Title of Invention

"A PROCESS FOR A NEW HETEROCYCLIC CALIXARENES AND THEIR DERIVATIVES"

Abstract

A process for new heterocyclic calixarenes and their derivatives and the calyx(n)arenes so obtained is disclosed The process comprises: (i) methylating debutylated calix[n]arenes wherein 'n' represents phenolic units and is equal to 4,6,8, and 10, such as herein described to get methylated calix[n]arenes (ii) formylating the methylated calix[n]arenes obtained from step-1 in a manner such as herein disclosed, to yield formylated calyx(n)arene, (iii) subjecting the said formylated calix[n]arenes obtained from step-2 to form linkage with respective heterocyclic moiety in a manner such as herein described to produce corresponding heterocyclyl calix[n]arenes wherein n is equal to 4,6,8 & 10.

Full Text

FIELD OF THE INVENTION: The present invention relates to a new heterocyclyl calixarenes and a process of preparation thereof. Particularly, the invention relates to a process for preparation of heterocyclyl calixarenes represented by the expression heterocylyl calix[n]arenes and their derivatives, wherein 'n' represents phenolic units and is equal to 4, 6, 8 or 10. More particularly it relates to preparation of heterocylyl calyx[n]arenes, wherein 'n' is equal to 6 or 8. Specifically the arenes and their derivatives find application in extraction and recovery of metal ions from the industrial waste. Additionally, the said arenes after recovery of metal ions can be recovered and reused. In accordance with the process of the present invention, debutylated calix(n)arenes are used as a starting material. BACKGROUND OF THE INVENTION: The loss of metal ions in the industrial wastes is the problem, which makes the industrial process not only cumbersome but also expensive. This problem is more damaging when the metal ions are expensive, particularly transition metal ions and are available in scarcity or their processing is possible only by difficult methodology. In view of above difficulties a great emphasis has been given to develop the processes for extraction and recovery of metal ions from the industrial wastes. The present invention is a step towards the development of products, which can be used in any of such processes. The term Calixarenes is chosen to describe the shape of the cylic tetramers when they assume that it is present in cone confirmation and extended to be applied to all those compounds from phenols and resorcinols even where calix is no longer of descriptive shape ("Calixarenes a versatile class of macrocyclic compounds"- Editors: J. Vicens and V. Bohmer 1991). Originally macrocyclic compounds capable of assuming a basket (or "calix") shaped conformation. They are formed from p-hydrocarbyl phenols and formaldehyde. The term now applies to a variety of derivatives by substitution of the hydrocarbon cyclo{oligo[(l,3-phenylene) methylene]}. C. D. Gutsche, Calixarenes, The Royal Society of Chemistry, 1989. (Formula Removed) Thus, calix[n]arenes are phenolic macrocyclic metacyclophanes that possess a cavity in their molecular structure [Calixarenes: A Versatile Class of Macrocyclic Compounds, 1991 and Calixarenes, Royal Society of Chemistry, Cambridge, 1989]. The dimensions of this cavity in the Calix[n]arenes can be varied by varying the value of n', which indicates the number of phenolic units. Such variation of cavity in calix[n]arenes can be affected by easy executable experimental conditions [Tetrahedron, 1993, 49, 8933]. The method of varying the dimensions of this cavity in calyx[n]arenes is known in the art [Calixarenes: A Versatile Class of Macrocyclic Compounds, 1991; Calixarenes, Royal Society of Chemistry, Cambridge, 1989; Tetrahedron, 1993, 49, 8933; Chem. Rev., 1998, 98, 2495; Chem. Rev., 1997, 97, 1713; Chem. Int. Ed.Engl., 1995, 34, 713]. Despite distinct possible applications very little work has been reported on the synthesis and applications of heterocyclyl calix[n]arenes. The parent calix[n]arenes are known to be inefficient ion extractants {Tetrahedron, 1993, 49, 8933], but some of the derivatives of calix[n]arenes have been determined to exert specific responses to barium, calcium and alkali metal ions. ADVANTAGES OF THE PRESENT INVENTION: The present invention is particularly a step towards the disclosure of a process for preparation of series of new heterocyclyl calix[n]arenes, wherein n represents phenolic units and the units present are 4,6,8 &10. Further, in case of the heterocyclyl calyx(n)arenas, the heterocyclic groups are connected through carbon carbon linkages. The title compounds can function as efficient extractants for metal ions, particularly transition metal ions from the industrial wastes in order to make the overall process more economical by affecting the recovery of such metal ions, particularly transition metal ions. The new heterocyclyl calix[n]arenes being reported in the presently disclosed invention are, particularly, useful for extraction of silver, calcium, magnesium, barium, lead, copper and zinc, and precious metals in addition to alkali metals like sodium, potassium and caesium from acidic solutions. The advantage of the present invention is that, the heterocyclyl calix[n]arenes synthesized in accordance to the presently disclosed invention, are suitable for extraction and recovery of large number of metal ions, as stated here in above. Further advantage of the present invention is that the heterocyclyl calix[n]arenes can be recovered after recovery of the metal ion, for reuse, hence results in more economic process of recovery of the metal ions from the industrial wastes. OBJECTS OF THE PRESENT INVENTION: The main object of the present invention is to disclose new heterocyclyl calix[n]arenes and their derivatives, wherein the heterocyclic group is linked through carbon carbon linkages, which are suitable for extraction of metal ions, particularly of silver, calcium, magnesium, barium, lead, copper and zinc and precious metals in addition to alkali metals like sodium, potassium and caesium. Other object is to produce heterocylyl calix[n]arenes and their derivatives, wherein 'n' represents phenolic units and is equal to 4, 6, 8 or 10, particularly, 'n' is equal to 6 or 8. Further object of the present invention is to make a complete disclosure of a process for preparation of series of new heterocyclyl calix[n]arenes. Yet another object of the present invention is to disclose new heterocyclyl calix[n]arenes and their derivatives, which can be recovered and reused after recovery of the metal ions. DESCRIPTION OF THE INVENTION: Accordingly, new heterocyclyl calix[n]arenes and the method of preparation thereof, particularly heterocylyl calix[n]arenes, wherein 'n' is equal to 4, 6, 8 or 10, more particularly heterocyclyl calix[n]arenes, wherein 'n' is equal to 6 or 8, and the process of preparation thereof are disclosed herein below. The heterocyclyl calix[n]arenes disclosed herein below are suitable for extraction of metal ions, particularly of silver, calcium, magnesium, barium, lead, copper and zinc and precious metals in addition to alkali metals like sodium, potassium and caesium. The presently disclosed heterocyclyl calix[n]arenes are prepared from debutylated calix[n]arenes, which in turn is prepared by any known method, particularly by debutylation of p-tert-butyl calyx[n]arene with phenol in presence of aluminium chloride in toluene solvent at about 40°C and working the reaction as reported in literature. The debutylated calix[n]arenes synthesized are analysed by IR and NMR spectra. The p-tert-butyl calix[n]arene is also prepared by any known method, particularly by condensation of p-tert-butyl phenol and formaldehyde solution in the presence of sodium hydroxide and working-up the reaction as reported in the literature. The debutylated calix[n]arenes are subjected to process of the presently disclosed invention to prepare new heterocyclyl calix[n]arenes. STATEMENT OF INVENTION: Accordingly the present invention provides new calyx(n)arenes and a method of preparation thereof wherein the new heterocyclyl calyx(n)arenes so obtained having general formula 1 (Formula Removed) wherein (i) w and z can be R, Ar, Het; R = alkyl with C=lto 16 Ar = aryl and Het = 5 or 6 membered heterocyclic components (ii) Y = N and X = NH,0, S preferably Y=X=N (iii) Rl = alkyl with C=lto 5 (iv) n = 4,6,8,or 10 preferably 4,6,or 8 which comprises: a) methylating debutylated calix[n]arenes wherein 'n' represents phenolic units and is equal to 4,6,8, and 10, such as herein described to get methylated calix[n]arenes b) (b)formylating the methylated calix[n]arenes obtained from step-1 in a manner such as herein disclosed, to yield formylated calyx(n)arene, c) subjecting the said formylated calix[n]arenes obtained from step-2 to form linkage with respective heterocyclic moiety by cyclising the said formylated calix(n)arenas in acidic solvent with aromaticdiketone and acid salt of alkalimetal or ammonium to produce corresponding heterocyclyl calix[n]arenas of general formula 1, wherein n is equal to 4,6,8 & 10. In accordance to the preferred embodiment of the present invention the debutylated calix[n]arenes is treated with alkyl halide, particularly methyl halide, more particularly methyl iodide in presence of metal hydride, particularly alkali metal hydride, more particularly sodium hydride in organic solvent, particularly mixture of tetrahydrofuran and dimethyl formamide methylated in Step-1 to yield methylated calix[n]arenes, particularly methoxycal ix [n] arenes. In accordance to another preferred embodiment of the present invention the methylated calix[n]arenes obtained from step-1 is dissolved in organic solvent, preferably in chloroform or methylene chloride or hexane or benzene, more preferably in chloroform and this solution of themethylated calix[n]arenes in organic solvent along with a freshly distilled titanium tetrachloride dissolved in organic solvent, preferably in benzene or chloroform, more particularly chloroform is added to a solution of alkyl ether, preferably of halide substituted dialkyl ether, more preferably 1,1-dichloromethylmethylether formylated inorganic solvent, preferably in chloroform and the mixture of these solutions of methylated calix[n]arenes in organic solvent and of titanium tetrachloride in organic solvent and of halide substituted dialkyl ether in organic solvent is allowed to react at a temperature of about 35 to 70°C, preferably at about 40 to 60°C in Step-2 to yield formylated calixfnjarenes. The formylation is also possible at a temperature ranging from 10°C to 70°C. In accordance to the preferred embodiment of the present invention the formylated calix[n]arenes obtained from step-2 is dissolved in an acidic solvent, preferably in phosphoric acid, acetic acid, hydrochloric acid or propionic acid, more preferably in hydrochloric acid and to this solution of formylated calix[n]arenes in acidic solvent a mixture of an aromatic diketone, preferably diphenyl hydroxy ketone and alkali metal or ammonium salt of acid taken, preferably ammonium salt of acid taken, more preferably ammonium chloride, if acid taken is hydrochloric acid, are added and the resultant solution is allowed to reflux for about 2 to 9 hrs, preferably for about 4 to 7 hrs in step-3 to yield the final product, that is heterocyclyl calix[n]arenes. In accordance to one of the preferred embodiments of this invention the heterocyclyl calix[n]arenes obtained in step-3 is separated from the reacted mass by pouring the reacted mass on water or alcohol-water mixture or chloroform-methanol mixture, preferably ice cold water or alcohol-water mixture or chloroform-methanol mixture to yield precipitates, which are in turn filtered, dried and then subjected to purification, preferably to column chromatography using eluents of increasing polarity to get the desired heterocyclyl calixarenes. The working of the present invention will be more apparent from the following particular set of experiment, which is not intended to limit the scope of the present invention. In accordance to one of the preferred embodiments of the present invention for preparation of the p-tert-butyl calix[n]arene about 25g of p-tert-butyl phenol is condensed with about 37% of about 30 ml of formaldehyde solution in the presence of sodium hydroxide and the reaction is subsequently worked as reported in the literature. The typical IR spectra of p-tert-butyl calix[n]arene, wherein 'n] is equal to 8 shows absorptions at 3150(br), 1600(sh), 1400(2h), 1375(m-sh), 1250(s), 1200(s), 882(s), 810(s), 780(s), 720(s), 700(bs) cm"1. In accordance to one of the preferred embodiments of the present invention about 13g or about 20mmol of p-tert-butyl calix[n]arene is reacted with about 9g or about 95mmol of phenol and about 15g or about l05mmol of aluminum chloride during debutylation step in toluene solvent at about 40°C and the reaction is subsequently worked-up as reported in literature to yield debutylated calix[n]arenes. The typical IR spectra of debutylated calix[n]arenes, wherein 'n' is equal to 8 shows absorptions at 2978(s), 1600(s), 1490(sh), 1405(sh), 1405(sh), 1265(s), 850(s), 720(s) cm'1. The typical NMR spectra of debutylated calix[n]arenes, wherein 'n' is equal to 8, when taken in deuterated chloroform solvent shows peaks at 9.8(s, 4H, D2O exchanged, OH,), 7.2-6.81(m, 12H, ArH), 3.94-3.49(brs, 8H, ArCH2Ar). In accordance to one of the preferred embodiments of the present invention about 1.25g or about 3mmol of debutylated calix[n]arenes is treated with about 2.5ml or about 50mmol methyl iodide in presence of about Ig or about 25mmol of sodium hydride in mixture of about 50ml of tetrahydrofuran and about 5ml of dimethyl formamide for methylation in Step-1 of the presently disclosed invention to yield methylated calix[n]arenes, particularly methoxycalix[n]arenes, wherein 'n' may be 4, 6, 8 or 10, preferably 6 or 8. The typical IR spectra of methoxycalix[n]arenes, wherein 'n' is equal to 8 shows absorptions at 2988(s), 2390(sh), 1495(s), 1450(s), 1405(sh), 1215(sh), 1180(sh), 1140(m-sh), 1100(w), 1050(m-sh), 810(s), 750(s) cm'1. The typical !H NMR spectra of methoxycalix[n]arenes, wherein 'n' is equal to 8 when taken in deuterated chloroform solvent shows peaks at 688 (s, 12H, ArH), 4.04(s, 8H, ArCH2Ar), 3.82(s, 12H, OCH3). In accordance to one of the preferred embodiments of the present invention about 2g of methoxycalix[n]arenes, wherein 'n' is equal to 8 obtained from step-1 is dissolved in about 50ml of chloroform and this solution of the methoxycalix[n]arenes in chloroform along with a freshly distilled about 5g of titanium tetrachloride dissolved in about 50ml of chloroform is added to a solution of about 2.5ml or about 22.0mmol or 1,1-dichloromethylmethylether in about 50ml of chloroform and the mixture of these solutions of methoxycalix[n]arenes, titanium tetrachloride and of 1,1-dichloromethylmethylether in chloroform is allowed to react at about 40 to 60°C in Step-2 to yield formylated calix[n]arenes, wherein 'n' may be 4, 6, 8 or 10, in particular in this experiment the formylated calix[n]arenes is obtained with n=8. The typical IR spectra of formylated calix[n]arenes, wherein 'n' is equal to 8 shows absorptions at 2976(sh), 2425(sh), 1780(s), 1628(sh), 1500(s), 1435(sh), 1292(s), 1136(s), 1050(s), 780(s) cm'1. The typical !H NMR spectra of formylated calix[n]arenes, wherein 'n' is equal to 8, when taken in deuterated chloroform solvent shows peaks at 9.74(s, 4H, CHO), 7.43(s, 8H, ArH), 4.12(s, 8H, ArCH2Ar), 3.75(s, 12H, OCH3). In accordance to one of the preferred embodiments of the present invention about 3g of formylated calix[n]arenes obtained in step-2 is dissolved in about 50ml of hydrochloric acid and to this solution of formylated calix[n]arenes in hydrochloric acid a mixture of about 1g of diphenyl hydroxy ketone and about 2g of ammonium chloride are added and the resultant solution is allowed to reflux for about 4 to 7 hrs in step-3 of cyclisation to yield the final product, that is heterocyclyl calix[n]arenes, wherein 'n' may be 4, 6, 8, or 10, in particular in this reaction it is equal to 8. In accordance to one of the preferred embodiments of this invention diphenyl hydroxy ketone and ammonium chloride are preferably taken in 1:2 ratio. In accordance to one of the preferred embodiments of this invention the heterocyclyl calix[n]arenes obtained in step-3 is separated from the reacted mass by pouring the reacted mass on ice cold chloroform-methanol mixture (about 100 to 500ml) to yield precipitates, which are in turn filtered, dried and then purified, preferably by column chromatography using eluents of increasing polarity to get the desired heterocyclyl calix[n]arenes, wherein 'n' may be equal to 4, 6, 8 or 10, particularly in this reaction the heterocyclyl calix[n]arene is obtained wherein 'n' is equal to 8. The typical IR spectra of heterocyclyl calix[n]arenes, wherein 'n' is equal to 8 shows absorptions at 3059(bs), 2935(sh), 1670.6(s), 1595.56(s), 1479, 1449.8, 1429(w), 1212(s), 1008.75(s), 765.83(s), 718.67(m), 696(s), 643.7(m) cm-1. The typical 'H NMR spectra of heterocyclyl calix[n]arenes, wherein 'n' is equal to 8, when taken in deutrated chloroform solvent shows peaks at 7.99-7.96(d, ArH), 7.69-7.64(m, ArH), 7.54-7.49(m.ArH), 3.93(s, OCH3), 4.21(bs, ArCH^Ar). The present invention has been explained with the help of above particular set of experiments, which are not intended to limit the scope of the present invention. WE CLAIM: 1. New heterocyclyl calyx(n)arenes and a method of preparation thereof where in the new heterocyclyl calix(n)arenes so obtained having general formula 1 (Formula Removed) wherein (i) w and z can be R, Ar, Het; R = alkyl with C= 1to 16 Ar = aryl and Het = 5 or 6 membered heterocyclic components (ii) Y = N and X = NH,O, S preferably Y=X=N (iii) Rl = alkyl with C-lto 5 (iv) n = 4,6,8,or 10 preferably 4,6,or 8 which comprises: (a) methylating debutylated calix[n]arenes wherein 'n' represents phenolic units and is equal to 4,6,8, and 10, such as herein described to get methylated calix[n]arenes (b) formylating the methylated calix[n]arenes obtained from step-1 in a manner such as herein disclosed, to yield formylated calyx(n)arene, (c) subjecting the said formylated calix[n]arenes obtained from step-2 to form linkage with respective heterocyclic moiety by cyclising the said formylated calix(n)arenas in acidic solvent with aromaticdiketone and acid salt of alkalimetal or ammonium to produce corresponding heterocyclyl calix[n]arenas of general formula 1, wherein n is equal to 4, 6, 8, & 10. 2. A process as claimed in claim 1, wherein the methylation in step (a) is effected by treating debutylated calix[n]arenes with methyl halide in presence of metal hydride in organic solvent. 3. A process as claimed in claims 1 and 2, wherein said methyl halide is preferably methyl iodide. 4. A process as claimed in preceding claims, wherein said metal hydride is preferably alkali metal hydride, more preferably sodium hydride. 5. A process as claimed in preceding claims, wherein the organic solvent used is mixture of tetrahydrofuran & dimethyl formamide. 6. A process as claimed in claim 1, wherein formylation in step (b) is carried out by dissolving the methylated calix[n]arenes obtained from said step-1 in organic solvent then adding the said solution with a freshly distilled titanium tetrachloride in organic solvent to alkyl ether in organic solvent. 7. A process as claimed in claims 1 and 7, wherein the organic solvent used for dissolving methylated calix(n)arenes and titanium tetrachloride is preferably chloroform or methylene chloride or hexane or benzene, more preferably chloroform. 8. A process as claimed in claims 1 and 7, wherein the alkyl ether used is preferably halide substituted dialkyl ether, more preferably 1,1 -dichloromethylmethylether. 9. A process as claimed in claims 1 and 7, wherein the addition is carried out at a temperature of about 35 C to 70 C, preferably at about 40°C to 60°C. 10. A process as claimed in claim 1, wherein the cyclisation in step (c) is conducted by cyclising formylated calix[n]arenes obtained from step (b) in an acidic solvent such as herein described with an aromatic diketone and acid salt of ammonium, in a ratio of 1:2 at a reflux temperature to yield heterocyclyl calix[n]arenes. 11. A process as claimed in claims 1 and 10, wherein said acidic solvent is organic or inorganic acid preferably, phosphoric acid, acetic acid, hydrochloric acid or propionic acid, more preferably hydrochloric acid. 12. A process as claimed in claims 1 and 10, wherein said aromatic diketone is preferably dipenyl hydroxy ketone. 13. A process as claimed in.claims 1 and 10, wherein the refluxing is carried out for about 2 to 9 hrs, preferably for about 4 to 7 hrs. 14. A new heterocyclyl calixarenes of general formula 1 obtained by the process as claimed in preceding claims substantially as herein described. 15. A process for the preparation of new heterocyclyl calyx(n)arenes substantially as described herein above.

Documents:

544-del-2000-abstract.pdf

544-DEL-2000-Assignment-(11-08-2009).pdf

544-del-2000-claims.pdf

544-DEL-2000-Correspondence-Others-(11-08-2009).pdf

544-del-2000-correspondence-others.pdf

544-del-2000-correspondence-po.pdf

544-del-2000-description (complete).pdf

544-del-2000-form-1.pdf

544-del-2000-form-13.pdf

544-del-2000-form-19.pdf

544-del-2000-form-2.pdf

544-del-2000-form-3.pdf

544-del-2000-form-6-(11-08-2009).pdf

544-del-2000-gpa.pdf