6636-01-7Relevant articles and documents
A chromatography-free and aqueous waste-free process for thioamide preparation with Lawesson's reagent
Wu, Ke,Ling, Yichen,Ding, An,Jin, Liqun,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
, p. 805 - 812 (2021/05/03)
After completing the thio-substitution with Lawesson's reagent, ethanol was found to be effective in the decomposition of the inherent stoichiometric six-membered-ring byproduct from the Lawesson's reagent to a highly polarized diethyl thiophosphonate. The treatment significantly simplified the following chromatography purification of the desired thioamide in a small scale preparation. As scaling up the preparation of two pincer-type thioamides, we have successfully developed a convenient process with ethylene glycol to replace ethanol during the workup, including a traditional phase separation, extraction, and recrystallization. The newly developed chromatography-free procedure did not generate P-containing aqueous waste, and only organic effluents were discharged. It is believed that the optimized procedure offers the great opportunity of applying the Lawesson's reagent for various thio-substitution reactions on a large scale.
Method for synthesizing thioamide compound from 1,2,3-thiodiazole compound and amine under catalysis of copper
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Paragraph 0045-0051, (2021/05/12)
The invention belongs to the technical field of organic chemistry, and discloses a method for synthesizing a thioamide compound from a 1,2,3-thiodiazole compound and amine under the catalysis of copper. The method comprises the following steps: in a protective atmosphere, taking an organic solvent as a reaction medium, reacting a 1,2,3-thiodiazole compound with an amine compound under the action of a copper salt catalyst or a copper catalyst and a phosphine ligand, and carrying out subsequent treatment to obtain the thioamide compound. According to the method, the copper salt is used as the catalyst, the phosphine ligand is adopted, the yield is high, and the substrate applicability is wide. In addition, the reaction takes the 1,2,3-thiodiazole compound and the amine compound as raw materials, and has the advantages that the raw materials are cheap and easy to prepare, the operation is simple and convenient, and the atom economy is high.
Structure-reactivity correlations in the aminolysis of aryl dithiomethyl- and dithiophenylacetates with anilines in acetonitrile
Oh, Hyuck Keun,Kim, Sun Kyung,Lee, Hai Whang,Lee, Ikchoon
, p. 1753 - 1757 (2007/10/03)
The kinetics and mechanism of the anilinolysis (XC6H4NH2) of dithio esters, RC(=S)SC6H4Z with R = C2H5 and C6H5CH2 are investigated in acetonitrile at 45.0 deg C. By application of various structure-reactivity correlations, selectivity parameters ρX, βX, ρZ, βZ and ρXZ are determined. The reactions are predicted to proceed stepwise with rate-limiting expulsion of the ArS- group. The dithio ester with R = C2H5 exhibits the fastest rate and the largest positive ρXZ value; this is interpreted to result from the strongest electron donating ability of the ethyl group in the intermediate and a crowded tetrahedral intermediate and transition state in which the nucleophile (X) and leaving group (Z) are in close proximity due to the bulky C2H5 group. Much faster rates are observed for the thiocarbonyl (C=S) rather than carbonyl (C=O) esters in the stepwise nucleophilic substitution reactions, which may be ascribed to the lower ?*C=S and ?*C-LG levels than those of the corresponding antibonding levels in the carbonyl esters. The normal kinetic isotope effects, kH/KD > 1.0, involving deuterated anilines suggest concurrent proton transfer with the expulsion of the ArS- leaving group in a four-center hydrogen bonded transition state.
New direct synthesis of thioamides from carboxylic acids
Borthakur, Naleen
, p. 6745 - 6746 (2007/10/02)
The synthesis of a series of thiomides by a novel one-pot reaction between carboxylic acids and amines in the presence of O,O-diethyl dithiophosphoric acid (DDTPA) is described.
Reaction of Phosphorus Pentasulfide with Organolithiums. An In Situ Reagent for the Preparation of Thiolactams
Goel, O. P.,Krolls, U.
, p. 162 - 164 (2007/10/02)
Phosphorus pentasulfide reacts under mild conditions with four equivalents of n-butyllithium, methyllithium or phenyllithium giving solutions in tetrahydrofuran.The new reagents in situ convert lactams to thiolactams and show significant selectivity in the type of reactive lactams.
SIMPLE NEW ROUTES TO OXIMINOPHOSPHONODITHIOATES, 1,3,5,2-OXATHIAZAPHOSPHOLES AND 1,3,2-THIAZAPHOSPHOLINES FROM OXIMES AND THEIR DERIVATIVES
El-Barbary, A. A.,Shabana, R.,Lawesson, S.-O.
, p. 375 - 382 (2007/10/02)
2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide, 1, reacted with ketoximes at 25o followed by alkylation with methyl iodide to give oximino-4-methoxyphenyl-S-methyl-phosphonodithioate, 4. p-Tolualdehyde oxime when treated with 1 gave 2,4,6-tri-p-tolyl-1,3,5-trithiolidine, 6.The reaction of benzohydroxamoyl chlorides with 1 yielded 1,3,5,2-oxathiazaphospholes, 8, whereas p-nitrobenzohydroxamoyl chloride gave 3,6-di(4-nitrophenyl)-1,4,2,5-dioxadiazine, 11.Diarylketoximes with 1 produced 13 and 14. 9-Benzanthrone oxime with 1 afforded 9-benzanthrone thione, 16.The reaction of oximes of phenyl phenylmethylketoximes or 1,3-diphenyl-2-propanone with 1 at 80o afforded 1,3,2-thiazaphospholines, 18.
