22808-03-3Relevant academic research and scientific papers
Synthesis of π-conjugated copolymers composed of benzo[2,1,3]thiadiazole and thiophene units bearing various alkyl groups and their application to photovoltaic cells
Lee, Kwang-Hoi,Lee, Ho-Jin,Kuramoto, Kouji,Tanaka, Yohei,Morino, Kazuhide,Sudo, Atsushi,Okauchi, Tatsuo,Tsuge, Akihiko,Endo, Takeshi
, p. 3543 - 3549 (2011)
π-Conjugated polymers, PTOTBT, PTEHTBT, and PTt-BTBT, composed of benzothiadiazole as an electron accepting unit and terthiophene as an electron donating unit in the backbone were prepared. PTOTBT, PTEHTBT, and PTt-BTBT contained side chain groups of n-octyl, 2-ethylhexyl, and t-butyl groups, respectively. Solubility, optical and thermal properties of the polymers showed strong dependences on their side chain groups. PTEHTBT having 2-ethylhexyl groups in the side chain exhibited absorption maximum (Imax) at longer wavelength (565 nm) than PTOTBT (534 nm) and PTt-BTBT (495 nm). PTOTBT showed higher thermal stability than the others. The prepared polymers were employed to polymer solar cells (PSCs) with a configuration of ITO/PEDOT-PSS/polymer: PC61BH/LiF/Al. Power conversion efficiency of the PSC-based on PTEHTBT was 1.32%.
Synthesis, Crystal, and Molecular Structure of 3,4-Di-t-butylthiophen
Brandsma, Lambert,Meijer, Johnny,Verkruijsse, Herman D.,Bokkers, Gysbertus,Duisenberg, Albert J. M.,Kroon, Jan
, p. 922 - 923 (1980)
A successful synthesis of the hitherto unknown 3,4-di-t-butylthiophen and the results of its crystal structure determination are reported.
Synthesis of an octa-tert-butylphthalocyanine: A low-aggregating and photochemically stable photosensitizer
Gobo, Nicholas R. S.,Brocksom, Timothy J.,Zukerman-Schpector, Julio,De Oliveira, Kleber T.
, p. 5028 - 5031 (2013)
The synthesis of a new octa-tert-butylphthalocyanine is described. First, the 4,5-di-tert-butylphthalonitrile building block was synthesized in a six-step approach, in which the last step is a three reaction domino sequence. Then, this phthalonitrile was cyclotetramerized to furnish a new phthalocyanine dye, which presented no aggregation in solution and good photophysical properties. The synthesis of a new octa-tert-butylphthalocyanine is described. First, the 4,5-di-tert-butylphthalonitrile building block was synthesized in a six-step approach, in which the last step is a three reaction domino sequence. Then, this phthalonitrile was cyclotetramerized to furnish a new phthalocyanine dye, which presented no aggregation in solution and good photophysical properties. Copyright
π-Face-selective hetero Diels-Alder reactions of 3,4-di-tert-butylthiophene 1-oxide. An excellent trapping reagent for thioaldehydes and thioketones
Takayama, Jun,Fukuda, Seiko,Sugihara, Yoshiaki,Ishii, Akihiko,Nakayama, Juzo
, p. 5159 - 5162 (2003)
Hetero Diels-Alder reactions of 3,4-di-tert-butylthiophene 1-oxide (1) with thioaldehydes and thioketones take place exclusively, except the reaction with thiobenzophenone, at the syn-π-face of 1 with respect to the S=O bond. The π-face selectivity was ex
The chemistry of the thiosulfinyl group: Preparation, structure, and spectroscopic and chemical properties of cyclic thionosulfites
Nakayama, Juzo,Yoshida, Sanae,Sugihara, Yoshiaki,Sakamoto, Akira
, p. 1451 - 1471 (2005)
Treatment of the tetrahydrothiophene-3,4-diol 5 with 1,1′-thiobis- (1H-benzimidazole) (6) furnished two diastereoisomers of the novel cyclic thionosulfite 4 with different configurations at the pseudo-tetrahedral center of the thiosulfinyl (S=S) group. The configuration of the S=S group of the major diastereoisomer (isolated in 45% yield) was established to be syn to the thiolane ring, as determined by X-ray crystallographic analysis, while that of the minor diastereoisomer (isolated in 10% yield) was anti. 1H-NMR Spectroscopic analysis clarified that the shielding and deshielding zones of the S=S group are similar to those of the well-documented S=O group. Characteristic absorptions of the S=S group in the IR, Roman, and UV/VIS spectra were assigned on the basis of calculations at the B3LYP/6-31G* level. The reactivity of the S=S group toward thermolysis, hydrolysis, and oxidation was examined. The S=S group is more resistant toward oxidation than the divalent sulfide S-atom, but is oxidatively converted to the S=O group.
SYNTHESIS AND REACTIONS OF 3,4-DI-t-BUTYLTHIOPHENE
Nakayama, Juzo,Yamaoka, Shoji,Hoshino, Masamatsu
, p. 1161 - 1164 (1988)
3,4-Di-t-butylthiophene (1) was surprisingly easily synthesized from readily accessible bis(2-t-butyl-2-oxoethyl) sulfide (2).Reactions of 1 with a variety of electrophiles were examined.
So2-extrusion of an 8-thiabicylo[3.2.1]octa-2,6-diene 8,8-dioxide and rearrangement of the resulting cycloheptatriene
Takayama, Jun,Sugihara, Yoshiaki,Nakayama, Juzo
, p. 132 - 137 (2007/10/03)
The reaction of 3,4-di-tert-butylthio-phene 1-oxide (8) with tetrachlorocyclopropene provided 6,7-di-tert-butyl-2,3,4,4-tetrachloro-8-thia- bicylo[3.2.1]-octa-2,6-diene 8-oxide (10), which was oxidized to the corresponding 8,8-dioxide 16 by m-chloroperbenzoic acid. The thermolysis of 16 in refluxing chlorobenzene, xylene, or octane gave 5-tert-butyl-1,2-dichloro-3- [(1,1-dichloro-2,2-dimethyl)propyl]benzene (18) with extrusion of SO2 and 2-tert-butyl-4,5,6-trichloro-9,9-dimethylbicyclo[5.2.0]nona-1,3,5-triene (19) with extrusion of SO2 and HCl in 73-78% combined yields. On the other hand, the thermolysis of 16 in the presence of triethylamine gave 19 as the sole product in 98% yield. A mechanism that involves the initial formation of 4,5-di-tert-butyl-1,2,7,7-tetrachlorocycloheptatriene (17) is proposed to explain the observed products.
Tetracyanoethylene oxide not only oxidizes sulfides to sulfoxides but also reduces sulfoxides to sulfides
Nakayama, Juzo,Tai, Ayako,Iwasa, Sachiko,Furuya, Tomohiro,Sugihara, Yoshiaki
, p. 1395 - 1397 (2007/10/03)
It was found that tetracyanoethylene oxide not only oxidizes sulfides to sulfoxides but also reduces sulfoxides to sulfides with generation of two molecules of carbonyl cyanide. The reaction thus also functions as a new method for generation of carbonyl cyanide.
Reversible disulfur monoxide (S2O)-forming retro-Diels-Alder reaction. Disproportionation of S2O to trithio-ozone (S3) and sulfur dioxide (SO2) and reactivities of S2O and S3
Nakayama, Juzo,Aoki, Satoshi,Takayama, Jun,Sakamoto, Akira,Sugihara, Yoshiaki,Ishii, Akihiko
, p. 9085 - 9093 (2007/10/03)
5,6-Di-tert-buty(-2,3,7-trithiabicyclo[2.2.1]hept-5-ene 7-endo-oxide (4) was prepared by addition of S2Cl2 to 3,4-di-tert- butylthiophene 1-oxide (3) in high yield. The oxidation of 4 with dimethyldioxirane gave a 7:1 isomeric mixture of 5,6-di-tert-butyl-2,3,7- trithiabicyclo[2.2.1]hept-5-ene 2-endo-7-endo-dioxide (5a) and 2-exo-7-endo-dioxide (5b) quantitatively. The thermally labile 5 was shown to undergo a retro-Diels-Alder reaction that produces S2O and 3 in a reversible way. The resulting S2O was trapped by Diels-Alder reactions with dienes to give 3,6-dihydro-1,2-dithiin 1 -oxides in good yields. In the absence of the dienes, S2O disproportionates to SO2 and S3, and the resulting S3 underwent a 1,3-dipolar cycloaddition with 3 on its syn-π-face with respect to the S=O bond to give a trithiolane derivative, whereas in the presence of excess norbornene, it produced the 1,3-dipolar cycloadduct with norbornene in good yield. Thus, the retro-Diels-Alder reaction of 5 functions as an S2O and S3 source. DFT calculations at the B3LYP/6-311+G(3df,2p) level were carried out in order to explain why S2O disproportionates to SO2 and S3 and why S2O acts as a dienophile and not 1,3-dipole, whereas O3 and S3 serve as 1,3-dipoles.
The thiosulfinyl group serves as a stereogenic center and shows diamagnetic anisotropy similar to that of the sulfinyl group
Tanaka, Sanae,Sugihara, Yoshiaki,Sakamoto, Akira,Ishii, Akihiko,Nakayama, Juzo
, p. 9024 - 9025 (2007/10/03)
The pseudotetrahedral geometry of the thiosulfinyl group (>SS) in the thionosulfite which was prepared by treatment of cis-3,4-di-tert-butylthiolane-3,4-diol with 1,1'-thiobisbenzimidazole is stable enough to allow the isolation of two diastereomers. X-ray crystallographic analysis revealed that the configuration of the >S S group of the major diastereomer (45% isolated yield) is syn to the thiolane ring, while that of the minor diastereomer (10% isolated yield) is anti to the thiolane ring. 1H NMR spectrum analysis clarified that the shielding and deshielding zones of the >SS group are similar to those >SS group; Chemical properties of the > 5 S group toward thermolysis, hydrolysis, and oxidation were clarified. The absorptions or bands in the UV/ vis IR and Raman spectra, which originate from the > SSgroup, were assigned on the basis of the B3LYP/ 6-31G* level calculations. Copyright
