- 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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Read Online
- The effect of medium on rate and mechanism: Aminolysis of O-4-nitrophenyl thionobenzoate in MeCN and H2O
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Pseudo-first-order rate constants (kobs) have been measured spectrophotometrically for reactions of O-4-nitrophenyl thionobenzoate (1) with a series of alicyclic secondary amines in MeCN and H2O at 25.0 ± 0.1 °C. The plot of kobs vs amine concentration exhibits an upward curvature in all cases, indicating that the reactions proceed through two tetrahedral intermediates (a zwitterionic T ± and its deprotonated anionic T-) regardless of the amine basicity and the nature of the reaction medium. However, all the amines investigated have been found to be much less reactive in MeCN than in H2O, although the amines are more basic in the former medium by 7-9 pKa units.
- Um, Ik-Hwan,Seok, Jin-A,Kim, Han-Tae,Bae, Sun-Kun
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- 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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- Metal-free three-component synthesis of thioamides from β-nitrostyrenes, amines and elemental sulfur
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A metal-free C[dbnd]C bond cleavage reaction of β-nitrostyrenes in the presence of elemental sulfur and secondary amines/amides is described. Elemental sulfur serves as both a raw material and an oxidant for C[dbnd]C bond cleavage, and secondary amines or amides are both feasible nitrogen sources. Besides mild reaction condition and simple work-up procedure, the method provided thioamides with good to excellent yields.
- Peng, Ling,Ma, Li,Ran, Ying,Chen, Yunfeng,Zeng, Zhigang
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supporting information
(2021/05/05)
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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.
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Paragraph 0056-0058
(2021/03/31)
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- Cobalt(iii)-catalyzed C-H amidation of: N, N -dialkyl thiobenzamides by sulfur coordination
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An efficient inexpensive cobalt(iii)-catalyzed intermolecular amidation of N,N-dialkyl thiobenzamides with 1,4,2-dioxazol-5-ones via C-H bond activation is described. The reaction proceeds with high functional group tolerance under external oxidant free conditions, providing a straightforward approach for the direct modification of thioamide derivatives, which are prevalent organic motifs found in vital biological and pharmaceutical molecules. This journal is
- Gao, Pengpeng,Zhang, Xiaohui,Zheng, Qing-Zhong
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p. 10332 - 10336
(2021/12/17)
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- Ruthenium(II)-catalyzed C-H arylation of N,N-dialkyl thiobenzamides with boronic acids by sulfur coordination in 2-MeTHF
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We report ruthenium(II)-catalyzed ortho-C-H arylation of N,N-dialkylthiobenzamides with boronic acids. The method employs [RuCl2(p-cym)]2 in the presence of Cu(OTf)2 and Ag2O oxidant. The reaction represents the first example of Ru-catalyzed C-H arylation directed by sulfur-containing groups and a rare example of C-H arylation directed by the versatile thiobenzamide moiety. As a further advantage, the method is performed in sustainable and eco-friendly 2-MeTHF as a solvent.
- Zhang, Jin,Liu, Ying,Jia, Qiangqiang,Wang, Yue,Ma, Yangmin,Szostak, Michal
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p. 6884 - 6890
(2020/09/15)
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- Sulfur-Catalyzed Oxidative Coupling of Dibenzyl Disulfides with Amines: Access to Thioamides and Aza Heterocycles
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In the presence of catalytic amounts of elemental sulfur, dibenzyl disulfide/DMSO was found to be an excellent thiobenzoylating agent of amines to provide a wide range of thioamides. The reaction becomes autocatalytic when anilines substituted by an o-cyclizable group were used as nucleophile, leading to the corresponding 2-aryl aza heterocycles. (Figure presented.).
- Nguyen, Thanh Binh,Nguyen, Le Phuong Anh,Nguyen, Thi Thu Tram
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supporting information
p. 1787 - 1791
(2019/02/26)
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- PHOTOCATALYTIC SYSTEM AND APPLICATIONS THEREOF
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The present invention relates to novel poly(heptazine imides), a photocatalytic system comprising such poly(heptazine imides) and a sulfur source as well as the application thereof in photocatalytic reactions.
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Page/Page column 35; 36
(2019/05/15)
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- Carbon nitride creates thioamides in high yields by the photocatalytic Kindler reaction
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Potassium poly(heptazine imide), a carbon nitride based photocatalyst, effectively promotes the Kindler reaction of thioamide bond formation using amines and elemental sulfur as building blocks under visible light irradiation. The feasibility of the developed methodology was confirmed using 14 different primary and secondary amines, including substituted benzylamines and heterocyclic and aliphatic methylamines, which were successfully converted into thioamides with 68-92% isolated yields.
- Kurpil,Kumru,Heil,Antonietti,Savateev
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supporting information
p. 838 - 842
(2018/03/05)
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- Sulfated polyborate catalyzed Kindler reaction: a rapid, efficient, and green protocol
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A rapid, green, and efficient one-pot, three-component Kindler reaction was developed using a sulfated polyborate catalyst. The method described the reaction of aldehydes, amines/ammonium acetate, and sulfur for the synthesis of thioamides using sulfated polyborate under a solvent free condition at 100?°C. The key features of the present protocol are high yields, short reaction time, easy workup, and recyclability of a catalyst which gives economical as well as ecological rewards. The present method also has an ability to tolerate a variety of functional groups. Graphical abstract: [Figure not available: see fulltext.].
- Khatri, Chetan K.,Mali, Anil S.,Chaturbhuj, Ganesh U.
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p. 1463 - 1468
(2017/07/18)
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- Kinetic study on aminolysis of 4-pyridyl benzoate and O-4-pyridyl thionobenzoate in acetonitrile: Factors influencing reactivity and reaction mechanism
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A kinetic study on nucleophilic substitution reactions of 4-pyridyl benzoate (2a) andO-4-pyridyl thionobenzoate (2b) with a series of cyclic secondary amines in acetonitrile at 25.0°C is reported. Plots of pseudo-first-order rate constant (kobsd) vs. [amine] are linear and pass through the origin for the reactions of 2a but curve upward for those of 2b. The upward curvature observed for the reactions of 2b is typical for reactions that proceed through a stepwise mechanism with a zwitterionic intermediate T±, which decomposes to the products via uncatalyzed and catalyzed routes competitively. The reaction of 2a has been suggested to proceed through a stepwise mechanism with T±, in which expulsion of the leaving group occurs in the rate-determining step on the basis of a linear Br?nsted-type plot with βnuc = 0.77. The catalyzed reaction of 2b from T± has been proposed to proceed through a concerted mechanism with a six-membered cyclic transition state rather than via a stepwise pathway with an anionic intermediate T-. Factors influencing reactivity and reaction mechanism are discussed in detail.
- Um, Ik-Hwan,Kim, Min-Young,Lee, Jae-In
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p. 1577 - 1581
(2016/10/13)
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- Iodine-Promoted Synthesis of Thioamides from 1,2-Dibenzylsulfane and Difurfuryl Disulfide
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Thioamides can be generated at 100 °C in high yield through the reaction of 1,2-dibenzyldisulfane with difurfuryldisulfide using iodine as oxidant and DMSO as solvent. The protocol is metal- and additive-free, providing a convenient and economical way for the synthesis of various kinds of thioamides under mild conditions.
- Chen, Sihai,Li, You,Chen, Jinyang,Xu, Xinhua,Su, Lebin,Tang, Zhi,Au, Chak-Tong,Qiu, Renhua
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supporting information
p. 2339 - 2344
(2016/09/28)
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- Sulfur promoted decarboxylative thioamidation of carboxylic acids using formamides as amine proxy
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An efficient decarboxylative thioamidation of arylacetic and cinnamic acids has been developed employing formamides as amine surrogate and sulfur as promoter. Thioamides with variant structural features are obtained under mild reaction conditions without the use of transition metal catalysts and oxidants.
- Kumar, Saurabh,Vanjari, Rajeshwer,Guntreddi, Tirumaleswararao,Singh, Krishna Nand
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p. 2012 - 2017
(2016/04/05)
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- Aqueous Compatible Protocol to Both Alkyl and Aryl Thioamide Synthesis
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An efficient aqueous synthesis of thioamides through aldehydes, sodium sulfide, and N-substituted formamides has been developed. Both alkyl and aryl aldehydes are amenable to this protocol. N-Substituted formamides are essential for this transformation. Readily available inorganic salt (sodium sulfide) serves as the sulfur source in water, which makes this method much more practical and efficient. Furthermore, the late-stage modification of bioactive molecules and derivatives through this protocol has been established.
- Wei, Jianpeng,Li, Yiming,Jiang, Xuefeng
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supporting information
p. 340 - 343
(2016/02/03)
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- Decarboxylative thioamidation of arylacetic and cinnamic acids: A new approach to thioamides
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A new decarboxylative strategy has been developed for the synthesis of thioamides via a three-component reaction involving arylacetic or cinnamic acids, amines and elemental sulfur powder, without the need of a transition metal and an external oxidant.
- Guntreddi, Tirumaleswararao,Vanjari, Rajeshwer,Singh, Krishna Nand
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supporting information
p. 3624 - 3627
(2014/08/05)
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- Thiol as a synthon for preparing thiocarbonyl: Aerobic oxidation of thiols for the synthesis of thioamides
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It is a constant challenge to develop an environmentally friendly, atom-economical, and step-economical method for the preparation of thioamides. Herein, we describe an oxidation method that affords the direct conversion of thiols to thioamides without the use of exogenous sulfur reagents. This is the first instance of a successful utilization of thiols as a synthon for the preparation of thioamides under economical conditions.
- Wang, Xi,Ji, Miran,Lim, Seungyeon,Jang, Hye-Young
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p. 7256 - 7260
(2014/08/18)
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- Sulfonic acid functionalized nano Γ-Al 2O 3: A new, efficient, and reusable catalyst for synthesis of thioamides
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Sulfonic acid functionalized nano γ-Al2O3 is easily prepared by the reaction of nano γ-Al2O3 with 1,3-propane sulfone. This reagent can be used as an eficient catalyst for the synthesis of thioamides. This new method consistently has the advantages of excellent yields and short reaction times. Further, the catalyst can be recovered for several times.
- Yin, Zhikui,Zheng, Bin,Ai, Fang
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p. 1412 - 1420
(2013/10/08)
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- Syntheses and antitumor activities of N′1, N′3-dialkyl-N′1,N′3-di- (alkylcarbonothioyl) malonohydrazide: The discovery of elesclomol
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A series of N′1,N′3-dialkyl- N′1,N′3-di(alkylcarbonothioyl) malonohydrazides have been designed and synthesized as anticancer agents by targeting oxidative stress and Hsp70 induction. Structure-activity relationship (SAR) studies lead to the discovery of STA-4783 (elesclomol), a novel small molecule that has been evaluated in a number of clinical trials as an anticancer agent in combination with Taxol.
- Chen, Shoujun,Sun, Lijun,Koya, Keizo,Tatsuta, Noriaki,Xia, Zhiqiang,Korbut, Timothy,Du, Zhenjian,Wu, Jim,Liang, Guiqing,Jiang, Jun,Ono, Mitsunori,Zhou, Dan,Sonderfan, Andrew
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p. 5070 - 5076
(2013/09/12)
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- Ruthenium catalyzed synthesis of enaminones
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The Grubbs first-generation catalyst has been found to be an effective catalyst for the synthesis of enaminones by coupling thioamides with α-diazodicarbonyl compounds. The reaction is successful in converting primary, secondary, and tertiary thioamides into their corresponding enaminones. The reaction is also suitable for the synthesis of chiral enaminones.
- Koduri, Naga Durgarao,Scott, Halee,Hileman, Bethany,Cox, Justin D.,Coffin, Michael,Glicksberg, Lindsay,Hussaini, Syed R.
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supporting information; experimental part
p. 440 - 443
(2012/03/10)
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- Sulfated tungstate: An efficient catalyst for synthesis of thioamides via Kindler reaction
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New application of sulfated tungstate, a mildly acidic solid inorganic acid, as reusable heterogeneous catalyst for efficient Kindler reaction, a three component reactions of aldehydes, amines and sulfur, for synthesis of thioamides is discussed.
- Pathare, Sagar P.,Chaudhari, Pramod S.,Akamanchi, Krishnacharya G.
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experimental part
p. 125 - 129
(2012/07/03)
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- A convenient one-pot preparation of N-substituted thioamides
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A convenient one-pot preparation of N-substituted thioamides from acyl halides, amines and H2O/PSCl3/Et3N in good to excellent yield has been reported through a solvent-free, microwave assisted method.
- Pandey, Lokesh Kumar,Pathak, Uma,Mazumder, Avik,Mathura, Sweta
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experimental part
p. 1225 - 1228
(2010/12/20)
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- Thioamides via thiatriazolines
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A method for thioamide formation from dithioacids and azides is described and a mechanistic framework is presented.
- Kolakowski, Robert V.,Shangguan, Ning,Williams, Lawrence J.
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p. 1163 - 1166
(2007/10/03)
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- Synthesis of S-thioacyl dithiophosphates, efficient and chemoselective thioacylating agents
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Easily available acyl dithiophosphates are not stable and isomerise reversibly to O-thioacyl monothiophosphates, especially when subjected to heating. Much slower but probably irreversible isomerisation to S-thioacyl monothiophosphates occurs. Since equilibrium states are established and S-thioacyl (mono)thiophosphates form slowly, reaction mixtures contain generally both thioacylating and acylating agents, and consequently cannot be used for efficient thioacylation. On the other hand, treatment of a mixture of isomeric anhydrides with an excess of a dithiophosphoric acid leads to exclusive formation of S-thioacyl dithiophosphates. They appear to be excellent thioacylating agents: relatively stable, inert towards water and oxygen and therefore easy to handle. Reactions with nitrogen or sulfur nucleophiles proceed very rapidly under ambient conditions, yielding respective thioacyl derivatives. Isolation of the products is very simple. Due to the low reactivity of S-thioacyl dithiophosphates towards oxygen nucleophiles they can be used for direct thioacylation of multifunctional nucleophiles with unprotected hydroxy groups. Respective thioacyl derivatives cannot readily be obtained using other methods.
- Doszczak, Leszek,Rachon, Janusz
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p. 1271 - 1279
(2007/10/03)
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- Facile preparation of amides from thioamides by ceric ammonium nitrate
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Ceric ammonium nitrate (CAN) is found to be a good oxidizing agent which converts thioamides into their oxygen analogues in aqueous acetic acid under very mild conditions.
- Movassagh, Barahman,Meibodi, Forhatosadat,Sobhani, Shahin
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p. 1296 - 1298
(2007/10/03)
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- New, efficient and chemoselective method of thioacylation, starting from carboxylic acids
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S-Acylation of dithiophosphoric acids yields mixed anhydrides 3; they readily isomerize to O-thioacyl 4 and S-thioacyl monothiophosphates 5, which treated with the excess of dithiophosphoric acid 2 can be easily converted into thioacyl dithiophosphates 6, excellent thioacylating reagents.
- Doszczak,Rachon
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p. 2093 - 2094
(2007/10/03)
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- Synthesis of oxazines and thiazines by cyclodehydration of hydroxy amides and thioamides
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Dihydro-1,3-oxazines and -thiazines were obtained by cyclodehydration of hydroxy amides and thioamides with PEG-linked Burgess reagent or under Mitsunobu conditions. Yields were generally higher with polymer-Burgess reagent, but both conditions failed to
- Wipf, Peter,Hayes, Gregory B.
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p. 6987 - 6998
(2007/10/03)
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- Addition-Elimination Mechanism of Aminolyses of 4-Nitrophenyl Benzoate and Its Sulfur Analogue
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The aminolysis of O-(4-nitrophenyl) thiobenzoate proceeds via an addition-elimination mechanism in which the rate-determining step is dependent on both concentration and basicity of amines.
- Um, Ik-Hwan,Kwon, Hye-Jin,Kwon, Dong-Sook
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p. 1801 - 1817
(2007/10/03)
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- Reactions of Phosphonate Carbanions with Selenium or Sulfur in the Presence of Amines. Synthesis of Seleno- and Thioamides
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The reaction of phosphonate carbanions with elemental selenium in the presence of amines afforded the corresponding selenoamides in moderate yields.The reaction of these anions with sulfur also gave thioamides.These reactions might proceed through thio- or selenoaldehyde intermediates.
- Okuma, Kentaro,Ikari, Koumei,Ohta, Hiroshi
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p. 131 - 134
(2007/10/02)
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- X=Y-ZH SYSTEMS AS POTENTIAL 1,3-DIPOLES. PART 20. DECARBOXYLATION OF α-IMINO ACIDS. MECHANIZM AND APPLICATIONS TO THIOAMIDE SYNTHESIS
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α-Imino acids, prepared from α-keto acids and primary amines, undergo facile decarboxylation to the corresponding imines on heating at =80 deg C in benzene or methylene chloride.Decarboxylation proceeds via a 1,2-ylide which can be trapped by sulphur to give the corresponding secondary thioamides in good yield. 1,2-Ylides from secondary amines and α-keto acids can be generated in situ and trapped with sulphur to give tertiary thioamides in excellent yield.
- Aly, Moustafa F.,Grigg, Ronald
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p. 7271 - 7282
(2007/10/02)
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- Ready Decarboxylation of Imines of α-Keto Acids. Mechanism and Application to Thioamide Synthesis
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α-Keto acids are readily decarboxylated via imine formation with primary and/or secondary amines even when imine-enamine isomerisation can occur; the process is thought to involve an intermediate zwitterion which can be trapped by sulphur to give thioamides in excellent yield.
- Aly, Moustafa F.,Grigg, Ronald
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p. 1523 - 1524
(2007/10/02)
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- The Triethylamine Catalyzed Reaction of N,N-Disubstituted Thioamide-Bromine Adducts With Unsubstituted Thiobenzamide
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The reaction of N,N-disubstituted thioamide-bromine adducts with unsubstituted thioamide, followed by treatment with triethylamine, affords novel N'-thiobenzoylamidines along with smaller amounts of secondary products.A mechanism is proposed for the formation of the amidines.The results give an insight into the initial steps of the mechanism by which thioamides are converted into 1,2,4-thiadiazoles.
- Corsaro, Antonino,Compagnini, Anna,Perrini, Giancarlo,Purrello, Giovanni
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p. 897 - 900
(2007/10/02)
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- Preparation and Some Reactions of Phenylmercury Thio- and Dithiocarboxylates
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It has been found that the reaction of diphenylmercury with an equimolar amount of thio- or dithio acids gave the corresponding phenylmercury thio- (1) or dithiocarboxylates (2), quantitatively, which further react with thio- or dithio acids to give mercury bis(thio-) (3) or bis(dithiocarboxylates) (4).The phenylmercury dithio salts (2) were found to be the very useful thioacylating agents for primary and secondary amines.The reaction of mercury bis(thiocarboxylates) (3) with dithiocarboxylic acids gave the unsymmetrical thio- and dithiocarboxylic acid mercury salts (5) in good yield. - Keywords: Phenylmercury Thiocarboxylates
- Kato, Shinzi,Hattori, Eiji,Sato, Hiroyuki,Mizuta, Masateru,Ishida, Masaru
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p. 783 - 790
(2007/10/02)
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- SEMICARBAZONES AND THIOSEMICARBAZONES OF THE HETEROCYCLIC SERIES. XLIV. CYCLIZATION OF ISATIN AND 1-ACETYLISATIN 3-THIOBENZOYLHYDRAZONES
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Isatin 3-thiobenzoylhydrazone undergoes cyclization with the addition of the sulfur atom to the C3 atom and closure of the thiadiazole ring.In contrast, 3-thioaroylhydrazones of 1-acetylisatin undergo cyclization with participation of C2 and close the thiadiazine ring with the formation of derivatives of the new heterocyclic system thiadiazinoindole.
- Tomchin, A.B.
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p. 504 - 510
(2007/10/02)
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- Infrared spectra of several thiopiperidides and thiomorpholides
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Infrared spectra in the 1700-500 cm-1 region have been studied for several types of thiopiperidides (thiobenzoylpiperidides, thiocinnamoylpiperidides and phenylthioacetpiperidides) and for the corresponding thiomorpholides.Three characteristic thioamide bands were located and assigned.The behaviour of these bands on molecular complexing (with iodine as an electron acceptor) was used to support the assignments.The experimental data were discussed in terms of the theoretical results obtained by an HMO procedure.
- Cornea, Felicia,Cercasov, Cornelia,Ciureanu, Mariana
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p. 775 - 782
(2007/10/02)
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