- Malonic Acid Derivatives on Duty as Electron-Withdrawing Units in Push–Pull Molecules
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Based on the 2-(N-piperidinyl)thiophene central donor, 32 model push–pull molecules with systematically varied malonic acid-derived peripheral acceptors have been prepared. Further property tuning has been achieved by modifying the π-linker and the structural arrangement (linear vs. quadrupolar D–π–A systems). Malonic acid derivatives such as cyanoacetic acid, malondinitrile, diethyl malonate, Meldrum′s acid, and N,N′-dibutyl(thio)barbituric acid as well as 1,3-diketo analogues dimedone and indan-1,3-dione were employed as acceptor moieties. Knoevenagel condensation with four thiophene aldehydes afforded the target chromophores in satisfactory yields. The electron-withdrawing abilities of malonic acid acceptors were examined both by experiment including X-ray analysis, differential scanning calorimetry, electrochemistry, and UV/Vis absorption spectroscopy, and by DFT calculations. Details of the structure–property relationships have been elucidated. According to the increasing electron-withdrawing ability, the widely used malonic acid acceptor units can be ordered: diethyl malonate ≤ cyanoacetic acid malondinitrile Meldrum's acid dimedone ≤ N,N′-dibutylbarbituric acid indan-1,3-dione ≤ N,N′-dibutylthiobarbituric acid.
- Klikar, Milan,Jelínková, Veronika,R??i?ková, Zdeňka,Mikysek, Tomá?,Pytela, Old?ich,Ludwig, Miroslav,Bure?, Filip
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- Synthesis of novel dithiocarbamates and xanthates using dialkyl azodicarboxylates: S–N bond formation
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A one?pot three?component route for the synthesis of a novel category of dithiocarbamates or xanthates is developed by a reaction of in-situ generated dithiocarbamic acids or xanthates with dialkyl azodicarboxylates under mild and catalyst-free conditions. The reaction is characterized by a wide scope, high efficiency and straightforward isolation protocol. The synthetic utility of the dithiocarbamates and xanthates was demonstrated on the preparation of symmetrical and unsymmetrical thioureas, isothiocyanates, and thiocarbamates.
- Ziyaei Halimehjani, Azim,Klepetá?ová, Blanka,Beier, Petr
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p. 1850 - 1858
(2018/03/06)
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- Nickle Catalysis Enables Access to Thiazolidines from Thioureas via Oxidative Double Isocyanide Insertion Reactions
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An efficient synthesis of thiazolidine-2,4,5-triimine derivatives was developed via Ni-catalyzed oxidative double isocyanide insertion to thioureas under air conditions, in which thioureas play three roles as a substrate, a ligand, and overcoming isocyanide polymerization. The reaction is featured by employing a low-cost and low loading Ni(acac)2 catalyst, without any additives, and high atom economy. This is the first example to directly apply a Ni(II) catalyst in oxidative double isocyanide insertion reactions.
- Yuan, Wen-Kui,Liu, Yan Fang,Lan, Zhenggang,Wen, Li-Rong,Li, Ming
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supporting information
p. 7158 - 7162
(2018/11/25)
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- Rapid and highly efficient synthesis of thioureas in biocompatible basic choline hydroxide
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A straightforward and convenient synthesis of symmetrical thiourea derivatives by the reaction of primary amines and carbon disulfide in biocompatible basic choline hydroxide is presented. A variety of biologically important thiourea derivatives can be obtained in good to excellent yields without a tedious work-up under mild reaction conditions. A series of primary aliphatic and aromatic amines with different substituted functional groups have been converted to thiourea derivatives under milder reaction conditions and short reaction times.
- Azizi, Najmedin,Farhadi, Elham
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p. 548 - 554
(2017/09/27)
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- Green process development for the synthesis of aliphatic symmetrical N,N'-disubstituted thiourea derivatives in aqueous medium
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A highly efficient green process for the synthesis of N,N'-disubstituted aliphatic thiourea derivatives using primary aliphatic amines and carbon disulfide in aqueous medium at room temperature via a nonisothiocyanate route is described. This protocol illustrates the rapid preparation of N,N'-disubstituted aliphatic thiourea derivatives in excellent yields with some advantages such as no catalyst and simple workup without any side product formation. Moreover the new route is concise, chromatography-free, and adaptable to pilot-scale preparation.
- Jangale, Asha D.,Kumavat, Priyanka P.,Wagh, Yogesh B.,Tayade, Yogesh A.,Mahulikar, Pramod P.,Dalal, Dipak S.
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supporting information
p. 236 - 244
(2015/10/29)
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- Green Process Development for the Synthesis of Aliphatic Symmetrical N,N ′-Disubstituted Thiourea Derivatives in Aqueous Medium
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A highly efficient green process for the synthesis of N,N′-disubstituted aliphatic thiourea derivatives using primary aliphatic amines and carbon disulfide in an aqueous medium at room temperature via a nonisothiocyanate route is described. This protocol illustrates the rapid preparation of N,N′-disubstituted aliphatic thiourea derivatives in excellent yields with some advantages such as no catalyst and simple workup without any side product formation. Moreover, the new route is concise, does not require chromatography, and is adaptable to pilot-scale preparation. GRAPHICAL ABSTRACT.
- Jangale, Asha D.,Kumavat, Priyanka P.,Wagh, Yogesh B.,Tayade, Yogesh A.,Mahulikar, Pramod P.,Dalal, Dipak S.
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supporting information
p. 376 - 385
(2015/10/29)
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- Convenient synthesis of 5-arylidene-2-imino-4-thiazolidinone derivatives using microwave irradiation
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A concise approach for the preparation of 5-arylidene-2-imino-4- thiazolidinone derivatives is described. Structurally diverse amines, isothiocyanates, aldehydes, and chloroacetyl chloride were combined under microwave irradiation to afford new 5-arylidene-2-imino-4-thiazolidinone derivatives. The one-pot synthesis involves the in situ formation of a thiourea followed by reaction with chloroacetyl chloride and an aldehyde to generate the target compounds. Georg Thieme Verlag Stuttgart New York.
- Sarkis, Manal,Tran, Diem-Ngan,Dasso Lang, Maria Chiara,Garbay, Christiane,Braud, Emmanuelle
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p. 1257 - 1262
(2014/06/10)
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- Synthesis of thioureas in ionic liquid medium
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A highly efficient procedure for the synthesis of symmetrical thioureas by means of simple condensation of primary amines and carbon disulfide in 1-butyl-3-methylimidazolium chloride [BMIM][Cl] as a cheap and commercially available ionic liquid is presented. This procedure works for aromatic and aliphatic primary amines and give high to excellent yields of symmetrical thioureas without need for any catalyst or tedious work-up.
- Halimehjani, Azim Ziyaei,Farahbakhsh, Fataneh
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p. 284 - 288
(2013/08/26)
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- Novel thiofomylation of primary and secondary amines using N-aryl-1,2,3,4,5,7-pentathiazocanes
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Heating of N-aryl-1,2,3,4,5,7-pentathiazocanes 1 in the presence of primary and secondary amines afforded N-Alkyl or N,N-dialkylthioformamides 5, and similar heating of 1 in the absence of amines afforded an inseparable mixture of acyclic polysulfides 4 bearing a thioformanilide moiety on each terminal. Bisthioformanilides 4 were also converted into 5 by treating with these amines, and the thioformylation was assumed to proceed through a pathway involving the ring fission of 1 and the subsequent nucleophilic attack of these amines onto the thioformyl group of 4. Copyright Taylor & Francis Group.
- Shimada, Kazuaki,Shibuya, Hiroki,Makino, Kenshiro,Otsuka, Tatsuya,Onuma, Yuki,Aoyagi, Shigenobu,Takikawa, Yuji
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scheme or table
p. 1077 - 1089
(2010/09/04)
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- Carbon tetrabromide promoted reaction of amines with carbon disulfide: Facile and efficient synthesis of thioureas and thiuram disulfides
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A novel carbon tetrabromide promoted one-pot reaction of amines and carbon disulfide under mild conditions has been developed, which provides a straightforward and efficient access to thioureas and thiuram disufides, depending on the nature of the amines employed. The promotion effect is explained as the transient formation of a sulfenyl bromide intermediate from dithiocarbamate and carbon tetrabromide during the reaction. Georg Thieme Verlag Stuttgart · New York.
- Liang, Fushun,Tan, Jing,Piao, Chengri,Liu, Qun
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experimental part
p. 3579 - 3584
(2009/07/04)
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- An environmentally benign method for the synthesis of symmetrical N,N′-disubstituted thioureas in a water medium
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An environmentally benign method for the synthesis of symmetrical N,N′-disubstituted thioureas in a water medium using poly(ethylene glycol)-400 (PEG-400) as a catalyst and a microwave as a heating source is described. Diaryl- and dialkyl-thioureas efficiently are synthesized by the reactions of thiourea with a variety of amines. This protocol has advantages of (a) no use of hazardous reagents and volatile organic solvents, (b) a rapid reaction rate, (c) a high yield, and (d) a simple work-up procedure. Copyright Taylor & Francis Inc.
- Li, Zheng,Wang, Zhi-Yuan,Zhao, Yan-Long,Xing, Yu-Lin,Zhu, Wei
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p. 2745 - 2750
(2007/10/03)
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- A Concise and Convenient Method for the Synthesis of Pure Substituted Thioureas
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Zinc dialkyldithiocarbamates offer excellent substrates for pure thioureas required for the ntifungal and X-ray crystallographic studies.
- Ramadas, K.,Janarthanan, N.
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p. 1101 - 1108
(2007/10/03)
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- A CONVENIENT METHOD FOR THE PREPARATION OF N,N'-DISUBSTITUTED THIOUREAS USING 2-CHLOROPYRIDINIUM SALT, SODIUM TRITHIOCARBONATE AND AMINES
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N,N'-Disubstituted thioureas were prepared in high yields by treating 2-chloropyridinium salt with sodium trithiocarbonate and subsequently adding amines.
- Takikawa, Yuji,Inoue, Noriyuki,Sato, Ryu,Takizawa, Saburo
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p. 641 - 642
(2007/10/02)
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- INVESTIGATIONS IN THE FIELD OF XANTHIC ACIDS AND THEIR DERIVATIVES. III. REACTION OF BUTYLAMMONIUM ISOPROPYL XANTHATE WITH BUTYLAMINE
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The reaction of butylammonium isopropyl xanthate with butylamine involves the preferential occurence of two consecutive reactions of first order (2 and 7 kJ/mole) with the formation of N,N'-dibutylthiourea as product.A reaction mechanism which agrees well with the data from kinetic measurements is proposed.
- Khardin, A. P.,Val'dman, A. I.,Pestova, G. A.,Val'dman, D. I.,Gnatyuk, P.P.,et al.
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p. 1863 - 1867
(2007/10/02)
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- Cephalosporin displacement reaction
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The present invention is directed to a process for the displacement of the acetoxy group of a cephalosporanic acid by a sulfur nucleophile, in an organic solvent and under essentially anhydrous conditions.
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