29806-58-4

Upstream product

• 100-01-6 4-nitro-aniline 
• 2420-60-2 O-phenyl N-(4-nitrophenyl)thiocarbamate 
• 100-46-9 benzylamine 
• 622-78-6 Benzyl isothiocyanate 
• 2131-61-5 p-nitrophenyl isothiocyanate 

Downstream Products

• 76746-82-2 Benzyl-(4-nitro-phenyl)-carbodiimide 
• 13141-87-2 N-benzyl-N’-(4-nitrophenyl)urea 
• 76746-72-0 C₁₅H₁₅N₅O₂S*ClH 
• 76746-62-8 3-amino-5-benzylimino-4-p-nitrophenyl-4,5-dihydro-1,2,4-thiadiazole 

Relevant academic research and scientific papers

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).

Synthesis and molecular docking of N,N′-disubstituted thiourea derivatives as novel aromatase inhibitors

A three series of thioureas, monothiourea type I (4a–g), 1,4-bisthiourea type II (5a–h) and 1,3-bisthiourea type III (6a–h) were synthesized. Their aromatase inhibitory activities have been evaluated. Interestingly, eight thiourea derivatives (4e, 5f–h, 6d, 6f–h) exhibited the aromatase inhibitory activities with IC50 range of 0.6–10.2 μM. The meta-bisthiourea bearing 4-NO2 group (6f) and 3,5-diCF3 groups (6h) were shown to be the most potent compounds with sub-micromolar IC50 values of 0.8 and 0.6 μM, respectively. Molecular docking also revealed that one of the thiourea moieties of these two compounds could mimic steroidal backbone of the natural androstenedione (ASD) via hydrophobic interactions with enzyme residues (Val370, Leu477, Thr310, and Phe221 for 6f, Val370, Leu477, Ser478, and Ile133 for 6h). This is the first time that the bisthioureas have been reported for their potential to be developed as aromatase inhibitors, in which the 4-NO2 and 3,5-diCF3 analogs have been highlighted as promising candidates.

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.

One-Pot Synthesis of C2 Symmetric and Asymmetric N,N′,N″-Substituted Guanidines from Aryl Isothiocyanates and Amines

Highly substituted guanidines were conveniently prepared through a one-pot reaction between aryl isothiocyanates and amines mediated by the Ph3P-I2/Et3N system. The C 2-symmetric N,N′,N″-substituted guanidines were readily accessed using a 1:2 molar ratio of an aryl isothiocyanate and an amine; while sequential addition of two different amines in equimolar ratios gave rise to asymmetric derivatives. Both primary and secondary amines were found to react preferentially with electron-deficient aryl isothiocyanates, rapidly providing guanidines in good yields under mild conditions.

Convenient synthesis of unsymmetrical N,N′-disubstituted thioureas in water

A simple and convenient two-step method has been developed and used to synthesise 25 (4 of which are novel) unsymmetrical N,N′-disubstituted thioureas in water. Alkylamines or variously substituted arylamines reacted smoothly with phenyl chlorothionoformate at room temperature to form thiocarbamates, which were then reacted with another alkyl- or arylamine in water at reflux to afford the unsymmetrical N,N′-disubstituted thioureas in good to excellent yields. Mild conditions, simple work-up, high yields as well as using water as solvent are the major advantages of the method.

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.

A model for a solvent-free synthetic organic research laboratory: Click-mechanosynthesis and structural characterization of thioureas without bulk solvents

The mechanochemical click coupling of isothiocyanates and amines has been used as a model reaction to demonstrate that the concept of a solvent-free research laboratory, which eliminates the use of bulk solvents for either chemical synthesis or structural characterization, is applicable to the synthesis of small organic molecules. Whereas the click coupling is achieved in high yields by simple manual grinding of reactants, the use of an electrical, digitally controllable laboratory mill provides a rapid, quantitative and general route to symmetrical and non-symmetrical aromatic or aromatic-aliphatic thioureas. The enhanced efficiency of electrical ball milling techniques, neat grinding or liquid-assisted grinding, over manual mortar-and-pestle synthesis is demonstrated in the synthesis of 49 different thiourea derivatives. Comparison of powder X-ray diffraction data of mechanochemical products with structural information found in the Cambridge Structural Database (CSD), or obtained herein through single crystal X-ray diffraction, indicates that the mechanochemically obtained thiourea derivatives are pure in a chemical sense, but can also demonstrate purity in a supramolecular sense, i.e. in all structurally explored cases the product consisted of a single polymorph. As an extension of our previous work on solvent-free synthesis of coordination polymers, it is now demonstrated that such polymorphic and chemical purity of selected thiourea derivatives, the latter being evidenced through quantitative reaction yields, can enable the direct solvent-free structural characterization of mechanochemical products through powder X-ray diffraction aided by solid-state NMR spectroscopy.

Isoprenyl-thiourea and urea derivatives as new farnesyl diphosphate analogues: Synthesis and in vitro antimicrobial and cytotoxic activities

A series of new isoprenyl-thiourea and urea derivatives were synthesized by the reaction of alkyl or aryl isothiocyanate or isocyanate and primary amines. The structures of the compounds were established by 1H NMR, 13C NMR, MS, HRMS

A simple and green procedure for the synthesis of N-benzylthioureas

A simple and efficient reaction protocol for the synthesis of N-benzylthioureas is described from benzylisothiocyanate (BITC: 94% pure/GC-MS), isolated from crushed papaya seeds.

The Kinetics and Mechanism of Aminolysis of Isothiocyanates

A study of the kinetics of aminolysis of p-nitrophenyl isothiocyanate by n-butylamine, benzylamine, dibenzylamine, p-anisidine, m-toluidine, N-methylaniline, and p-chloroaniline in diethyl ether and isooctane as solvents has shown that many of the reactio