chalcones ( 1,3-diphenyl-2-propen-1-ones )   are known to possess a range of important biological activities , such as antibacterial , antifungal , antileishmanial , antimalarial , antifilarial   anti - inflammatory [ 68 ] , antiprotozoal ( antileishmanial and antipanosomal ) , antimicrobial [ 1013 ] , larvicidal , anticonvulsant , anti - hiv , antitumor , and anticancer   activities , and they could be readily transformed into varieties of other compounds , many of which are biologically active heterocycles [ 19 , 20 ] . owing to such biological activities of chalcones , the chemical literature shows the synthesis of a wide range of chalcones and their analogues [ 4 , 813 , 2123 ] .
again , since macrocyclic compounds are well - known for their ability to show the important property of molecular recognition , macrocyclic systems containing the chalcone moiety are expected to generate compounds having interesting biological and material properties [ 24 , 25 ] .
our research on such compounds has been initiated through the synthesis of a number of macrocyclic bis- and monochalcones reported recently . in continuation of that study
we have synthesized a benzo - fused 26-membered macrocyclic bischalcone , namely , ( 19e,43e)-2.11.27.36-tetroxaheptacyclo [ 44.4.0.0.0.0.0.0 ] pentaconta-1(46),4(9),5,7,12(17),13,15,19,21,23,25,29,31,33,37,39,41,43,47,49-icosaene-18,45-dione ( 3 ) , and a benzo - fused 13-membered macrocyclic monochalcone , namely , ( 19e)-2.11-dioxatetracyclo[19.4.0.0.0 ] pentacosa-1(25),4(9),5,7,12(17),13,15,19,21,23-decaen-18-one ( 5 ) , by use of readily available starting materials .
alkylation products of salicylaldehyde and o - hydroxyacetophenone by the use of 1,2-(bis - bromobenzyl)benzene as alkylating agent were first prepared . the resulting dialdehyde ( 1 ) and diketone ( 2 ) , both new compounds ,
were then subjected to claisen - schmidt reaction under high dilution condition when the macrocyclic bischalcone 3 was obtained in moderate yield ( scheme 1 ) . in order to achieve the synthesis of 5 , 2,2-dihydroxychalcone ( 4 )
the reaction between 4 and 1,2-(bis - bromobenzyl)benzene was then done by following the typical procedure for alkylation of phenols ( k2co3/acetone , reflux , 12  h ) ( scheme 2 ) .
this reaction gave 5 in very good yield and no trace of any macrocyclic bischalcone 7 ( a possible product through bimolecular cyclization of the intermediate 6 ) ( scheme 3 ) .
the new compounds 3 and 5 were characterized from their analytical and spectral data which are presented in the experimental section as well as in the supplementary file in the supplementary material available online at http://dx.doi.org/10.1155/2014/485014 .
ir spectra were recorded on a perkin elmer ft - ir spectrophotometer ( spectrum bx ii ) in kbr pellets .
h and c nmr spectra were recorded in cdcl3 on a bruker av-300 ( 300  mhz ) spectrometer .
microanalytical data were recorded on a perkin - elmer 2400 series ii c , h , n analyzer .
esims(+ ) mass spectrum of 3 was measured with a waters micromass q - tof micro instrument .
column chromatography was performed with silica gel ( 100200  mesh ) and tlc with silica gel g made of srl pvt .
h and c nmr and mass spectra of different compounds can be found in the supplementary material .
this compound was prepared from o - xylene by benzylic bromination with nbs [ nbs ( 2.2 equiv . ) , ( phcoo)2 ( trace ) , refluxed in ccl4 , 12  h , yield : 83% ) , m.p .
s , 4h , ch2-br ) , 7.297.31 ( m , 2h , ar - h ) , 7.337.38 ( m , 2h , ar - h ) .
a mixture of salicylaldehyde ( 2  mmol ) and 1,2-bis(bromomethyl)benzene ( 1  mmol ) was refluxed in methanolic koh ( 5% , 25  ml ) for 7  h. removal of methanol by distillation and addition of water followed by extraction with ethyl acetate gave crude alkylation product 1 , which was purified by rapid column chromatography followed by crystallization from chcl3-petroleum ether ( yield : 66% ) .
the physical and spectral data of 1 were as follows : colourless needles , m.p .
118120c ; h nmr ( 300  mhz , cdcl3 ) :  5.31 ( br .
s , 4h , 2  och2 ) , 7.05 ( dt , 4h , j = 7.2 and 1.5  hz ) , 7.427.45 ( m , 2h , arh ) , 7.507.57 ( m , 4h ) , 7.82 ( dd , 2h , j = 7.8 and 1.8  hz ) , and 10.45 ( br .
a mixture of o - hydroxyacetophenone ( 2  mmol ) , 1,2-bis(bromomethyl)benzene ( 1  mmol ) and anhydrous k2co3 ( 3  g. ) was refluxed in dry acetone for 12  h. usual work - up followed by purification of the resulting crude material by column chromatography over silica gel afforded pure 2 ( yield : 78% ) .
the physical and spectral data of 2 were as follows : colourless needles ( chcl3-petroleum ether ) , m.p .
74c ; h nmr ( 300  mhz , cdcl3 ) :  2.53 ( s , 6h , 2  coch3 ) , 5.27 ( br .
s , 4h , och2 ) , 7.03 ( dt , 4h , j = 8.4 and 1.8  hz ) , 7.407.46 ( m , 4h ) , 7.54 ( dt , 2h , j = 8.4 and 1.8  hz ) , and 7.71 ( dd , 2h , j = 7.8 and 1.8  hz ) . a mixture of the dialdehyde 1 ( 1  mmol ) and the diketone 2 ( 1  mmol ) was dissolved in a koh solution ( 10% , 75  ml ) in meoh - h2o ( 3  :  1 ) and the mixture was stirred at room temperature .
the solid thus obtained was almost pure and it was further purified by column chromatography over silica gel followed by crystallization from chcl3-petroleum ether ( yield : 49% ) .
the analytical and spectral data of the macrocyclic product 3 were as follows : light yellow cubes ; m.p .
205207c ; ir ( kbr , cm ) : 1598 ( c = o ) , 1567 , 1485 , 1446 , 1384  cm ; h nmr ( 300  mhz , cdcl3 ) :  4.85 ( s , 4h , o 
ch2 ) , 5.06 ( s , 4h , ch2o ) , 6.77 ( d , 4h , j = 7.2  hz ) , 6.80 ( t , 2h , j = 7.5  hz ) , 6.97 ( t , 4h , j = 7.8  hz ) , 7.187.26 ( m , 10h ) , 7.27 ( d , 2h , j = 16.2  hz , 2  h- ) , 7.38 ( dt , 2h , j = 7.5 and 1.5  hz ) , 7.47 ( dd , 2h , j = 8.4 and 1.5  hz ) , 7.70 ( d , 2h , j = 16.2  hz , 2  h- ) ; c nmr ( 75  mhz , cdcl3 ) :  68.23 , 68.48 , 112.47 , 112.75 , 121.04 , 121.21 , 123.98 , 127.65 , 128.10 , 128.11 , 128.48 , 129.40 , 129.60 , 130.10 , 130.21 , 131.47 , 132.23 , 133.81 , 134.42 , 140.17 , 156.42 , 157.10 , 194.64 ( c = o ) ; ms ( tof ms es ) : m / z 707.18 ( m+na ) , 685.19 ( m+h ) .
elemental analysis : calcd . for c46h36o6:c , 80.68 ; h , 5.30 . found : c , 80.56 ; h 5.42% .
this chalcone was prepared by condensation of o - hydroxyacetophenone and salicylaldehyde with aqueous alkali , m.p .
d , 1h , j = 8.1  hz ) , 6.947.07 ( m , 3h ) , 7.32 ( dt , 1h , j = 7.8 and 1.8  hz ) , 7.52 ( dt , 1h , j = 7.5 and 1.5  hz ) , 7.63 ( dd , 1h , j = 7.8 and 1.9  hz ) , 7.87 ( d , 1h , j = 15.6  hz , h- ) , 7.96 ( dd , 1h , j = 8.1 and 1.5  hz ) , 8.21 ( d , 1h , j = 15.6  hz , h- ) , 12.92 ( s , 1h , 2-oh ) .
to a mixture of 4 ( 1  mmol ) and 1,2-bis(bromomethyl)benzene ( 1  mmol ) in dry acetone ( 25  ml ) , anhydrous k2co3 ( 3  g ) was added and the mixture was refluxed with stirring for 12  h. usual work - up of the reaction mixture followed by chromatography of the crude product over silica gel using petroleum ether - ethyl acetate ( 90  :  10 , v / v ) gave pure 5 as light yellow crystals ( yield : 57% ) , m.p .
160162c , ir ( kbr ) cm : 3028 , 2903 , 1585 , 1562 , 1470 , 1453 , 1436 , 1297 , 1249 , 1152 , 1058 , 960 , 745 .
h nmr ( 300  mhz , cdcl3 ) :  5.28 ( s , 4h , 2  arch2o ) , 7.017.10 ( m , 2h ) , 7.11 ( d , 1h , j = 16.5  hz , h- ) , 7.237.38 ( m , 7h ) , 7.457.51 ( m , 2h ) , 7.58 ( dd , 1h , j = 7.5 and 1.8  hz , proton ortho to c = o ) , 7.66 ( d , 1h , j = 16.5  hz , h- ) , c nmr ( 75  mhz , cdcl3 ) :  68.65 , 71.70 , 113.51 , 119.01 , 121.67 , 123.46 , 128.43 , 128.81 , 129.19 , 129.77 , 129.79 , 129.87 , 130.68 , 130.88 , 131.89 , 132.62 , 135.18 , 135.29 , 141.56 , 156.71 , 156.97 , 195.23 . ms ( tof ms es ) : m / z ( m+na ) 365.00 .
elemental analysis : calcd . for c23h18o3 : c , 80.68 ; h , 5.30 . found : c , 80.45 ; h , 5.44% .
thus , we report very simple syntheses of two new benzo - fused macrocycles incorporating chalcone moiety by the use of very common starting materials . the compounds may find important applications .
 simple syntheses of the benzo - fused 26-membered macrocyclic bischalcone ( 19e,43e)-2.11.27.36-tetroxaheptacyclo[44.4.0.04,9.012,17.021,26.029,34.037,42]pentaconta-1(46),4(9),5,7,12(17),13,15,19,21,23,25,29,31,33,37,39,41,43,47,49-icosaene-18,45-dione ( 3 ) and the benzo - fused 13-membered macrocyclic chalcone ( 19e)-2.11-dioxatetracyclo[19.4.0.04,9.012,17]pentacosa-1(25),4(9),5,7,12(17),13,15,19,21,23-decaen-18-one ( 5 ) using very common starting materials and reagents are described . 
 the compounds are new and they have been characterized from their analytical and spectral data . 
1. Introduction 
2. Results and Discussion
3. Experimental 
4. Conclusion