- Copper-Catalyzed Double Thiolation to Access Sulfur-Bridged Imidazopyridines with Isothiocyanate
-
A copper(I)-catalyzed sulfur-bridged dimerization of imidazopyridines has been developed using isothiocyanate as the sulfur source. This method enables a switchable synthesis of bis(imidazo[1,2-a]pyridin-3-yl)sulfanes or bis(2-(imidazo[1,2-a]pyridin-2-yl)phenyl)sulfanes in the presence of 4-dimethylaminopyridine (DMAP) or K2CO3 when different imidazopyridines were employed. Under optimized conditions, a variety of sulfur-bridged imidazopyridines were obtained in good yields. Moreover, thiourea was proved to be the key intermediate under catalytic system A.
- Tian, Lu-Lu,Lu, Shuai,Zhang, Zhe-Hua,Huang, En-Ling,Yan, Hua-Ting,Zhu, Xinju,Hao, Xin-Qi,Song, Mao-Ping
-
-
Read Online
- Synthesis and characterisation of [(en)2Co]3+ complexes coordinated by substituted thiourea ligands
-
Substituted thiourea ligands bind in a bidentate manner forming a four-membered ring through the sulfur atom and a deprotonated thiourea nitrogen atom when reacted with [(en)2Co(OSO2CF3)2]+ in tetramethylene sulfone. Reaction of unsymmetrical ligands results in the formation of coordination isomers, some of which can be separated by column chromatography using Sephadex SPC-25. Coordination isomers are easily distinguishable based on visible and 1H NMR spectroscopy . Twelve para-substituted and one meta-substituted ligands were studied: N,N′-dibenzylthiourea (1a); N-(R)phenyl-N′-benzylthiourea R≤H (2a), NO2 (2b), CH3 (2c); N-(R)phenyl-N′-(R′)phenylthiourea R, R′: H, H (3a), H, CH3 (3b), OCH3, NO2 (3c), CH3, NO2 (3d); N-methyl-N′-(R)phenylthiourea R≤H (4a), CH3 (4b), OCH3 (4c), NO2 (4d), 3-CH3 (4e). The solid state structure (X-ray) of one isomer of Co-4a as its perchlorate salt confirms the coordination mode suggested by 1H NMR spectroscopy and shows that the Co-N bond trans to the coordinated thiourea sulfur induces a structural trans effect of 0.019A.
- Roecker, Lee,Aiyegbo, Mohammed,Al-Haddad, Aladdin,Fletcher, Emily,Kc, Ravi,Hurst, Jason,Lane, Timothy,Larsen, Ryan,Noinaj, Nicholas,Teh, Say Lee,Wade, Samuel K.,Parkin, Sean
-
-
Read Online
- Rapid synthesis of a 13C6-benzothiazolium salt from 13C6-aniline
-
13C6-labeled aniline was used as a starting material for the facile synthesis of 13C6-benzothiazolium salt (1). Copyright
- Galliford, Chris V.,Voronin, Kimberly,Hesk, David,Koharski, David,McNamara, Paul
-
-
Read Online
- Coupling of single droplet micro-extraction with desorption electrospray ionization-mass spectrometry
-
Single droplet micro-extraction (SDME) is a powerful preconcentration and purification technique for trace chemical analysis, but the detection of the resulting single droplet extract is often time-consuming with traditional detection methods such as GC/MS or LC/MS. In this study, desorption electrospray ionization-mass spectrometry (DESI-MS) was coupled with SDME to serve as a fast detection method for the first time, demonstrated by the trace analysis of methamphetamine (MA) in aqueous solution and the detection of an organic reaction product from an ionic liquid (IL). In the former application, three-phase liquid SDME was conducted to enrich MA in aqueous solution to an organic solvent and then to back-extract the analyte to a single aqueous droplet. Subsequent DESI-MS analysis can be performed either to a single droplet or multiple droplets in a row. The average enrichment factor obtained for MA was 390-fold. In the latter case, two-phase liquid SDME was conducted to directly extract the product of an organic reaction performed in a room temperature ionic liquid (i.e., the nucleophilic addition of aniline to phenyl isothiocyanate to form N,N′-diphenylthiourea in 1-butyl-3-methyl- imidazolium tetrafluoroborate). The ionization of the resulting droplet extract by DESI allows one to directly examine the reaction product without interference from the ionic liquid. Such an analysis uses a few microliters of an organic solvent, achieving green chemistry. This combined SDME/DESI-MS method is characterized with high preconcentration efficiency, high throughput capability and minimizing organic solvent waste.
- Sun, Xiaobo,Miao, Zhixin,Yuan, Zongqian,Harrington, Peter De B.,Colla, Jennifer,Chen, Hao
-
-
Read Online
- Barbiturate squaraine dyes as fluorescent probes for serum albumins detection
-
Three indolenine-based barbiturate squaraine dyes were synthesized, characterized and subjected to photophysical studies, including their affinity with human serum albumin and bovine serum albumin as protein models in phosphate buffer solution. All dyes successfully interact with both proteins with high affinity binding constants. It was found that dyes with hydrophobic substituents had superior binding constants with both proteins. The fluorescence intensity of all dyes increased in the presence of both proteins which allowed the determination of detection and quantifications limits in the tens of nanomolar, using a protein concentration of 0–3.5 μM. Concerning to the study on the binding sites of the synthesized dyes using the warfarin and ibuprofen markers, the results of this study suggest that, one dye binds to both BSA binding sites while the two others dyes binds only to site I, and that all three dyes bind to both HSA binding sites.
- Almeida, Paulo,Boto, Renato E. F.,Gomes, Vanessa S. D.,Gon?alves, Helena M. R.,Reis, Lucinda V.
-
-
Read Online
- Structural requirement of phenylthiourea analogs for their inhibitory activity of melanogenesis and tyrosinase
-
Effect of a series of 1-phenylthioureas 1a-k and 1,3-disubstituted thioureas 2a-k were evaluated against melanin formation in melanoma B16 cell line and mushroom tyrosinase. Inhibitory activity of tyrosinase of 1-phenylthioureas 1a-k is parallel to their melanogenic inhibition. Thus, the melanogenic inhibition in melanoma B16 cells of 1-phenylthioureas could be the result of inhibition of tyrosinase. However, 1,3-diaryl or 1-phenyl-3- alkylthioureas, 2a-k, appears as melanogenic inhibitor without inhibition of tyrosinase. The molecular docking study of 1e and 2b to binding pocket of tyrosinase provided convincing explanation regarding the necessity of direct connection of planar phenyl to thiourea unit without N′-substitution of phenylthioureas 1 as tyrosinase inhibitor and 2 as non-tyrosinase inhibitor.
- Thanigaimalai, Pillaiyar,Lee, Ki-Cheul,Sharma, Vinay K.,Joo, Cheonik,Cho, Won-Jea,Roh, Eunmiri,Kim, Youngsoo,Jung, Sang-Hun
-
-
Read Online
- A CONVENIENT METHOD FOR THE PREPARATION OF N,N'-DISUBSTITUTED THIOUREAS USING 2-CHLOROPYRIDINIUM SALT, SODIUM TRITHIOCARBONATE AND AMINES
-
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
-
-
Read Online
- Naphthyridine derivatives as a model system for potential lithium-sulfur energy-storage applications
-
Naphthyridines have been identified as structural elements in sulfurized polyacrylonitrile, which is a common electrode material in lithium-sulfur batteries. Some dibenzonaphthyridine derivatives with a fused dithiolo moiety were prepared as model compounds for battery studies. These heterocyclic systems were prepared via the corresponding diphenyldicarbamide intermediate. Followed by naphthyridione formation, stepwise installation of the dithiolane subunit occurred in a straightforward manner. In the solid state, the heteroaromatic system is completely planar and was thoroughly characterized. Initial battery cycling tests indicated a potential use of such structural motifs in sulfur-lithium systems.
- Resch, Sebastian,Schneider, Anna-Rebekka,Beichler, Ronja,Spera, Marcelle B. M.,Fanous, Jean,Schollmeyer, Dieter,Waldvogel, Siegfried R.
-
-
Read Online
- A synthetic route to novel 3-substituted-2,1-benzisoxazoles from 5-(2-nitrobenzylidene)(thio)barbiturates
-
2,1-Benzisoxazoles, also called anthranils, are one of the two types of aromatic bicyclic heterocycles having a benzene ring fused with an isoxazole, which are particularly recognized as valuable intermediates in organic synthesis. Nevertheless several methods can be found in the literature to prepare 2,1-benzisoxazoles, we herein report a new, efficient, simple, mild, and alternative procedure to prepare 3-substituted-2,1-benzisoxazoles from 5-(2-nitrobenzylidene)barbiturates in moderate to good yields (51–82%). All the novel benzisoxazoles showed spectral data fully consistent with the assigned structures, which were unequivocally confirmed by single crystal X-ray analysis. A possible mechanism of the reaction is proposed. In addition, a screening of the bioactivity of these benzisoxazoles as xanthine oxidase inhibitors, antioxidants, and cytotoxic compounds was performed. The benzisoxazole formed from barbituric acid revealed moderate xanthine oxidase inhibitory effects (IC50 = 22.10 μM).
- Serrano, Jo?o L.,Cavalheiro, Eunice,Barroso, Sónia,Rom?o, Maria J.,Silvestre, Samuel,Almeida, Paulo
-
-
Read Online
- One-pot synthesis of highly functionalized benzo [1,3] thiazine from isocyanides, aniline, and heterocumulene via Cu-catalyzed intramolecular C-H activation reactions
-
A one-pot synthesis of functionalized benzo thiazine derivatives via a Cu-catalyzed, multicomponent reaction of isocyanides, aniline, and heterocumulenes in acetonitrile at room temperature was developed. Transition metal-catalyzed activation of C-H bonds
- Dastjerdi, Hossein F.,Nematpour, Manijeh,Rezaee, Elham,Jahani, Mehdi,Tabatabai, Sayyed A.
-
-
Read Online
- Unclicking of thioureas: Base catalyzed elimination of anilines and isothiocyanates from thioureas
-
Bisaromatic thioureas are widely used in e.g. asymmetric organocatalysis and considered to be robust compounds. Herein we show, in strong contrast to common notion, that thioureas dissociate to amines and isothiocyanates in a base catalyzed reaction under mild conditions. This ‘unclicking’ process can occur in the presence of weak organic bases even at moderate temperatures. The influence of the substituents at the aromatic rings of the thiourea on the regioselectivity of this unclicking process is also shown.
- Vlatkovi?, Matea,Feringa, Ben L.
-
-
Read Online
- Thermolysis of symmetrical dithiobiurea and thioureidoethylthiourea derivatives
-
Microwave and thermal heterocyclization of N,N′-disubstituted hydrazinecarbothioamide 1a,b and substituted thioureidoethylthioureas 2a-c as well as 1-phenyl-3[2-(3-phenylthio-ureido)phenyl]-thiourea 6 are reported.
- Hassan, Alaa A.,Mourad, Aboul-Fetouh E.,El-Shaieb, Kamal M.,Abou-Zied, Ashraf H.,Doepp, Dietrich
-
-
Read Online
- A general and facile one-pot process of isothiocyanates from amines under aqueous conditions
-
A general and facile one-pot protocol for the preparation of a broad range of alkyl and aryl isothiocyanates has been developed from their corresponding primary amines under aqueous conditions. This synthetic process involves an in situ generation of a dithiocarbamate salt from the amine substrate by reacting with CS2 followed by elimination to form the isothiocyanate product with cyanuric acid as the desulfurylation reagent. The choice of solvent is of decisive importance for the successful formation of the dithiocarbamate salt particularly for highly electron-deficient substrates. This novel and economical method is suitable for scale-up activities.
- Sun, Nan,Li, Bin,Shao, Jianping,Mo, Weimin,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
-
-
Read Online
- Thermolysis of N,N″-1,ω-alkanediyl-bis[N′- organylthiourea] derivatives
-
The course of microwave assisted or conventional thermal intramolecular heterocyclization of the title compounds has been found to be dependent on the length of the alkanediyl chain. While 1,3-propanediyl-bisthioureas 5a-c gave both 2-thioxoperhydropyrimidine-1-carbothioamides 8a-c and 8-amino-3,4,5,6- tetrahydro-1,3,7-thiadiazocine-2-thiones 10a-C, thermolysis of 1,4-butanediyl-bisthioureas 6a-c and 1,6-hexanediyl-bisthioureas 7a-c under the same conditions gave solely 9-amino-4,5,6,7-tetrahydro-1,3,8-thiadiazonine-2- thiones 11a-c and 11-amino-1-thia-3,10-diazacycloundec-10-ene-2-thiones 12a-c, respectively. Symmetric N,N′-diorganylthioureas 4a-c were formed in all cases as minor byproducts.
- Hassan, Alaa A.,Doepp, Dietrich
-
-
Read Online
- Carbon tetrabromide promoted reaction of amines with carbon disulfide: Facile and efficient synthesis of thioureas and thiuram disulfides
-
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
-
-
Read Online
- Formation of 1,4,2-Dithiazolidines or 1,3-Thiazetidines from 1,1-Dichloro-2-nitroethene and Phenylthiourea Derivatives
-
A method for preparation of 1,4,2-dithiazolidine or 1,3-thiazetidine heterocycles was developed by reactions of phenylthioureas with 1,1-dichloro-2-nitroethene. The solvent has a significant influence on the type of product formation. 1,4,2-Dithiazolidines were formed in the aprotic solvent chloroform, while in the protic solvent ethanol, 1,3-thiazetidines were the main products.
- Feng, Yian,Zou, Minming,Song, Runjiang,Shao, Xusheng,Li, Zhong,Qian, Xuhong
-
-
Read Online
- Quantitative estimation of the α-effect in the reactions yielding phosphorus-containing thiosemicarbazides
-
The α-effect in the reactions of O,O-diaryl phosphorohydrazidothioates with phenyl isothiocyanate in benzene at 25°C was quantitatively evaluated from the kinetic data. The probable reaction mechanism was suggested, and the causes of the α-effect in these reactions are discussed. An approximate linear correlation is observed between the α-effect in the reactions of O,O-diaryl phosphorohydrazidothioates with phenyl isothiocyanate, basicity constants of the hydrazides, and σp constants of the substituents at the P atom. The value of the α-effect is largely determined by the structure of the transition state. Nauka/Interperiodica 2006.
- Yanchuk
-
-
Read Online
- 1-(Methyldithiocarbonyl)imidazole: A useful thiocarbonyl transfer reagent for synthesis of substituted thioureas
-
1-(Methyldithiocarbonyl)imidazole 1 and its N-methyl quaternary salt 2 have been shown to be efficient methyldithiocarbonyl and thiocarbonyl transfer reagents for the synthesis of dithiocarbamates, symmetrical and unsymmetrical mono-, di- and tri-substituted thioureas in high yields under mild and simple non-hazardous reaction conditions. (C) 2000 Elsevier Science Ltd.
- Mohanta, Pramod K.,Dhar, Sanchita,Samal,Ila,Junjappa
-
-
Read Online
- CuI-catalyzed sulfenylation of 1-aryl trifluoromethyl pyrazolones: Direct formation of C-S-C bond using aryl iodides and carbon disulfide
-
A novel approach for CuI-catalyzed sulfenylation of 1-aryl-3-trifluoromethyl pyrazolones (2a-d) with aryl iodides (1a-j) and carbon disulfide as sulfenylating agent has been described. The protocol was found to be simple and efficient benign to access a broad array of fluorinated sulfenyl pyrazolones in good yields. The formation of C-S-C bond was achieved by using inexpensive and readily available starting materials.
- Avalani, Jemin R.,Kamani, Ronak D.,Prajapati, Ronak V.,Prajapati, Vaibhav D.,Purohit, Vishal B.,Raval, Dipak K.,Sapariya, Nirav H.
-
supporting information
(2021/11/20)
-
- Di-tert-butyl peroxide (DTBP)-mediated synthesis of symmetrical N,N′-disubstituted urea/thiourea motifs from isothiocyanates in water
-
ABATRACT: A direct approach to N,N′-disubstituted urea/thiourea from the self-condensation reactions of isothiocyanates in water has been developed. This access tolerated a wide range of functional groups on the aromatic ring, providing a practical and environment-friendly process to N,N′-disubstituted urea/thiourea in moderate to excellent yields from safe and easily available starting materials. A plausible mechanism of the desulfurization self-condensation reaction for urea was also proposed and the role of di-tert-butyl peroxide (DTBP) and copper catalyst in the present strategy was demonstrated with the help of ESI mass spectrometry of intermediate studies.
- Chen, Ling,Dong, Yibo,Wu, Yangjie,Yang, Jinchen,Zhang, Jinli
-
supporting information
(2021/12/01)
-
- The coordination chemistry of sulfonyl-substituted thioureas towards the d8 metal centres platinum(II), palladium(II), nickel(II) and gold(III)
-
Reactions of the complexes cis-[PtCl2(PPh3)2], [PtCl2(dppp)] (dppp = Ph2P(CH2)3PPh2), [MCl2(dppe)] (dppe = Ph2P(CH2)2PPh2, M = Ni, Pd), [PdCl2(bipy)] (bipy = 2,2′-bipyridine) and [AuCl2(bp)] (bp = cyclometallated 2-benzylpyridine) with p-TolSO2NHC(S)NHPh and Et3N in refluxing methanol gave a series of new thiourea complexes containing the ligand bound as a dianion through the S and the NPh groups. The related thioureas RSO2NHC(S)NHPh (R = Me, Et) and p-TolSO2NHC(S)NHCH2CH=CH2 were also reacted with cis-[PtCl2(PPh3)2] to form the corresponding complexes [Pt{RSO2NC(S)NPh}(PPh3)2] and [Pt{TolSO2NC(S)NCH2CH=CH2}(PPh3)2] respectively. X-ray structure determinations were carried out on the thiourea MeSO2NHC(S)NHPh and its platinum complex [Pt{MeSO2NC(S)NPh}(PPh3)2], as well as [Pt{TolSO2NC(S)NPh}(PPh3)2]. Both complexes form the distal isomer with a remote NSO2R group, and no evidence was observed for isomerisation of these platinum complexes in solution. The palladium complexes [Pd{TolSO2NC(S)NPh}L2] [L2 = Ph2PCH2CH2PPh2 (dppe), or 2,2′-bipyridine (bipy)] undergo decomposition in solution to form the sulfide-bridged aggregates [Pd3S2(L2)3]2+, identified by ESI MS and 31P NMR.
- Henderson, William,Risi, Matthew C.,Saunders, Graham C.
-
-
- Hydroamination and Hydrophosphination of Isocyanates/Isothiocyanates under Catalyst-Free Conditions
-
Symmetrical and unsymmetrical N,N’-disubstituted as well as trisubstituted ureas/thioureas by the hydroamination of isocyanates/isothiocyanates, and various phosphathioureas by the hydrophosphination of isothiocyanates have been synthesized in good to excellent yields under catalyst-free and mild conditions. This protocol is also applicable for the efficient synthesis of chiral ureas and thioureas and common herbicides, such as fenuron and monuron.
- Zhu, Xiancui,Xu, Mengchen,Sun, Jinrong,Guo, Dianjun,Zhang, Yiwei,Zhou, Shuangliu,Wang, Shaowu
-
p. 5213 - 5218
(2021/10/19)
-
- Identification of organophosphorus simulants for the development of next-generation detection technologies
-
Organophosphorus (OP) chemical warfare agents (CWAs) represent an ongoing threat but the understandable widespread prohibition of their use places limitations on the development of technologies to counter the effects of any OP CWA release. Herein, we describe new, accessible methods for the identification of appropriate molecular simulants to mimic the hydrogen bond accepting capacity of the PO moiety, common to every member of this class of CWAs. Using the predictive methodologies developed herein, we have identified OP CWA hydrogen bond acceptor simulants for soman and sarin. It is hoped that the effective use of these physical property specific simulants will aid future countermeasure developments.
- Ellaby, Rebecca J.,Clark, Ewan R.,Allen, Nyasha,Taylor, Faith R.,Ng, Kendrick K. L.,Dimitrovski, Milan,Chu, Dominique F.,Mulvihill, Daniel P.,Hiscock, Jennifer R.
-
p. 2008 - 2014
(2021/03/16)
-
- PREPARATION METHOD OF 2-SUBSTITUTED 1,2,3,4-TETRAHYDROQUINOLINE COMPOUND
-
2 -substituted quinoline compounds are disclosed. The present invention relates to a 2 -substituted 2 -tetrahydroquinoline compound by hydroconversion of 1, 2, 3, 4 -substituted quinoline compounds using a catalyst composition comprising an isothiuronium salt and a Handoesr. In accordance with the present invention, 2 -substituted 1, 2, 3, 4 -tetrahydroquinoline compounds can be produced in high yield with improved reaction efficiency and reaction rate.
- -
-
Paragraph 0098-0102
(2021/08/05)
-
- S-Benzyl-N,N'-diphenyl substituted isothiouronium iodide as a highly efficient organocatalyst for transfer hydrogenation of 2-substituted quinolines
-
An isothiouronium organocatalyst prepared from thiourea was first employed to catalyze the transfer hydrogenation of various 2-alkyl and arylquinolines with Hantzsch ester as the hydrogen source. This metal-free catalyzed reduction of 2-substituted quinoline efficiently rendered good to excellent yields of tetrahydroquinolines under mild conditions with a small amount of catalyst (5 mol%).
- Kang, Sungmin,Kim, Taek Hyeon
-
supporting information
(2021/10/14)
-
- Synthesis of thiazolidinimines/thiazinan-2-imines via three-component coupling of amines, vic-dihalides and isothiocyanates under metal-free conditions
-
An expeditious approach for the synthesis of thiazolidin-2-imines and 1,3-thiazinan-2-imines through three-components coupling (TCC) of amines, isothiocynates and dihalides under metal-free conditions has been described. Dichloroethane (DCE) employed as two carbon (C2) source for the annulation and obtained saturated five membered heterocycles.With 1,3-dibromopropane, six membered heterocycles were obtained in good yields. The metal-free, broad substrate scope, functional group tolerance and applicability at gram scale synthesis are the advantages of the present protocol.
- Kumar, Rahul,Joshi, Abhisek,Rawat, Deepa,Adimurthy, Subbarayappa
-
supporting information
p. 1340 - 1352
(2021/02/22)
-
- Hydroamination of isocyanates and isothiocyanates by alkaline earth metal initiators supported by a bulky iminopyrrolyl ligand
-
A series of new heteroleptic alkaline earth (Ae) metal complexes of general formula [{(Ph2CHN-CH)2C4H2N}AeI(THF)3] {Ae = Ca (2), Sr (3), and Ba (4)} were synthesizedviasalt metathesis by reacting potassium salt of ligand1-K[{(Ph2CHN-CH)2C4H2N}K(THF)2] with anhydrous alkaline earth metal diiodides (AeI2). The homoleptic calcium and barium complexes [{(Ph2CHN-CH)2C4H2N}2Ae] [Ae = Ca (5), Ba (6)] were prepared by treating metal bis-hexamethyldisilazide [Ae{N(SiMe3)2}2(THF)2] with the protic ligand1-H[(Ph2CH-N-CH)2C4H2NH] in a 1:2 molar ratio. Calcium complex5was used as an active pre-catalyst for the addition of N-H bond of arylamines across the heterocumulenes such as phenylisocyanate (PhNCO) and phenylisothiocyanate (PhNCS) under neat conditions, and up to 99% yields of the corresponding urea and thiourea derivatives were obtained.
- Bano, Kulsum,Anga, Srinivas,Jain, Archana,Nayek, Hari Pada,Panda, Tarun K.
-
supporting information
p. 9419 - 9428
(2020/06/17)
-
- Visible-light-promoted oxidative desulphurisation: A strategy for the preparation of unsymmetrical ureas from isothiocyanates and amines using molecular oxygen
-
A green and efficient visible-light promoted oxidative desulphurisation protocol has been proposed for the construction of unsymmetrical ureas under mild conditions with broad substrate scope and good functional group tolerance. Most appealingly, the reaction can proceed smoothly without adding any strong oxidants. Control experiments and computational studies support a mechanism involving water-assisted in situ generation of thioureas and photocatalytic oxidative desulphurisation. The present method provides a promising synthesis strategy for the formation of diverse and useful unsymmetrical urea derivatives in the fields of pharmaceutical and synthetic chemistry.
- Deng, Weiseng,Gan, Ziyu,Jiang, Yuan-Ye,Li, Guoqing,Yan, Qiuli,Yang, Daoshan
-
supporting information
p. 2956 - 2962
(2020/06/17)
-
- Thiourea-Catalyzed C?F Bond Activation: Amination of Benzylic Fluorides
-
We describe the first thiourea-catalyzed C?F bond activation. The use of a thiourea catalyst and Ti(OiPr)4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S- and O-based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.
- Houle, Camille,Savoie, Paul R.,Davies, Clotilde,Jardel, Damien,Champagne, Pier Alexandre,Bibal, Brigitte,Paquin, Jean-Fran?ois
-
supporting information
p. 10620 - 10625
(2020/07/24)
-
- Tunable NIR-II emitting silver chalcogenide quantum dots using thio/selenourea precursors: Preparation of an MRI/NIR-II multimodal imaging agent
-
Aqueous-stable, Cd- and Pb-free colloidal quantum dots with fluorescence properties in the second near-infrared region (NIR-II, 1000-1400) are highly desirable for non-invasive deep-tissue optical imaging and biosensing. The low band-gap semiconductor, silver chalcogenide, offers a non-toxic and stable alternative to existing Pd, As, Hg and Cd-based NIR-II colloidal quantum dots (QDs). We report facile access to NIR-II emission windows with Ag2X (X = S, Se) QDs using easy-to-prepare thio/selenourea precursors and their analogues. The aqueous phase transfer of these QDs with a high conservation of fluorescence quantum yield (retention up to ～90%) and colloidal stability is demonstrated. A bimodal NIR-II/MRI contrast agent with a tunable fluorescence and high T1 relaxivity of 408 mM-1 s-1 per QD (size ～ 2.2 nm) and 990 mM-1 s-1 per QD (size ～ 4.2 nm) has been prepared by grafting 50 and 120 monoaqua Gd(iii) complexes respectively to two differently sized Ag2S QDs. The size of the nanocrystals is crucial for tuning the Gd payload and the relaxivity.
- Basel, Siddhant,Bhardwaj, Karishma,Borthakur, Sukanya,Brito, Beatriz,Clarke, Mitchell,Pariyar, Anand,Pradhan, Sajan,Roy, Pankaj,Saikia, Lakshi,Shankar, Amit,Stasiuk, Graeme J.,Tamang, Sudarsan,Thapa, Surakcha
-
supporting information
p. 15425 - 15432
(2020/11/18)
-
- Synthesis Of di- and tri-substituted thiourea derivatives in water using choline chloride–urea catalyst
-
In this work, di- and tri-substituted thiourea derivatives have been synthesized via a one-pot, three-component reaction from carbon disulfide and aliphatic or aromatic amines using choline chloride-urea deep eutectic solvent as a catalyst in water. Both cyclic and acyclic thiourea derivatives with two or three substituents were synthesized successfully. The reactions were done at 25–100°C, using 5–20 mol% catalyst, in 3–5 h and the GC-Mass yields were between 60% and 95%. All products were characterized using FT-IR, 1H-NMR, 13C-NMR, GC-MS and melting point analyses. The results showed that both water and the DES have important effects on the yield and the rate of this reaction and both of them are necessary to obtain higher yields in less time. The extra experiment, which was designed to study the mechanism of the reaction, showed that an isothiocyanate intermediate was formed in the reaction. Finally, the results showed that by the increase of the amine's nucleophilicity, the reaction occurs faster and gives higher yield.
- Tavakol, Hossein,Mahmoudi, Amir,Ranjbari, Mohammad-Amin
-
p. 113 - 123
(2018/10/24)
-
- Citric acid stabilized on the surface of magnetic nanoparticles as an efficient and recyclable catalyst for transamidation of carboxamides, phthalimide, urea and thiourea with amines under neat conditions
-
Abstract: Citric acid-coated magnetic nanoparticles (Fe3O4–CA NPs) were successfully prepared and characterized. This magnetic nanocatalyst was employed as an efficient, recyclable, and environmentally benign heterogeneous catalyst for the transamidation of carboxamides, phthalimide, urea and thiourea with amines. Several derivatives of formylated and transamidated products were synthesized in good to excellent yields in the presence of this catalytic system. And, the catalyst could be easily separated from the reaction mixture using an external magnet and can be reused six times without any significant loss in its catalytic activity. Graphical abstract: [Figure not available: see fulltext.].
- Arefi, Marzban,Kazemi Miraki, Maryam,Mostafalu, Ramin,Satari, Mohammad,Heydari, Akbar
-
p. 393 - 400
(2019/01/28)
-
- (Thio)urea-catalyzed friedel-crafts reaction: Synthesis of bis(indolyl)-methanes
-
Bis(indolyl)methane derivatives (BIMs) were synthesized in moderate to good yields by (thio)urea catalyzed electrophilic substitution of indole (2) with various aldehydes 1. Reactions were performed under conventional and microwave (MW) heating, either using 1,2-dichloroetane as solvent or without solvent. The procedure using microwave heating was also applied to the synthesis of the natural products vibrindole A (3n), arsindoline A (3i), arundine (3o) and tris(1H-indol-3-yl)methane (3j). Additionally, the synthesis of streptindole was carried out via intermediate 3g. This methodology is well suited for the synthesis of bis(indolyl)methanes: it offers good yields of products, low sensitivity to moisture and oxygen, high tolerance to different functional groups on the aldehydes such as al-kynes and trimethylsilane, and simplicity in operation
- Rivas-Loaiza, Juan A.,Reyes-Escobedo, Carlos E.,Lopez, Yliana,Rojas-Lima, Susana,García-Merinos, Juan Pablo,López-Ruiz, Heraclio
-
p. 959 - 968
(2019/11/22)
-
- Use of sulfur and selenium compounds as precursors to nanostructured materials
-
The presently disclosed subject matter provides processes for preparing nanocrystals, including processes for preparing core-shell nanocrystals. The presently disclosed subject matter also provides sulfur and selenium compounds as precursors to nanostructured materials. The presently disclosed subject matter also provides nanocrystals having a particular particle size distribution.
- -
-
Page/Page column 23-24
(2019/04/26)
-
- Micelle-Enabled One-Pot Guanidine Synthesis in Water Directly from Isothiocyanate using Hypervalent Iodine(III) Reagents under Mild Conditions
-
In this work, we developed a one-pot synthesis of guanidine directly from isothiocyanate using DIB (diacetoxyiodobenzene) as a desulfurizing agent under micellar conditions in water. Our optimization study revealed that the use of 1 % TPGS-750-M as a surfactant with NaOH as an additive base at room temperature can convert a variety of isothiocyanates and amines into corresponding guanidines in excellent yields (69–95 %). This synthetic process in water can be applied to prepare guanidine at gram-scale quantity. Our aqueous micellar medium also demonstrated high reusability as the reaction can be performed for several cycles without losing its efficiency. The reaction is metal-free, utilizes water as solvent and practical (room temperature and open flask).
- Srisa, Jakkrit,Tankam, Theeranon,Sukwattanasinitt, Mongkol,Wacharasindhu, Sumrit
-
p. 3335 - 3343
(2019/09/12)
-
- Annulation Reactions of In-Situ-Generated N-(Het)aroyldiazenes with Isothiocyanates Leading to 2-Imino-1,3,4-oxadiazolines
-
A novel annulation reaction of N-(het)aroyldiazenes and isothiocyanates has been established. This transformation involves a sequential cyclization and desulfurization/intramolecular rearrangement to produce 2-imino-1,3,4-oxadiazolines. The less-stable N-(het)aroyldiazenes can be conveniently generated in situ by I2-mediated oxidation of hydrazides, which allows a one-pot synthesis of the products directly from readily accessible hydrazide and isothiocyanate substrates. This operationally simple synthetic process requires no use of malodorous isocyanides and can be conveniently conducted on a gram scale.
- Zhao, Qiongli,Ren, Linning,Hou, Jiao,Yu, Wenquan,Chang, Junbiao
-
supporting information
p. 210 - 213
(2019/01/04)
-
- Synthesis and decrosslinking of networked polymers having zwitterion structure consisted by cyclic amidine and isothiocyanate
-
We have already found that the polymers, which are obtained by the polymerization of 4-vinylphenyl isothoiocyanate after the zwitterion formation with cyclic amidines, are networked through the ionic interaction among the zwitterions becoming insoluble to various solvents. We report here on the results of the reaction of nucleophilic reagents such as amines and alcohols with the zwitterionic adduct to investigate about the decrosslinking through the resolution of ionic interactions. In the model reactions of amines and alcohols with the zwitterion compounds, which were consisted of the phenyl isothiocyanate and cyclic amidines, the reaction of nucleophilic reagents and zwitterionic adducts having methyl group at the 2-position of the amidine proceed quantitatively. Based on the model reaction, such nucleophilic addition was applicable to decrosslinking reaction of the networked polymers containing the zwitterion structure in the side-chain.
- Yamauchi, Akira,Yoshida, Yoshiaki,Endo, Takeshi
-
p. 2131 - 2137
(2019/10/22)
-
- Novel non-peptidic small molecule inhibitors of secreted aspartic protease 2 (SAP2) for the treatment of resistant fungal infections
-
Targeting secreted aspartic protease 2 (SAP2), a kind of virulence factor, represents a new strategy for antifungal drug discovery. In this report, the first-generation of small molecule SAP2 inhibitors was rationally designed and optimized using a structure-based approach. In particular, inhibitor 23h was highly potent and selective and showed good antifungal potency for the treatment of resistant Candida albicans infections.
- Dong, Guoqiang,Liu, Yang,Wu, Ying,Tu, Jie,Chen, Shuqiang,Liu, Na,Sheng, Chunquan
-
supporting information
p. 13535 - 13538
(2019/01/05)
-
- Trisubstituted barbiturates and thiobarbiturates: Synthesis and biological evaluation as xanthine oxidase inhibitors, antioxidants, antibacterial and anti-proliferative agents
-
Barbituric and thiobarbituric acid derivatives have become progressively attractive to medicinal chemists due to their wide range of biological activities. Herein, different series of 1,3,5-trisubstituted barbiturates and thiobarbiturates were prepared in moderate to excellent yields and their activity as xanthine oxidase inhibitors, antioxidants, antibacterial agents and as anti-proliferative compounds was evaluated in vitro. Interesting bioactive barbiturates were found namely, 1,3-dimethyl-5-[1-(2-phenylhydrazinyl)ethylidene]pyrimidine-2,4,6(1H,3H,5H)-trione (6c) and 1,3-dimethyl-5-[1-[2-(4-nitrophenyl)hydrazinyl]ethylidene]pyrimidine-2,4,6(1H,3H,5H)-trione (6e), which showed concomitant xanthine oxidase inhibitory effect (IC50 values of 24.3 and 27.9 μM, respectively), and 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity (IC50 values of 18.8 and 23.8 μM, respectively). In addition, 5-[1-(2-phenylhydrazinyl)ethylidene]pyrimidine-2,4,6(1H,3H,5H)-trione (6d) also revealed DPPH radical scavenger effect, with an IC50 value of 20.4 μM. Moreover, relevant cytotoxicity against MCF-7 cells (IC50 = 13.3 μM) was observed with 5-[[(2-chloro-4-nitrophenyl)amino]methylene]-2-thioxodihydropyrimidine-4,6(1H,5H)-dione (7d). Finally, different 5-hydrazinylethylidenepyrimidines revealed antibacterial activity against Acinetobacter baumannii (MIC values between 12.5 and 25.0 μM) which paves the way for developing new treatments for infections caused by this Gram-negative coccobacillus bacterium, known to be an opportunistic pathogen in humans with high relevance in multidrug-resistant nosocomial infections. The most promising bioactive barbiturates were studied in silico with emphasis on compliance with the Lipinski's rule of five as well as several pharmacokinetics and toxicity parameters.
- Figueiredo, Joana,Serrano, Jo?o L.,Cavalheiro, Eunice,Keurulainen, Leena,Yli-Kauhaluoma, Jari,Moreira, Vania M.,Ferreira, Susana,Domingues, Fernanda C.,Silvestre, Samuel,Almeida, Paulo
-
p. 829 - 842
(2017/12/13)
-
- 2-Picolylamino(diphenylphosphinoselenoic)amide supported zinc complexes: Efficient catalyst for insertion of N–H bond into carbodiimides, isocyanates, and isothiocyanate
-
We report here the hydroamination of heterocumulenes such as carbodiimides, isocyanates, and isothiocyanates by zinc complexes supported by the ligand 2-picolylamino-(diphenylphosphinoselenoic)amide [{(Ph2P-(?Se)}2NCH2(C5H4N)] (1). A series of zinc complexes [κ2-{(Ph2P-(?Se)}2NCH2(C5H4N)ZnX2] [(X?Cl (2), Br (3a), I (4)] were prepared from ligand 1 and the corresponding zinc dihalide in a 1:1 molar ratio at 60°C in a chloroform solvent. The reaction of ligand 1 and ZnBr2 in methanol yielded another zinc complex [κ2-{(Ph2P-(?Se)}2NCH2(C5H4N)ZnBr2(CH3OH)] (3b). The molecular structures of compounds 3a, 3b, and 4 were established through single-crystal X-ray diffraction analyses. The solid-state structures of all the complexes revealed a κ2- chelation through pyridine nitrogen and selenium atoms of ligand 1 to the zinc ion. Complex 2 proved to be a competent pre-catalyst for the addition of the amine N–H bond to carbodiimides, isocyanates, and isothiocyanates. The reaction scope was expanded to reactions of aliphatic and aromatic amines with phenylisocyanate and phenylisothiocyanate in toluene solvents, which proceeded rapidly at room temperature with 5 mol% catalyst loading to yield (up to 99%) the corresponding derivatives of urea and thio-urea. However, a temperature of 90°C was needed for the hydroamination of N,N′ dicyclohexylcarbodiimide. We also report the most plausible mechanism of the hydroamination reaction.
- Harinath, Adimulam,Bano, Kulsum,Ahmed, Shakil,Panda, Tarun K.
-
supporting information
p. 23 - 32
(2017/09/25)
-
- Mechanism-Based Condition Screening for Sustainable Catalysis in Single-Electron Steps by Cyclic Voltammetry
-
A cyclic-voltammetry-based screening method for Cp2TiX-catalyzed reactions is introduced. Our mechanism-based approach enables the study of the influence of various additives on the electrochemically generated active catalyst Cp2TiX, which is in equilibrium with catalytically inactive [Cp2TiX2]?. Thioureas and ureas are most efficient in the generation of Cp2TiX in THF. Knowing the precise position of the equilibrium between Cp2TiX and [Cp2TiX2]? allowed us to identify reaction conditions for the bulk electrolysis of Cp2TiX2 complexes and for Cp2TiX-catayzed radical arylations without having to carry out the reactions. Our time- and resource-efficient approach is of general interest for the design of catalytic reactions that proceed in single-electron steps.
- Liedtke, Theresa,Spannring, Peter,Riccardi, Ludovico,Gans?uer, Andreas
-
supporting information
p. 5006 - 5010
(2018/03/30)
-
- A facile method for the preparation of carbodiimides from thioureas and (Boc)2O
-
A concise method for the preparation of carbodiimides from thioureas using di-tert-butyl dicarbonate [(Boc)2O] as the dehydrosulfurizative reagent has been developed. Using DMAP as the catalyst, a variety of symmetric and asymmetric 1,3-diaryl thioureas were converted into the corresponding carbodiimides efficiently in a short time.
- Wu, He,Sun, Yan-Fang,Zhang, Chen,Miao, Chun-Bao,Yang, Hai-Tao
-
supporting information
p. 739 - 742
(2018/01/27)
-
- RE[N(SiMe3)2]3-Catalyzed Guanylation/Cyclization of Amino Acid Esters and Carbodiimides
-
The example of rare-earth metal-catalyzed guanylation/cyclization of amino acid esters and carbodiimides is well-established, forming 4(3H)-2-alkylaminoquinazolinones in 65-96% yields. The rare-earth metal amides RE[N(TMS)2]3 (RE = Y, Yb, Nd, Sm, La; TMS = SiMe3) showed high activities, and La[N(TMS)2]3 performed best for a wide scope of the substrates.
- Lu, Chengrong,Gong, Chao,Zhao, Bei,Hu, Lijuan,Yao, Yingming
-
p. 1154 - 1159
(2018/02/10)
-
- Inhibition of adipogenesis by thiourea derivatives
-
Background: Obesity is one of the major health problems with inherent risk of type 2 diabetes, hypertension, CVDs, etc. Adipogenesis is a major contributor in the process of obesity. Inhibition of adipocytes differentiation is one of the key approaches to treat obesity. Objective: To discover the new inhibitors of adipogenesis as the treatment for obesity. Method: We describe here, the synthesis, and anti-adipogenic activity of thiourea derivatives 1-14. These derivatives were synthesized by the reactions of phenyl and pentafluorophenyl isothiocyanate with different aromatic amines. Pure compounds 1-14 were evaluated for their in vitro antiadipogenesis activity employing 3T3-L1 cells lines. Results: Compounds 1-3, 5-9, and 11-14 significantly inhibited the pre-adipocyte differentiation into adipocytes, which was measured by staining the cells, and through morphological examination. Compound 10 (1-(4"-Chlorophenyl)-3-(pentafluorophenyl)-thiourea) showed a potent inhibition of adipocyte differentiation with IC50 = 740.00 ± 2.36 nM, which was more potent than the standards, epigallocatechin gallate (IC50 = 16.73 ± 1.34 μM), and curcumin (IC50 = 18.62 ± 0.74 μM). All other compounds showed a moderate to weak anti-adipogenesis activity. Compounds 1- 14 were also evaluated for their cytotoxicity. Compounds 3, 10, and 14 showed some toxicity to the cancer cell lines, while compounds 2, 3, 10, 12, and 14 showed a moderate to weak cytotoxicity against the normal cell lines. Conclusion: All the compounds reported in this paper are known, except compound 11. They have been identified as new inhibitors of Adipogenesis. Adipogenesis is the process of adipocytes differentiation from pre-adipocytes. This extensively studied model of cell diff differentiation. Further synthetic modifications, and optimization of anti-adipogenic activity may lead to the development of anti-obesity agents.
- Siddiqui, Hina,Shafi, Sarah,Mukhtar, Farah,Ejaz, Asma,Atta-Ur-Rahman,Choudhary, M. Iqbal
-
p. 508 - 515
(2018/07/25)
-
- Palladium catalyzed carbonylative annulation of the C(sp2)-H bond of N,1-diaryl-1H-tetrazol-5-amines and N,4-diaryl-4H-triazol-3-amines to quinazolinones
-
Pd(ii) catalyzed direct C-H carbonylative annulation of N,1-diaryl-1H-tetrazol-5-amines and N,4-diaryl-4H-1,2,4-triazol-3-amines gave the corresponding triazole and tetrazole fused quinazolinones in good yields. This methodology offers a convenient method for the synthesis of these important heterocyclic scaffolds in a highly atom economical process. On the mechanistic aspect weakly nucleophilic triazole and tetrazole moieties function as both directing as well as intramolecular nucleophiles. The catalytically active C-H activated intermediate dimeric Pd complex was isolated and characterized which on exposure to CO gas gave the corresponding tetrazole fused quinazolinone derivative. On the basis of isolation of the intermediate and observed kinetic isotope effects, a mechanism has been proposed for the C-H activated direct carbonylative annulation reaction.
- Chandrasekhar, Attoor,Ramkumar, Venkatachalam,Sankararaman, Sethuraman
-
supporting information
p. 8629 - 8638
(2018/12/12)
-
- Nickle Catalysis Enables Access to Thiazolidines from Thioureas via Oxidative Double Isocyanide Insertion Reactions
-
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
-
supporting information
p. 7158 - 7162
(2018/11/25)
-
- Synthesis of thiazol, thiazinan, thiadiazin, thiazolidin, triazine, thioxo-pyrimidin and thioxo-imidazolidine by inter-intra molecular cyclization
-
Syntheses of five and six membered heterocyclic derivatives by the reaction of disubstituted thiocarbamides with interintramolecular cyclizations in catalyst free condition have been reported. The simple product isolation without column, good yields under mild condition, and applicable green matrix are the advantages of present protocol.
- Zade, Mangesh N.,Katiya, Manish M.,Deotale, Vinod D.,Sontakke, Madhuri M.,Dhonde, Madhukar G.,Berad, Baliram N.
-
p. 1493 - 1500
(2019/05/21)
-
- Base-controlled chemoselectivity reaction of vinylanilines with isothiocyanates for synthesis of quinolino-2-thione and 2-aminoquinoline derivatives
-
Here, we report a base-controlled chemo-selective reaction of vinylanilines with alkyl/aryl isothiocyanates to afford quinolino-2-thione and 2-aminoquinoline derivatives. The quinolino-2-thiones could be obtained in high yields in the presence of Et3N. Particularly interesting is that the reaction could produce the 2-aminoquinolines in the presence of K3PO4 with high selectivity.
- Zhang, Xi,Wang, Tong-Lin,Huo, Cong-De,Wang, Xi-Cun,Quan, Zheng-Jun
-
supporting information
p. 3114 - 3117
(2018/03/28)
-
- Novel self-condensation of ammonium dithiocarbamates leading to symmetrical substituted thioureas
-
For the first time, the formation of symmetrical substituted thiourea analogues generated by the selfcondensation of trialkylammoniumdithiocarbamates is reported. The reactions occurred under mild conditions. The method allows the use of amines possessing a weak nucleophilic feature in good yields. The highlight of the study is a novel self-condensation mechanism based on dithiocarbamates as a basic compound in organic chemistry.
- üng?ren, ?evket Hakan,S?r?a, Fatih
-
-
- A sulfur on behalf of the barbituric acid derivative for the probe molecule detecting secondary amine method and its preparation
-
The invention discloses a method for detecting secondary amine with thiobarbituric acid derivatives (TBAs) serving as ultraviolet-visible light (UV-vis) spectrophotometric method probe molecules and preparation of the thiobarbituric acid derivatives for detecting secondary amine. The probe molecules are prepared from primary amine through a preparation line of a system. The probe molecules are provided with a furan ring (or thiophene ring) for recognizing secondary amine, an independent probe molecule solution is yellow, and along with addition of secondary amine, the solution becomes red from yellow. A molecular probe is high in selectivity and sensitivity to secondary amine, the response range to secondary amine is 100 micrometers to 400 micrometers, and the limit of detection (LOD) is 12 micrometers. Test paper can be prepared from the probe molecules, and qualitative detection on secondary amine can be achieved fast with low cost. The method can be widely applied to fast and sensitive detection such as online detection of secondary amine compounds, food analysis and environmental monitoring in the industrial process.
- -
-
-
- Method for synthesizing accelerator DPTU
-
The invention discloses a method for synthesizing an accelerator DPTU. The method comprises the following steps of: mixing aniline with an alkali aqueous solution uniformly; dissolving sulfur in carbon disulfide, and mixing until the sulfur completely dissolves; mixing the two mixtures uniformly, and then carrying out the reaction under normal pressure to obtain the accelerator DPTU. The invention adopts alkali aqueous solution as the solvent, and needs not to add an emulsifier, the generated hydrogen sulfide gas is absorbed and removed immediately during the reaction, so that the reaction is carried out toward the positive reaction direction to a greater extent, the reaction rate and the aniline conversion rate are improved, the yield is increased, the hydrogen sulfide gas recovery is more complete, the generation of hydrogen sulfide waste gas is reduced, and the production conditions are greatly improved.
- -
-
Paragraph 0021; 0024; 0025; 0026; 0027; 0028; 0029-0034
(2017/04/11)
-
- Rapid and highly efficient synthesis of thioureas in biocompatible basic choline hydroxide
-
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
-
p. 548 - 554
(2017/09/27)
-
- Substituted thiazole ketones secreted aspartic protease inhibitors and its preparation method
-
The invention relates to a substituted thiazole ketones secretory aspartic protease inhibitor and a preparation method thereof, and particularly provides a novel thiazole ketones compound. The general structural formula of the novel thiazole ketones compound is shown as follows. The thiazole ketones compound is high in Sap2 enzyme inhibiting activity and nematode and mouse in-vivo antifungal activity, and has good antifungal medicine combination effect on fluconazole resistant bacteria, thereby being capable of being used for preparing medicine for preventing fungal infection or being combined with existing antifungal medicine. A new approach is created for deeply studying and developing novel antifungal medicine.
- -
-
Paragraph 0098; 0099
(2017/08/31)
-
- Antileishmanial thioureas: Synthesis, biological activity and in Silico evaluations of new promising derivatives
-
Leishmaniasis is a neglected tropical disease caused by protozoan parasites belonging to the genus Leishmania. Currently, the drugs available for treatment of this disease present high toxicity, along with development of parasite resistance. In order to overcome these problems, efforts have been made to search for new and more effective leishmanicidal drugs. The aim of this study was to synthesize and investigate the leishmanicidal effect of N,N′-disubstituted thioureas against Leishmania amazonensis, with evaluation of their in silico pharmacokinetics and toxicity profiles. Our results showed that different thioureas could be obtained in high to moderate yields using simple reaction conditions. Nine thiourea derivatives (3e, 3i, 3k, 3l, 3p, 3q, 3v, 3x and 3z) were active against parasite promastigotes (IC50 21.48–189.10μM), with low cytotoxicity on mice peritoneal macrophages (CC50>200μM), except for thiourea 3e (CC50=49.22μM). After that, the most promising thioureas (3k, 3l, 3p, 3q and 3v) showed IC50 ranging from 70 to 150μM against L. amazonensis amastigotes in infected macrophages. Except for thiourea 3p, the leishmanicidal activity of the derivatives were independent of nitric oxide (NO) production. Thioureas 3q and 3v affected promastigotes cell cycle without disturbing the mitochondrial membrane potential. Furthermore, our derivatives showed satisfactory theoretical absorption, distribution, metabolism, excretion, toxicity (ADMET) properties. These data indicate that thiourea derivatives are good candidates as leading compounds for the development of new leishmanicidal drugs.
- Viana, Gil Mendes,Do Amaral, Lilian Henriques,Meireles, Paloma Wetler,Nunes, Raquel Pinto,Da Silva, Luiz Cláudio Rodrigues Pereira,De Sousa, Valeria Pereira,Sathler, Plínio Cunha,Cabral, Lucio Mendes,Soares, Deivid Costa,Saraiva, Elvira Maria,Santana, Marcos Vinicius,Castro, Helena Carla,De Sequeira Aguiar, Lúcia Cruz,Rodrigues, Carlos Rangel,Abreu, Paula Alvarez
-
p. 911 - 919
(2018/10/31)
-
- Metal-Free Synthesis of 2-Aminobenzothiazoles via Iodine-Catalyzed and Oxygen-Promoted Cascade Reactions of Isothiocyanatobenzenes with Amines
-
In this paper, a highly efficient and sustainable synthesis of 2-aminobenzothiazoles through the cascade reactions of isothiocyanatobenzenes with primary or secondary amines by using iodine as a catalyst and oxygen as an oxidant is presented. Mechanistically, the formation of the title compounds involves the in situ formation of the required benzothiourea intermediate followed by its intramolecular cross dehydrogenative coupling of a C(sp2)-H bond and a S-H bond. To our knowledge, this should be the first example in which 2-aminobenzothiazoles are efficiently prepared from simple and cheap isothiocyanates and amines under metal-free conditions by using iodine as a catalyst and molecular oxygen as an oxidant with water as the byproduct. Compared with literature protocols, this method eliminates the use of ortho-halo-substituted precursors, expensive transition-metal catalysts, and hazardous oxidants.
- Xu, Yuanshuang,Li, Bin,Zhang, Xinying,Fan, Xuesen
-
p. 9637 - 9646
(2017/09/23)
-
- Dual roles of substituted thiourea as reductant and ligand in CuAAC reaction
-
A highly efficient catalytic system, CuSO4·5H2O/1-(4-methoxyphenyl)-3-phenylthiourea, for the copper(I)-catalyzed azide–alkyne cycloaddition reaction (CuAAC) was discovered. In the above catalytic system, substituted thiourea acts both as a reductant and a ligand. CuSO4·5H2O/1-(4-methoxyphenyl)-3-phenylthiourea is both an economical and efficient catalyst for the CuAAC reaction. In addition, the new catalytic system has advantageous features including mild and green reaction conditions, and broad substrate compatibility. A variety of 1,4-disubstituted 1,2,3-triazoles have been prepared with good to excellent yields with the CuSO4·5H2O/1-(4-methoxyphenyl)-3-phenylthiourea catalytic system in aqueous solution.
- Wang, Siyu,Jia, Kai,Cheng, Jiajia,Chen, Yu,Yuan, Yaofeng
-
supporting information
p. 3717 - 3721
(2017/09/01)
-
- Ph3P/I2-mediated synthesis of N,N′,N″-substituted guanidines and 2-iminoimidazolin-4-ones from aryl isothiocyanates
-
A convenient one-pot procedure for the synthesis of acyclic and cyclic guanidines mediated by the Ph3P/I2 system is described. Sequential condensation of aryl isothiocyanates with amines followed by dehydrosulfurization and guanylation could lead to both symmetric and unsymmetric N,N′,N″-substituted derivatives. Through a tandem guanylation-cyclization, a series of 2-iminoimidazolin-4-ones could also be prepared in good yields from the reaction of aryl isothiocyanates with amino acid methyl esters.
- Wangngae, Sirilak,Pattarawarapan, Mookda,Phakhodee, Wong
-
p. 10331 - 10340
(2018/05/31)
-
- Cadmium Bis(phenyldithiocarbamate) as a Nanocrystal Shell-Growth Precursor
-
Cadmium bis(phenyldithiocarbamate) [Cd(PTC)2] is prepared and structurally characterized. The compound crystallizes in the monoclinic space group P21/n. A one-dimensional polymeric structure is adopted in the solid state, having bridging PTC ligands and 6-coordinate pseudo-octahedral Cd atoms. The compound is soluble in DMSO, THF, and DMF and insoluble in EtOH, MeOH, CHCl3, CH2Cl2, and toluene. {CdSe[n-octylamine]0.53} quantum belts and Cd(PTC)2 react to deposit epitaxial CdS shells on the nanocrystals. With an excess of Cd(PTC)2, the resulting thick shells contain spiny CdS nodules grown in the Stranski-Krastanov mode. Stoichiometric control affords smooth, monolayer CdS shells. A base-catalyzed reaction pathway is elucidated for the conversion of Cd(PTC)2 to CdS, which includes phenylisothiocyanate and aniline as intermediates, and 1,3-diphenylthiourea as a final product.
- Morrison, Calynn E.,Wang, Fudong,Rath, Nigam P.,Wieliczka, Brian M.,Loomis, Richard A.,Buhro, William E.
-
p. 12920 - 12929
(2017/11/15)
-
- An isocyanide based multi-component reaction under catalyst- and solvent-free conditions for the synthesis of unsymmetrical thioureas
-
A new and efficient method for the synthesis of thiourea derivatives by a sequential one-pot, three-component reaction between aromatic isocyanides, amines, and 1,2-di-tert-butyldisulfane (DTBS) was developed and 27 different examples were synthesized in good to excellent yields. DTBS was identified as an effective sulfur surrogate without the use of both catalysts and solvents. This protocol does not employ any transition metal catalyst or special experimental setup.
- Singh, Karandeep,Sharma, Siddharth
-
p. 197 - 201
(2016/12/28)
-
- METHODS OF PRODUCING METAL SUFLIDES, METAL SELENIDES, AND METAL SULFIDES/SELENIDES HAVING CONTROLLED ARCHITECTURES USING KINETIC CONTROL
-
The present invention is directed to methods of preparing metal sulfide, metal selenide, or metal sulfide/selenide nanoparticles and the products derived therefrom. In various embodiments, the nanoparticles are derived from the reaction between precursor metal salts and certain sulfur- and/or selenium-containing precursors each independently having a structure of Formula (I), (II), or (III), or an isomer, salt, or tautomer thereof, where Q1,Q2,Q3,R1,R2,R3,R5, and X are defined within the specification.
- -
-
Paragraph 0204; 0205; 0207
(2017/05/28)
-
- Transamidation of primary carboxamides, phthalimide, urea and thiourea with amines using Fe(OH)3@Fe3O4 magnetic nanoparticles as an efficient recyclable catalyst
-
The highly efficient transamidation of primary amides, phthalimide, urea and thiourea with amines catalyzed by magnetic Fe(OH)3@Fe3O4 nanoparticles is described. This magnetic nanocomposite is able to catalyze transamidation reactions of a wide range of the above-mentioned substrates with amines, generating a new amide bond in moderate to good yields. The catalyst exhibited very good recyclability and reusability up to five runs without significant loss of its catalytic activity.
- Arefi, Marzban,Heydari, Akbar
-
p. 24684 - 24689
(2016/03/16)
-
- Hydroamination of carbodiimides, isocyanates, and isothiocyanates by a bis(phosphinoselenoic amide) supported titanium(IV) complex
-
The hydroamination of heterocumulenes such as carbodiimides, isocyanates, and isothiocyanates by a bis(phosphinoselenoic amide) supported titanium(iv) complex as a precatalyst is reported here. The titanium(iv) complex [{Ph2P(Se)NCH2CH2NPPh2(Se)}Ti(NMe2)2] (1) was synthesised by the reaction of tetrakis-(dimethylamido)titanium(iv) [Ti(NMe2)4] with [{Ph2P(Se)NHCH2CH2NHPPh2(Se)}] in toluene at ambient temperature. Titanium complex 1 proved to be a competent pre-catalyst for the addition of an amine N-H bond to carbodiimides, isocyanates, and isothiocyanates. The reaction scope was expanded to reactions of aliphatic and aromatic amines with phenylisocyanates and phenylisothiocyanates in toluene solvents proceeding rapidly at room temperature with 5 mol% catalyst loadings to yield the corresponding urea and thio-urea derivatives up to 99%. However, ambient temperature was needed for hydroamination of 1,3-dicyclohexylcarbodiimide. The amine addition reactions with isocyanates showed first order kinetics with respect to catalyst 1 as well as substrates. The most plausible mechanism for the hydroamination reaction was established by isolating 1,1-dimethylphenyl urea as a side product.
- Bhattacharjee, Jayeeta,Das, Suman,Kottalanka, Ravi K.,Panda, Tarun K.
-
supporting information
p. 17824 - 17832
(2016/11/18)
-
