5925-72-4Relevant academic research and scientific papers
Palladium Catalyzed Direct Carbonylative Thiomethylation of Aryldiazonium Salts and Amines with 4-(Methylthio)-2-Butanone as (Methylthio) Transfer Agent
Tian, Qingqiang,Xu, Shasha,Zhang, Chiying,Liu, Xinyi,Wu, Xiangwei,Li, Yahui
, p. 8797 - 8804 (2021/07/19)
Herein, an interesting palladium-catalyzed procedure for the direct carbonylative thiomethylation of aromatic amine derivatives with 4-methylthio-2-butanone is developed. Using 4-methylthio-2-butanone as (methylthio) transfer agent, a variety of corresponding thioesters are obtained with moderate to good yields under base-free condition. In addition, good functional group tolerance can be observed.
Palladium-catalyzed intermolecular transthioetherification of aryl halides with thioethers and thioesters
Li, Yahui,Bao, Gao,Wu, Xiao-Feng
, p. 2187 - 2192 (2020/03/11)
Functional group transfer reactions are an important synthetic tool in modern organic synthesis. Herein, we developed a new palladium-catalyzed intermolecular transthioetherification reaction of aryl halides with thioethers and thioesters. The synthetic utility and practicality of this catalytic protocol are demonstrated in a wide range of successful transformations (>70 examples). This catalytic protocol is applicable in carbonylative coupling processes as well, and the first example of carbonylative methylthioesterification of aryl halides has been achieved. Notably, this work also provides an approach to using natural products, such as methionine and selenomethionine, as the functional group sources.
One-pot odourless synthesis of thioesters via in situ generation of thiobenzoic acids using benzoic anhydrides and thiourea
Abbasi, Mohammad,Khalifeh, Reza
supporting information, p. 1265 - 1273 (2015/08/18)
An efficient and odourless procedure for a one-pot synthesis of thioesters by the reaction of benzoic anhydrides, thiourea and various organic halides (primary, allylic, and benzylic) or structurally diverse, electron-deficient alkenes (ketones, esters, and nitriles) in the presence of Et3 N has been developed. In this method, thiobenzoic acids were in situ generated from the reaction of thiourea with benzoic anhydrides, which were subjected to conjugate addition with electron-deficient alkenes or a nucleophilic displacement reaction with alkyl halides.
A Fast and Solvent-Free Conversion of Thioamides into Thioesters
Darabi, Hossein R.,Aghapoor, Kioumars,Tabar-Heidar, Kourosh
, p. 79 - 81 (2007/10/03)
Solvent-free irradiation of thiomorpholides with two kinds of methylating agents under microwave or ultrasonic conditions gave the corresponding thioesters in high yield. The method is simple and avoids prolonged heating with solvents.
REACTION OF para-SUBSTITUTED AROMATIC ACIDS WITH METHYL THIOCYANATE IN TRIFLUOROACETIC ACID
Polivin, Yu. N.,Karakhanov, R. A.,Vinokurov, V. A.,Silin, M. A.,Bratkov, A. A.
, p. 324 - 328 (2007/10/02)
We have investigated the reactions of aromatic carboxylic acids (p-XC6H4COOH, in which X = F, Cl, Br, I, NO2, CH3, H, OCH3) with methyl thiocyanate in trifluoroacetic acid.It was shown that the starting acids are converted to S-methyl benzothioates and the nitrile of the acid .In addition to starting acid, in the reaction mixtures products of the reaction of CF3COOH with methyl thiocyanate were identified. Keywords: methyl thiocyanate, trifluoroacetic acid, S-methyl benzothioates, methyl mercaptan.
Hydrolysis of Mixed O,S-Ortho Esters of p-Methoxybenzoic Acid. Reactivity and Partitioning of the Tetrahedral Intermediates
Okuyama, Tadashi,Kitano, Masakazu,Fueno, Takayuki
, p. 2657 - 2661 (2007/10/02)
Hydrolyses of four ortho esters of p-methoxybenzoic acid, ArC(OMe)3-n(SMe)n (n = 0-3), have been examined at 30 deg C in aqueous solution.All the hydrolyses are catalyzed by acid, rate decreasing with increasing number of methylthio groups (n).Uncatalyzed reaction was observed for the thio ortho esters (n = 1-3).Products from the mixed O,S-ortho esters (n = 1 and 2) are mixtures of the ester ArCOOMe and the thio ester ArCOSMe.Fraction of the latter increases with acidity of the medium, following a sigmoid curve (pK3b = 0.8) from 0 to 0.68 in the case of n = 1 and following a biphasic sigmoid from 0 to 0.86 (pK1c = 4.73) and then to 0.96 (pK3b = 0.8) in the case of n = 2.These results are interpreted in terms of different partitioning in acid-catalyzed and spontaneous breakdowns of the tetrahedral intermediate as well as O,S-ortho esters.
Reaction of Aryl Aldehydes with Thiocyanates in the Presence of Tributylphosphine
Yokoyama, Masataka,Ohteki, Hiroko,Kurauchi, Masahiko,Hoshi, Kazuko,Yanagisawa, Eizaburo,et al.
, p. 2635 - 2640 (2007/10/02)
Aryl aldehydes react with methyl thiocyanate in the presence of tributylphosphine to afford S-methyl thiobenzoates and arylacetonitriles in good yields.This is a novel disproportionation reaction involving carbon-carbon bond formation.These compounds thus obtained are easily converted into deoxybenzoins using sodium hydride.On the other hand, p-dialkylaminobenzaldehydes react with methyl thiocyanate under the same conditions to furnish both the corresponding trans-dicyanostilbenes and succinonitriles in moderate yields.Finally, the reaction was carried out with aryl thiocyanates resulting in the formation of addition products.
Aromatic Substitution. 46. Methyl (Ethyl) Thio(Dithio)carboxylation of Aromatics with S-Methyl (S-Ethyl) Thiocarboxonium and Dithiocarboxonium Fluoroantimonates
Olah, George A.,Bruce, Mark R.,Clouet, Francoise L.
, p. 438 - 442 (2007/10/02)
S-Methyl(S-ethyl)thio(dithio)carboxinium ions were prepared by reacting methyl(ethyl) fluoride-antimony pentafluoride with carbonyl sulfide (carbon disulfide) and studied with 1H and 13C NMR spectroscopy.The ions were subsequently used in the novel carboxylation reaction of arenes to S-methyl (S-ethyl) thio(dithio)benzoates.The method was also found to be adaptable to the carboxylation of polystyrene to poly(styrenecarboxylic acid) without degradation of the polymer backbone.
A NOVEL DISPROPORTIONATION REACTION OF AROMATIC ALDEHYDES INVOLVING C-C BOND FORMATION
Kurauchi, Masahiko,Imamoto, Tsuneo,Yokoyama, Masataka
, p. 4985 - 4986 (2007/10/02)
The reaction of aromatic aldehydes with methyl thiocyanate in the presence of tributylphosphine afforded both S-methyl thiobenzoates and phenylacetonitriles via a novel disproportionation pathway involving carbon-carbon bond formation.
