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CONVENIENT ONE POT PROCEDURE FOR SYNTHESISOF FORMYLATED CALIX[n]ARENESH M Chawla a amp Anuradha Santra aa Chemistry Department Indian Institute of Technology New Delhi 110 016 India

Version of record first published 09 Nov 2006

To cite this article H M Chawla amp Anuradha Santra (2001) CONVENIENT ONE POT PROCEDURE FOR SYNTHESIS OFFORMYLATED CALIX[n]ARENES Synthetic Communications An International Journal for Rapid Communication of SyntheticOrganic Chemistry 3117 2605-2611

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CONVENIENT ONE POT PROCEDURE

FOR SYNTHESIS OF FORMYLATED

CALIX[n]ARENES

H M Chawla and Anuradha Santra

Chemistry Department Indian Institute of TechnologyNew Delhi 110 016 India

ABSTRACT

A convenient one pot procedure for obtaining formyl calix[n]arenes via condensation with 11-dichloromethylmethyl-ether is described

Calix[n]arenes are phenolic metacyclophanes12 obtained through baseor (less often) acid catalysed condensation of p-substituted phenols withformaldehyde34 The presence of both hydrophilic and hydrophobic sitesat the lower and upper rim of the calixarene molecular basket provides acavity whose dimensions can be easily varied12 to allow development ofdiverse applications and potential molecular devices25ndash9 Various aspectsof calixarene chemistry have been reviewed10ndash13

Although functionalization of lower rim calixarene hydroxyls is rela-tively well understood upper rim derivatization requires careful selection ofreagents and experimental conditions14ndash16 Introduction of a formyl groupat the upper rim provides an important intermediate that can be employedfor a variety of chemical transformations Generation of formyl derivatives

2605

Copyright amp 2001 by Marcel Dekker Inc wwwdekkercom

Corresponding author

SYNTHETIC COMMUNICATIONS 31(17) 2605ndash2611 (2001)

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2606 CHAWLA AND SANTRA

through Reimer-Tiemann reaction provides very low yields and complicatedmixtures17 The alternative procedure requiring chloromethylation hydro-lysis and oxidation of the benzylic alcohol involves a large number of stepsand offers only low yields of final products1819 Claisen migration of ally-lated calixarenes followed by ozonolysis or oxidative double bond cleavagealso suffers from similar disadvantages16 Formylation of alkoxy calixarenesby hexamethylene tetramine in trifluoroacetic acid20 requires a long reactiontime and the reaction is considered good only for calix[4]arenes (very pooryields are obtained for calix[8]arenes) Friedel Crafts reactions on longchain alkyloxy calixarenes by dichloromethyl methylether and subsequent

hydrolysis have been reported to provide a mixture of mono- di- tri- andtetraaldehydes of calix[4]arenes which are often difficult to separate18 Thisprocedure also suffers from the disadvantage that the conformation of thecalixarene framework is dependent upon the alkyl halide used21 and thereported method is valid only for calix[4]arenes often running into difficul-ties when attempted on higher calix[n]arenes (ngt4) Details publishedrecently by Pochini and coworkers indicate that the dichloromethylmethyl ether (active formylating reagent) is used in a twenty to fifty foldexcess21 The quantity of dichloromethyl methyl ether reportedly used evenfor monoformylation was twenty times the required stoichiometric quantitySimilarly the catalyst (TiCl4) is used in over twenty to sixty molar equiva-lents Such high concentrations of reagents add to overall costs and affectlarge scale work on applications of calixarenes in diverse fields It has beenfound that the reaction is very sensitive to temperature and invariably anintractable mixture of products is obtained even for simple calix[4]arenesThe prerequisite for the reaction ie prior alkylation with long chain alkylhalides also consumes huge quantities of the reagents and hence is incon-venient The yields of products obtained are low and extensive chromato-graphic and other separation methods are required The low temperaturesrequired for the reaction are also impractical for large-scale preparations

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CALIX[n]ARENES 2607

In this communication we present our results on development of reac-tion conditions for obtaining formylated calixarenes in good yields Onenot only can obtain formylated calix[4]arenes but also higher formyl calix[n]arenes (nfrac14 6 8) The products are easily isolable and the process involvesinexpensive methyl iodide for protecting the calixarene to preserve initialcalixarene conformation The quantities of reagents employed are low Itis significant to note that no dealkylation takes place under the reactionconditions and products obtained are clean

In a typical experiment a solution of dichloromethyl methyl ether indichloromethane was added to a solution of octamethylated calix[8]arenein dichloromethane A solution of freshly distilled titanium tetrachloride orSnCl4 in CH2Cl2 was added quickly (2min) The reaction mixture wasstirred and maintained at 38ndash42C for one hour after which it was quenchedby adding ice cold water The dichloromethane soluble portion when passedthrough a column of silica gel using ethyl acetate-hexane as the eluent gavethe formylated calixarene derivative which could be identified by IR NMRand molecular weight determination It has also been determined that use oftitanium tetrachloride as catalyst gives better yields than does the use ofstannic chloride

EXPERIMENTAL

Melting points are uncorrected 1H NMR spectra were recordedon a Bruker 300DPX instrument IR spectra were recorded on a Nicolet5DX spectrometer Molecular weight determinations were carried outby using a Knauer vapour pressure osmometer and mass spectra wererecorded on a Jeol SX mass spectrometer Dichloromethane and chloroformwere dried over phosphorus pentoxide before use SnCl4 was preparedby passing chlorine over granulated tin followed by vacuum distillation ofthe crude stannic chloride

Synthesis of p-tert-Butyl Calix[4]arene

Condensation of p-tert-butyl phenol (25 g 0166mol) and form-aldehyde (37 02075mol) in the presence of sodium hydroxide (03 g75103mol) by the procedure reported by Gutsche et al1 gave the titlecompound as a colourless crystalline compound (153 g 57) mpgt250C1H NMR (CDCl3 d) 104 (s 4H D2O exch OH) 705 (s 8H ArH) 42(d Jfrac14 12Hz 4H ArCH2Ar) 35 (d Jfrac14 12Hz 4H ArCH2Ar) 125 (s 36HC(CH3)3)

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2608 CHAWLA AND SANTRA

Synthesis of 25262728-Tetrahydroxy Calix[4]arene

A slurry of p-t-butyl calix[4]arene (133 g 20mmol) phenol (902 g96mmol) and AlCl3 (14 g 105mmol) was stirred in toluene (125ml) atroom temperature for 1 h under a nitrogen atmosphere The mixture waspoured into 250ml of 02N HCl and the organic phase was separated andtoluene evaporated Addition of MeOH yielded a precipitate which wasfiltered and recrystallized from CHCl3-MeOH to give colourless crystals(65 g 75) mpgt260C (lit2 315ndash318C) 1H NMR (CDCl3 d) 102(s 4H D2O exch OH) 704 (d 8H ArH) 672 (t 4H ArH) 42 (bs 4HArCH2Ar) 35 (bs 4H ArCH2Ar)

Synthesis of p-tert-Butyl Calix[8]arene

The procedure adopted for synthesis of the title compound has beenreported earlier1 The formation of p-tert-butylcalix[8]arene was confirmedby comparison with a standard sample of p-tert-butylcalix[8]arene (167 g62) mpgt250C 1H NMR (CDCl3 d) 96 (s 8H D2O exch OH) 717(s 16H ArH) 436 (d Jfrac14 128Hz 8H ArCH2Ar) 350 (d Jfrac14 128Hz 8HArCH2Ar) 125 (s 36H C(CH3)3)

Synthesis of 4950515253545556-Octahydroxycalix[8]arene

A slurry of p-tert-butyl calix[8]arene (70 g 54mmol) phenol (51 g54mmol) and AlCl3 (90 g 675mmol) was stirred in toluene (150ml) atroom temperature for 1h under a nitrogen atmosphere after which the reac-tion mixture was poured into 02N HCl (150ml) to yield an emulsion fromwhich toluene was distilled to yield a grey solid which was washed withacetone HCl MeOH CHCl3 acetone and ethyl ether to give a colourlesssolid (396 g 86) mpgt260C 1H NMR (pyridine-d5) d 60ndash70 (m 3HArH) 35 (bs 2 ArCH2Ar)

Synthesis of 25262728-Tetramethoxycalix[4]arene

Tetrahydroxycalix[4]arene (127 g 3mmol) dissolved in THF (50ml)containing DMF (5ml) was refluxed with NaH (1 g 25mmol) andCH3I (912 g 64mmol) for 12 h The product obtained after evaporation

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CALIX[n]ARENES 2609

of solvent was washed with water and recrystallized from MeOH-CHCl3 toyield colourless crystals (095 g 66) mp 232ndash234C (Lit16 mpt234ndash235C) 1H NMR (CDCl3 d) 684ndash654 (m 12H ArH) 43ndash31 (m20H ArCH2Ar and -OCH3) molecular mass (vapour pressure osmometry)492 (calcd 480)

Synthesis of 4950515253545556-Octamethoxy Calix[8]arene

A mixture containing octahydroxycalix[8]arene (20 g 24mmol) NaH(22 g 92mmol) and CH3I (18 g 127mmol) in THF (100ml) and DMF(10ml) was refluxed for 12 h The solvent was removed on a rotary evapora-tor and water (100ml) was added to the residue The collected solid wasrecrystallized from MeOH-CHCl3 to give colourless crystals (17 g 75)mp 255ndash258C (lit3 mp 256ndash258C) 1H NMR (CDCl3) d 68 (s 24HArH) 40 (s 16H ArCH2Ar) 35 (s 24H -OCH3) molecular mass(vapour phase osmometry) 1002 (calcd 960)

Synthesis of 5111723-Tetraformyl-25262728-

tetrakis(methoxy)calix[4]arene

A solution of 11-dichloromethyl methyl ether (203 g 177mmol) inCH2Cl2 (100ml) was added to a solution of tetramethylated calix[4]arene(024 g 05mmol) in CHCl3 (100ml) with stirring at room temperaturefollowed by addition of a solution of titanium tetrachloride (45 g237mmol) in CHCl3(100ml) in one portion as quickly as possible Thereaction mixture was stirred for a further period of 1h and then treatedwith water ( 50ml) The organic layer was separated washed twice withwater and dried (Na2SO4) and the solvent evaporated under reduced press-ure The residue was purified by passing through a column (silica gel60ndash120mesh) and eluted with hexane-ethyl acetate (7525) to yield tetra-formyl calix[4]arene as pale yellow crystals (018 g yield 608) mp218ndash220C Anal calcd for C36H32O8 C 7297 H 540 Found C 7286H 559 IR (vmax KBr) 1693 (s) 1597 (s) 1471 (m) 14283 (m) 1385 (m)1283 (s) 1128 (s) 1H NMR (CDCl3 d) 296ndash444 (m 20H ArCH2ArOCH3) 682 784 719 764 (4s 8H ArH) 99 957 944 (2s 1d 4HCHO) MS mz 593 (MthornHthorn) UV (CHCl3) max 269 nm Though this com-pound seems to have been prepared by Komori et al through a differentroute no spectral data has been published20

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Synthesis of 511172329354147-Octaformyl

4950515253545556-Octakis(methoxy) Calix[8]arene

To a solution of 6 (082 g 086mmol) in dichloromethane (20ml) asolution of dichloromethyl methyl ether (254g 221mmol) in dichloromethane(15ml) was added with stirring Immediately after a solution of freshlydistilled titanium tetrachloride (43 g 228mmol) in dichloromethane(15ml) was added to the reaction mixture very quickly with vigorous stir-ring The reaction temperature was maintained between 38ndash42C by usingan oil bath Stirring was continued for 1h and ice cold water (50ml) wasslowly added to the solution The reaction mixture was further stirred for15min and extracted with dichloromethane The organic layer was washedtwice with water (50ml2) and dried over anhydrous sodium sulphate Thesolvent was evaporated under reduced pressure and the residue purified bypassing through a column of silica gel (50 g 60ndash120mesh) to give paleyellow solid (069 g 68) mpgt250C Anal calcd for C72H64O16 C7297 H 540 Found C 7283 H 533 Molecular mass (vapour pressureosmometry) 1160 (Calcd 1184) IR (vmax KBr) 1693(s) 1598(s) 1472(m)1428(sh) 1385(m) 1283(s) 1H NMR (CDCl3 d) 967 (s 8H CHO) 695 (s16H ArH) 412 (s 16H ArCH2Ar) 36 (s 24H -OCH3) UV(CHCl3 max)265 nm

ACKNOWLEDGMENT

The authors are thankful to Department of Science amp Technology andCSIR for financial assistance and a research fellowship to AS

REFERENCES

1 Gutsche CD Calixarenes monographs in supramolecular chemistryVol 1 Stoddart JF Ed The Royal Society of ChemistryCambridge 1989

2 Bohmer V Calixarenes a versatile class of macrocyclic compoundsKluwer Academic Dordrecht 1989

3 Gutsche CD Iqbal M Org Synth 1990 68 2344 Gutsche CD Iqbal M Stewart D J Org Chem 1986 51 7425 Steward DR Gutsche CD J Am Chem Soc 1999 121 4136ndash41466 Kubo Y Maeda S Nakamura M Tokita S J Chem Soc Chem

Commun 1994 1725

2610 CHAWLA AND SANTRA

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7 Daitch CE Hampton PD Duesler ED Alam TM J Am

Chem Soc 1996 118 7769ndash7773

8 Kobo Y Maruyama S Ohhara N Nakamivea M Tokita S J

Chem Soc Chem Commun 1995 1727

9 Reichwein A Verboom W Reinhoudt DN J Chem Soc Perkin

Trans 1994 1167

10 Bohmer V Angew Chem Int Engl 1995 34 713ndash745

11 Ikeda A Shinkai S Chem Rev 1997 97 1713ndash1734

12 De Namor FD Cleverley RM Zapata-Osmachea ML Chem

Rev 1998 98 2498ndash2525

13 Diamond D Mckervey A Chem Rev 1996 15ndash24

14 Almi M Arduini A Casnati A Pochini A Ungaro R

Tetrahedron 1989 45 2177

15 Zhang WC Zheng Y S Huang ZT Syn Commun 1997 27(21)

3763ndash3767

16 Gutsche CD Pagoria PF J Org Chem 1985 50 5795ndash5802

Gutsche CD Lin LG Tetrahedron 1986 42 1633

17 Aggarwal YK Jain VK Personal communication

18 Arduini A Manfredi G Pochini A Sicuri A R Ungaro R

J Chem Soc Chem Commun 1991 936

19 Van Loon JD Arduini A Coppi L Verboom W Pochini A

Ungaro R Harkema S Reinhoudt DN J Org Chem 1990

55 5639

20 Komori T Shinkai S Chemistry Letters 1992 901

21 Arduini A Fanni S Manfredi G Pochini A Ungaro R Sicuri

AR Ugozzoli F J Org Chem 1995 60 1448ndash1453

Received in the UK June 1 2000

CALIX[n]ARENES 2611

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2606 CHAWLA AND SANTRA

through Reimer-Tiemann reaction provides very low yields and complicatedmixtures17 The alternative procedure requiring chloromethylation hydro-lysis and oxidation of the benzylic alcohol involves a large number of stepsand offers only low yields of final products1819 Claisen migration of ally-lated calixarenes followed by ozonolysis or oxidative double bond cleavagealso suffers from similar disadvantages16 Formylation of alkoxy calixarenesby hexamethylene tetramine in trifluoroacetic acid20 requires a long reactiontime and the reaction is considered good only for calix[4]arenes (very pooryields are obtained for calix[8]arenes) Friedel Crafts reactions on longchain alkyloxy calixarenes by dichloromethyl methylether and subsequent

hydrolysis have been reported to provide a mixture of mono- di- tri- andtetraaldehydes of calix[4]arenes which are often difficult to separate18 Thisprocedure also suffers from the disadvantage that the conformation of thecalixarene framework is dependent upon the alkyl halide used21 and thereported method is valid only for calix[4]arenes often running into difficul-ties when attempted on higher calix[n]arenes (ngt4) Details publishedrecently by Pochini and coworkers indicate that the dichloromethylmethyl ether (active formylating reagent) is used in a twenty to fifty foldexcess21 The quantity of dichloromethyl methyl ether reportedly used evenfor monoformylation was twenty times the required stoichiometric quantitySimilarly the catalyst (TiCl4) is used in over twenty to sixty molar equiva-lents Such high concentrations of reagents add to overall costs and affectlarge scale work on applications of calixarenes in diverse fields It has beenfound that the reaction is very sensitive to temperature and invariably anintractable mixture of products is obtained even for simple calix[4]arenesThe prerequisite for the reaction ie prior alkylation with long chain alkylhalides also consumes huge quantities of the reagents and hence is incon-venient The yields of products obtained are low and extensive chromato-graphic and other separation methods are required The low temperaturesrequired for the reaction are also impractical for large-scale preparations

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CALIX[n]ARENES 2607

In this communication we present our results on development of reac-tion conditions for obtaining formylated calixarenes in good yields Onenot only can obtain formylated calix[4]arenes but also higher formyl calix[n]arenes (nfrac14 6 8) The products are easily isolable and the process involvesinexpensive methyl iodide for protecting the calixarene to preserve initialcalixarene conformation The quantities of reagents employed are low Itis significant to note that no dealkylation takes place under the reactionconditions and products obtained are clean

In a typical experiment a solution of dichloromethyl methyl ether indichloromethane was added to a solution of octamethylated calix[8]arenein dichloromethane A solution of freshly distilled titanium tetrachloride orSnCl4 in CH2Cl2 was added quickly (2min) The reaction mixture wasstirred and maintained at 38ndash42C for one hour after which it was quenchedby adding ice cold water The dichloromethane soluble portion when passedthrough a column of silica gel using ethyl acetate-hexane as the eluent gavethe formylated calixarene derivative which could be identified by IR NMRand molecular weight determination It has also been determined that use oftitanium tetrachloride as catalyst gives better yields than does the use ofstannic chloride

EXPERIMENTAL

Melting points are uncorrected 1H NMR spectra were recordedon a Bruker 300DPX instrument IR spectra were recorded on a Nicolet5DX spectrometer Molecular weight determinations were carried outby using a Knauer vapour pressure osmometer and mass spectra wererecorded on a Jeol SX mass spectrometer Dichloromethane and chloroformwere dried over phosphorus pentoxide before use SnCl4 was preparedby passing chlorine over granulated tin followed by vacuum distillation ofthe crude stannic chloride

Synthesis of p-tert-Butyl Calix[4]arene

Condensation of p-tert-butyl phenol (25 g 0166mol) and form-aldehyde (37 02075mol) in the presence of sodium hydroxide (03 g75103mol) by the procedure reported by Gutsche et al1 gave the titlecompound as a colourless crystalline compound (153 g 57) mpgt250C1H NMR (CDCl3 d) 104 (s 4H D2O exch OH) 705 (s 8H ArH) 42(d Jfrac14 12Hz 4H ArCH2Ar) 35 (d Jfrac14 12Hz 4H ArCH2Ar) 125 (s 36HC(CH3)3)

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2608 CHAWLA AND SANTRA

Synthesis of 25262728-Tetrahydroxy Calix[4]arene

A slurry of p-t-butyl calix[4]arene (133 g 20mmol) phenol (902 g96mmol) and AlCl3 (14 g 105mmol) was stirred in toluene (125ml) atroom temperature for 1 h under a nitrogen atmosphere The mixture waspoured into 250ml of 02N HCl and the organic phase was separated andtoluene evaporated Addition of MeOH yielded a precipitate which wasfiltered and recrystallized from CHCl3-MeOH to give colourless crystals(65 g 75) mpgt260C (lit2 315ndash318C) 1H NMR (CDCl3 d) 102(s 4H D2O exch OH) 704 (d 8H ArH) 672 (t 4H ArH) 42 (bs 4HArCH2Ar) 35 (bs 4H ArCH2Ar)

Synthesis of p-tert-Butyl Calix[8]arene

The procedure adopted for synthesis of the title compound has beenreported earlier1 The formation of p-tert-butylcalix[8]arene was confirmedby comparison with a standard sample of p-tert-butylcalix[8]arene (167 g62) mpgt250C 1H NMR (CDCl3 d) 96 (s 8H D2O exch OH) 717(s 16H ArH) 436 (d Jfrac14 128Hz 8H ArCH2Ar) 350 (d Jfrac14 128Hz 8HArCH2Ar) 125 (s 36H C(CH3)3)

Synthesis of 4950515253545556-Octahydroxycalix[8]arene

A slurry of p-tert-butyl calix[8]arene (70 g 54mmol) phenol (51 g54mmol) and AlCl3 (90 g 675mmol) was stirred in toluene (150ml) atroom temperature for 1h under a nitrogen atmosphere after which the reac-tion mixture was poured into 02N HCl (150ml) to yield an emulsion fromwhich toluene was distilled to yield a grey solid which was washed withacetone HCl MeOH CHCl3 acetone and ethyl ether to give a colourlesssolid (396 g 86) mpgt260C 1H NMR (pyridine-d5) d 60ndash70 (m 3HArH) 35 (bs 2 ArCH2Ar)

Synthesis of 25262728-Tetramethoxycalix[4]arene

Tetrahydroxycalix[4]arene (127 g 3mmol) dissolved in THF (50ml)containing DMF (5ml) was refluxed with NaH (1 g 25mmol) andCH3I (912 g 64mmol) for 12 h The product obtained after evaporation

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CALIX[n]ARENES 2609

of solvent was washed with water and recrystallized from MeOH-CHCl3 toyield colourless crystals (095 g 66) mp 232ndash234C (Lit16 mpt234ndash235C) 1H NMR (CDCl3 d) 684ndash654 (m 12H ArH) 43ndash31 (m20H ArCH2Ar and -OCH3) molecular mass (vapour pressure osmometry)492 (calcd 480)

Synthesis of 4950515253545556-Octamethoxy Calix[8]arene

A mixture containing octahydroxycalix[8]arene (20 g 24mmol) NaH(22 g 92mmol) and CH3I (18 g 127mmol) in THF (100ml) and DMF(10ml) was refluxed for 12 h The solvent was removed on a rotary evapora-tor and water (100ml) was added to the residue The collected solid wasrecrystallized from MeOH-CHCl3 to give colourless crystals (17 g 75)mp 255ndash258C (lit3 mp 256ndash258C) 1H NMR (CDCl3) d 68 (s 24HArH) 40 (s 16H ArCH2Ar) 35 (s 24H -OCH3) molecular mass(vapour phase osmometry) 1002 (calcd 960)

Synthesis of 5111723-Tetraformyl-25262728-

tetrakis(methoxy)calix[4]arene

A solution of 11-dichloromethyl methyl ether (203 g 177mmol) inCH2Cl2 (100ml) was added to a solution of tetramethylated calix[4]arene(024 g 05mmol) in CHCl3 (100ml) with stirring at room temperaturefollowed by addition of a solution of titanium tetrachloride (45 g237mmol) in CHCl3(100ml) in one portion as quickly as possible Thereaction mixture was stirred for a further period of 1h and then treatedwith water ( 50ml) The organic layer was separated washed twice withwater and dried (Na2SO4) and the solvent evaporated under reduced press-ure The residue was purified by passing through a column (silica gel60ndash120mesh) and eluted with hexane-ethyl acetate (7525) to yield tetra-formyl calix[4]arene as pale yellow crystals (018 g yield 608) mp218ndash220C Anal calcd for C36H32O8 C 7297 H 540 Found C 7286H 559 IR (vmax KBr) 1693 (s) 1597 (s) 1471 (m) 14283 (m) 1385 (m)1283 (s) 1128 (s) 1H NMR (CDCl3 d) 296ndash444 (m 20H ArCH2ArOCH3) 682 784 719 764 (4s 8H ArH) 99 957 944 (2s 1d 4HCHO) MS mz 593 (MthornHthorn) UV (CHCl3) max 269 nm Though this com-pound seems to have been prepared by Komori et al through a differentroute no spectral data has been published20

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Synthesis of 511172329354147-Octaformyl

4950515253545556-Octakis(methoxy) Calix[8]arene

To a solution of 6 (082 g 086mmol) in dichloromethane (20ml) asolution of dichloromethyl methyl ether (254g 221mmol) in dichloromethane(15ml) was added with stirring Immediately after a solution of freshlydistilled titanium tetrachloride (43 g 228mmol) in dichloromethane(15ml) was added to the reaction mixture very quickly with vigorous stir-ring The reaction temperature was maintained between 38ndash42C by usingan oil bath Stirring was continued for 1h and ice cold water (50ml) wasslowly added to the solution The reaction mixture was further stirred for15min and extracted with dichloromethane The organic layer was washedtwice with water (50ml2) and dried over anhydrous sodium sulphate Thesolvent was evaporated under reduced pressure and the residue purified bypassing through a column of silica gel (50 g 60ndash120mesh) to give paleyellow solid (069 g 68) mpgt250C Anal calcd for C72H64O16 C7297 H 540 Found C 7283 H 533 Molecular mass (vapour pressureosmometry) 1160 (Calcd 1184) IR (vmax KBr) 1693(s) 1598(s) 1472(m)1428(sh) 1385(m) 1283(s) 1H NMR (CDCl3 d) 967 (s 8H CHO) 695 (s16H ArH) 412 (s 16H ArCH2Ar) 36 (s 24H -OCH3) UV(CHCl3 max)265 nm

ACKNOWLEDGMENT

The authors are thankful to Department of Science amp Technology andCSIR for financial assistance and a research fellowship to AS

REFERENCES

1 Gutsche CD Calixarenes monographs in supramolecular chemistryVol 1 Stoddart JF Ed The Royal Society of ChemistryCambridge 1989

2 Bohmer V Calixarenes a versatile class of macrocyclic compoundsKluwer Academic Dordrecht 1989

3 Gutsche CD Iqbal M Org Synth 1990 68 2344 Gutsche CD Iqbal M Stewart D J Org Chem 1986 51 7425 Steward DR Gutsche CD J Am Chem Soc 1999 121 4136ndash41466 Kubo Y Maeda S Nakamura M Tokita S J Chem Soc Chem

Commun 1994 1725

2610 CHAWLA AND SANTRA

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04

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012

ORDER REPRINTS

7 Daitch CE Hampton PD Duesler ED Alam TM J Am

Chem Soc 1996 118 7769ndash7773

8 Kobo Y Maruyama S Ohhara N Nakamivea M Tokita S J

Chem Soc Chem Commun 1995 1727

9 Reichwein A Verboom W Reinhoudt DN J Chem Soc Perkin

Trans 1994 1167

10 Bohmer V Angew Chem Int Engl 1995 34 713ndash745

11 Ikeda A Shinkai S Chem Rev 1997 97 1713ndash1734

12 De Namor FD Cleverley RM Zapata-Osmachea ML Chem

Rev 1998 98 2498ndash2525

13 Diamond D Mckervey A Chem Rev 1996 15ndash24

14 Almi M Arduini A Casnati A Pochini A Ungaro R

Tetrahedron 1989 45 2177

15 Zhang WC Zheng Y S Huang ZT Syn Commun 1997 27(21)

3763ndash3767

16 Gutsche CD Pagoria PF J Org Chem 1985 50 5795ndash5802

Gutsche CD Lin LG Tetrahedron 1986 42 1633

17 Aggarwal YK Jain VK Personal communication

18 Arduini A Manfredi G Pochini A Sicuri A R Ungaro R

J Chem Soc Chem Commun 1991 936

19 Van Loon JD Arduini A Coppi L Verboom W Pochini A

Ungaro R Harkema S Reinhoudt DN J Org Chem 1990

55 5639

20 Komori T Shinkai S Chemistry Letters 1992 901

21 Arduini A Fanni S Manfredi G Pochini A Ungaro R Sicuri

AR Ugozzoli F J Org Chem 1995 60 1448ndash1453

Received in the UK June 1 2000

CALIX[n]ARENES 2611

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Order now

Reprints of this article can also be ordered at

httpwwwdekkercomservletproductDOI101081SCC100105385

Request Permission or Order Reprints Instantly

Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content

All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved

Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom

The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details

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ORDER REPRINTS

CALIX[n]ARENES 2607

In this communication we present our results on development of reac-tion conditions for obtaining formylated calixarenes in good yields Onenot only can obtain formylated calix[4]arenes but also higher formyl calix[n]arenes (nfrac14 6 8) The products are easily isolable and the process involvesinexpensive methyl iodide for protecting the calixarene to preserve initialcalixarene conformation The quantities of reagents employed are low Itis significant to note that no dealkylation takes place under the reactionconditions and products obtained are clean

In a typical experiment a solution of dichloromethyl methyl ether indichloromethane was added to a solution of octamethylated calix[8]arenein dichloromethane A solution of freshly distilled titanium tetrachloride orSnCl4 in CH2Cl2 was added quickly (2min) The reaction mixture wasstirred and maintained at 38ndash42C for one hour after which it was quenchedby adding ice cold water The dichloromethane soluble portion when passedthrough a column of silica gel using ethyl acetate-hexane as the eluent gavethe formylated calixarene derivative which could be identified by IR NMRand molecular weight determination It has also been determined that use oftitanium tetrachloride as catalyst gives better yields than does the use ofstannic chloride

EXPERIMENTAL

Melting points are uncorrected 1H NMR spectra were recordedon a Bruker 300DPX instrument IR spectra were recorded on a Nicolet5DX spectrometer Molecular weight determinations were carried outby using a Knauer vapour pressure osmometer and mass spectra wererecorded on a Jeol SX mass spectrometer Dichloromethane and chloroformwere dried over phosphorus pentoxide before use SnCl4 was preparedby passing chlorine over granulated tin followed by vacuum distillation ofthe crude stannic chloride

Synthesis of p-tert-Butyl Calix[4]arene

Condensation of p-tert-butyl phenol (25 g 0166mol) and form-aldehyde (37 02075mol) in the presence of sodium hydroxide (03 g75103mol) by the procedure reported by Gutsche et al1 gave the titlecompound as a colourless crystalline compound (153 g 57) mpgt250C1H NMR (CDCl3 d) 104 (s 4H D2O exch OH) 705 (s 8H ArH) 42(d Jfrac14 12Hz 4H ArCH2Ar) 35 (d Jfrac14 12Hz 4H ArCH2Ar) 125 (s 36HC(CH3)3)

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ORDER REPRINTS

2608 CHAWLA AND SANTRA

Synthesis of 25262728-Tetrahydroxy Calix[4]arene

A slurry of p-t-butyl calix[4]arene (133 g 20mmol) phenol (902 g96mmol) and AlCl3 (14 g 105mmol) was stirred in toluene (125ml) atroom temperature for 1 h under a nitrogen atmosphere The mixture waspoured into 250ml of 02N HCl and the organic phase was separated andtoluene evaporated Addition of MeOH yielded a precipitate which wasfiltered and recrystallized from CHCl3-MeOH to give colourless crystals(65 g 75) mpgt260C (lit2 315ndash318C) 1H NMR (CDCl3 d) 102(s 4H D2O exch OH) 704 (d 8H ArH) 672 (t 4H ArH) 42 (bs 4HArCH2Ar) 35 (bs 4H ArCH2Ar)

Synthesis of p-tert-Butyl Calix[8]arene

The procedure adopted for synthesis of the title compound has beenreported earlier1 The formation of p-tert-butylcalix[8]arene was confirmedby comparison with a standard sample of p-tert-butylcalix[8]arene (167 g62) mpgt250C 1H NMR (CDCl3 d) 96 (s 8H D2O exch OH) 717(s 16H ArH) 436 (d Jfrac14 128Hz 8H ArCH2Ar) 350 (d Jfrac14 128Hz 8HArCH2Ar) 125 (s 36H C(CH3)3)

Synthesis of 4950515253545556-Octahydroxycalix[8]arene

A slurry of p-tert-butyl calix[8]arene (70 g 54mmol) phenol (51 g54mmol) and AlCl3 (90 g 675mmol) was stirred in toluene (150ml) atroom temperature for 1h under a nitrogen atmosphere after which the reac-tion mixture was poured into 02N HCl (150ml) to yield an emulsion fromwhich toluene was distilled to yield a grey solid which was washed withacetone HCl MeOH CHCl3 acetone and ethyl ether to give a colourlesssolid (396 g 86) mpgt260C 1H NMR (pyridine-d5) d 60ndash70 (m 3HArH) 35 (bs 2 ArCH2Ar)

Synthesis of 25262728-Tetramethoxycalix[4]arene

Tetrahydroxycalix[4]arene (127 g 3mmol) dissolved in THF (50ml)containing DMF (5ml) was refluxed with NaH (1 g 25mmol) andCH3I (912 g 64mmol) for 12 h The product obtained after evaporation

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ORDER REPRINTS

CALIX[n]ARENES 2609

of solvent was washed with water and recrystallized from MeOH-CHCl3 toyield colourless crystals (095 g 66) mp 232ndash234C (Lit16 mpt234ndash235C) 1H NMR (CDCl3 d) 684ndash654 (m 12H ArH) 43ndash31 (m20H ArCH2Ar and -OCH3) molecular mass (vapour pressure osmometry)492 (calcd 480)

Synthesis of 4950515253545556-Octamethoxy Calix[8]arene

A mixture containing octahydroxycalix[8]arene (20 g 24mmol) NaH(22 g 92mmol) and CH3I (18 g 127mmol) in THF (100ml) and DMF(10ml) was refluxed for 12 h The solvent was removed on a rotary evapora-tor and water (100ml) was added to the residue The collected solid wasrecrystallized from MeOH-CHCl3 to give colourless crystals (17 g 75)mp 255ndash258C (lit3 mp 256ndash258C) 1H NMR (CDCl3) d 68 (s 24HArH) 40 (s 16H ArCH2Ar) 35 (s 24H -OCH3) molecular mass(vapour phase osmometry) 1002 (calcd 960)

Synthesis of 5111723-Tetraformyl-25262728-

tetrakis(methoxy)calix[4]arene

A solution of 11-dichloromethyl methyl ether (203 g 177mmol) inCH2Cl2 (100ml) was added to a solution of tetramethylated calix[4]arene(024 g 05mmol) in CHCl3 (100ml) with stirring at room temperaturefollowed by addition of a solution of titanium tetrachloride (45 g237mmol) in CHCl3(100ml) in one portion as quickly as possible Thereaction mixture was stirred for a further period of 1h and then treatedwith water ( 50ml) The organic layer was separated washed twice withwater and dried (Na2SO4) and the solvent evaporated under reduced press-ure The residue was purified by passing through a column (silica gel60ndash120mesh) and eluted with hexane-ethyl acetate (7525) to yield tetra-formyl calix[4]arene as pale yellow crystals (018 g yield 608) mp218ndash220C Anal calcd for C36H32O8 C 7297 H 540 Found C 7286H 559 IR (vmax KBr) 1693 (s) 1597 (s) 1471 (m) 14283 (m) 1385 (m)1283 (s) 1128 (s) 1H NMR (CDCl3 d) 296ndash444 (m 20H ArCH2ArOCH3) 682 784 719 764 (4s 8H ArH) 99 957 944 (2s 1d 4HCHO) MS mz 593 (MthornHthorn) UV (CHCl3) max 269 nm Though this com-pound seems to have been prepared by Komori et al through a differentroute no spectral data has been published20

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ORDER REPRINTS

Synthesis of 511172329354147-Octaformyl

4950515253545556-Octakis(methoxy) Calix[8]arene

To a solution of 6 (082 g 086mmol) in dichloromethane (20ml) asolution of dichloromethyl methyl ether (254g 221mmol) in dichloromethane(15ml) was added with stirring Immediately after a solution of freshlydistilled titanium tetrachloride (43 g 228mmol) in dichloromethane(15ml) was added to the reaction mixture very quickly with vigorous stir-ring The reaction temperature was maintained between 38ndash42C by usingan oil bath Stirring was continued for 1h and ice cold water (50ml) wasslowly added to the solution The reaction mixture was further stirred for15min and extracted with dichloromethane The organic layer was washedtwice with water (50ml2) and dried over anhydrous sodium sulphate Thesolvent was evaporated under reduced pressure and the residue purified bypassing through a column of silica gel (50 g 60ndash120mesh) to give paleyellow solid (069 g 68) mpgt250C Anal calcd for C72H64O16 C7297 H 540 Found C 7283 H 533 Molecular mass (vapour pressureosmometry) 1160 (Calcd 1184) IR (vmax KBr) 1693(s) 1598(s) 1472(m)1428(sh) 1385(m) 1283(s) 1H NMR (CDCl3 d) 967 (s 8H CHO) 695 (s16H ArH) 412 (s 16H ArCH2Ar) 36 (s 24H -OCH3) UV(CHCl3 max)265 nm

ACKNOWLEDGMENT

The authors are thankful to Department of Science amp Technology andCSIR for financial assistance and a research fellowship to AS

REFERENCES

1 Gutsche CD Calixarenes monographs in supramolecular chemistryVol 1 Stoddart JF Ed The Royal Society of ChemistryCambridge 1989

2 Bohmer V Calixarenes a versatile class of macrocyclic compoundsKluwer Academic Dordrecht 1989

3 Gutsche CD Iqbal M Org Synth 1990 68 2344 Gutsche CD Iqbal M Stewart D J Org Chem 1986 51 7425 Steward DR Gutsche CD J Am Chem Soc 1999 121 4136ndash41466 Kubo Y Maeda S Nakamura M Tokita S J Chem Soc Chem

Commun 1994 1725

2610 CHAWLA AND SANTRA

Dow

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by [

Uni

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f Il

linoi

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hica

go]

at 0

108

04

Aug

ust 2

012

ORDER REPRINTS

7 Daitch CE Hampton PD Duesler ED Alam TM J Am

Chem Soc 1996 118 7769ndash7773

8 Kobo Y Maruyama S Ohhara N Nakamivea M Tokita S J

Chem Soc Chem Commun 1995 1727

9 Reichwein A Verboom W Reinhoudt DN J Chem Soc Perkin

Trans 1994 1167

10 Bohmer V Angew Chem Int Engl 1995 34 713ndash745

11 Ikeda A Shinkai S Chem Rev 1997 97 1713ndash1734

12 De Namor FD Cleverley RM Zapata-Osmachea ML Chem

Rev 1998 98 2498ndash2525

13 Diamond D Mckervey A Chem Rev 1996 15ndash24

14 Almi M Arduini A Casnati A Pochini A Ungaro R

Tetrahedron 1989 45 2177

15 Zhang WC Zheng Y S Huang ZT Syn Commun 1997 27(21)

3763ndash3767

16 Gutsche CD Pagoria PF J Org Chem 1985 50 5795ndash5802

Gutsche CD Lin LG Tetrahedron 1986 42 1633

17 Aggarwal YK Jain VK Personal communication

18 Arduini A Manfredi G Pochini A Sicuri A R Ungaro R

J Chem Soc Chem Commun 1991 936

19 Van Loon JD Arduini A Coppi L Verboom W Pochini A

Ungaro R Harkema S Reinhoudt DN J Org Chem 1990

55 5639

20 Komori T Shinkai S Chemistry Letters 1992 901

21 Arduini A Fanni S Manfredi G Pochini A Ungaro R Sicuri

AR Ugozzoli F J Org Chem 1995 60 1448ndash1453

Received in the UK June 1 2000

CALIX[n]ARENES 2611

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at 0

108

04

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ust 2

012

Order now

Reprints of this article can also be ordered at

httpwwwdekkercomservletproductDOI101081SCC100105385

Request Permission or Order Reprints Instantly

Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content

All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved

Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom

The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details

Dow

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Uni

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at 0

108

04

Aug

ust 2

012

ORDER REPRINTS

2608 CHAWLA AND SANTRA

Synthesis of 25262728-Tetrahydroxy Calix[4]arene

A slurry of p-t-butyl calix[4]arene (133 g 20mmol) phenol (902 g96mmol) and AlCl3 (14 g 105mmol) was stirred in toluene (125ml) atroom temperature for 1 h under a nitrogen atmosphere The mixture waspoured into 250ml of 02N HCl and the organic phase was separated andtoluene evaporated Addition of MeOH yielded a precipitate which wasfiltered and recrystallized from CHCl3-MeOH to give colourless crystals(65 g 75) mpgt260C (lit2 315ndash318C) 1H NMR (CDCl3 d) 102(s 4H D2O exch OH) 704 (d 8H ArH) 672 (t 4H ArH) 42 (bs 4HArCH2Ar) 35 (bs 4H ArCH2Ar)

Synthesis of p-tert-Butyl Calix[8]arene

The procedure adopted for synthesis of the title compound has beenreported earlier1 The formation of p-tert-butylcalix[8]arene was confirmedby comparison with a standard sample of p-tert-butylcalix[8]arene (167 g62) mpgt250C 1H NMR (CDCl3 d) 96 (s 8H D2O exch OH) 717(s 16H ArH) 436 (d Jfrac14 128Hz 8H ArCH2Ar) 350 (d Jfrac14 128Hz 8HArCH2Ar) 125 (s 36H C(CH3)3)

Synthesis of 4950515253545556-Octahydroxycalix[8]arene

A slurry of p-tert-butyl calix[8]arene (70 g 54mmol) phenol (51 g54mmol) and AlCl3 (90 g 675mmol) was stirred in toluene (150ml) atroom temperature for 1h under a nitrogen atmosphere after which the reac-tion mixture was poured into 02N HCl (150ml) to yield an emulsion fromwhich toluene was distilled to yield a grey solid which was washed withacetone HCl MeOH CHCl3 acetone and ethyl ether to give a colourlesssolid (396 g 86) mpgt260C 1H NMR (pyridine-d5) d 60ndash70 (m 3HArH) 35 (bs 2 ArCH2Ar)

Synthesis of 25262728-Tetramethoxycalix[4]arene

Tetrahydroxycalix[4]arene (127 g 3mmol) dissolved in THF (50ml)containing DMF (5ml) was refluxed with NaH (1 g 25mmol) andCH3I (912 g 64mmol) for 12 h The product obtained after evaporation

Dow

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ded

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at 0

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04

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012

ORDER REPRINTS

CALIX[n]ARENES 2609

of solvent was washed with water and recrystallized from MeOH-CHCl3 toyield colourless crystals (095 g 66) mp 232ndash234C (Lit16 mpt234ndash235C) 1H NMR (CDCl3 d) 684ndash654 (m 12H ArH) 43ndash31 (m20H ArCH2Ar and -OCH3) molecular mass (vapour pressure osmometry)492 (calcd 480)

Synthesis of 4950515253545556-Octamethoxy Calix[8]arene

A mixture containing octahydroxycalix[8]arene (20 g 24mmol) NaH(22 g 92mmol) and CH3I (18 g 127mmol) in THF (100ml) and DMF(10ml) was refluxed for 12 h The solvent was removed on a rotary evapora-tor and water (100ml) was added to the residue The collected solid wasrecrystallized from MeOH-CHCl3 to give colourless crystals (17 g 75)mp 255ndash258C (lit3 mp 256ndash258C) 1H NMR (CDCl3) d 68 (s 24HArH) 40 (s 16H ArCH2Ar) 35 (s 24H -OCH3) molecular mass(vapour phase osmometry) 1002 (calcd 960)

Synthesis of 5111723-Tetraformyl-25262728-

tetrakis(methoxy)calix[4]arene

A solution of 11-dichloromethyl methyl ether (203 g 177mmol) inCH2Cl2 (100ml) was added to a solution of tetramethylated calix[4]arene(024 g 05mmol) in CHCl3 (100ml) with stirring at room temperaturefollowed by addition of a solution of titanium tetrachloride (45 g237mmol) in CHCl3(100ml) in one portion as quickly as possible Thereaction mixture was stirred for a further period of 1h and then treatedwith water ( 50ml) The organic layer was separated washed twice withwater and dried (Na2SO4) and the solvent evaporated under reduced press-ure The residue was purified by passing through a column (silica gel60ndash120mesh) and eluted with hexane-ethyl acetate (7525) to yield tetra-formyl calix[4]arene as pale yellow crystals (018 g yield 608) mp218ndash220C Anal calcd for C36H32O8 C 7297 H 540 Found C 7286H 559 IR (vmax KBr) 1693 (s) 1597 (s) 1471 (m) 14283 (m) 1385 (m)1283 (s) 1128 (s) 1H NMR (CDCl3 d) 296ndash444 (m 20H ArCH2ArOCH3) 682 784 719 764 (4s 8H ArH) 99 957 944 (2s 1d 4HCHO) MS mz 593 (MthornHthorn) UV (CHCl3) max 269 nm Though this com-pound seems to have been prepared by Komori et al through a differentroute no spectral data has been published20

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ORDER REPRINTS

Synthesis of 511172329354147-Octaformyl

4950515253545556-Octakis(methoxy) Calix[8]arene

To a solution of 6 (082 g 086mmol) in dichloromethane (20ml) asolution of dichloromethyl methyl ether (254g 221mmol) in dichloromethane(15ml) was added with stirring Immediately after a solution of freshlydistilled titanium tetrachloride (43 g 228mmol) in dichloromethane(15ml) was added to the reaction mixture very quickly with vigorous stir-ring The reaction temperature was maintained between 38ndash42C by usingan oil bath Stirring was continued for 1h and ice cold water (50ml) wasslowly added to the solution The reaction mixture was further stirred for15min and extracted with dichloromethane The organic layer was washedtwice with water (50ml2) and dried over anhydrous sodium sulphate Thesolvent was evaporated under reduced pressure and the residue purified bypassing through a column of silica gel (50 g 60ndash120mesh) to give paleyellow solid (069 g 68) mpgt250C Anal calcd for C72H64O16 C7297 H 540 Found C 7283 H 533 Molecular mass (vapour pressureosmometry) 1160 (Calcd 1184) IR (vmax KBr) 1693(s) 1598(s) 1472(m)1428(sh) 1385(m) 1283(s) 1H NMR (CDCl3 d) 967 (s 8H CHO) 695 (s16H ArH) 412 (s 16H ArCH2Ar) 36 (s 24H -OCH3) UV(CHCl3 max)265 nm

ACKNOWLEDGMENT

The authors are thankful to Department of Science amp Technology andCSIR for financial assistance and a research fellowship to AS

REFERENCES

1 Gutsche CD Calixarenes monographs in supramolecular chemistryVol 1 Stoddart JF Ed The Royal Society of ChemistryCambridge 1989

2 Bohmer V Calixarenes a versatile class of macrocyclic compoundsKluwer Academic Dordrecht 1989

3 Gutsche CD Iqbal M Org Synth 1990 68 2344 Gutsche CD Iqbal M Stewart D J Org Chem 1986 51 7425 Steward DR Gutsche CD J Am Chem Soc 1999 121 4136ndash41466 Kubo Y Maeda S Nakamura M Tokita S J Chem Soc Chem

Commun 1994 1725

2610 CHAWLA AND SANTRA

Dow

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ded

by [

Uni

vers

ity o

f Il

linoi

s C

hica

go]

at 0

108

04

Aug

ust 2

012

ORDER REPRINTS

7 Daitch CE Hampton PD Duesler ED Alam TM J Am

Chem Soc 1996 118 7769ndash7773

8 Kobo Y Maruyama S Ohhara N Nakamivea M Tokita S J

Chem Soc Chem Commun 1995 1727

9 Reichwein A Verboom W Reinhoudt DN J Chem Soc Perkin

Trans 1994 1167

10 Bohmer V Angew Chem Int Engl 1995 34 713ndash745

11 Ikeda A Shinkai S Chem Rev 1997 97 1713ndash1734

12 De Namor FD Cleverley RM Zapata-Osmachea ML Chem

Rev 1998 98 2498ndash2525

13 Diamond D Mckervey A Chem Rev 1996 15ndash24

14 Almi M Arduini A Casnati A Pochini A Ungaro R

Tetrahedron 1989 45 2177

15 Zhang WC Zheng Y S Huang ZT Syn Commun 1997 27(21)

3763ndash3767

16 Gutsche CD Pagoria PF J Org Chem 1985 50 5795ndash5802

Gutsche CD Lin LG Tetrahedron 1986 42 1633

17 Aggarwal YK Jain VK Personal communication

18 Arduini A Manfredi G Pochini A Sicuri A R Ungaro R

J Chem Soc Chem Commun 1991 936

19 Van Loon JD Arduini A Coppi L Verboom W Pochini A

Ungaro R Harkema S Reinhoudt DN J Org Chem 1990

55 5639

20 Komori T Shinkai S Chemistry Letters 1992 901

21 Arduini A Fanni S Manfredi G Pochini A Ungaro R Sicuri

AR Ugozzoli F J Org Chem 1995 60 1448ndash1453

Received in the UK June 1 2000

CALIX[n]ARENES 2611

Dow

nloa

ded

by [

Uni

vers

ity o

f Il

linoi

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hica

go]

at 0

108

04

Aug

ust 2

012

Order now

Reprints of this article can also be ordered at

httpwwwdekkercomservletproductDOI101081SCC100105385

Request Permission or Order Reprints Instantly

Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content

All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved

Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom

The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details

Dow

nloa

ded

by [

Uni

vers

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f Il

linoi

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hica

go]

at 0

108

04

Aug

ust 2

012

ORDER REPRINTS

CALIX[n]ARENES 2609

of solvent was washed with water and recrystallized from MeOH-CHCl3 toyield colourless crystals (095 g 66) mp 232ndash234C (Lit16 mpt234ndash235C) 1H NMR (CDCl3 d) 684ndash654 (m 12H ArH) 43ndash31 (m20H ArCH2Ar and -OCH3) molecular mass (vapour pressure osmometry)492 (calcd 480)

Synthesis of 4950515253545556-Octamethoxy Calix[8]arene

A mixture containing octahydroxycalix[8]arene (20 g 24mmol) NaH(22 g 92mmol) and CH3I (18 g 127mmol) in THF (100ml) and DMF(10ml) was refluxed for 12 h The solvent was removed on a rotary evapora-tor and water (100ml) was added to the residue The collected solid wasrecrystallized from MeOH-CHCl3 to give colourless crystals (17 g 75)mp 255ndash258C (lit3 mp 256ndash258C) 1H NMR (CDCl3) d 68 (s 24HArH) 40 (s 16H ArCH2Ar) 35 (s 24H -OCH3) molecular mass(vapour phase osmometry) 1002 (calcd 960)

Synthesis of 5111723-Tetraformyl-25262728-

tetrakis(methoxy)calix[4]arene

A solution of 11-dichloromethyl methyl ether (203 g 177mmol) inCH2Cl2 (100ml) was added to a solution of tetramethylated calix[4]arene(024 g 05mmol) in CHCl3 (100ml) with stirring at room temperaturefollowed by addition of a solution of titanium tetrachloride (45 g237mmol) in CHCl3(100ml) in one portion as quickly as possible Thereaction mixture was stirred for a further period of 1h and then treatedwith water ( 50ml) The organic layer was separated washed twice withwater and dried (Na2SO4) and the solvent evaporated under reduced press-ure The residue was purified by passing through a column (silica gel60ndash120mesh) and eluted with hexane-ethyl acetate (7525) to yield tetra-formyl calix[4]arene as pale yellow crystals (018 g yield 608) mp218ndash220C Anal calcd for C36H32O8 C 7297 H 540 Found C 7286H 559 IR (vmax KBr) 1693 (s) 1597 (s) 1471 (m) 14283 (m) 1385 (m)1283 (s) 1128 (s) 1H NMR (CDCl3 d) 296ndash444 (m 20H ArCH2ArOCH3) 682 784 719 764 (4s 8H ArH) 99 957 944 (2s 1d 4HCHO) MS mz 593 (MthornHthorn) UV (CHCl3) max 269 nm Though this com-pound seems to have been prepared by Komori et al through a differentroute no spectral data has been published20

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ORDER REPRINTS

Synthesis of 511172329354147-Octaformyl

4950515253545556-Octakis(methoxy) Calix[8]arene

To a solution of 6 (082 g 086mmol) in dichloromethane (20ml) asolution of dichloromethyl methyl ether (254g 221mmol) in dichloromethane(15ml) was added with stirring Immediately after a solution of freshlydistilled titanium tetrachloride (43 g 228mmol) in dichloromethane(15ml) was added to the reaction mixture very quickly with vigorous stir-ring The reaction temperature was maintained between 38ndash42C by usingan oil bath Stirring was continued for 1h and ice cold water (50ml) wasslowly added to the solution The reaction mixture was further stirred for15min and extracted with dichloromethane The organic layer was washedtwice with water (50ml2) and dried over anhydrous sodium sulphate Thesolvent was evaporated under reduced pressure and the residue purified bypassing through a column of silica gel (50 g 60ndash120mesh) to give paleyellow solid (069 g 68) mpgt250C Anal calcd for C72H64O16 C7297 H 540 Found C 7283 H 533 Molecular mass (vapour pressureosmometry) 1160 (Calcd 1184) IR (vmax KBr) 1693(s) 1598(s) 1472(m)1428(sh) 1385(m) 1283(s) 1H NMR (CDCl3 d) 967 (s 8H CHO) 695 (s16H ArH) 412 (s 16H ArCH2Ar) 36 (s 24H -OCH3) UV(CHCl3 max)265 nm

ACKNOWLEDGMENT

The authors are thankful to Department of Science amp Technology andCSIR for financial assistance and a research fellowship to AS

REFERENCES

1 Gutsche CD Calixarenes monographs in supramolecular chemistryVol 1 Stoddart JF Ed The Royal Society of ChemistryCambridge 1989

2 Bohmer V Calixarenes a versatile class of macrocyclic compoundsKluwer Academic Dordrecht 1989

3 Gutsche CD Iqbal M Org Synth 1990 68 2344 Gutsche CD Iqbal M Stewart D J Org Chem 1986 51 7425 Steward DR Gutsche CD J Am Chem Soc 1999 121 4136ndash41466 Kubo Y Maeda S Nakamura M Tokita S J Chem Soc Chem

Commun 1994 1725

2610 CHAWLA AND SANTRA

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linoi

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hica

go]

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04

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012

ORDER REPRINTS

7 Daitch CE Hampton PD Duesler ED Alam TM J Am

Chem Soc 1996 118 7769ndash7773

8 Kobo Y Maruyama S Ohhara N Nakamivea M Tokita S J

Chem Soc Chem Commun 1995 1727

9 Reichwein A Verboom W Reinhoudt DN J Chem Soc Perkin

Trans 1994 1167

10 Bohmer V Angew Chem Int Engl 1995 34 713ndash745

11 Ikeda A Shinkai S Chem Rev 1997 97 1713ndash1734

12 De Namor FD Cleverley RM Zapata-Osmachea ML Chem

Rev 1998 98 2498ndash2525

13 Diamond D Mckervey A Chem Rev 1996 15ndash24

14 Almi M Arduini A Casnati A Pochini A Ungaro R

Tetrahedron 1989 45 2177

15 Zhang WC Zheng Y S Huang ZT Syn Commun 1997 27(21)

3763ndash3767

16 Gutsche CD Pagoria PF J Org Chem 1985 50 5795ndash5802

Gutsche CD Lin LG Tetrahedron 1986 42 1633

17 Aggarwal YK Jain VK Personal communication

18 Arduini A Manfredi G Pochini A Sicuri A R Ungaro R

J Chem Soc Chem Commun 1991 936

19 Van Loon JD Arduini A Coppi L Verboom W Pochini A

Ungaro R Harkema S Reinhoudt DN J Org Chem 1990

55 5639

20 Komori T Shinkai S Chemistry Letters 1992 901

21 Arduini A Fanni S Manfredi G Pochini A Ungaro R Sicuri

AR Ugozzoli F J Org Chem 1995 60 1448ndash1453

Received in the UK June 1 2000

CALIX[n]ARENES 2611

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012

Order now

Reprints of this article can also be ordered at

httpwwwdekkercomservletproductDOI101081SCC100105385

Request Permission or Order Reprints Instantly

Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content

All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved

Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom

The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details

Dow

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by [

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f Il

linoi

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hica

go]

at 0

108

04

Aug

ust 2

012

ORDER REPRINTS

Synthesis of 511172329354147-Octaformyl

4950515253545556-Octakis(methoxy) Calix[8]arene

To a solution of 6 (082 g 086mmol) in dichloromethane (20ml) asolution of dichloromethyl methyl ether (254g 221mmol) in dichloromethane(15ml) was added with stirring Immediately after a solution of freshlydistilled titanium tetrachloride (43 g 228mmol) in dichloromethane(15ml) was added to the reaction mixture very quickly with vigorous stir-ring The reaction temperature was maintained between 38ndash42C by usingan oil bath Stirring was continued for 1h and ice cold water (50ml) wasslowly added to the solution The reaction mixture was further stirred for15min and extracted with dichloromethane The organic layer was washedtwice with water (50ml2) and dried over anhydrous sodium sulphate Thesolvent was evaporated under reduced pressure and the residue purified bypassing through a column of silica gel (50 g 60ndash120mesh) to give paleyellow solid (069 g 68) mpgt250C Anal calcd for C72H64O16 C7297 H 540 Found C 7283 H 533 Molecular mass (vapour pressureosmometry) 1160 (Calcd 1184) IR (vmax KBr) 1693(s) 1598(s) 1472(m)1428(sh) 1385(m) 1283(s) 1H NMR (CDCl3 d) 967 (s 8H CHO) 695 (s16H ArH) 412 (s 16H ArCH2Ar) 36 (s 24H -OCH3) UV(CHCl3 max)265 nm

ACKNOWLEDGMENT

The authors are thankful to Department of Science amp Technology andCSIR for financial assistance and a research fellowship to AS

REFERENCES

1 Gutsche CD Calixarenes monographs in supramolecular chemistryVol 1 Stoddart JF Ed The Royal Society of ChemistryCambridge 1989

2 Bohmer V Calixarenes a versatile class of macrocyclic compoundsKluwer Academic Dordrecht 1989

3 Gutsche CD Iqbal M Org Synth 1990 68 2344 Gutsche CD Iqbal M Stewart D J Org Chem 1986 51 7425 Steward DR Gutsche CD J Am Chem Soc 1999 121 4136ndash41466 Kubo Y Maeda S Nakamura M Tokita S J Chem Soc Chem

Commun 1994 1725

2610 CHAWLA AND SANTRA

Dow

nloa

ded

by [

Uni

vers

ity o

f Il

linoi

s C

hica

go]

at 0

108

04

Aug

ust 2

012

ORDER REPRINTS

7 Daitch CE Hampton PD Duesler ED Alam TM J Am

Chem Soc 1996 118 7769ndash7773

8 Kobo Y Maruyama S Ohhara N Nakamivea M Tokita S J

Chem Soc Chem Commun 1995 1727

9 Reichwein A Verboom W Reinhoudt DN J Chem Soc Perkin

Trans 1994 1167

10 Bohmer V Angew Chem Int Engl 1995 34 713ndash745

11 Ikeda A Shinkai S Chem Rev 1997 97 1713ndash1734

12 De Namor FD Cleverley RM Zapata-Osmachea ML Chem

Rev 1998 98 2498ndash2525

13 Diamond D Mckervey A Chem Rev 1996 15ndash24

14 Almi M Arduini A Casnati A Pochini A Ungaro R

Tetrahedron 1989 45 2177

15 Zhang WC Zheng Y S Huang ZT Syn Commun 1997 27(21)

3763ndash3767

16 Gutsche CD Pagoria PF J Org Chem 1985 50 5795ndash5802

Gutsche CD Lin LG Tetrahedron 1986 42 1633

17 Aggarwal YK Jain VK Personal communication

18 Arduini A Manfredi G Pochini A Sicuri A R Ungaro R

J Chem Soc Chem Commun 1991 936

19 Van Loon JD Arduini A Coppi L Verboom W Pochini A

Ungaro R Harkema S Reinhoudt DN J Org Chem 1990

55 5639

20 Komori T Shinkai S Chemistry Letters 1992 901

21 Arduini A Fanni S Manfredi G Pochini A Ungaro R Sicuri

AR Ugozzoli F J Org Chem 1995 60 1448ndash1453

Received in the UK June 1 2000

CALIX[n]ARENES 2611

Dow

nloa

ded

by [

Uni

vers

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f Il

linoi

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hica

go]

at 0

108

04

Aug

ust 2

012

Order now

Reprints of this article can also be ordered at

httpwwwdekkercomservletproductDOI101081SCC100105385

Request Permission or Order Reprints Instantly

Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content

All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved

Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom

The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details

Dow

nloa

ded

by [

Uni

vers

ity o

f Il

linoi

s C

hica

go]

at 0

108

04

Aug

ust 2

012

ORDER REPRINTS

7 Daitch CE Hampton PD Duesler ED Alam TM J Am

Chem Soc 1996 118 7769ndash7773

8 Kobo Y Maruyama S Ohhara N Nakamivea M Tokita S J

Chem Soc Chem Commun 1995 1727

9 Reichwein A Verboom W Reinhoudt DN J Chem Soc Perkin

Trans 1994 1167

10 Bohmer V Angew Chem Int Engl 1995 34 713ndash745

11 Ikeda A Shinkai S Chem Rev 1997 97 1713ndash1734

12 De Namor FD Cleverley RM Zapata-Osmachea ML Chem

Rev 1998 98 2498ndash2525

13 Diamond D Mckervey A Chem Rev 1996 15ndash24

14 Almi M Arduini A Casnati A Pochini A Ungaro R

Tetrahedron 1989 45 2177

15 Zhang WC Zheng Y S Huang ZT Syn Commun 1997 27(21)

3763ndash3767

16 Gutsche CD Pagoria PF J Org Chem 1985 50 5795ndash5802

Gutsche CD Lin LG Tetrahedron 1986 42 1633

17 Aggarwal YK Jain VK Personal communication

18 Arduini A Manfredi G Pochini A Sicuri A R Ungaro R

J Chem Soc Chem Commun 1991 936

19 Van Loon JD Arduini A Coppi L Verboom W Pochini A

Ungaro R Harkema S Reinhoudt DN J Org Chem 1990

55 5639

20 Komori T Shinkai S Chemistry Letters 1992 901

21 Arduini A Fanni S Manfredi G Pochini A Ungaro R Sicuri

AR Ugozzoli F J Org Chem 1995 60 1448ndash1453

Received in the UK June 1 2000

CALIX[n]ARENES 2611

Dow

nloa

ded

by [

Uni

vers

ity o

f Il

linoi

s C

hica

go]

at 0

108

04

Aug

ust 2

012

Order now

Reprints of this article can also be ordered at

httpwwwdekkercomservletproductDOI101081SCC100105385

Request Permission or Order Reprints Instantly

Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content

All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved

Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom

The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details

Dow

nloa

ded

by [

Uni

vers

ity o

f Il

linoi

s C

hica

go]

at 0

108

04

Aug

ust 2

012

Order now

Reprints of this article can also be ordered at

httpwwwdekkercomservletproductDOI101081SCC100105385

Request Permission or Order Reprints Instantly

Interested in copying and sharing this article In most cases US Copyright Law requires that you get permission from the articlersquos rightsholder before using copyrighted content

All information and materials found in this article including but not limited to text trademarks patents logos graphics and images (the Materials) are the copyrighted works and other forms of intellectual property of Marcel Dekker Inc or its licensors All rights not expressly granted are reserved

Get permission to lawfully reproduce and distribute the Materials or order reprints quickly and painlessly Simply click on the Request PermissionReprints Here link below and follow the instructions Visit the US Copyright Office for information on Fair Use limitations of US copyright law Please refer to The Association of American Publishersrsquo (AAP) website for guidelines on Fair Use in the Classroom

The Materials are for your personal use only and cannot be reformatted reposted resold or distributed by electronic means or otherwise without permission from Marcel Dekker Inc Marcel Dekker Inc grants you the limited right to display the Materials only on your personal computer or personal wireless device and to copy and download single copies of such Materials provided that any copyright trademark or other notice appearing on such Materials is also retained by displayed copied or downloaded as part of the Materials and is not removed or obscured and provided you do not edit modify alter or enhance the Materials Please refer to our Website User Agreement for more details

Dow

nloa

ded

by [

Uni

vers

ity o

f Il

linoi

s C

hica

go]

at 0

108

04

Aug

ust 2

012