for the simultaneous
determination of eletriptan and UK 120.413, Journal of the Serbian Chemical Society (2006), 71(11), 1195-1205.
[3] Suneetha, D.; Rao, A. Lakshmana, RP-HPLC method for the estimation of eletriptan in pharmaceutical dosage forms, International
Journal of Chemical, Environmental and Pharmaceutical Research (2010), 1(2), 95-99.
[4] Kumar, A. Phani; Ganesh, V. R. L.; Prasad, K. Hari; Hariharakrishnan, V. S.; Dubey, P. K.; Rao, B. Venugopala , HPLC method for
the enantiomeric purity of eletriptan hydrobromide, Asian Journal of Chemistry (2011), 23(4), 1621-1624.
[5] El-Bagary, Ramzia I.; Mohammed, Nashwah G.; Nasr, Heba A, Two chromatographic methods for the determination of some
antimigraine drugs, Analytical Chemistry Insights (2012), 7, 13-21.
[6] KumaraSwamy, G.; Kumar, J. M. R.; Sheshagiri Rao, J. V. L. N., Development and validation of RP - HPLC method for the
estimation of Eletriptan hydrobromide in bulk and tablet dosage form, Journal of Pharmacy Research (2012), 5(1), 538-540.
[7] Sagirli, Olcay; Onal, Armagan; Sensoy, Demet, LC assay of eletriptan in tablets and in vitro dissolution studies, Chromatographia
(2008), 68(3/4), 269-273.
[8] Jocic, Biljana; Zecevic, Mira; Zivanovic, Ljiljana; Protic, Ana; Jadranin, Milka; Vajs, Vlatka, Study of forced degradation behavior
of Eletriptan hydrobromide by LC and LC-MS and development of stabilityindicating method, Journal of Pharmaceutical and
Biomedical Analysis (2009), 50(4), 622-629.
[9] Ponnuru, Venkata Suresh; Challa, B. R.; Nadendla, Ramarao, Quantitative analysis of eletriptan in human plasma by HPLC-MS/MS
and its application to pharmacokinetic study, Analytical and Bioanalytical Chemistry (2011), 401(8), 2539-2548.
[10] Speir, J. Paul; Perkins, George; Berg, Christian; Pullen, Frank, Fast, generic gradient high performance liquid chromatography
coupled to Fourier transform ion cyclotron resonance mass spectrometry for the accurate mass analysis of mixtures, Rapid
Communications in Mass Spectrometry (2000), 14(20), 1937-1942.

Abstract: Characterization and modification of natural zeolite (ZA) produced in Sukabumi, West Java, Indonesia, as well as metal supported onto the zeolite for hydrocracking catalysts of polyethylene terephthalat (PET) have been conducted. The natural zeolite was refluxed in HCl 3M for 30 min., drying and heated in a microwave produced the ZAA sample. The transition metal such as Cu, Cr, Ni, or Pd was loaded into the ZAA sample under reflux in methanol using salt precursor of each metal, produced the Cu/ZAA, Cr/ZAA, Ni/ZAA, and Pd/ZAA catalysts. The zeolite based samples were characterized by means of determination of acidity by vapor adsorption of NH3 and pyridine, catalyst crystalinity by X-ray diffraction (XRD), surface area by surface area analyzer NOVA-1000 and TO4 (T= Si and Al) site by Infra Red Spectrophotometer (IR). The PET was pyrolyzed in 350 ºC produced liquid fraction as a feed for hydrocracking process. The hydrocracking of the PET was carried out in a fixed bed reactor of stainless steel at temperature of 350 oC, H2 flow rate of 20 mL/min., feed/catalyst ratio of 10. Liquid products of the hydrocracking were analyzed using GC and GC-MS. The characterization results showed that the Indonesian natural zeolite produced in Sukabumi consisted mainly of mordenite crystalline. The HCl treatment towards the natural zeolite caused dealumination, increased its acidity and surface area. Loading of Ni, Cu, Cr, or Pd metal on to the zeolite did not affect the zeolite crystallinity. However, the metal loading decreased surface area of the zeolite. Products of the hydrocracking were liquid, coke, and gas fractions. The liquid products consisted mainly of gasoline fraction (C5-C12). The highest liquid product conversion was produced by the Pd/ZAA catalyst, i.e. 34.05 wt. %, with selectivity towards gasoline fractions was 97.99 wt. %.
Keywords: natural zeolite, characterization, modification, hydrocracking, metal loading, polyethylene terephthalat.

[1] P. Shivakumar and K. Anbarasu, Catalytic Pyrolysis of Dairy Industrial Waste LDPE Film Into Fuel, Intern. J. Chem. Res. 3 (2012)
52 – 55.
[2] M.F. Ali and M.N. Siddiqui, Thermal and catalytic decomposition behavior of PVC mixed plastic waste with petroleum residue, J .
Anal. Appl. Pyrolysis 74 (2005) 282 – 289.
[3] S. Kumar and R.K. Singh, Recovery of Hydrocarbon Liquid From waste High Density Polyethilene By Thermal Pyrolisi, 28 (2011)
659 – 667.
[4] J. Aguado, D.P. Serrano, J.M. Escola, and A. Peral, Catalytic Cracking of Polyethilene Over Zeolite Mordenite With Enhanced
Textural Properties, J. Anal. Appl. Pyrolysis 85 (2009) 352 – 358.
[5] A. Peral, J. Aguado, D.P. Serrano, J.M. Escolla, Catalytic cracking of polyethylene over zeolite mordenite with enhanced textural
properties, J. Anal. Appl. Pyrolysis 85 (2009) 352–358.
[6] A. Bonila, D. Baudouin, and J. Perez-Ramirez, Desilication of ferrierite zeolite for porosity generation and improved effectiveness in
polyethylene pyrolysis, Journal of Catalysis 265 (2009) 170–180.
[7] A. López, I. de Marco, B.M. Caballero, M.F. Laresgoiti , A. Adrados, A. Aranzabal, 2011, Catalytic pyrolysis of plastic wastes with two different types of catalysts: ZSM-5 zeolite and Red Mud, Applied Catalysis B: Environmental 104 (2011) 211–219.
[8] W. Trisunaryanti, R. Shiba, M. Miura, M. Nomura, N. Nishiyama, M. Matsukata, Characterization and Modification of Indonesian
Natural Zeolites and Their Properties for Hydrocracking of a Paraffin, J. Jpn. Petr.Inst. 1 (1996) 20-25.
[9] W. Trisunaryanti, A. Syoufyan, S. Purwono, I.Izul Fallah, Padi, P., The effect of hydrochloric acid solution treatment towards
characters of Indonesian natural zeolite, Proceeding of The 2nd International Conference On Chemical Sciences, Yogyakarta, 2010.
[10] W. Trisunaryanti, Triyono, Purwono, S., and K. Dewi, Characteristicsof Metals Supported-Zeolites Catalysts On Steam Reforming of Bioethanol, J. Materiala Science and Engineering, 5 (2011) 239-246.

Abstract: The effect of ionic strength on the rate of Acetophenone-Phenylhydrazine reaction has been studied by determining the rate in the presence of added neutral salts NaNO3 and NaCl. The kinetics were also carried out for substituted acetophenones with phenylhydrazine in the presence of NaNO3 and NaCl. The rate constants were determined and fitted into extended LFER equation and ρI/ρR were determined.

[1] L.P. Hammett, Phy. Org. Chem., The Hammett's Equation, McGraw Hill, New York, Edn. 1(1940).
[2] L.P. Hammett, Phy. Org. Chem., The Hammett Equation and Chemical Reactivity, McGraw Hill,New York, edn. 2 (1970).
[3] K. Nagajyothi, P S Raghavan and R Gopalan, Solvent and Substituent Effect on
[4] Acetophenone-Phenylhydrazone Formation, Asian Journal of Chemistry, 839-842, Vol. 22, No. 2 (2010)
[5] K. Nagajyothi, P S Raghavan and R Gopalan, Micellar Effect on The Reaction of Acetophenone with Phenylhydrazine,
[6] Asian Journal of Chemistry, 829-833, Vol. 22, No. 2 (2010).

Abstract: In the process development of dutasteride in the laboratory analysis showed some impurity peaks in HPLC ranging from 0.05 to 0.1%. The same samples were analyzed by LCMS method and identified peak at m/z 508 (desmethyl dutasteride), 530 (dihydro dutasteride) and 528 (isomer of dutasteride). Among these impurities a simple and rapid preparative high-performance liquid chromatography (HPLC) method has been developed to isolate and characterized 17alpha-N-[2,5-bis(trifluoromethyl) phenyl] carbamoyl-4-aza-5alpha-androst-1-ene-3-one (alpha-isomer of dutasteride). Different isolation technique conducted and finally Isomeric impurityof dutasteride separated and Characterized by using Preparative HPLC,MS,1H and 13C NMR spectroscopy.
Keywords: Dutasteride, Impurities,Synthesis,Isolation,Characterization,flashchromatography, preparative
hplc, mass spectra, nmr.

[1] Hudson, P.B: Boake, R: Trachtenberg, J: Romas, N.A: Rosenblett, S: Naragan, P: Geller, J: Lieber, M.M: Elhilali, M: Norman, R.
Urology, 1999, 53(3): 690-692.
[2] Connell, J.D: Bruskewitz, R: Walsh, P: Andriol, G: Lieber, M: Holtgrewe, H.L: Albertsen, P: Roehrborn, C.G: Nickel, J.C: Wang,
D,Z: Taylor, A,M: Waldstreicher,J.N: Engl. J. Med, 1998, 338(5): 557-559.
[3] Xie, H.W. Tianjin Pharm, 2002, 14 (3): 15-16.
[4] Harris, G; Azzolina, B; Baginsky, W; Cimis, G; Rasmusson, G.H; Tolman, R. L; Raetz, C. H; Ellsworth, K. Identification and
selective inhibition of an isozyme of steroid 5∞-reductase in human scalp. Proc. Natl. Acad. Sci, U.S.A. 1992, 89, 10787-10791.
[5] Isaacs, J. T. 5 alpha reductase Inhibitors and treatment of benign prostatic hyperplasia. Drugs Today 1993, 29, 335- 342.
[6] Smith, L. S; Tegeler, J. J. Advances in dermatology. Ann. Rep.Med, Chem 1989, 24, 1177- 1186.
[7] Brooks, J. R. Treatment of hirsutism with 5∞-reductase inhibitors. Clin, Endocrinol, Metab, 1986, 15, 391- 405.
[8] Gadwood, J. R; Fiedler, V. C. Pathogenesis and treatment of alopecia. Ann. Rep. Med, Chem 1989, 24, 187- 196.
[9] International Conference on Harmonization, Draft Revised. Federal Register Q3B (R) 2000, 65(139), 4479.
[10] K. Satyanarayana, K. Srinivas, V. Himabidu, G. Mahesh Reddy. " Impurity profile study of dutasteride" Pharmazie 2007, 62, 743 - 746 .

Abstract: The power of Nuclear Magnetic Resonance spectroscopy (NMR) in structure elucidation derives in large part from its ability to establish bonding connectivity (via J- coupling interaction) or through space proximity (via dipolar coupling interactions) of nuclei. The amount of time consumed in elucidating a structure depends on the rate at which these interaction can be detected by NMR and analyzed.1D NMR methods most often explore interactions between only few nuclei at a time: spin-spin decoupling measurements are used to demonstrate through-bond connectivity; and NOE measurements are used to probe inter-nuclear distances, 2- Dimensional NMR experiments provide much more structural information in a given time period. Correlation spectroscopy was used to elucidate the aromatic proton position in NMR spectra.
Keywords: NMR, J-coupling, dipolar coupling, NOE, 2 dimensional NMR.

[1] J. Jeener, Ampe`re International Summer School, Basko Polje, (former) Yugoslavia, 1971.
[2] W. P. Aue, E. Bartholdi and R. R. Ernst, J. Chem. Phys., 1976, 64, 2229–2246.
[3] J. N. S. Evans, Biomolecular NMR Spectroscopy, Oxford University Press, Oxford, 1995.
[4] J. Cavanagh, W. J. Fairbrother, A. G. Palmer, N. J. Skelton and M. Rance, Protein NMR Spectroscopy:Principles and Practice, 2nd
edition Academic Press (Elsevier), San Diego, 2006.
[5] J. Hahn, Higher-order 31P NMR spectroscopy of polyphosphorus compounds In: Phosphorus-31 NMR Spectroscopy in
Stereochemical Analysis (Eds.: J.G. Verkade and L.D. Quin) VCH, Florida, 1987,pp. 331–364.
[6] D. J. States, R. A. Haberkorn and D. J. Ruben, J. Magn. Reson., 1982, 48, 286–292.
[7] M. Ohuchi, M. Hosono, K. Furihata and H. Seto, J. Magn. Reson., 1987, 72, 279–297.
[8] D. Marion and K. Wu¨thrich, Biochem. Biophys. Res. Commun., 1983, 113, 967–974.
[9] J. Keeler and D. Neuhaus, J. Magn. Reson., 1985, 63, 454–472.
[10] D. Marion, M. Ikura, R. Tschudin and A. Bax, J. Magn. Reson., 1989, 85, 393–399.