Greener protocol for one pot synthesis of coumarin styryl dy(3)

S.B.Phadtareetal./DyesandPigments97(2013)105e112107

OH

N

OH

EtO

O

70-75CN

O

O

o

4-(diethylamino)-2-hydroxybenzaldehyde

(1)

Ethyl aceto acetate

(2)

3-acetyl-7-(diethylamino)-2H-chromen-2-one

(3)

CN

70-75CDES

Ar

CN

N

O

OArCHO

o

(4)

3

CN

6a-6h30-40oCDES

NOO

(7a-7h)

2-(1-(7-(diethylamino)-2-oxo-2H-chromen

-3-yl)ethylidene)malononitrile

(5)

Where, Ar for

O

6a and 7a =6b and 7b =6c and 7c =6d and 7d =

HCO

6e and 7e =6f and 7f =

N

6g and 7g =6h and 7h =

OPh

Scheme1.Generalreactionscheme.

(E)-2-(1-(7-(Diethylamino)-2-oxo-2H-chromen-3-yl)-3-phenylallylidene)malononitrileTable17a:browncoloredsolid.Yield:1.6g(78%).Meltingpoint(measured)185e187 C;lmax(chloroform)/nm:376;nmax/cmÀ1:2975,2219(CN),1697,1585,1510,1242,1132,and709;1HNMR(500MHz;CDCl3;TMS)1.28(6H,t,J¼7.0Hz,(eCH3)2),3.51(4H,q,J¼7.1Hz,(eCH2)2),6.57(1H,d,J¼2.0Hz),6.67(1H,dd,J¼7.0,2.2Hz),7.15(1H,d,J¼15.8Hz,vinylproton),7.39(1H,d,J¼7.0Hz)"and"7.54(1H,d,J¼15.8Hz,vinylproton),7.57(2H,d,J¼8.0Hz,phenylring),7.67(1H,s,vinylproton);13CNMR(100MHz,CDCl3,TMS)d14.1,22.7,47.8,72.5,98.9,106.3,107.1,113.6,114.6,124.0,125.6,126.3,127.5,128.0,129.1,133.2,148.7,151.4,158.0,158.5,180.7;m/z(EI)394(MÀ1);Mol.Wt.:395.45;Anal.CalcdforC25H21N3O2:C,75.93;H,5.35;N,10.63.Found:C,75.52;H,5.02;N,11.01.

(E)-2-(1-(7-(Diethylamino)-2-oxo-2H-chromen-3-yl)-3-(3-methoxyphenyl)allylidene)malononitrileTable1,7b:browncoloredsolid.Yield:1.7g(75%).Meltingpoint(measured)131e133 C;lmax(chloroform)/nm:394;nmax/cmÀ12217(CN),1712,1618,1579,1510,1238,and796;1HNMR(500MHz;CDCl3;TMS)1.26(6H,t,J¼7.0Hz,(eCH3)2),3.47(4H,q,J¼7.0Hz,(eCH2)2),6.55(1H,d,J¼2.5Hz),6.65(1H,dd,J¼8.7,2.5Hz),6.96(1H,dd,J¼8.0,2.0Hz,phenylring),7.03(1H,t,J¼7.5Hz,phenylring),7.08(1H,d,J¼15.5Hz,vinylproton),7.14(1H,dt,J¼7.5Hz,phenylring),7.31(1H,t,J¼8.0Hzphenylring),7.35(1H,J¼8.7Hz,phenylring),7.49(1H,d,J¼15.5Hz,vinylproton),7.66(1H,s,vinylproton,coumarinring);13CNMR(100MHz,CDCl3,TMS)d14.1,22.3,47.8,56.6,73.0,98.7,106.4,107.3,113.8,114.8,123.8,125.2,126.4,127.5,127.9,129.5,133.2,148.7,151.3,158.0,158.3,180.8;m/z(EI)424(MÀ1);Mol.Wt.:425.48;Anal.CalcdforC26H23N3O3:C,73.39;H,5.45;N,9.88.Found:C,73.81;H,5.03;N,10.02.

(E)-2-(1-(7-(Diethylamino)-2-oxo-2H-chromen-3-yl)-3-(4-(dimethylamino)phenyl)allylidene)malononitrileTable1,7c:browncoloredsolid.Yield:1.9g(84%).Meltingpoint(measured)110e112 C;lmax(chloroform)/nm:484;nmax/cmÀ1:2972,2214,1710,1571,1502,1116,815;1HNMR(300MHz;CDCl3;TMS)1.25(6H,t,J¼7.0Hz,(eCH3)2),3.48(4H,q,J¼7.0Hz,(eCH2)2),6.55(1H,d,J¼2.0Hz),6.64(1H,d,J¼9.0Hz),7.02(1H,d,J¼15.0Hz,vinylproton),7.26(2H,dd,J¼8.0,2.0Hz),7.34(2H,dd,J¼8.0,2.0Hz)7.44(1H,d,J¼9.0Hz),7.49(1H,d,J¼15.0Hz,vinylproton),7.61(1H,s,vinylprotoncoumarinring);13CNMR(100MHz,CDCl3,TMS)d12.8,41.9,47.2,53.5,54.1,58.5,98.8,107.9,108.9,111.8,114.4,128.5,128.5,128.8,128.8,129.1,151.9,152.9,156.8,159.0,179.9;m/z:(EI)439(Mþ1);Mol.Wt.:438.52;Anal.CalcdforC27H26N4O2:C,73.95;H,5.98;N,12.78.Found:C,74.02;H,5.92;N,12.88.

(E)-2-(1-(7-(Diethylamino)-2-oxo-2H-chromen-3-yl)-3-(3-phenoxyphenyl)allylidene)malononitrileTable1,7d:browncoloredsolid.Yield:1.8g(71%).Meltingpoint(measured)123e125 C;lmax(chloroform)/nm:397;nmax/cmÀ12217(CN),1708,1571,1240,1027;1HNMR(500MHz;CDCl3;TMS)1.22(6H,t,J¼7.0Hz,(eCH3)2),3.47(4H,q,J¼7.0Hz,(eCH2)2),6.56(1H,d,J¼2.5Hz),6.67(1H,dd,J¼9.0,2.5Hz),7.07(1H,d,J¼15.5Hz,vinylproton),7.33-7.40(5H,m),7.48(1H,s,vinylprotoncoumarin