- Transition-Metal-Free, General Construction of Thioamides from Chlorohydrocarbon, Amide and Elemental Sulfur
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A general method for one-pot synthesis of thioamides is developed through a three-component reaction involving chlorohydrocarbon, amide and elemental sulfur. Such a strategy does not only avoid residual transition metal in the product but also prevent the generation of C?N coupling by-product. The latter is prone to be generated when alkane halide and amine are present. With the protocol proposed in this work, both alkyl and aryl thioamides can be obtained in moderate to excellent yields with a high tolerance of various functional groups. External oxidants are not required in the reaction. In addition, the reaction mechanisms are addressed using a combination of controlling experiments and quantum chemical calculations.
- Chen, Xinzhi,Ge, Xin,Jin, Hao,Qian, Chao,Zhou, Shaodong
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supporting information
p. 3403 - 3406
(2021/06/25)
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- Method for preparing aryl thioamide compound
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The invention discloses a method for preparing an aryl thioamide compound. The method comprises the following steps: under the protection of inert gas, performing stirring to react for 6-12 hours at the reaction temperature of room temperature to 60 DEG C by taking aryl methanol as a substrate, sublimed sulfur as a sulfur source, an alkali metal complex formed by combining alkali metal salt and ligand as a catalyst, alkali as an accelerant, formamide as a solvent and an amine source; and carrying out post-treatment on the reaction product to obtain the aryl thioamide compound. According to theinvention, cheap and easily available aryl methanol is used as a substrate for three-component reaction to prepare the corresponding thioamide compound; the method for preparing the aryl thioamide compound has the technical advantages of simple technological process, high yield, less pollution, safety, environmental protection, greenness, mildness and the like.
- -
-
Paragraph 0047-0049
(2021/03/31)
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- Transition-Metal-Free Cleavage of C-C Triple Bonds in Aromatic Alkynes with S8 and Amides Leading to Aryl Thioamides
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A novel transition-metal-free cleavage reaction of C-C triple bonds in aromatic alkynes with S8 and amides furnishes aryl thioamides in moderate to excellent yields. The remarkable features of this thioamidation include the metal-free cleavage of C-C triple bond, mild reaction conditions, as well as wide substrate scope that is particularly compatible with some internal aromatic alkynes and acetamides.
- Xu, Kai,Li, Ziyi,Cheng, Fangyuan,Zuo, Zhenzhen,Wang, Tao,Wang, Mincan,Liu, Lantao
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supporting information
p. 2228 - 2231
(2018/04/30)
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- Oxidative Coupling-Thionation of Amines Mediated by Iron-Based Imidazolium Salts for the Preparation of Thioamides
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An efficient and selective multicomponent oxidative coupling, involving the use of two different amines, sodium phosphate, and elemental sulfur have been described for the preparation of thioamides, employing microwave irradiation. The use of an iron(III)-based imidazolium salt is essential as catalyst. Indeed, the iron-based catalyst is involved in the oxidative coupling of the two amines and in the subsequent C-S bond formation. The protocol is useful for a wide variety of primary benzylamines and alkylamines, as coupling partners. Thus, various electron-rich and electron-poor substituents in the aromatic rings and also fused piperidine derivatives, are suitable starting materials in this reaction. Some of the obtained products are important synthetic intermediates for natural products.
- Gisbert, Patricia,Pastor, Isidro M.
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supporting information
p. 3031 - 3040
(2018/07/06)
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- A one-pot route to thioamides discovered by gas-phase studies: palladium-mediated CO2 extrusion followed by insertion of isothiocyanates
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A new palladium mediated “one pot” synthesis of thioamides from aromatic carboxylic acids (ArCO2H + RNCS → ArC(S)NHR + CO2) was discovered by gas-phase experiments and theoretical studies. Palladium-mediated decarboxylation of aromatic carboxylic acids followed by addition of substituted isothiocyanates leads to the corresponding thioamide derivatives.
- Noor, Asif,Li, Jiawei,Khairallah, George N.,Li, Zhen,Ghari, Hossein,Canty, Allan J.,Ariafard, Alireza,Donnelly, Paul S.,O'Hair, Richard A. J.
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supporting information
p. 3854 - 3857
(2017/04/06)
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- Bioorthogonal Click and Release Reaction of Iminosydnones with Cycloalkynes
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We report the discovery of a new bioorthogonal click-and-release reaction involving iminosydnones and strained alkynes. This transformation leads to two products resulting from the ligation and fragmentation of iminosydnones under physiological conditions. Optimized iminosydnones were successfully used to design innovative cleavable linkers for protein modification, thus opening up new areas in the fields of drug release and target-fishing applications. This click-and-release technology offers the possibility of exchanging tags on proteins for functionalized cyclooctynes under mild and bioorthogonal conditions.
- Bernard, Sabrina,Audisio, Davide,Riomet, Margaux,Bregant, Sarah,Sallustrau, Antoine,Plougastel, Lucie,Decuypere, Elodie,Gabillet, Sandra,Kumar, Ramar Arun,Elyian, Jijy,Trinh, Minh Nguyet,Koniev, Oleksandr,Wagner, Alain,Kolodych, Sergii,Taran, Frédéric
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supporting information
p. 15612 - 15616
(2017/12/02)
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- A multipathway coupled domino strategy: I2-mediated oxidative thionation for direct synthesis of thiobenzamides from miscellaneous substrates
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An efficient iodine-mediated multipathway coupled domino reaction has been developed for the synthesis of thiobenzamides from benzylamines, benzylamines/aldehydes, and N-alkyl benzylamines under the same reaction conditions. This approach combines two consecutive domino processes in one pot using iodine as the oxidant.
- Li, Hong-Zheng,Xue, Wei-Jian,Yin, Guo-Dong,Wu, An-Xin
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supporting information
p. 5843 - 5846
(2015/11/02)
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- Desulfurization and H-migration of secondary thioamides catalyzed by an iron complex to yield imines and their reaction mechanism
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Secondary thioamides were converted into imines as the major products using hydrosilane in the presence of an iron catalyst. An iron carbene complex with a silyl thiolato ligand was isolated as one of the intermediates of the catalytic cycle and was characterized by X-ray analysis.
- Fukumoto, Kozo,Sakai, Akane,Hayasaka, Kazumasa,Nakazawa, Hiroshi
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supporting information
p. 2889 - 2892
(2013/06/27)
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- Microwave-assisted synthesis of thioamides with elemental sulfur
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Thioamides are prepared in moderate-to-good yields from the benzylamines or benzylamine derivatives by treatment with elemental sulfur under microwave and solvent-free conditions at 170.C in 15 min.
- Milen, Matyas,Abranyi-Balogh, Peter,Dancso, Andras,Keglevich, Gyoergy
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experimental part
p. 33 - 41
(2012/07/01)
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- Efficient and green protocol for the synthesis of thioamides in C 6 (mim)2Cl2 as a dicationic ionic liquid
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A simple, efficient, facile and eco-friendly process for the synthesis of thioamides from nitriles using 1,6-bis(3methylimidazolium-1-yl)hexane chloride [C6(mim)2Cl2] as a dicationic ionic liquid (DIL) was developed. The ionic liquid was easily separated from the reaction mixture and was recycled at least four times without any loss of its activity.
- Khosropour,Noei,Mirjafari
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experimental part
p. 752 - 758
(2010/11/04)
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- P4S10/dimethicone tandem: Efficient reagent for thionation of various aromatic amides and esters
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Organosulfur compounds are valuable because of their rich and varied chemistry especially in biological field. We report a new and efficient way for thionation of various aromatic amides and esters using P4S 10/ dimethicone tandem. The ease of handling and higher yield makes this protocol economical.
- Cho, Dongho,Ahn, Jiyoung,De Castro, Kathlia A.,Ahn, Hyunseok,Rhee, Hakjune
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supporting information; experimental part
p. 5583 - 5588
(2010/10/02)
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- Dichlorothiophosphoric acid and dichlorothiophosphate anion as thionating agents in the synthesis of thioamides
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A method for the thionation of carboxylic acid amides with dichlorothiophosphoric acid and dichlorothiophosphate anion, providing thioamides in high yields, was developed. The facility of the thionation and the yields of the final products were shown to depend on the nature of the starting amide. The optimal reaction conditions are reported.
- Bezgubenko,Pipko,Sinitsa
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experimental part
p. 1341 - 1344
(2009/02/07)
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- Copper-catalyzed oxidative desulfurization-oxygenation of thiocarbonyl compounds using molecular oxygen: An efficient method for the preparation of oxygen isotopically labeled carbonyl compounds
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A novel copper-catalyzed oxidative desulfurization reaction of thiocarbonyl compounds, using molecular oxygen as an oxidant and leading to formation of carbonyl compounds, has been developed, and the utility of the process is demonstrated by its application to the preparation of a carbonyl-18O labeled sialic acid derivative. The Royal Society of Chemistry.
- Shibahara, Fumitoshi,Suenami, Aiko,Yoshida, Atsunori,Murai, Toshiaki
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p. 2354 - 2356
(2008/02/09)
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- Comparative studies on the pyrolysis of N-arylideneaminoamides: Kinetic and mechanistic studies
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Rates of thermal decomposition of title compounds have been measured using a static reaction system. They undergo a unimolecular first-order elimination to give arylnitrile and the corresponding substituted amides. The decomposition parallels that of N-arylidenamino cyclic amide. The relative elimination rates at 600 K were calculated. The kinetic data reveal that the electronic effects of substituents, such as methyl, phenyl, benzyl, and allyl groups, are associated with the opposing directions in which the lone pair of electrons on the nitrogen atom of the arylidene moiety is being delocalized.
- Al-Awadi, Nouria A.,Ibrahim, Yehia A.,Patel, Mehul,George, Bobby J.,Al-Etiabi, Alya M.
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- Lawesson's reagent for direct thionation of hydroxamic acids: Substituent effects on LR reactivity
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To explore the generality and scope of direct thionation of hydroxamic acids (HAs), the reaction of various structurally diverse HAs with Lawesson's reagent was investigated. The yield of thiohydroxamic acid (THAs) is poor when HAs possess bulky acyl and/or N-substituents, acidic α-hydrogen atoms, or an N-phenyl ring. THAs yields were correlated with Brown sigma parameter. The relative rates of two subsequent processes kT2 and kR2 were also measured. Correlation was also found for methine proton chemical shifts of N-isopropyl benzothiohydroxamic acids.
- Przychodzen, Witold
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p. 676 - 684
(2007/10/03)
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- Mild method for the conversion of amides to thioamides
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Aqueous ammonium sulfide was found to be an ideal substitute for hydrogen sulfide for the thiolysis of activated amides. High yields of the corresponding thioamides were obtained for a broad range of substrates, using two different procedures that are both operationally simple and inexpensive, as well as amenable to large-scale preparation. Preliminary results indicate that aqueous ammonium sulfide may also replace hydrogen sulfide in the synthesis of thionoesters from amides.
- Charette, Andre B.,Grenon, Michel
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p. 5792 - 5794
(2007/10/03)
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- Benzylic metallation of thiobenzamides and thionaphthamides
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Various secondary thiobenzamides and thionaphthamides have been prepared, and features of their conformations [orthogonality of the arene and thioamide planes, (Z) geometries in solution etc.] have been determined. Deprotonation with sec-butyllithium selectively provided either the monoanion or the dianion, according to the stoichiometry of the base. The monoanion reacted with soft electrophiles (alkyl halides) through the sulfur atom and with hard electrophiles (acyl halides) through the nitrogen centre. Formation of the dianion, more reactive than the thioamide anionic moiety, allowed reaction at the benzylic centre. Addition of electrophiles allowed selective formation of C-C or C-X bonds. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
- Ach, David,Reboul, Vincent,Metzner, Patrick
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p. 2573 - 2586
(2007/10/03)
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- A polymer-supported thionating reagent
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A new polymer-supported reagent for the conversion of carbonyls to thiocarbonyls has been developed and its use demonstrated on a range of amides. Secondary or tertiary amides are converted cleanly and efficiently through to the corresponding thioamides and primary amides are converted to the corresponding nitriles. The reactions can be facilitated by conventional heating. However, if microwave heating is used, in the presence of an ionic liquid, enhanced reaction rates are achieved.
- Ley, Steven V.,Leach, Andrew G.,Storer, R.Ian
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p. 358 - 361
(2007/10/03)
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- Synthesis and reactivity of phenyl-N-methyl-N-thiobenzoylcarbamate in basic media
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Phenyl-N-methyl-N-thiobenzoylcarbamate was prepared from the reaction of thiobenzamide anion with phenylchloroformate in DMF and kinetic data obtained for the basic hydrolysis, have been interpreted in terms of a B(Ac)2 mechanism involving general bases catalysis.
- Norberto,Santos,Rodrigues,Pazos,Herves
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p. 400 - 401
(2007/10/03)
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- Synthesis, characterization and blood cell labelling evaluation of new (99m)Tc nitrido radiopharmaceuticals with thioamide [R1C(=S)NHR2] derivatives
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The synthesis of a series of new (99m)Tc-thioamide complexes with the [Tc=N]2+ nitrido core, in which the thioamide ligand substituents were varied to include different lengths of atiphatic alkyl chains or a phenyl group is reported. TLC analysis shows that the complexes are neutral and lipophilic compounds. The (99m)Tc complexes have a low blood cell labelling efficiency in whole blood compared to the reference complex of dithiocarbamate (99m)TcN(Et(EtO)NCS2)2.
- Mevellec,Demaimay,Roucoux,Moisan,Noiret,Patin
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p. 863 - 869
(2007/10/03)
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- Photochemical reactions of thiobenzamides bearing an allylic substituent on the nitrogen atom: Double-bond migration via tandem 1,4- And 1,6-hydrogen transfer
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N-(2-Phenylprop-2-enyl)thiobenzamides 1a-d underwent double-bond migration on irradiation to give N-(2-phenylprop-1-enyl)thiobenzamides 2a-d via consecutive 1,4- and 1,6-hydrogen transfer. Photoreaction of an N-(prop-2-enyl)thiobenzamide 1e and an N-(3-phenylprop-2-enyl)thiobenzamide if did not give migration products, but afforded pyrroles 3e and 3f and dealkylation products 4a in low yields.
- Aoyama, Hiromu
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p. 1851 - 1854
(2007/10/03)
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- New direct synthesis of thioamides from carboxylic acids
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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.
- Borthakur, Naleen
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p. 6745 - 6746
(2007/10/02)
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- Studies on chromone derivatives: regioselective 1,3-dipolar and 1,4-cycloaddition reactions of 3-cyano-4H-1-benzopyran-4-thione
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1,3-Dipolar cycloaddition reactions of 3-cyano-4H-1-benzopyran-4-thione 1 with nitrilimines 3, nitrile oxides 7 and aldonitrones 8 yielded regioselective cycloadducts involving the thione function.In the latter two classes, the unstable cycloadducts fragmented to yield 3-cyanochromone 11 and isothiocyanate 12 or thioamide 13, respectively.In contrast, dienamines 14 preferred to react at the carbon-carbon double bond in a 1,4-cycloaddition yielding xanthione (9H-xanthene-9-thione) 16 by elimination of HCN and the amine moiety.Keywords: 1,3-dipolar cycloaddition / 1,4-cycloaddition / 4H-1-benzopyran-4-thione / nitrilimine / nitrile oxide / nitrone
- Sain, Bir,Prajapati, Dipak,Mahajan, Asha R,Sandhu, Jagir S
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p. 313 - 316
(2007/10/02)
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- REARRANGEMENT OF 1,2-DIMETHYL-1,2-DI(THIOAROYL)HYDRAZINES TO BIS(N-METHYLARYLIMIDOYL) DISULFIDES
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The thermal rearrangement of 1,2-dimethyl-1,2-di(thioaroyl)hydrazines to bis(N-methylarylimidoyl) disulfides was realized.It is suggested that the transformation takes place by a concerted -sigmatropic shift mechanism.
- Przheval'skii, N. M.,Stankevich, I. V.,Chistyakov, A. L.,Drozd, V. N.
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- Dicoordinated Phosphorus Compounds: a Novel 4,5-Disubstituted 1,2,3,4-Triazaphosphole. X-Ray Molecular Structures of a 2-N-BF3 Complex of 4,5-Diisopropyl-1,2,3,4-triazaphosphole and of its Tetramer. Conformation in the Crystalline Form and in Solution
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The synthesis of the title compound is described.It may be stabilised by the reaction of its tetramer with BF3.The tetramer displays several isomers and conformers in solution; one of them has been isolated and its crystal structure determined.The crystal structure of the 2-N-BF3 complex of the parent 4,5-diisopropyl-1,2,3,4-triazaphosphole has also been obtained.
- Haddad, Moncef,Dahan, Francoise,Legros, Jean-Pierre,Lopez, Lucien,Boisdon, Marie-Therese,Barrans, Jean
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p. 671 - 678
(2007/10/02)
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- A New Route to N-Monosubstituted Thioamides Utilizing Phosphoramidothionates as Reagents for the Thioamidation of Carboxylic Acids
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Several N-monosubstituted thioamides have been synthesized from the corresponding carboxylic acid chlorides and primary amines by a new procedure.The procedure utilizes a commercially available and inexpensive organophosphorus reagent (dimethyl chlorothiophosphate) to derivatize the amine, form the carboxamide bond, and accomplish the thionation of the carbonyl by an intramolecular rearrangement.The phosphoryl group is then cleaved from the resulting thiocarbonyl phosphoryl mixed imide by a simple hydrolysis.Thioamides (RCSNHR') containing a variety of functionality(R= simple alkyl, phenyl, bulky alkyl, cycloalkylalkyl, α,β-unsaturated, and alkyl with remote keto, ester, or amide carbonyl groups; R'= methyl, benzyl, allyl) have been prepared by this method in generally high overall yields (50-80 percent).Competing thionation of remote carbonyl groups or epimerization of a chiral center containing a proton α to a ketone group was not observed.
- DeBruin, Kenneth E.,Boros, Eric E.
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p. 6091 - 6098
(2007/10/02)
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- HETEROCYCLIZATION OF DERIVATIVES OF THIONCARBOXYLIC ACIDS TO 1,3,4-THIADIAZOLES UNDER THE ACTION OF TERT-BUTYL HYPOCHLORITE
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A method for synthesis of 2-alkyl-5-aryl- and 2,5-diaryl-1,3,4-thiadiazoles by successive reaction of thioamides with tert-butyl hypochlorite and benzothiohydrazides was developed.The first step in the formation of 1,3,4-thiadiazoles consists of oxidation
- Demchuk, D. V.,Lutsenko, A. I.,Troyanskii, E. I.,Nikishin, G. I.
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p. 1690 - 1695
(2007/10/02)
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- SOME NOVEL ASPECTS OF REGIOSELECTIVITY IN 1,3 DIPOLAR CYCLOADDITIONS OF 4H-1-BENZOPYRAN-4-THIONE
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4H-1-Benzopyran-4-thione (1) reacted smoothly with nitrilimines (3a-e) to afford regioselective cycloadducts (4a-e) in good yields.In contrast,benzonitrile oxide (6) and aldonitrones (7a-d) reacted preferentially at the thione function.The unstable cycloadduct (8) or (9) ruptured to give as isolable products chromone (10) and phenyl isothiocyanate (11) and the thioamides (12a-d).This indirectly proves the site of attack of the dipole at the thione group.
- Baruah, Arpan K.,Prajapati, Dipak,Sandhu, Jagir S.
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p. 6137 - 6142
(2007/10/02)
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- Photochemistry of the N-acyllactam and acyclic thioimide systems. Competition between Paterno-Buechi type and Norrish type I reactions
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Irradiation of semicyclic- (4) and acyclic thioimides (9) gave thietanes (6, 7, and 10) and/or α-cleavaged products (8 and 11), formations of those were explained in terms of Paterno-Buechi type and Norrish type I processes.
- Oda, Kazuaki,Machida, Minoru,Kanaoka, Yuichi
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p. 2417 - 2422
(2007/10/02)
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- A GENERAL METHOD FOR THE N-ALKYLATION OF THIOAMIDES.
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Thioamides are N-alkylated in a two-step procedure: (i) Reaction with an aldehyde and benzotriazole yields an adduct which is (ii) reduced to the N-alkylthioamide by NaBH4.
- Katritzky, Alan R.,Drewniak, Malgorzata
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p. 1755 - 1758
(2007/10/02)
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- The Invention of New Radical Chain Reactions. Part 9. Further Radical Chemistry of Thiohydroxamic Esters; Formation of Carbon-Carbon Bonds
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Carbon radicals derived from the esters of several types of thiohydroxamic acids have been trapped in a number of different ways.Particular attention has been paid to carbon-carbon bond formation by addition to suitably activated ethylenic linkages.Carboxylic acids can be conveniently converted into homo- and bishomo-acids by free radical chemistry based on thiohydroxamic esters.In a coda the tautomerism of the thiohydroxamic acids have been examined by physical methods.It is confirmed that the esters used are derivatives of the thione tautomer.
- Barton, Derek H.R.,Crich, David,Kretzschmar, Gerhard
-
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- Utilization of thiocarbonyl transfer reagents. Preparation of thioamides, mercapto esters, and thiapyran derivatives
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The reaction of 1,1'-thiocarbonyldiimidazole and 1,1'-thiocarbonylbis(1,2,4-triazole) with several aldonitrones has been found to afford thioamides in good yield.Several 1,1'-thiocarbonylbisazoles, which have been shown to undergo Diels-Alder additions wi
- Harpp, David N.,MacDonald, J. Gavin,Larsen, Charles
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p. 951 - 957
(2007/10/02)
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- SYNTHESIS OF THIOAMIDES FROM ALDONITRONES UTILIZING THIOCARBONYL TRANSFER REAGENTS
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The reaction of 1,1'-thiocarbonyldiimidazole and 1,1'-thiocarbonylbis(1,2,4-triazole) with several aldonitrones has been found to afford thioamides in good yield.The effect of solvent polarity and base is discussed.
- Harpp, David N.,MacDonald J. Gavin
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p. 4927 - 4930
(2007/10/02)
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- RADICAL CHEMISTRY OF THIOHYDROXAMIC ACID ESTERS
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Thiohydroxamic esters in general decompose smoothly by a radical chain reaction to give carbon radicals which can be quenched in a synthetically useful manner.
- Barton, Derek H. R.,Kretzschmar, Gerhard
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p. 5889 - 5892
(2007/10/02)
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- Reactions of Aldonitrones with Phenylphosphonothioic Dichloride and Related Compounds. Formation of 2-Arylbenzothiazoles from α,N-Diarylnitrones
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Reactions of α-aryl-N-methylnitrones with phenylphosphonothioic dichloride (1), diphenylphosphinothioic chloride (6), or thiophosphoryl trichloride (7) gave N-methylbenzamide and N-methylthiobenzamide derivatives, and the latter became major in the presence of tertiary amine. α,N-Diarylnitrones (4) reacted with 1 to give 2-arylbenzothiazoles (5) at room temperature in moderate yields.Reaction of 4 with 6 (at room temperature) or 7 (in refluxing THF) gave 5 in a low yield, whereas a similar reaction of 4 with 7 at 0 deg C afforded N-benzylidene-2-chloroaniline in a high yield.A mechanism for the formation of 5 has been discussed briefly.
- Yoshifuji, Masaaki,Nagase, Rihei,Kawashima, Takayuki,Inamoto, Naoki
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p. 870 - 872
(2007/10/02)
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- Reaction of Mesoionic Thiazolones with m-Chloroperbenzoic Acid. Oxidative Dipole Extensions
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The oxidation of anhydro-4-hydroxy-2,3,5-triarylthiazolium hydroxides (1) with m-chloroperbenzoic acid gave (in primary alcohols) 2,5-dialkoxy-2,3,5-triarylthiazolidin-4-ones (5) and N-aroylthiobenzanilides (6).Oxidation of anhydro-5-hydroxy-3-methyl-2-phenylthiazolium hydroxide (2) gave 3-methyl-2-phenylthiazolidine-4,5-dione (8) and N-formyl-N-methylthiobenzamide (9).The products arise from initial oxidations at the carbon atoms at position 5 of 1 and position 4 of 2, and transformation modes to the final products are discussed.These oxidations are the first examples of oxidative dipole extensions.
- Sheradsky, Tuvia,Zbaida, David
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p. 4850 - 4853
(2007/10/02)
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