TY - JOUR
T1 - Selective syntheses of vinylenedithiathiophenes (VDTTs) and dithieno[2,3-b;2′,3′-d]thiophenes (DTTs); Building blocks for π-conjugated systems
AU - Osken, Ipek
AU - Sahin, Onur
AU - Gundogan, Ali S.
AU - Bildirir, Hakan
AU - Capan, Asli
AU - Ertas, Erdal
AU - Eroglu, Mehmet S.
AU - Wallis, John D.
AU - Topal, Kevser
AU - Ozturk, Turan
PY - 2012/1/28
Y1 - 2012/1/28
N2 - Selective syntheses of 3,4-vinylenedithiathiophenes (VDTTs) and dithieno[2,3-b;2′,3′-d]thiophenes (DTTs), having Ph, 4-CH 3OC 6H 4, 4-BrC 6H 4, 4-NO 2C 6H 4 and 4-(CH 3) 2NC 6H 4 groups, were achieved through the reaction of 1,8-diketone with phosphorus decasulfide (P 4S 10). The reaction could be shifted between VDTT and DTT by adding base (sodium bicarbonate) or acid (para-toluenesulfonic acid), respectively, to the reaction mixture. While the VDTTs were obtained in moderate yields, an important achievement has been made with the syntheses of the DTTs, obtaining them in higher yields compared with the previous report. Polymers of the VDTTs, which are the analogues of ethylenedioxythiophene, EDOT, were prepared using FeCl 3. Unfortunately, all attempts for their electropolymerization failed. Spin density calculations revealed that none of the VDTTs had a significant positive spin density at the 'α' carbon atoms of the thiophene ring. Considering their solubility and functional groups, which could be further derivatized, they are useful building blocks for the preparation of new organic materials.
AB - Selective syntheses of 3,4-vinylenedithiathiophenes (VDTTs) and dithieno[2,3-b;2′,3′-d]thiophenes (DTTs), having Ph, 4-CH 3OC 6H 4, 4-BrC 6H 4, 4-NO 2C 6H 4 and 4-(CH 3) 2NC 6H 4 groups, were achieved through the reaction of 1,8-diketone with phosphorus decasulfide (P 4S 10). The reaction could be shifted between VDTT and DTT by adding base (sodium bicarbonate) or acid (para-toluenesulfonic acid), respectively, to the reaction mixture. While the VDTTs were obtained in moderate yields, an important achievement has been made with the syntheses of the DTTs, obtaining them in higher yields compared with the previous report. Polymers of the VDTTs, which are the analogues of ethylenedioxythiophene, EDOT, were prepared using FeCl 3. Unfortunately, all attempts for their electropolymerization failed. Spin density calculations revealed that none of the VDTTs had a significant positive spin density at the 'α' carbon atoms of the thiophene ring. Considering their solubility and functional groups, which could be further derivatized, they are useful building blocks for the preparation of new organic materials.
KW - Dithienothiophene
KW - Ethylenedioxythiophene
KW - Phosphorus decasulfide (P S )
KW - Vinylenedithiathiophene
UR - http://www.scopus.com/inward/record.url?scp=84855457402&partnerID=8YFLogxK
U2 - 10.1016/j.tet.2011.11.059
DO - 10.1016/j.tet.2011.11.059
M3 - Article
AN - SCOPUS:84855457402
SN - 0040-4020
VL - 68
SP - 1216
EP - 1222
JO - Tetrahedron
JF - Tetrahedron
IS - 4
ER -