5732-24-1Relevant academic research and scientific papers
Air promoted annulation of thiophenols with alkynes leading to benzothiophenes
Wang, Yajun,Wu, Rui,Zhao, Shijun,Quan, Zhengjun,Su, Yingpeng,Huo, Congde
supporting information, p. 1667 - 1671 (2018/03/21)
Air promoted intermolecular annulation of thiophenols with alkynes, leading to complex benzothiophenes, is reported. This atom-economical reaction is performed in the absence of any catalyst, chemical oxidant and additive. Only a solvent and an air atmosp
Synthesis and spectral study of tetra(2,3-thianaphtheno)-porphyrazine, its tetra-tert-butyl derivative and their Mg(II), Al(III), Ga(III) and In(III) complexes
Taraymovich, Ekaterina S.,Korzhenevskii, Andrey B.,Mitasova, Yulia V.,Kumeev, Roman S.,Koifman, Oscar I.,Stuzhin, Pavel A.
experimental part, p. 54 - 65 (2012/02/16)
Starting from easily available thiophenols (PhSH (1a), 4-tert-butyl-PhSH (1b)) and oxalylchloride we have prepared 2,3-thianaphtenequinones 2a,b which were then successively converted to thianaphthene-2,3-dicarboxylic acids 4a,b their imides 10a,b, diamides 9a,b and finally to thianaphthene-2,3- dicarbonitriles 11a,b the key precursors for the series of novel porphyrazines bearing four 2,3-annulated thianaphthene moieties. The free-bases 12a,b were obtained by cyclotetramerization of the dinitrile 11a,b in the presence of lithium in n-pentanol, while the reaction with magnesium(II) butoxide in n-butanol leads to the Mg(II) complex 13a. Complexes with Al(III) (14a,b), Ga(III) (14a,b) and In(III) (14a,b) were obtained by the template cyclotetramerization of the dinitriles 11a,b in a melt with the corresponding (hydroxy)acetates. Tetra(2,3-thianaphtheno)porphyrazine 12a and its metal complexes 13a15a are only sparingly soluble in common organic solvents, the solubility is enhanced for their tert-butyl substituted derivatives 12b, 14b16b. The study of the electronic absorbtion spectra has revealed that the extension of the porphyrazine π-chromophore by fusion of four thianaphthene fragments due to the angular type of their annulation (similar to that found in 1,2-naphthalocyanines) and negative inductive effect of the sulfur atoms has an effect on its spectral properties which is less than in the case of the isoelectronic naphthalene rings fusion and is comparable with the influence of four benzene rings in phthalocyanines.
Synthesis of New Type Benzo[b]thiophene Fused Quinones and their Tetracyanoquinodimethane Derivatives
Ohba, Yoshihiro,Murakami, Yasuo,Sone, Tyo,Awano, Hiroshi
, p. 781 - 787 (2007/10/03)
A series of new type of benzo[b]thiophene-fused 1,4-benzoquinones and their tetracyanoquinodimethane derivatives were synthesized. The cyclic voltammetric data of new type quinones and tetracyanoquinodimethane derivatives displayed different behavior. All new quinones exhibit two reduction waves corresponding to the radical anion and dianion. On the other hand, most tetracyanoquinodunethane derivatives display a singlewave reduction to the dianion. The benzo[b]thiophene moiety fused tetracyanoquinodimethane derivatives reveal more negative reduction potentials than that of tetracyanoquinodimethane.
Thermolysis of Thiophenedicarboxylic Acid Anhydrides as a Route to Five-Membered Hetarynes
Reinecke, Manfred G.,Newsom, James G.,Chen, Lao-Jer
, p. 2760 - 2769 (2007/10/02)
Flow vacuum thermolysis (FVT) of the anhydrides of thiophene-2,3- (5) and -3,4-dicarboxylic acid (6) and of thianaphthene-2,3-dicarboxylic acid (7) in the presence of thiophene, 1,3-cyclohexadiene, or benzene gave thianthrene (15a), presumably by aromatization of an intermadiate Diels-Alder adduct of the diene traps and the aryne 2,3-didehydrothiophene (8).A similar rationale explains the formation of dibenzothiophene from 7 and thiophene, the four monomethylthianaphthenes 22-25 from 5 and cyclopentadiene, 5,6-dimethylthianaphthene (15f) from 5 and 2,3-dimethylbutadiene, and a mixture of hydroxythianaphthenes (15d) from 5 and furan.The latter reaction also produces a mixture of isomeric cyclopentanothiophenes (19) which probably arise by decarbonylation of 15d.An FVT reaction of 5 with propyne as the trap gave a mixture of allenyl-(28) and propynylthiophenes 29 which probably arise by an ene reaction of the trap and the aryne 8.Decomposition of the anhydrides 5 and 6 in molten anthracene led only to Friedel-Crafts products such as thienylanthracenes 33 and quinones 34 from 5 and 39 and 40 from 6.The diene reactivity of thiophene 13a in the gas phase was demonstrated by the formation of naphthalene from its reaction with benzyne generated from the thermolysis of indanetrione and by the formation of indene from 13a plus cyclopentadiene.Possible, but improbable, interpretations of the FVT results without invoking a five-membered hetaryne intermediate are considered.
