5310-20-3Relevant academic research and scientific papers
Contribution of Solvents to Geometrical Preference in the Z/ E Equilibrium of N-Phenylthioacetamide
Chan, Erika S.,Hyodo, Tadashi,Ikeda, Hirotaka,Inagaki, Satoshi,Ohwada, Tomohiko,Otani, Yuko,Song, Shuyi,Tang, Yulan,Vu, Kim Anh L.,Yamaguchi, Kentaro
, (2021/06/28)
We studied the Z/E preference of N-phenylthioacetamide (thioacetanilide) derivatives in various solvents by means of 1H NMR spectroscopy, as well as molecular dynamics (MD) and other computational analyses. Our experimental results indicate that the Z/E isomer preference of secondary (NH)thioamides of N-phenylthioacetamides shows substantial solvent dependency, whereas the corresponding amides do not show solvent dependency of the Z/E isomer ratios. Detailed study of the solvent effects based on molecular dynamics simulations revealed that there are two main modes of hydrogen (H)-bond formation between solvent and (NH)thioacetamide, which influence the Z/E isomer preference of (NH)thioamides. DFT calculations of NH-thioamide in the presence of one or two explicit solvent molecules in the continuum solvent model can effectively mimic the solvation by multiple solvent molecules surrounding the thioamide in MD simulations and shed light on the precise nature of the interactions between thioamide and solvent. Orbital interaction analysis showed that, counterintuitively, the Z/E preference of NH-thioacetamides is mainly determined by steric repulsion, while that of sterically congested N-methylthioacetamides is mainly determined by thioamide conjugation.
Rational design and synthesis of 2-anilinopyridinyl-benzothiazole Schiff bases as antimitotic agents
Shaik, Thokhir B.,Hussaini, S.M. Ali,Nayak, V. Lakshma,Sucharitha, M. Lakshmi,Malik, M. Shaheer,Kamal, Ahmed
supporting information, p. 2549 - 2558 (2017/05/09)
Based on our previous results and literature precedence, a series of 2-anilinopyridinyl-benzothiazole Schiff bases were rationally designed by performing molecular modeling experiments on some selected molecules. The binding energies of the docked molecules were better than the E7010, and the Schiff base with trimethoxy group on benzothiazole moiety, 4y was the best. This was followed by the synthesis of a series of the designed molecules by a convenient synthetic route and evaluation of their anticancer potential. Most of the compounds have shown significant growth inhibition against the tested cell lines and the compound 4y exhibited good antiproliferative activity with a GI50 value of 3.8?μM specifically against the cell line DU145. In agreement with the docking results, 4y exerted cytotoxicity by the disruption of the microtubule dynamics by inhibiting tubulin polymerization via effective binding into colchicine domain, comparable to E7010. Detailed binding modes of 4y with colchicine binding site of tubulin were studied by molecular docking. Furthermore, 4y induced apoptosis as evidenced by biological studies like mitochondrial membrane potential, caspase-3, and Annexin V-FITC assays.
Organocatalytic, difluorocarbene-based S-difluoromethylation of thiocarbonyl compounds
Fuchibe, Kohei,Bando, Masaki,Takayama, Ryo,Ichikawa, Junji
, p. 133 - 138 (2015/03/04)
Upon treatment with trimethylsilyl 2,2-difluoro-2-fluorosulfonylacetate (TFDA) and a catalytic amount of N,N,N′,N′-tetramethyl-1,8-diaminonaphthalene, secondary thioamides and thiocarbamates undergo selective difluoromethylation on the sulfur atom to give S-difluoromethyl thioimidates and thioiminocarbonates in good yields, respectively. This is the first report on the synthesis of acyclic difluoromethyl thioimidates and thioiminocarbonates. The key for S-difluoromethylation is the organocatalytic generation of difluorocarbene (:CF2) under mild conditions, which prevents decomposition of the substrates. This process provides an efficient approach to pharmaceuticals and agrochemicals bearing a difluoromethylsulfanyl group, starting from widely available thiocarbonyl compounds.
Facile synthesis of thioamides via P2S5-mediated beckmann rearrangement of oximes
Li, Jiangsheng,Cheng, Chao,Zhang, Xinrui,Li, Zhiwei,Cai, Feifei,Xue, Yuan,Liu, Weidong
, p. 1687 - 1689 (2012/10/29)
A facile and efficient approach to the synthesis of secondary thioamides from ketoximes via Beckmann rearrangement has been established, using phosphorus pentasulfide as a dehydrating and thiating agent. It is also efficient for the preparation of primary thiobenzamide from benzaldoxime. This approach features simple-operation, easy-control and good to excellent yields.
O,O-Diethyl dithiophosphoric acid mediated direct synthesis of thioamides from aldehydes and ketones
Yadav, Arvind K.,Srivastava, Vishnu P.,Yadav, Lal Dhar S.
, p. 7113 - 7116 (2013/01/15)
A general and convenient method for a one-pot conversion of aldehydes and ketones into thioamides has been developed. The protocol involves oximation of aldehydes and ketones followed by deoxygenative thioamidation of oximes with O,O-diethyl dithiophosphoric acid which acts as an acid as well a source of sulfur. The method is operationally simple, high yielding, and also applicable to the conversion of amides and nitriles into the corresponding thioamides.
Facile and odorless one-pot process for the synthesis of N-substituted thioamides via TsCl-mediated Beckmann rearrangement of ketoximes
Liu, Li-Feng,An, Na,Pi, Hong-Jun,Ying, Jun,Du, Wenting,Deng, Wei-Ping
supporting information; experimental part, p. 979 - 981 (2011/06/11)
A facile and odorless one-pot thionation process for the synthesis of N-substituted thioamides using chemically stable and inexpensive thiourea reagent via the Beckmann rearrangement of ketoximes, has been described. Georg Thieme Verlag Stuttgart · New York.
Ketoximes to N-substituted thioamides via PSCl3 mediated Beckmann rearrangement
Pathak, Uma,Pandey, Lokesh Kumar,Mathur, Sweta,Suryanarayana
scheme or table, p. 5409 - 5411 (2009/12/08)
N-Substituted thioamides were accessed from ketoximes by utilising PSCl3 as a uniquely capable reagent to induce Beckmann rearrangement as well as to capture the intermediate nitrilium ion. The Royal Society of Chemistry 2009.
Kinetics and Mechanism of the Aminolysis of Phenyl Dithioacetates in Acetonitrile
Oh, Hyuck Keun,Woo, So Young,Shin, Chul Ho,Park, Young Sook,Lee, Ikchoon
, p. 5780 - 5784 (2007/10/03)
The aminolysis reactions of phenyl dithioacetates with anilines (AN), N,N-dimethylanilines (DMA), and benzylamines (BA) in acetonitrile are investigated. The mechanism is relatively simple, involving a zwitterionic tetrahedral intermediate, T±, and is uncomplicated by the fast proton transfer step which may become rate limiting in the aminolysis of thiono and dithio esters and carbonates with poor leaving groups in water. The mechanism changes from rate-limiting expulsion of the leaving group with βX = 0.80-0.86 and βZ = -0.71 to -0.84 for ANs and DMAs to rate-limiting attack by the nucleophile with much smaller magnitudes of βX and βZ for BAs. The relatively large βXZ values for the former series and a smaller βXZ for the latter series support the proposed mechanistic change.
