Title of Invention	"A NOVEL SUBSTITUTED CALIX(4) PYRROLE"
Abstract	A novel compounds of substituted calix (4) pyrroles and a process for synthesis of calix (4) pyrroles by reacting pyrrole with cyclic or acyclic ketones in dichloro methane (DCM)solvent over molecular sieve catalysts which provides an eco-friendly, more economical and selective heterogeneous method.

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Field of the invention The present invention relates to a novel calix (4) pyrroles. Background and Prior Art references Calix pyrroles represent a subset of class of macrocycles that was previously termed as porphyrinogens. Porphyrinogens are non-conjugated macrocyclic species composed of four pyrrole rings linked to the position via sp3 hybridized carbon atoms. Porphyrinogens that carry meso-hydrogen atoms are prone to oxidation to the corresponding phorphyrins and renamed the term porphyrinogen as calixpyrrole due to the analogues properties of calixarenes. Fully meso non-hydrogen substituted phorphyrongens are generally stable crystalline materials. The first such macrocycle, meso octamethyl calix (4) pyrrole was reported over a century ago by Bayer (Ber. Disctz. Chem. Ger. 1886, 19, 2184) using condensation between acetone and pyrrole catalyzed by HC1, however, the structure of the molecule was not elucidated. This method was refined by Dennstedt and Zimmerman (Ber. Disctz. Chem. Ger. 1887, 20, 850) by replacing the HC1 with "chlorzink" and heating the reaction. Chelintzev and Toronov synthesized calix (4) pyrrole by the method of condensing acetone and pyrrole, methyl ethyl ketone and pyrrole, methyl hexyl ketone and pyrrole and a mixture of acetone and methyl ethyl ketone with pyrrole (J. Russ. Phys. Chem. Soc. 1916, 48, 1197; Chem Abstr. 1917, 11, 1418). Further, Chelintzev, Tronov and Kurmunov reported the production of calixpyrroles by condensing cyclohexanone with pyrrole and a mixture of acetone and cyclohexanone with pyrrole (J. Russ. Phys. Chem. Soc. 1916, 48, 1210). Rothenmund and Gage refined Dennstedt and Zimmermann's method by replacing the acid catalyst with methane sulphonic acid (J. Am. Chem. Soc. 1955, 55, 3740). In 1971, Brown, Iluichioson and Mackinon (Can. J. of Chem. 1971, 49, 4017) repeated the synthesis of mesotetracyclohexyl calixpyrrole and assigned a tetrameric macrocyclic structure. J.M. Lehn and coworkers have synthesized meso-octa-3-chloro propyl calix (4) pyrrole by an unpublished procedure and converted into meso-octa-3-cyano propyl calix pyrrole (B. Dietrich, P. Viout and J.M. Lehn in macrocyclic chemistry, VCH, Publishers, Weinhein 1993, pg82). The metal cation binding of deprotanated calix (4) pyrrole macrocyclics has been studied by Floriani and co-workers (Chem. Commun. 1996,. 1257). Floriani has developed a method for expanding the pyrrole rings of metal bound deprotanated calix (4) pyrroles forming calix (1) pyridino (3) pyrroles and calix (2) pyridino (2) pyrroles (J. Am. Chem. Soc. 1995, 117, 2793). A further a prior art method reports using pyrrole, a C4-C6 saturated acyclic ketone and an acid containing vinyl groups are triple bonds to form a polymerized resin (WO 93/13150). In this case, the resulting products are undefined, since it appears to be unknown where the modifying group is attached to the product. By making use of calixarenes as templates P.A. Gale et al synthesized Calixarene-calix pyrrole dimers (calixarene capped- calixpyrrole) and expanded cahxpyrroles (Tet Lett 37(44), 1996,7881) and also reported the synthesis of calixpyridino pyrroles and calix pyridines from cahxpyrroles (Chem com 1998, 1). Macrocycles have unexpected properties that make them particularly useful. Calixpyrroles bind anion and neutral molecular species in solution and in the solid state in such an effective and selective way the anions or neutral molecular species can be separated from other anions and neutral molecular species. Further the affinity a macrocycle has for a particular species can be 'tuned' by strategic choice of electron-donating or electron-withdrawing peripheral substituents for the synthesis of macrocycles. • According to W.O.Pat.No. 97/37995, various types of cahxpyrroles was synthesized using different ketones including tetrahydrothiopyran-4-one, diphenylacetone, 10-nonadecanone, acetyl ferrocenes and chiral cahxpyrroles by using chiral ketones. And also reported the synthesis of expanded cahxpyrroles, where n4, (i.e. Calix (5) pyrrole, Calix (6) pyrrole, calix (8) pyrroles), calix pyridino pyrroles, calix pyridines and their applications. Application of these properties for removal of biological ions or neutral molecule species for medical uses, removal of undesirable ions or neutral molecule species from environmental sources provides only a few of the practical and important uses. These calix (4) pyrroles can be used in the dialysis of bodily fluids. Examples of dialyzable substrates include, but are not limited to phosphate containing molecules or halide waste (i.e. diabetes or drug overdoses and kidney dialysis). Clean technology is fast replacing the various processes, which were once catalyzed by highly corrosive liquid acids, due to the growing concern for the environment. In these eco-friendly processes, solid acids which are highly selective and active with strong proton donating sites distributed uniformly within the pores, have been found to be an attractfrig replacement for the non-reusable, hazardous liquid acids. Porous materials created by nature or by synthetic have found great utility in all aspects of human activity. The pore structure of solids is usually formed in the stages of crystallization or subsequent treatment. Depending on their predominant pore size, the solid materials are classified as microporous, mesoporous and macroporous materials. The only class of porous materials possessing rigorously uniform pore sizes is that of Zeolites and related molecular sieves. Zeolites are uniform porous crystalline aluminosilicates and their lattice is composed by T04 tetrahedral (T=A1 and Si) linked by sharing the apical oxygen atoms (Breck D.W., Zeolite molecular sieves: Structure, Chemistry and Use; Wiley and Sons; London 1974). As Zeolites act as sieves at the molecular level, these are considered as a subclass of molecular sieves. Zeolites have a number of interesting physical and chemical properties. The classes of phenomena that are of greatest practical importance are the availability to sorb organic and inorganic substances, to act as cation exchangers and to catalyze a wide variety of reactions. But due to the smaller pore size of these molecular sieves restricted their wide range applications, especially in case of larger molecules. But this has been overcome by the report of Mesoporous molecular sieves by Mobil researchers (C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli and J.S. Beck, Nature 359 (1992) 710) in 1992. These Mesoporous molecular sieve (MCM-41) has been opened a new era in the zeolite catalysis. Till then many reports have been published on the applications of this material for the catalytic activity towards oxidation, acylation and alkylation. And support material for enzymes, whole cell immobilization, and nano particles. The previous processes have the disadvantage that (a) in all the cases mineral acids used as catalysts which are highly corrosive, (b) in all the cases inert atmosphere should be maintained, (c) in all the cases tedious work-up procedure is present, such as neutralization of acid etc, (c) separation and reusability of the catalyst is not possible, (d) in some cases more than a single step is carried out to get a particular calix pyrrole selectively, and (e) in some cases dry conditions should be maintained in order to obtain the corresponding compound. Increasing the applications of these calix pyrroles demands an eco-friendly, environmentally clean, economical and free handling process. The present invention provides an eco-friendly process, which can overcome all the above drawbacks. Objects of the invention The main object of the present invention is to provide calyx (4) pyrroles over zeolite molecular sieves, which is an eco-friendly heterogeneous catalytic method. Accordingly, the present invention provides a novel compounds of substituted calix(4) pyrroles namely tetraspiro cycloheptyl calix (4) pyrrole, tetraspiro cyclooctyl calix (4) pyrrole and tetraspiro (2-methyl cyclohexyl) calix (4) pyrrole as shown in structural formulae 1,2 & 3 (Formula Removed) Formula 1 & 2 Formula 3 Wherein, when n=3, Formula 1 n=4, Formula 2 for use in Another object of the present invention is to provide a process for the synthesis of novel calix (4) pyrrole selected from the group consisting of tetrasppirocycloheptyl calix (4) pyrrole, tetraspirocyclooctyl calyx (4) pyrrole and tetraspiro (2-methylcyclohexyl) calyx (4) pyrrole with sufficiently good yields. Still another object of the present invention is to synthesize calyx (4) pyrroles over molecular sieve catalysts under microwave irradiation, which is a solvent free reaction. Yet another object is to provide a method wherein the kind and composition of calix (4) pyrrole can be varied within limits by a proper selection of catalyst. Yet another object of this invention is to provide an efficient and economical method for synthesizing calix (4) pyrroles from pyrrole and ketones over solid acid catalysts. Yet another object of this invention is to provide an efficient and economical method for synthesizing calix (4) pyrroles from pyrrole and ketones over solid acid catalysts. The present invention relates to novel calix (4) pyrroles. The invention particularly relates to heterogeneous eco-friendly methodology for the synthesis of calyx (4) pyrroles by using pyrrole and ketone in dichloromethane solvent. Specifically, the present invention relates to the synthesis calix (4) pyrroles from corresponding pyrrole and ketone over mesoporous (Mesoporous molecular sieve) MCM-41 molecular sieves with a high yield and selectivity. In an embodiment of the invention, the catalyst is selected from MCM-41, HZSM- 5(30), Hß, HY and SAPO-5. In another embodiment of the invention, the catalysts MCM-41, HZSM-5(30), Hß, HY and SAPO-5 are conventional zeolite catalysts. In another embodiment of the invention, the amount of catalyst used is ranging from 0.1 g to 1.0 g. In still another embodiment of the invention, the solvent used for refluxing is selected from dichloromethane, methanol, and acetonitrile. In yet another embodiment of the invention, the catalysts used are having the following surface area and pore size as given in the table below. (Table Removed) In yet another embodiment of the invention, the pore size and surface area of the catalysts used in the reaction are given in the following table. (Table Removed) In yet another embodiment of the invention, the molar ratio of pyrrole to ketone is selected in between 1:1 to 1:4. In yet another embodiment of the invention, the cycloketone is selected from the group comprising cyclohexanone, cycloheptanone, cyclopentanone and cyclooctanone. In yet another embodiment of the invention, the acyclic ketone is selected from the group comprising methyl ethyl ketone and 3-pentanone. In yet another embodiment of the invention, acyclic products are obtained using the catalyst HY. In yet another embodiment of the invention, major amounts of liner products are obtained using catalyst HZSM-5 (30). In yet another embodiment of the invention, the yield of the cafix (4) pyrrole is up to 70%. In yet another embodiment of the invention, the selectivity of the calix (4) pyrrole is up to 90 %. In one more embodiment of preparing calix (4) pyrroles or tetraspiro calix (4) pyrroles, said method comprising mixing a pyrrole with a acyclic or cyclic ketones over a molecular sieve solid acid catalyst and subjecting the mixture to microwave radiation at a radiation level of about 2450 MHz (HI power) for 3 to 10 minutes and optionally, refluxing using a solvent for extracting the compounds. In another embodiment, the solvent used for refluxing is selected from dichloromethane, methanol, and acetonitrile. In yet another embodiment of the present invention, in the equimolar reaction, the molar ratio of pyrrole to ketone is 1:1 and dichloromethane is used as a solvent for refluxing to obtain cyclic products. In yet another embodiment, the catalyst used is mesoporus molecular sieve catalyst (MCM-41). In yet another embodiment, the acyclic ketone used is acetone. In yet another embodiment, the cyclic ketone used is cyclohexanone. In yet another embodiment, the preparation of calix (4) pyrroles or tetraspiro calix (4) pyrroles is a solvent free process. The catalyst can be synthesized from the well known defined methods. The starting materials used in the process are acyclic and cyclic ketones, which are readily available. Reacting the pyrrole with acyclic ketones, which are selected from acetone, methyl ethyl ketone, and 3-pentanone leads to form octamethyl calix (4) pyrrole, tetramethyl tetraethyl calix (4) pyrrole, and octaethylcalix (4) pyrroles correspondingly. In case of cyclic ketones, cyclohexanone, cyclopentanone, cycloheptanone, 2- methylcyclochexanone, cyclo octanone forms tetraspirocyclochexyl calix (4) pyrrole, tetraspirocyclopentyl calix (4) pyrrole, tetraspirocycloheptyl calix (4) pyrrole, tetraspiro (2- methylcyclohexyl) calix (4) pyrrole and tetraspirocyclooctyl calix (4) pyrrole correspondingly. The catalyst MCM-41 (Mesoporous molecular sieve) prepared by an aqueous solution of aluminum isopropoxide (0.38 g) and to it an aqueous solution of sodium hydroxide (0.3g) was added in 50 ml beaker and stirred in hot conditions, till a clear solution was formed. Then 9.4 ml of tetraethyl ammonium hydroxide (TEAOH) and Ludox colloidal silica (9.26 g) were added drop wise while stirring at room temperature. Then hexadecyl tri-methylammonium bromide (10.55 g) was added slowly to the above solution. The pH of the mixture was maintained at 11.0-11.5. Finally, the gel mixture was transferred into an autoclave and heated at 100°C for 24 h. The solid product was recovered by filtration, washed with deionized water and dried in air. All the as-synthesized samples were calcined at 773K in air. The catalyst weight can be varied in this reaction from 0.lg to Ig. The pyrrole to acetone molar ratio can be varied from 1:1 to 1:4. In the reaction, an equimolar ratio of pyrrole and cyclohexanone was refluxed in dichloromethane (DCM) for 10 h in presence of MCM-41 catalyst. Along with the cyclized product, tetraspirocyclo hexyl calix (4) pyrrole 4a, the acyclic condensed products viz., dimer, trimer and tetramer (4b, 4c and 4d) were also formed. In place of MCM-41 catalyst when HY was used, instead of cyclic product only the acyclic products were formed. When HZSM-5 (30) was used as catalyst, along with the cyclized product calix (4) pyrrole, linear products also formed but the linear products are in major. When HP was used as catalyst, along with the cyclized product calix (4) pyrrole, linear products are also formed. The reaction time will be varied depending upon the nature of ketone and the catalyst. In the one of equimolar reaction, pyrrole and acetone was mixed thoroughly and 0.5 gm of MCM-41 catalyst was added and then subjected to microwave irradiation for 3 min at a radiation level of about 2450 MHz and extract the compound by using dichloromethane as solvent, resulting low selectivity of cyclic product (la). The reaction time is varied from 3 min to 10 min. In another equimolar reaction, pyrrole and cyclohexanone was mixed thoroughly and added 0.5 gm of MCM-41 catalyst and then subjected to microwave irradiation for 3 min and extracted the compound by using dichloromethane as solvent, resulting low selectivity of cyclic product (4a). The reaction time is varied from 3 min to 10 min. The radiation level is maintained at about 2450 MHz. Mixed calix pyrroles such as tetramethyl dicyclohexyl calix (4) pyrrole, hexamethyl cyclohexyl calix (4) pyrrole, dimethyl tri cyclohexyl calix (4) pyrrole has been obtained by reacting the acetone, cyclohexanone in required molar ratio over MCM-41 catalyst in dicholoromethane solvent by refluxing for 15 h. Pore size and surface area of the catalysts plays a major role in this reaction. All the catalysts were characterized by X-ray diffraction, Infrared spectroscopy, BET- surface area and NH3-Temperature programmed desorption. The inventors found that the dichloromethane (DCM) was better solvent than other solvents like methanol, acetonitrile. Acetone as solvent did not found the selectivity towards higher selectivity of octamethyl calix (4) pyrrole. After the reaction was completed the catalyst was separated by filtration, then the solvent was vacuum evaporated and the residue was mounted on the silica column and the products were separated through n-hexane: ethylacetate (95:5) media and confirmed by H1 NMR, C13 NMR and Mass spectroscopy and for la, single crystal XRD also. Brief description of the accompanying drawings Figure 1 shows structure of octa alkyl substituted calix (4) pyrrole, wherein R1 and R2 = CH3 for octamethyl calix (4) pyrrole (la), R1 =CH3 and R2 = CH2CH3 for Tetraethyl Tetra methyl calix (4) pyrrole (2a), and R1=R2 = CH2CH3 for octaethyl calix (4) pyrrole (3a). Figure 2 shows structure of tetraspiro cyclohexyl calix (4) pyrrole (4a). Figure 3 shows structure of tetraspiro cycloalkyl substituted calix (4) pyrrole wherein, n = 1 for tetraspiro cyclopentyl calix (4) pyrrole (5a), n =2 for tetraspiro cycloheptyl calix (4) pyrrole (6a), and n =4 for tetraspiro cyclooctyl calix (4) pyrrole (7a). Figure 4 shows structure of (2-methyl cyclohexyl) calix (4) pyrrole (8a). Figure 5 shows structures of condensed products viz. dimer (4b), trimer (4c) and tetrameter (4d). Figure 6 shows structure of alkyl substituted linear (dimer) products, wherein R1 and R2 - CH3 for la, R1 =CH3 and R2 = CH2CH3 for 2a, and R1=R2 = CH2CH3 for 3a. Figure 7 shows structure of cyclic products, wherein n = 1 for 5b; n - 3 for 6b and n = 4 for 7b. Figure 8 shows structure of dimer product of 2-methylcyclohexyl (8b). The process of this invention is described in further detail herein below by way of the following examples, which are only illustrative and are not intended to limit the scope of this invention. EXAMPLES Example 1 Synthesis of Octamethyl calix (4) pyrrole In a 50ml round bottom flask, 20ml of dichloromethane (DCM) was introduced and 0.5 ml of pyrrole, 0.503ml of acetone, and 0.5g of MCM-41 catalyst were added to it. Then the reaction mixture was refluxed for 10 h. The cooled reaction mixture filtered, washed with DCM (5 X 10ml). Then the solvent DCM was removed under reduced pressure and product was purified by column chromatography on silicagel (hexane eluent) affording the product as a white powder. The product was confirmed by NMR and Mass spectrometry. Yield of octamethyl calix (4) pyrrole was 67.5 %; Selectivity was 73.0; Conversion of pyrrole was 92.4 %. Selectivity was calculated as follows Selectivity = Yield / Conversion la: 'HNMR (200 MHz, CDC13): δ= 1.49 (s, 24H, -CH3), δ.85 (br, d, 8H; (pyrrole-ßH), 6.89-6.99 (br, S, 4H, pyrrole-NH); HR-MS(EI): for calcd for C28 H36 N4: calcd: 428.2939; found: 428.2938. Example 2 In a 50ml round bottom flask 20ml of dichloromethane (DCM) was introduced and 0.5ml of pyrrole, 0.503 ml of acetone, and 0.5g of HZSM-5 (30) catalyst were added to it. Then the mixture was refluxed for 10 h. The cooled reaction mixture filtered, washed with DCM (5 X 10ml). Then the solvent DCM was removed under reduced pressure and product was purified by column chromatography on silicagel (hexane eluent) the products were confirmed by NMR and estimation was done by high pressure thin layer chromatography (HPTLC). The Results are as follows: Conversion of pyrrole is 81.4%. (Table Removed) Example 3 In a 50ml round bottom flask 20ml of dichloromethane (DCM) was introduced and 0.5ml of pyrrole, 0.503 ml of acetone, and 0.5g of HY catalyst was added to it. Then the mixture was refluxed for 10 h. The cooled reaction mixture filtered, washed with DCM (5 X 10ml). Then the solvent DCM was removed under reduced pressure and product was purified by column chromatography on silicagel (hexane eluent) the products were confirmed by NMR and estimation was done by high pressure thin layer chromatography (HPTLC). The results as follows: conversion of pyrrole is 72.5%. (Table Removed) Ib: 'HNMR (200 MHz, CDC13): δ= 1.62 (s, 6H, -CH3), δ.01-6.11 (m, 4H, pyrrole-ßH), 6.48-6.56 (m, 2H, pyrrole-αH), 7.42-7.78 9br, s, 2H, NH), 13C NMR (50 MHz, CDC13): 6= 29.30, 35.32, 103.74, 107.72, 117.03, 138.21; HR-MS (El) for C11H14N2: calcd: 174.1156; found: 174.1148 Example 4 Synthesis of tetramethyl tetraethyl calix (4) pyrrole In a 50ml round bottom flask 20ml of dichloromethane (DCM) was introduced and 0.5ml of pyrrole, 0.65 ml of Methyl ethyl ketone, and 0.5g of Al-MCM-41 catalyst was added to it. Then the mixture was refluxed for 72h. The cooled reaction mixture filtered, washed with DCM (5 X 10ml). Then the solvent DCM was removed under reduced pressure and product was purified by column chromatography on silicagel (hexane eluent) the products were confirmed by NMR and estimation was done by high pressure thin layer chromatography (HPTLC). The results as follows: conversion of pyrrole is 48.0%. (Table Removed) 2a: 'HNMR (200 MHz, CDC13): δ= 0.63-0.8 (t, J(H,H)=2Hz, 12H), 1.34-1.48 (br, s, 12H, -CH3), 1.86-1.96 (q, 8H, CH3CH3), 5.85 (br, d, 8H), 6.89-7.09 (br, s, 4H, NH); 13C NMR ( 50MHz, CDC13): 137.26, 103.75, 39.18, 33.21, 26.04, 8.65; HR-MS (El) for C32H44N4 calcd: 484.3565, found: 484.3561. 2b: 'HNMR (200 MHz, CDC13): δ=0.72-0.85 (t, J-8.37, 3H. -CH2CH3), 1.53 (s, 3H, -CH3), 1.92-2.06 (q, J=4.65, 6.97 Hz, 2H, -CH2CH3), 6.0-6.10 (m, 4H, pyrrole-ßH), 6.50-6.58 (m, 2H,pyrrole-αH), 7.6 (BR, S, 2H, pyrrole-NH). I3C NMR: 138.04, 116.29, 107.61, 104.66, 39.35, 33.63, 25.57, 8.91; HR-MS (El) for C12H16N2: calcd: 188.1313, found: 188.1317. Example 5 Synthesis of octaethyl calix (4) pyrrole In a 50ml round bottom flask 20ml of dichloromethane (DCM) was introduced and 0.5ml of pyrrole, 0.73 ml of 3-Pentanone, and 0.5g of Al-MCM-41 catalyst was added to it. Then the mixture was refluxed for 5 days. The cooled reaction mixture filtered, washed with DCM (5 X 10ml). Then the solvent DCM was removed under reduced pressure and product was purified by column chromatography on silicagel (hexane eluent) the products were confirmed by NMR and estimation was done by high pressure thin layer chromatography (HPTLC). The results as follows: conversion of pyrrole is 77.0 %. (Table Removed) 3a: 'HNMR (200 MHz, CDC13): δ= 5.85-5.93 (br, d, J (H,H)=2.27 Hz, 8H, pyrrole-ßH), 6.96-7.05 (br, s, 4H, pyrrole-NH); HR-MS (El) for C36H52N4 : calcd: 540.4191, found:540.4194. 3b: 'HNMR (200 MHz, CDC13): δ= 0.68-0.76 (t, J=7.17, 6H, CH2CH3), 1.88-2.01 (q, J=5.12, 7.69 Hz, 4H, CH2-CH3), 6.01-6.12 (br, s, 4H, pyrrole-ßH), 6.5-6.59 (br, s, 2H), 7.45-7.65 (br, s, 2H, pyrrole-NH); HR-MS (El) for C13Hi9N2: calcd: 202.1469, found: 202.1475. Example 6 Synthesis of tetraspiro cyclohexyl calix (4) pyrrole In a 50ml round bottom flask 20ml of dichloromethane (DCM) was introduced and 0.5ml of pyrrole, 0.75 ml of Cyclohexanone, and 0.5g of calcined and dried Al-MCM-41 catalyst was added to it. Then the mixture was refluxed for 10 h The cooled reaction mixture filtered, washed with DCM (5 X 10ml). Then the solvent DCM was removed under reduced pressure and product was purified by column chromatography on silicagel (hexane eluent) the products were confirmed by NMR and estimation was done by high pressure thin layer chromatography (HPTLC). The results as follows: conversion of pyrrole is 95.0%. (Table Removed) 4a : 'H NMR (200 MHz, CDC13): δ= 1.38-1.68(m,24H, cyclohexyl), 1.88-2.12(m,16H, cyclohexyl), 5.86 (br.d, 8H; pyrrole-ßH), 6.95 (br.s, 4H, pyrrole NH), 13C NMR (50 MHz,CDCl3): δ = 22.75, 26.04, 37.17, 39.63, 103.44 (pyrrole-ßH), 136.50(pyrrole-aH); HR-MS(EI) for C40H52N4 (H+): calcd:588.4191; found: 588.4169. Example 7 In a 50ml round bottom flask 20ml of dichloromethane (DCM) was introduced and 0.5ml of pyrrole, 0.75 ml of Cyclohexanone, and 0.5g of HZSM-5 (30) catalyst was added tojt. Then .the mixture was refluxed for 10 h. The cooled reaction'mixture filtered, washed with DCM (5 X 10ml). Then the solvent DCM was removed under reduced pressure and product was purified by column chromatography on silicagel (hexane eluent) the products were confirmed by NMR and estimation was done by high pressure thin layer chromatography (HPTLC). The results as follows: Conversion of pyrrole is 69.6%. (Table Removed) Example 8 In a 50ml round bottom flask 20ml of dichloromethane (DCM) was introduced and 0.5ml of pyrrole, 0.75 ml of Cyclohexanone, and 0.5g of HY catalyst was added to it. Then the mixture was refluxed for 10 h. The cooled reaction mixture filtered, washed with DCM (5 X 10ml). Then the solvent DCM was removed under reduced pressure and product was purified by column chromatography on silicagel (hexane eluent) the products were confirmed by NMR and estimation was done by high pressure thin layer chromatography (HPTLC). The results as follows: conversion of pyrrole is 78.9%. 4b (Table Removed) 'H NMR (200 MHz, CDC13): δ = 1.36-1.65(m,6H, cyclohexyl),1.95- 2.12(m,4H,cyclohexyl),6.01-6.12(m,4H,pyrrole-ßH), 6.45(br.d, 2H; pyrrole-aH), 7.32-7.68 (br.s, 2H, pyrrole NH); 13C NMR(50 MHz,CDCl3):δ = 22.17, 26.32, 37.65, 41.21, 104.64, 108.27,116.99,139.21; HR-MS(EI) for C14H18N2 (H+): calcd:214.1469; found: 214.1460.M+: 214(100%), 171,148 4d: HR-MS (El) for C H N: calcd: 508.3546; found = 508.3565 Example 9 Synthesis of tetraspiro cyclopentyl calix (4) pyrrole In a 50ml round bottom flask 20ml of dichloromethane (DCM) was introduced and 0.5ml of pyrrole, 0.64 ml of Cyclopentanone, and 0.5g of Al-MCM-41 catalyst was added to it. Then the mixture was refluxed for 20 h. The cooled reaction mixture filtered, washed with DCM (5 X 10ml). Then the solvent DCM was removed under reduced pressure and product was purified by column chromatography on silicagel (hexane eluent) the products were confirmed by NMR and estimation was done by high pressure thin layer chromatography (HPTLC). The results as follows: conversion of pyrrole is 74.3%. (Table Removed) 5a: 'HNMR (200 MHz, CDC13) : δ= 1.55-1.8 (m, 16H, cyclopentyl), 1.85-2.01 (m, 16H, cyclopentyl), 5.8 (br, d, J=0.38 Hz, 8H, pyrrole-ßH),7.0 (br, s, 4H, pyrrole-NH); 13C NMR: ( 50 MHz, CDC13): 137.20 (pyrrole-aH), 103.04 (pyrrole-ßH), 46.93, 39.02, 23.91; HR-MS (El) for C36H44N4: calcd: 532.3565, found: 532.6575. Example 10 Synthesis of tetraspiro cycloheptyl calix (4) pyrrole In a 50ml round bottom flask 20ml of dichloromethane (DCM) was introduced and 0.5ml of pyrrole, 0.85ml of Cycloheptanone, and 0.5g of Al-MCM-41 catalyst was added to it. Then the mixture was refluxed for 3 days. The cooled reaction mixture filtered, washed with DCM (5 X 10ml). Then the solvent DCM was removed under reduced pressure and product was purified by column chromatography on silicagel (hexane eluent) the products were confirmed by NMR and estimation was done by high pressure thin layer chromatography (HPTLC). The results as follows: conversion of pyrrole is 69.8%. (Table Removed) 6a: 'HNMR (200 MHz, CDC13): δ= 1.45-1.72 (m, 32H, cycloheptyl), 1.94-2.12 (m,16H, Cycloheptyl), 5.83 (br, d,8H, pyrrole-ßH), 6.78-6.88 (br,s,4H,NH),; HR-MS (El) for C44H6oN4: calcd: 644.4817, found: 644.4752. 6b: 'HNMR (200 MHz, CDC13): δ=2.12-2.26(m,8H,cycloheptyl), 2.42-2.58 (m,4H, cycloheptyl), 6.01-6.13 (m, 4H,pyrrole-ßH), 6.52-6.61 (m,2H, pyrrole-αH),7.51-7.71 (br,s,2H, pyrrole-NH); HR-MS (El) for C15H20N2: calcd: 228.1626, found 228.1616. Example 11 Synthesis of tetraspiro cycle octyl calix (4) pyrrole In a 50ml round bottom flask 20ml of dichloromethane (DCM) was introduced and 0.5ml of pyrrole, 0.9ml of Cyclooctanone, and 0.5g of Al-MCM-41 catalyst was added to it. Then the mixture was refluxed for 5days. The cooled reaction mixture filtered, washed with DCM (5 X 10ml). Then the solvent DCM was removed under reduced pressure and product was purified by column chromatography on silicagel (hexane eluent) the products were confirmed by NMR and estimation was done by high pressure thin layer chromatography (HPTLC). The results as follows: conversion of pyrrole is 78.0%. (Table Removed) 7a: 'HNMR (200 MHz, CDC13): δ=1.18-1.82 (m, 56H, cyclooctyl), 5.93 (br,d,8H, pyrrole-ßH), 6.91-6.99 (br,s,4H, pyrrole-NH); HR-MS (El) for C48N68N4: calcd; 700.5443, found: 700.5456. 7b: 'HNMR (200 MHz, CDC13): δ=1.42-1.80(m,10H, cyclooctyl), 2.09-2.2l(m,4H, cyclooctyl), 5.99-6.16 (m,4H,pyrrole-ßH), 6.48-6.57 (m,2H,pyrrole-aH),7.42-7.69(br,s,2H,pyrrole-NH),; HR-MS(EI) forC16N22N2: calcd: 242.1782, found: 242.1777. Example 12 Synthesis of tetraspiro (2-methylcyclohexyl) calix (4) pyrrole In a 50ml round bottom flask 20ml of dichloromethane (DCM) was introduced and 0.5ml of pyrrole, 0.875ml of 2-Methyl cyclohexanone, and 0.5g of Al-MCM-41 catalyst was added to it. Then the mixture was refluxed for 10 h. The cooled reaction mixture filtered, washed with DCM (5 X 10ml). Then the solvent DCM was removed under reduced pressure and product was purified by column chromatography on silicagel (hexane eluent) the products were confirmed by NMR and estimation was done by high pressure thin layer chromatography (HPTLC). The results as follows: conversion of pyrrole is 60.2%. (Table Removed) 8a: HR-MS (El) for C44H60N4: calcd: 644.4817, found 644.4847. 8b: 'HNMR (200 MHz, CDC13): δ=0.8(d,3H,J(H,H)=7.2 Hz,CH3), 1.24- 2.34(m,9H,cyclohexyl), 6.01-6.14 (m,4H,pyrrole-ßH), 6.42-6.54 (m,2H ,pyrrole- αH),7.48(br,s,2H,pyrrole-NH); HR-MS (El) for C15H20N2: calcd: 228.1626, found:228.1634. The main advantages of the present invention are: 1. 2. 3. 4. The present invention is an improved process that comprises environmentally clean technology with low wastage, easy separable and reusability of the catalyst. This method provides a selective heterogeneous catalyst with longer life. The catalysts used in this process are easily separable by the simple filtration It also provides a method wherein the kind and composition of calix (4) pyrrole can be varied within limits by a proper selection of catalyst.1 5. Tetraspirocyclopentyl calix (4) pyrrole has been synthesized for the first time over the heterogeneous method as well as homogeneous method. 6. Tetraspirocycloheptyl calix (4) pyrrole has been synthesized for the first time over the heterogeneous method as well as homogeneous method. 7. Tetraspirocyclooctyl calix (4) pyrrole has been synthesized for the first time over the heterogeneous method as well as homogeneous method. 8. Tetraspiro (2-Methylcyclohexyl) calix (4) pyrrole has been synthesized for the first time over the heterogeneous method as well as homogeneous method. The salient futures of the process are i) the present invention provides an improved process that comprises environmentally clean technology with low wastage, easy separable and reusability of the catalyst, ii) the catalysts used in this process are easily separable by the simple filtration, iii) this process provides an eco-friendly method with higher selectivity, iv) a method provides a selective heterogeneous catalyst with longer life, and v) a method wherein the kind and composition of calix(4)pyrrole can be varied within limits by a proper selection of catalyst and this invention provides an efficient and economical method for synthesizing calix(4)pyrroles from pyrrole and ketones over solid acid catalysts. We claim : 1.A novel compounds of substituted calix(4) pyrroles namely tetraspiro cycloheptyl calix (4) pyrrole, tetraspiro cyclooctyl calix (4) pyrrole and tetraspiro (2-methyl cyclohexyl) calix (4) pyrrole as shown in structural formulae 1,2 & 3 (Formula Removed) Formula 1 & 2 Wherein, when n=3, Formula 1 Formula 3 for use in removal of biological iors or neubel molecular spcies for medied user A novel compounds of substituted calix (4) pyrroles substantially as herein described with reference to the examples and drawing accompanying this specification.

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