209-22-3Relevant academic research and scientific papers
Sulfur monoxide transfer from peri -substituted trisulfide-2-oxides to dienes: Substituent effects, mechanistic studies and application in thiophene synthesis
Grainger, Richard S.,Patel, Bhaven,Kariuki, Benson M.,Male, Louise,Spencer, Neil
supporting information; experimental part, p. 5843 - 5852 (2011/06/22)
Three peri-substituted trisulfide-2-oxides are prepared by treatment of 1,8-naphthalene dithiols with thionyl chloride and pyridine. The 1,2,3-trithiane-2-oxide ring adopts a sofa conformation in the solid state, with a pseudoaxial oxygen and evidence of ring strain (peri-interaction). Heating the trisulfide-2-oxides in the presence of a diene results in formal sulfur monoxide (SO) transfer to form unsaturated cyclic sulfoxides, along with a recyclable 1,8-naphthalene disulfide. The presence of o-methoxy or o-tert-butyl substituents on the naphthalene ring lowers the temperature and increases the rate at which SO transfer occurs. Trapping experiments and kinetic studies are consistent with the generation of triplet SO, followed by in situ trapping by diene. Transfer of SO also occurs upon irradiation at room temperature, but yields of sulfoxide are lower. Dehydration of the sulfoxides under Pummerer conditions gives thiophenes, including the naturally occurring thioperillene. Two dienes form thiophenes directly under the SO transfer conditions. The methodology is applied in a formal synthesis of the antiplatelet medication Plavix.
A chemical model for the inner-ring deiodination of thyroxine by iodothyronine deiodinase
Manna, Debasish,Mugesh, Govindasamy
scheme or table, p. 9246 - 9249 (2011/02/22)
The I of the beholder: The presented chemical model for the inner-ring deiodination of thyroxine (T4) and 3,5,3′-triiodothyronine (T3) by iodothyronine deiodinase (see scheme) highlights the importance of an in-built thiol group in proximity to the selenium atom. The effective removal of iodine in the case of T4 indicates that an enol-keto tautomerism is not required for deiodination. Copyright
Photochemical studies on the through-space S···S interaction of 2- phenylnaphtho[1,8-de][1,3]dithiin 1-oxide, 5-phenyl[1]benzothieno[4,3,2- def][1,3]benzodithiepin 4-oxide, and 2-phenyldibenzo[d,f][1,3]dithiepin 1- oxide
Fujii, Takayoshi,Kusanagi, Hiroki,Takahashi, Ohgi,Horn, Ernst,Furukawa, Naomichi
, p. 5027 - 5046 (2007/10/03)
2-Phenylnaphtho[1,8-de][1,3]dithiin 1-oxide (4a), 5- phenyl[1]benzothieno[4,3,2-def][1,3]benzodithiepin 4-oxide (4b), and 2- phenyldibenzo[d,f][1,3]dithiepin 1-oxide (4c) underwent facile consecutive photochemical reactions to give the corresponding disulfide, naphtho[1,8- cd][1,2]dithiole (1a), [1]benzothieno[4,3,2-cde][1,2]benzodithiin (1b), and dibenzo[c,e][1,2]dithiin (1c) and benzaldehyde (7), respectively, via the sulfur-sulfur (S···S) interaction. The proposed mechanism for these photochemical reactions is based on the quantum yields measurements, photo- intensity effects, and sensitizer effects. Ab initio calculations were also carried out for a model compound of the primary photoproduct, which showed that the S···S distance becomes shorter and the S-O distance becomes longer upon the excitation to the S1 state.
Generation of ketenes by photolysis of naphtho[1,8-de]-1,3- dichalcogeninylidene 1-oxides
Kobayashi, Kenji,Shinhara, Satoshi,Moriyama, Masaya,Fujii, Takayoshi,Horn, Ernst,Yabe, Akira,Furukawa, Naomichi
, p. 5211 - 5214 (2007/10/03)
The photolysis of naphtho[1,8-de]-1,3-dichalcogeninylidene 1-oxide derivatives (4 and 5) at >290 nm generates ketenes together with naphtho[1,8- cd]-1,2-dichalcogenole, which were confirmed by the trapping experiments and the direct observation using IR spectroscopy. The generation of ketenes from the selenium compounds 5 is more effective than that from the sulfur analogs 4.
Evidence of transannular bonding interaction between two sulfur atoms on photolysis of naphtho[1,8-ef][1,4]dithiepins
Fujii, Takayoshi,Takahashi, Ohgi,Furukawa, Naomichi
, p. 6233 - 6239 (2007/10/03)
Naphtho[1,8-ef][1,4]dithiepins 5 were prepared by the reaction of naphtho[1,8-de]-1,3-dithiins 3 with diethyl diazomalonate in the presence of copper acetylacetonate. The X-ray crystallographic analysis of 2,3-dihydro-2,2-bis(ethoxycarbonyl)-3-phenylnaphtho[1,8-ef][1,4]dithie pin (5a) revealed that the S···S distance is shorter than the sum of their van der Waals radii, indicating that compounds 5 have a strong through-space interaction between the two sulfur atoms. Direct irradiation of 5 with a 500 W high-pressure mercury lamp (313 nm) at room temperature gave the corresponding olefins 6 and naphtho[1,8-cd]-1,2-dithiole (1) quantitatively. The quantum yields of the consumption of 5a and the formation of 6a and 1 were 0.34. The mechanism of this reaction was investigated by examining the effect of sensitization and light intensity. The results indicate that the reaction may proceed by a one-photon process from an excited singlet state. Ab initio calculations were carried out on model compound 7, and it was shown that the excitation to the S1 state causes a bonding interaction between the two sulfur atoms, making the reaction possible.
Mechanism for photodecomposition of naphtho[1,8-de][1,3] dithiin-1-bis(ethoxycarbonyl)methylides
Fujii, Takayoshi,Sakuragi, Hirochika,Furukawa, Naomichi
, p. 8039 - 8042 (2007/10/02)
Naphtho[1,8-de][1,3]dithiin-1-bis(ethoxycarbonyl)methylides (3) were prepared by the reaction of naphtho[1,8-de]dithiins with diethyl diazomalonate in the presence of copper acetylacetonate. The sulfonium ylides 3 underwent photo-rearrangement giving olefin 5 quantitatively together with naphthalene-1,8-dithiole.
Preparation of N-p-Tosylaldimines by the Intramolecular Photo-Imino Group Migration of Naphthodithiin-1-N-tosylsulfilimines
Fujii, Takayoshi,Kimura, Takeshi,Furukawa, Naomichi
, p. 1075 - 1078 (2007/10/02)
Naphthodithiin-1-N-tosylsulfilimines (4) were prepared by the reaction of napthodithiins with chloramine-T.Photolysis of 4 undergoes intramolecular imino group rearrangement to give N-tosylaldimines quantitatively together with naphthalene
The Simple Preparation of Aldehydes and Ketones by the Photo-Oxygen Rearrangement of Naphthodithiin Monooxides
Furukawa, Naomichi,Fujii, Takayoshi,Kimura, Takeshi,Fujihara, Hisashi
, p. 1007 - 1010 (2007/10/02)
Naphthalene-1,8-dithiol reacted with aldehydes to give dithioacetals which were oxidized to 2-substituted naphtho1,3-dithiin-1-oxides (4). 2,2-Disubstituted naphtho1,3-dithiin-1-oxides (5) were obtained on treatment of 4 with NaH/electrophiles.Photolysis of 4 and 5 undergoes intramolecular oxygen rearrangement to generate aldehydes and ketones quantitatively together with naphthalene-1,8-dithiole.
HIGH-TEMPERATURE ORGANIC SYNTHESIS. XXVIII. LIQUID-PHASE REACTIONS OF THIOLS WITH AROMATIC BROMINE COMPOUNDS
Papernaya, L. K.,Panova, G. M.,Deryagina, E. N.,Voronkov, M. G.
, p. 1774 - 1777 (2007/10/02)
In the liquid phase at 125-215 deg C thiophenol only reacts effectively with 2- and 4-bromophenol, 1-bromo-2-napthol, 1-bromonapthalene, and 9-bromoanthracene, forming the corresponding phenyl aryl sulfides. 2-Thiophenethiol and 1-thionapthol reduce the same bromine derivatives to the corresponding arenes.The disulfides formed here undergo secondary transformations.The reactions of thiophenol with 2- and 4-bromophenol and 1-bromo-2-napthol are convenient preparative methods for the synthesis of the previously difficulty obtainable phenyl hydroxyaryl sulfides.
