Thiocarbohydrazide Research Articles

Thiocarbohydrazide-cross-linked pectin: A promising support material for palladium nanoparticles in the water-mediated Suzuki-Miyaura cross-coupling reaction and the catalytic reduction of 4-nitrophenol

Suzuki-Miyaura reaction is a classic palladium-catalyzed reaction for forming Csp2-Csp2 bonds. However, the leaching of Pd species and using organic solvents are two important problems that adversely affect their performance, reusability, and greenness. Considering the abundant resources, cheapness, and availability of pectin (Pec), a Pec-based catalyst for the Suzuki reaction in pure water as a non-toxic reaction medium was developed for the first time. In this regard, Pec was chosen as a benign support and cross-linked by thiocarbohydrazide (TCH) to prepare Pec-TCH. The Pec-TCH acted as an efficient reducing and stabilizing agent for in-situ fabrication of Pd(0) nanoparticles. The heterogeneous and air-stable Pec-TCH-Pd(0) nanoparticles were thoroughly characterized. The results exhibited a significant catalytic activity (up to 99%) and reusability (at least 7 times) for in-water Suzuki-Miyaura cross-coupling reaction. The use of TBAB as a phase-transfer catalyst improved the yield of Suzuki reaction since it prevented the problems related to the immiscibility of water and aryl halides as well as the gelation of catalyst. The catalyst was also utilized for water-mediated 4-nitrophenol reduction to 4-aminophenol with NaBH4 which showed excellent activity (k = 9.2 × 10−3 s−1). A very good compatibility with iodobenzene, bromobenzene, and chlorobenzene was observed for the Suzuki reaction. Because of various binding sites such as amino, hydroxyl, carbonyl and thiocarbonyl groups, negligible leach of Pd nanoparticles was observed, as shown by ICP-MS after runing 7th of reusability studies. Moreover, the leaching, mercury poisoning, and large-scale tests showed its potential for industrial applications.

Kinetics and oxidation of thiocarbohydrazide by hexacyanoferrate(III) in aqueous perchloric acid medium

Hexacyanoferrate(III) [HCF(III)] was used to oxidize thiocarbohydrazide (TCH) in an aqueous perchloric acid (HClO4) medium, and the reaction kinetics were studied spectrophotometrically at 420 nm while keeping a constant ionic strength of 1.0 mol dm−3 and modulating the temperature between 298K–318K. The stoichiometry of the reaction among TCH and HCF in the HClO4 medium is 1:2. The reaction has a lower than unit order in both TCH and HClO4 and is of the first order in HCF. The impact of varying the ionic strength and dielectric constant of the medium on the rate has been investigated. The effect of temperature on the reaction rate was studied, and different activation parameters of reaction Ea, ΔH#, ΔS#, ΔG#, and log10 A were calculated. The products of oxidation were analyzed by simple qualitative analysis. On the basis of the collected data, the rate law has been derived, and a probable mechanism has been proposed.

Design and Facile Synthesis of Spiro-s-tetrazine Derivatives of 2,4- diphenyl-3-azabicyclo[3.3.1]nonane-9-one.

Literature survey suggested various methods of synthesis of the 3- azabicyclo [3.3.1] nonanes which include, Mannich reaction, α, α'-Annelation of Cyclic Ketones or through Enamines, Michael addition, Intramolecular Cyclizations, etc. However, a mechanism following a Michael addition path through the formation of the dibenzylidene cyclohexanone intermediate can not be ignored. Thus to ensure the mechanistic pathway for the formation of 2,4-diphenyl- 3-azabicyclo[3.3.1]nonan-9-one and to understand the reactivity of a conformationally and biologically important molecule for the synthesis of spiro-s-tetrazine derivatives and its further functionalization with thiazole and thiazolidinone derivatives the present work has been undertaken. Direct reaction of dibenzylidene cyclohexanone and ammonium acetate has been tried to get the confirmation of Mannich/ Michael reaction pathway for the formation of 2,4-diphenyl-3- azabicyclo[3.3.1]nonan-9-one. Synthesis of the spiro-s-tetrazine derivative has been accomplished by the simple condensation reaction of azabicyclic system and thiocarbohydrazide (TCH). Simple methods have been adopted for the installation of heterocyclic moieties like thiazolidinone, thiazole. Failure of the attempts to prepare 2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-onedirectly from dibenzylidene cyclohexanone ruins the possibility of Michael addition reaction and supports the formation of the product through Mannich reaction. Synthesis of the spiro derivatives containing tetrazine, thiazole, thiazolidinone moieties were achieved by using simple techniques and products were obtained in good yield. FTIR, NMR spectroscopy are used for the characterization of all the molecules. Formation of 2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-onewas confirmed by using some additional data like mass and single crystal XRD. Confirmation of the mechanistic route for the 2 2,4-diphenyl-3- azabicyclo[3.3.1]nonan-9-one was achieved and simple methods for the formation of spiro derivatives containing tetrazine, thiazole, thiazolidinone were established.

Effect of the addition of silver nanoparticles on the biological activity of thiocarbohydrazide derivatives

Thiocarbohydrazide (TCH) derivatives [(II), (III) and (IV)] were prepared and characterized by X-RAY diffraction (XRD), infra-red spectrum (FTIR). Also silver nanoparticles was prepared by chemical reduction and characterized by X-RAY diffraction (XRD), infra-red spectrum (FTIR), atomic force microscope (AFM) and scanning electron microscope (SEM). Thiocarbohydrazide derivatives were functionalized with silver nanoparticles by sonication. The pure and functionalized TCH derivatives were used to study the biological activity against Staphylococcus aureus bacteria. The functionalized compounds with Ag nanoparticles have more Inhibition effect against Staphylococcus aureus than unfunctionalized compounds due to the small size and high surface area of Ag nanoparticles.

Spectroscopic characterization, molecular docking and machine learning studies of sulphur containing hydrazide derivatives.

Machine learning applied in chemistry is a growing field of research. For assessing structure-property variations, this paper describes in silico studies of the hydrazide derivatives of thiosemicarbazide (TSCZ) and thiocarbohydrazide (TCHZ). The structures of TSCZ and TCHZ have been elucidated using modern spectroscopic techniques. The UV-vis spectra showed strong charge transfer transitions (π-π*) for TSCZ and TCHZ with high extinction coefficients. The NBO analysis showed orbital overlap between lp1 (N2) and σ* (C3-S4) in TSCZ and TCHZ due to intramolecular charge transfer. The first hyperpolarizabilities (β0) for TSCZ and TCHZ were found to be 0.7155 and 2.1615 × 10-30 esu, respectively, indicating their greater suitability for NLO applications as compared to standard reference urea. The strong electrophilic behaviour of TSCZ and TCHZ has been indicated by their global elecrophilicity index. The electrophilic reactivity descriptor analysis indicated that the investigated molecules could serve as precursors for the targeted synthesis of new heterocyclic derivatives. The docking studies showed appreciable binding energies with target proteins having PDB IDs 2WJE and 6CLU of Gram-positive bacteria, namely, Streptococcus pneumoniae phosphatase (PTP-CPS4B) and Staphylococcus aureus dihydropteroate synthase (saDHPS), respectively, for TSCZ and TCHZ, predicting good antimicrobial activity.

A novel Fe3O4@TCH@Ni(II) nanoparticle: An efficient magnetically retrievable nanocatalyst for C–C and C–heteroatom bond formation reaction

Layered Ni(II) complex on magnetic nanoparticle as heterogeneous, efficient, novel, green, and reusable catalyst was used to cross‐coupling reaction, including carbon–carbon, carbon–nitrogen, and carbon–oxygen formations. The covalent functionalization of organic ligand, thiocarbohydrazide (TCH), on the surface of magnetic nanoparticle (Fe3O4) was determined that leading to an exceptional adsorptive ability for supporting Ni(II). The magnetic nano‐composite was characterized and investigated by using Fourier‐transform infrared spectroscopy (FT‐IR), thermogravimetric analysis (TGA), energy dispersive X‐ray (EDX), X‐ray diffraction (XRD), scanning electron microscope (SEM), inductively coupled plasma–optical emission spectrometry (ICP‐OES), transmission electron microscopy (TEM), and Brunauer–Emmett–Teller (BET). Also, three cross‐coupling reactions in the presence of Fe3O4@TCH@Ni(II) were optimized in terms of temperature, amount of catalyst, solvent, and time.

Cu/TCH-pr@SBA-15 nano-composite: a new organometallic catalyst for facile three-component synthesis of 4-arylidene-isoxazolidinones.

A copper complex supported on SBA-15 nanoparticles (Cu/TCH-pr@SBA-15) was synthesized by the post-synthesis modification of nano-mesoporous silica with 3-chloropropyltriethoxysilane (CPTES) and thiocarbohydrazide (TCH) and subsequent metal–ligand coordination with Cu(ii). These nanocomposites were thoroughly characterized by FT-IR spectroscopy, TEM, FE-SEM, EDX, atomic absorption spectroscopy and N2 adsorption–desorption (BET) studies. Then, a solvent-free method was developed for the three-component synthesis of 4-arylidene-isoxazolidinones via condensation of hydroxylamine hydrochloride, ethyl acetoacetate and various aromatic aldehydes using Cu/TCH-pr@SBA-15 as a highly efficient nanocatalyst. This new economic and eco-friendly methodology has remarkable advantages such as excellent yields, a shorter reaction time, an easy purification procedure, simplicity, green conditions, solvent-free conditions, and recoverability of the nanocatalyst.

Synthesis of new TCH/Ni‐based nanocomposite supported on SBA‐15 and its catalytic application for preparation of benzimidazole and perimidine derivatives

A stable nickel‐decorated SBA‐15 nanocomposite (Ni/TCH@SBA‐15) was synthesized through surface modification of silica nanoparticles with 3‐chloropropyltriethoxysilane (CPTES) and thiocarbohydrazide (TCH) followed by metal–ligand coordination with Ni (II). The structure of this organometallic nanocomposite was characterized by Fourier transform‐infrared, field emission‐scanning electron microscopy, EDAX, transmission electron microscopy, atomic absorption spectroscopy and N2 adsorption–desorption (Brunauer–Emmett–Teller) techniques. The catalytic performance of Ni/TCH@SBA‐15 (NNTS‐15) was determined for the synthesis of 2‐aryl‐substituted benzimidazoles and 2,3‐dihydroperimidines. The excellent yields within shorter reaction times, simplicity of catalytic methods, non‐toxicity and clean reactions, mild reaction conditions and easy work‐up procedure are the important merits of these synthetic protocols. Moreover, the Ni (II) bonded to the SBA‐15 surface was stable under the catalytic reaction conditions resulting in its efficient recycling and reuse.

Performance Analysis of Thiocarbonohydrazide as a Novel Selective Depressant for Chalcopyrite in Molybdenite-Chalcopyrite Separation

A novel surfactant, thiocarbonohydrazide (TCH), was synthesized and tested for the first time as a selective chalcopyrite depressant in Cu-Mo separation. Its adsorption mechanisms on chalcopyrite were studied by flotation tests, zeta potential, FTIR, XPS and ToF-SIMS measurements. FTIR and zeta potential analyses suggested that there was a strong chemisorption reaction between TCH and chalcopyrite, resulting in the formation of TCH–copper complexes. XPS and ToF-SIMS measurements further confirmed the chemisorption of TCH onto the chalcopyrite surface and showed that this chemisorption reaction is due to its S and N atoms, which form five-membered chelating rings by releasing H ions.

Addition of Some Primary and Secondary Amines to Graphene Oxide, and Studying Their Effect on Increasing its Electrical Properties

Previously many properties of graphene oxide in the field of medicine, biological environment and in the field of energy have been studied. This diversity in properties is due to the possibility of modification on the composition of this Nano compound, where the Graphene oxide is capable of more modification via addition other functional groups on its surface or at the edges of the sheet. The reason for this modification possibility is that the Sp3 hybridization (tetrahedral structure) of the carbon atoms in graphene oxide, and it contains many oxygenic functional groups that are able to reac with other groups. In this research the effect of addition of some amine compounds on electrical properties of graphene oxide has been studied by the preparation of graphene oxide - amino containing compound, which could be classified under Nano carbon compounds containing nitrogen (N-doped carbon nanomaterials). These amines are used as expanders for the distance between the layers of graphene oxide (spacers), and thus prevent agglomeration of graphene oxide layers in addition to enhanced electric properties of graphene oxide. The following amines (thiocarbohydrazide(TCH),o-phenylenediamine(oPD) and poly aniline(PAni)) were used for the preparation of the corresponding amino graphene oxide (GO-TCH, GO-containing Benzoimidazol & benzoxazole, and GO-PAni), and characterized by X-RAY diffraction (XRD) ,infra red spectrum (FTIR) and atomic force microscope (AFM) , also the electrical properties of these materials were studied using inductance, capacitance, and resistance ( LCR) measurements.

Addition of Some Primary and Secondary Amines to Graphene Oxide, and Studying Their Effect on Increasing its Electrical Properties

Previously many properties of graphene oxide in the field of medicine, biological environment and in the field of energy have been studied. This diversity in properties is due to the possibility of modification on the composition of this Nano compound, where the Graphene oxide is capable of more modification via addition other functional groups on its surface or at the edges of the sheet. The reason for this modification possibility is that the Sp3 hybridization (tetrahedral structure) of the carbon atoms in graphene oxide, and it contains many oxygenic functional groups that are able to reac with other groups. In this research the effect of addition of some amine compounds on electrical properties of graphene oxide has been studied by the preparation of graphene oxide - amino containing compound, which could be classified under Nano carbon compounds containing nitrogen (N-doped carbon nanomaterials). These amines are used as expanders for the distance between the layers of graphene oxide (spacers), and thus prevent agglomeration of graphene oxide layers in addition to enhanced electric properties of graphene oxide. The following amines (thiocarbohydrazide(TCH),o-phenylenediamine(oPD) and poly aniline(PAni)) were used for the preparation of the corresponding amino graphene oxide (GO-TCH, GO-containing Benzoimidazol & benzoxazole, and GO-PAni), and characterized by X-RAY diffraction (XRD) ,infra red spectrum (FTIR) and atomic force microscope (AFM) , also the electrical properties of these materials were studied using inductance, capacitance, and resistance ( LCR) measurements.

Computer-aided sensor design and analysis of thiocarbohydrazide in biological matrices using electropolymerized-molecularly imprinted polypyrrole modified pencil graphite electrode

Abstract In this work, molecularly imprinted polymer (MIP) of thiocarbohydrazide (TCH) was prepared through electropolymerization and electrodeposition of pyrrole on a pencil graphite electrode. The ability of the fabricated MIP to act as a sensor of determining TCH in a few biological matrices was investigated. Preparation of MIP and quantitative measurements were performed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), respectively. Several important parameters controlling the performance of the polypyrrole and the method efficiency were investigated and optimized. The molecularly imprinted layer exhibited selectivity and sensitivity toward TCH. The selection of monomer was performed computationally using ab initio calculations. A computational study based on restricted MP2 was performed to evaluate the template–monomer geometry and interaction energy in the prepolymerization mixture. The calibration curve demonstrated linearity over a concentration range of 0.5–6 mM with a correlation coefficient ( r 2 ) of 0.9805. The detection limit of TCH was obtained 5.0 × 10 −5 M.

Biological evaluation of some triazole and triazolothiadiazine derivatives

ABSTRACT: Triazole and triazoles fused with six-membered ring systems are found to possess diverse applications in the field of medicine, agriculture and industry. The 1,2,4-triazole and 1,2,4-triazolo[3,4-b][1,3,4]thiadiazines derivatives were synthesized as cholinesterase inhibitors. The reaction of 1H-indol-3-acetic acid with thiocarbohydrazide gave the 4-amino- 3-mercapto-5-[(1H-indol-3-yl)methyl]-4H-1,2,4-triazole. The reaction of triazole with arylaldehydes in ethanol gave the 4-arylideneamino-3-mercapto-5-[(1H-indol-3-yl)methyl]-4H- 1,2,4-triazoles. The 3-[(1H-indol-3-yl)methyl]-6-aryl-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines were obtained by condensing triazole with phenacylbromides in absolute ethanol. The chemical structures of the compounds were elucidated by IR, 1H-NMR and FAB+-MS spectral data and elemental analysis. Each derivative was evaluated for its ability to inhibit acetylcholinesterase (AChE) using a modification of Ellman’s spectrophotometric method. Compounds 1b and 1c can be identified as promising anticholinesterase agents due to their inhibitory effect on AChE with IC50 value of 96.45±8.14 and 76.24±6.42 μM respectively when compared with Donepezil (IC50 =0.056±0.001μM). KEY WORDS: Indole, triazole, triazolothiadiazine, cholinesterase inhibitors

Physicochemical study of new polydentane ligand systems based on 2,6-diformyl-4-tert-butylphenol

New polydentate ligand systems, products of condensation of 2,6-diformyl-4-tert-butylphenol with 1,3-diaminopropanol-2 and carbo(thiocarbo)hydrazide, were synthesized and their structure was determined based on the data of elemental analysis, 1H NMR and IR spectroscopy. The acid-base properties of bisazomethine I have been studied. Spatial structure and spectral properties of the ligand system were simulated using quantum-chemical calculations.

Schiff-염기인 옥타아자-거대고리 리간드의 UO2(VI), Th(IV), ZrO(IV) 및 VO(IV) 착물 합성 및 특성

A series of macrocyclic complexes of the type [M(L/L')(NO 3 ) n ].mH 2 O and [VO(L/L')(SO 4 )].2H 2 O, where L/L' is a Schiff base 3,4,10,11-tetraphenyl/tetramethyl-1,2,5,6,8,9,12,13-octaaza cyclotetradeca-2,4,9,11-tetraene-7,14-dithione derived from thiocarbohydrazide (TCH), benzilmonohydrazone (BMH)/diacetylmonohydrazone (DMH) and carbon disulphide, M = UO 2 (VI), Th(IV) and ZrO(IV), n = 2, 4, m = 2, 3, have been synthesized via metal ion template methods. The complexes are characterized on the basis of elemental analysis, thermal analysis, molar conductivity, magnetic moment, electronic, infrared and 1 H-NMR spectral studies. The ESR and cyclic voltammetry studies of the vanadyl complexes have been carried out. The results indicate that the VO(IV) ion is penta-coordinated yielding paramagnetic complexes; UO 2 (VI) and ZrO(IV) ions are hexa-coordinated where as Th(IV) ion is octa-coordinated yielding diamagnetic complexes of above composition.

Effect of protonation on the inhibition efficiency of thiourea and its derivatives as corrosion inhibitors

PurposeThioureas (TUs) have been studied extensively, but their inhibition mechanism is not fully understood. Experimental results and theoretical calculations were used to investigate the effect of TU and its derivatives on the corrosion reaction of mild steel in 1 M H2SO4 at 40°C. An attempt was made to correlate some molecular parameters of these compounds with their corrosion inhibitor efficiency.Design/methodology/approachThe influence of the additives' N‐substituted derivatives of TU such as methylthiourea (MTU), phenylthiourea (PHTU), thiosemicarbazide (TSC) and thiocarbazide (TC) on the dissolution process of the specimen in sulphuric acid was monitored chemically by hydrogen evolution measurements.FindingsThe results show that inhibitor efficiency increased with increase in inhibitor concentration. The protonation process appeared to be the effective parameter with lowering of the inhibition efficiency. Alkyl N‐substituted TU with the least protonation and with the maximum adsorption was a better inhibitor than TU and aryl N‐substituted TU. The thiocarbazide molecule showed less efficiency with the highest protonation due to high charge density on the sulphur atom as well as lengthening and weakening of the C‐ S bond than the thiosemicarbazide.Originality/valueThe paper provides useful information relative to the corrosion inhibition efficiency of N‐substituted TU. It presents the experimental results and theoretical calculations that were used to investigate the effect of derivatives TU on their inhibition efficiency.

3-(2,4-Dichlorophenyl)-4-[(1E)-(2,4-dichlorophenyl)methyleneamino]-4,5-dihydro-1H-1,2,4-triazole-5-thione dimethylformamide solvate

The title triazole compound, C15H8Cl4N4S·C3H7NO, has been obtained as an unexpected product when attempting to prepare Schiff bases of thio­carbohydrazide (TCH). The triazole ring is planar within 0.004 (8) Å because of conjugation. The dihedral angles between the 1,2,4-triazole ring and the two benzene rings are 24.9 (2) and 70.0 (2)°. The interplanar angle between the two benzene rings is 83.4 (2)°. The packing of the mol­ecules is stabilized both by van der Waals interactions and by N—H⋯O intermolecular hydrogen bonds between the triazole N atom and the carbonyl O atom of the di­methyl­form­amide solvent mol­ecule.

Ultrastructure and function of Sertoli cell processes in the Korean native goat.

The ultrastructure of Sertoli cell in the testes of Korean native goats was investigated by scanning and transmission electron microscopy to elucidate the relationship between germ cell and Sertoli cell processes in the spermiogenetic cycle. Type-A Sertoli cells at stage V of the spermiogenetic cycle and type-B Sertoli cells at stage VII of the spermiogenetic cycle were used for analysis. Morphologically, the Sertoli cell processes were classified into sheet-like and slender cord-like processes. The sheet-like process originated solely from the Sertoli cell column while the slender cord-like process projected either from the Sertoli cell column or the sheet-like process. Periodic acid (PA)-thiocarbohydrazide (TCH)-silver protein (SP)-physical development (PD)-positive granules were found diffusively both in the sheet-like and slender cord-like processes near the round spermatid, whereas they had accumulated near the head of the elongated spermatid. The morphological variation and glucoconjugate histochemical reaction of the Sertoli cell processes reflect nourishment, movement and transformation of the spermatogenic cells in accordance with spermiogenesis.

Mechanistic studies on the effect of ferrocene bonding agents in composite solid propellents

Five compounds, viz. 1,1'-ferrocenediyldiethylidene bis(thiocarbonohydrazide) (DAFT), 1,1-diacetylferrocene disemicarbazone (DAFS), 1,1-diacetylferrocenebenzoyl hydrazone (FDBAH), 1,1-diacetylferrocene- p-nitrobenzoyl hydrazone (FDNBAH), and p-toluenesulfonic acid 1,1'-ferrocenediyldiethylidene dihydrazide (TFDD) were found to be bonding agents as well as burning-rate modifiers for the ammonium perchlorate + hydroxy-terminated polybutadiene system. The tensile strength and percentage elongation significantly increased in the presence of these bonding agents (except FDBAH). The bonding agents generally did not adversely affect the slurry viscosity during processing. The bonding sites were located by infrared spectroscopy, supported by determination of the dissolution kinetics of the bonding agents and scanning electron microscopy. The bonding agents did not undergo any side-reactions with the curing agents.

Comparison ofmalusinfection by the pathogenerwinia amylovoraand colonisation by the saprophyteerwinia herbicolaby electron microscopy

Abstract Erwinia amylovora infection of either apple stem or leaf tissue resulted in xylem occlusion by a fibrillar matrix material, determined by Thiery’ s thiocarbohydrazide (TCH) test to be the extracellular polysaccharide from E. amylovora. Plasmolysis of the xylem‐parenchyma was also detected and was most likely a result of a toxin produced by the pathogen. This plasmolysis resulted in the collapse and death of the cell. An Erwinia herbicola isolate which had previously expressed inhibitory effects on E. amylovora was contained at the site of inoculation.