Organic Reactions in Ionic Liquids:Ionic Liquid-promoted EfficientSynthesis of Disubstituted and Trisubstituted Thioureas Derivatives

In ionic liquid [Bmim][BF4], a series of disubstituted and trisubstituted thiourea derivativeswere synthesized from phenyl and butyl isothiocyanate with a variety of amine in excellent yield.

Novel chiral thioureas for highly enantioselective Michael reactions of malonates to nitroalkenes

Highly efficient Michael addition reactions of malonates to nitroalkenes catalyzed by novel chiral thioureas derived from optically pure BINOL and amino acids are reported. Various trans-nitroalkenes reacted with malonates affording the desired products in up to 95% yield with excellent enantioselectivities （up to 97% ee）.

A Rapid and Efficient Synthesis of Diaryl Thioureas via Solvent-Free Reaction Using Microwave

A rapid and efficient method for the preparation of diaryl thiourea compounds was reported for the first time. Twelve diaryl thiourea compounds that possessing biological activity have been synthesized in excellent yields (91-97%). The reaction proved to be extremely simple and highly efficient (in 1.5-4.5 min).

Facile Synthesis of Novel Chiral Bicyclic Thioureas and Their Crystal Structures

The novel well-defined chiral bicyclic thioureas based on enantiopure unsymmetric cis-2,5-disustituted pyrrolidine skeleton were firstly synthesized and fully characterized by their 1H NMR, 13C NMR and HRMS. Their absolute configurations were also determined by single-crystal X-ray analysis.

Camphor-derived thioureas: Synthesis and application in asymmetric Kabachnik-Fields reaction

A series of camphor-derived thiourea organocatalysts 3a–f were designed and synthesized from（1R,3S）-camphoric acid 1 and applied to the one-pot three-component Kabachnik–Fields reaction. Catalyst 3c was found to be an efficient organocatalyst for the reaction of 2-cyclopropylpyrimidin-4-carbaldehyde 4,various amines 5, and diphenylphosphite 6 to yield the corresponding enantioselective a-aminophosphonates 7a–e in 74%–82% yields and 14%–35% ee.

Synthesis and Insecticidal Activity of Novel N-Pyridylpyrazole Carbonyl Thioureas

A series of novel N-pyridylpyrazole carbonyl thioureas were designed and synthesized. Their structures were characterized by melting points, 1H NMR, IR and elemental analysis or HRMS. The bioassay tests indicated that some of these compounds exhibited moderate insecticidal activity against Mythirnna separata Walker and Culex pipiens pallens. Among 17 compounds, 5n and 5p showed 100% larvicidal activity against Mythimna separata Walker at the test concentration of 100 mg/L.

Design, Synthesis and Antifungal Activity of Novel Thioureas Containing 1,3,4-Thiadiazole and Thioether Skeleton

To find new lead compounds with high antifungal activity, a series of new thiourea derivatives containing 1,3,4-thiadiazole and thioether skeleton was designed via linking the active sub-structures. The target compounds were prepared via three steps from the commercially available thiosemicarbazide. Their structures were characterized by means of HRMS, IH NMR, 13C NMR and IR spectroscopy. The preliminary results indicate that the title compounds show various antifungal activity against the tested fungi. Compounds 4c, 4g, 4h, 4k, 4n, 4o, 4p, 4q and 4r display excellent antifungal activities against one or more tested fungi with inhibitory efficiencies of 90%--100% at 200 μg/mL. Especially, compound 4o shows the best inhibitory effect against Curvularia lunata, Cotton Fusarium Wilt, P P var nicotianae and Fusarium spp. with the EC50 values of 28.12, 30.41, 15.2 and 6.22 μg/mL, respectively, which are even superior to those of triadimefon（98.73, 96.58, 105.37 and 102.18 μg/mL）. The preliminary structure-activity relationship indicates that allyl and aromatic groups are favorable to their antifungal activities.

Thiourea crystal growth kinetics,mechanism and process optimization during cooling crystallization

In the cooling crystallization process of thiourea,a significant issue is the excessively wide crystal size distribution(CSD)and the abundance of fine crystals.This investigation delves into the growth kinetics and mechanisms governing thiourea crystals during the cooling crystallization process.The fitting results indicate that the crystal growth rate coefficient,falls within the range of 10^(-7)to 10^(-8)m·s^(-1).Moreover,with decreasing crystallization temperature,the growth process undergoes a transition from diffusion-controlled to surface reaction-controlled,with temperature primarily influencing the surface reaction process and having a limited impact on the diffusion process.Comparing the crystal growth rate,and the diffusion-limited growth rate,at different temperatures,it is observed that the crystal growth process can be broadly divided into two stages.At temperatures above 25℃,1/qd(qd is diffusion control index)approaches 1,indicating the predominance of diffusion control.Conversely,at temperatures below 25℃,1/qd increases rapidly,signifying the dominance of surface reaction control.To address these findings,process optimization was conducted.During the high-temperature phase(35-25℃),agitation was increased to reduce the limitations posed by bulk-phase diffusion in the crystallization process.In the low-temperature phase(25-15℃),agitation was reduced to minimize crystal breakage.The optimized process resulted in a thiourea crystal product with a particle size distribution predominantly ranging from 0.7 to 0.9 mm,accounting for 84%of the total.This study provides valuable insights into resolving the issue of excessive fine crystals in the thiourea crystallization process.

Improvement of octane number in FCC gasoline through the extraction with urea/thiourea complex based on property analysis

In the research described in this paper,the uses of the urea/thiourea complexation approach were employed to enhance the octane number of FCC gasoline by extracting n-alkanes.It was observed that adding thiourea improved the removal of the n-alkanes from gasoline,and matching results were obtained from experiments using model samples.Molecular dynamics simulation revealed that the stability of urea complexes increased as the carbon number of the n-alkanes was raised,whereas lighter n-alkane molecules exhibited a lower propensity for complex formation with urea.This finding is in agreement with the results of the DSC measurement at the decomposition temperature.Furthermore,infrared spectrum analysis,XRD characterization,and reaction heat measurements indicated that although thiourea was introduced into the reaction system,it did not actively participate in the complexation reaction.In summary,the introduction of thiourea resulted in an increased solubility of urea in an ethanol solution and enhanced the reaction heat,suggesting its beneficial role in promoting urea complex formation and facilitating n-alkane removal from FCC gasoline.

Continuous flow synthesis of PbS/CdS quantum dots using substituted thioureas

To enhance the reproducibility and scale up the synthesis of colloidal quantum dots(QDs),continuous flow synthesis is an appealing alternative to the widely used batch synthesis.Amongst other advantages,the strongly enhanced heat and mass transfer in small tubular reactors combined with controlled pressure can be cited.Nonetheless,the widespread use of this technique is hampered by special requirements such as the absence of solid or gaseous products and the room-temperature solubility of precursors.Therefore,the transfer of established reaction conditions from batch to flow is not straightforward and in most reported works the optical properties of the obtained QDs lag behind those prepared in batch reactions.This is also the case for PbS-based QDs,which are established near infrared(NIR)absorbers/emitters.Here we identified experimental conditions giving access to high-quality PbS core and PbS/CdS core/shell QDs obtained in an automated,easily scalable continuous flow synthesis.In particular,substituted thioureas have been selected as the sulfur source and ex-situ synthesized lead and cadmium oleate as the metal precursors,and appropriate solvent mixtures have been identified for each precursor.Highly luminescent PbS/CdS QDs emitting at the target wavelengths 940 and 1130 nm of special interest for NIR light-emitting diodes have been prepared,exhibiting a photoluminescence quantum yield up to 91%.

Tungsten carbide-reduced graphene oxide intercalation compound as co-catalyst for methanol oxidation

Highly dispersed tungsten carbide（WC） nanoparticles（NPs） sandwiched between few-layer reduced graphene oxide（RGO） have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The metatungstate ion,[H2W（12）O（40）]^6-,is assembled on thiourea-modified graphene oxide（GO） by an impregnation method.The WC NPs,with a mean diameter of 1.5 nm,are obtained through a process whereby ammonium metatungstate first turns to WS2,which then forms an intercalation compound with RGO before growing,in situ,to WC NPs.The Pt/WC-RGO electrocatalysts are fabricated by a microwave-assisted method.The intimate contacts between Pt,WC,and RGO are confirmed by X-ray diffraction,scanning electron microscope,transmission electron microscope,and Raman spectroscopy.For methanol oxidation,the Pt/WC-RGO electrocatalyst exhibited an electrochemical surface area value of 246.1 m^2/g Pt and a peak current density of1364.7 mA/mg Pt,which are,respectively,3.66 and 4.77 times greater than those of commercial Pt/C electrocatalyst（67.2 m^2/g Pt,286.0 mA/mg Pt）.The excellent CO-poisoning resistance and long-term stability of the electrocatalyst are also evidenced by CO stripping,chronoamperometry,and accelerated durability testing.Because Pt/WC-RGO has higher catalytic activity compared with that of commercial Pt/C,as a result of its intercalated structure and synergistic effect,less Pt will be required for the same performance,which in turn will reduce the cost of the fuel cell.The present method is facile,efficient,and scalable for mass production of the nanomaterials.

Synthesis of 4-methyl Guanidine Butyric Acid

N-methyl pyrrolidone,hydrochloric acid and thiourea dioxide were adopted as the raw material,and 4-methyl guanidine butyric acid was synthesized through two-step reaction.The optimum synthesis condition for the first step was as follows：n（N-methyl pyrrolidone）∶n（10% HCl）= 1∶2.0,reaction temperature 135 ℃,reaction time 5 h;at that moment,the yield of intermediate 4-methyl-amino butyric acid hydrochloride was 72.89%.The optimum synthesis condition for the second step was as follows：n（4-methyl-amino butyric acid hydrochloride）∶n（thiourea dioxide）= 1∶2.0,reaction temperature 25 ℃,reaction time 12 h,at that moment,the yield of target product was 82.68%.Structure characterization on the intermediates and the target products were carried out through Fourier transform infrared spectroscopy and elemental analysis.

Synthesis and X-ray Structural Studies of 2-(2-Benzofuroylimino)-3-aryl-4-phenyl-1,3-thiazolines

The synthesis for acyliminothiazolines by treatment of N, N□-substituted thioureas with α-bromoacetophenone under aqueous media was described. 2-（2-Benzofuroylimino）-3-aryl- 4-phenyl-1,3- thiazolines were characterized by infrared, NMR spectroscopy and elemental analysis. The single crystals of compounds 4a and 4b were grown by slow evaporation of 80% ethanol solution at room temperature. Compounds 4a and 4b crystallize in triclinic space group P1 and monoclinic space group P21/c, respectively.

Structural and Spectral Studies of Some Geometric Isomers of N-Pivaloyl-Nˊ-dichlorophenyl Thiourea

N-pivaloyl-Nˊ-（3,4-dichlorophenyl）thiourea （1）： monoclinic, P21/a, a=11.57（1）, b=9.278（8）, c=13.51（1）, β=103.85（1）°, V=1408（2）3 , Z=4, μ=0.598 mm-1 ; N-pivaloyl-N＇-（3,5- dichlorophenyl）thiourea （2）： monoclinic, P21/a, a=7.176（2）, b=16.441（4）, c=11.923（2）, β=92.48（1）°, V=1405.3（6）3 , Z=4, μ=0.600 mm-1 ; N-pivaloyl-Nˊ-（2,6-dichlorophenyl）thiourea （3）： orthorhombic, Pnma, a=26.79（1）, b=8.780（4）, c=5.955（3）, V=1400.7（11）3 , Z=4, μ=0.601 mm-1 . All three complexes have an intramolecular hydrogen bond between NˊH and the carbonyl oxygen. Solution 1H NMR studies （CDCl3） show the NH resonance considerable downfield for each thiourea and their positions, as well as that of NH, is affected by substituents on the phenyl ring.

Effect of N-substituents on performance of thiourea collectors by density functional theory calculations

Using density functional methods,some properties were studied such as the energies and compositions of frontier molecular orbitals and the atomic charges,which are related to the reactive behavior of thioureas containing different N-substituent groupings.The calculation results indicate that the N-substituent groupings have significant effect on the flotation performance of thiourea collectors.The order of electron-donating ability is N-propyl-N'-benzyl-thiourea(PBZYTU)>N-propyl-N'-ethyl-thiourea (PETU)>N-propyl-N'-allyl-thiourea(PALTU)>>N-propyl-N'-acetyl-thiourea(PACTU)>N-propyl-N'-ethoxycarbonyl-thiourea (PECTU)>N-propyl-N'-benzoyl-thiourea(PBZOYTU),and the order of feedback-electron-accepting ability is PBZOYTU> PACTU>PECTU>>PALTU>PETU>PBZYTU.This implies that PBZOYTU,PACTU or PECTU can react with copper atoms having(t2g) 6 (eg) 3Cu(II)or t 6e 4Cu(I)configuration on the surfaces of copper sulfide minerals through normal covalent bond and back donation covalent bond,and exhibit excellently collecting performance for copper sulfide minerals.These are consistent with the experimental data reported in the literatures.

SELECTIVE DISSOLUTION OF GOLD IN AN ALKALINETHIOUREA SOLUTION BY ELECTROLYSIS

Anodic polarization behavior of gold, silver, copper, nickel and iron in potentiostatic condition has been examined in an alkaline aqueous thiourea solution, where gold is hardly dissoluble normally. The addition of Na2SO3 into the solution can accelerate anodic dissolution of gold. The factors affecting selective dissolution of gold in the alkaline thiourea solution by electrolysis have been studied, and the optimum condition was obtained. In 0.1 mol/L thiourea solution of pH 12. 5 containing 0. 5 mol/L Na2SO3 and 2. 5% acetone, at the potential of 0. 34 V vs NHE, at the temperature of 323 K, the dissolved mass of gold anode with the exposed area of 1. 0 cm2 reached more than 300 mg·dm-3 within 30 min, and other metals such as silver, copper, nickel and iron could hardly dissolve.

DISSOLUTION THEORY OF GOLD IN ALKALINE THIOUREA SOLUTION(Ⅰ) Anodic Behavior on Gold in Alkaline Thiourea Solution Containing Na_2SO_3

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Dissolution theory of gold in alkaline thiourea solution(Ⅲ) ——Thermodynamics on dissolution of gold in alkaline thiourea solution containing Na _2SO_3

The oxidants of gold were investigated in an alkaline thiourea solution containing Na 2CO 3, in which Na 2S 2O 8 is a proper oxidant for dissolving gold because of in such homogeneous sulfur system coexisting complex agent, oxidant and stabilizing agent. The thermodynamic analyses were conducted on the dissolving of gold in the alkaline thiourea solution containing Na 2SO 3 by the oxidants oxygen or Na 2S 2O 8. The results show that the possibility of gold dissolution reduces with increasing pH value, while oxygen acts as oxidant; and when Na 2S 2O 8 acts as the oxidant of gold in the alkaline thiourea solution of pH 12.5, decomposition potential of thiourea decreases from the standard value 0.42 V to -0.32 V, also the dissolution trend of gold enhances with shifting the mix potential of the solution to the positive direction.

Resonance Raman Spectroscopic and Theoretical Study of Geometry Distortion of Thiourea in 2^1A State

The A-band resonance Raman spectra of thiourea were obtained in water and acetonitrile solution. B3LYP/6-311＋＋G（3df,3pd） and RCIS/6-311＋＋G（3df,3pd） calculations were done to elucidate the ultraviolet electronic transitions, the distorted geometry structure and the saddle point of thiourea in 21A excited state, respectively. The resonance Raman spectra were assigned. The absorption spectrum and resonance Raman intensities were modeled using Heller＇s time-dependent wavepacket approach to resonance Raman scattering. The results indicate that largest change in the displacement takes place with the C--S stretch mode u6 （｜△｜=0.95） and noticeable changes appear in the H5N3H6＋H8N4H7 wag v5 （｜△｜=0.19）, NCN symmetric stretch^-C--S stretch＋N3H6＋H8N4 wag v4 （｜△｜=0.18）, while the moderate intensities of 2-15 and 4-15 are mostly due to the large excited state frequency changes of v15, but not due to its significant change in the normal mode displacement. The mechanism of the appearance of even overtones of the S-CN2 out of plane deformation is explored. The results indicate that a Franck-Condon region saddle point is the driving force for the quadric phonon mechanism within the standard A-term of resonance Raman scattering, which leads to the pyramidalization of the carbon center and the geometry distortion of thiourea molecule in 21A excited state.

Flotation and electrochemical behaviors of chalcopyrite and pyrite in the presence of N-propyl-N′-ethoxycarbonyl thiourea

The characteristics of N-propyl-N′-ethoxycarbonyl thiourea（PECTU） were studied in the flotation experiments of chalcopyrite and pyrite compared with butyl xanthate（BX）. The interaction mechanism between mineral and PECTU was investigated according to zeta potential and electrochemistry measurements in the presence of PECTU. The results proved that PECTU performed a stronger ability to capture chalcopyrite and a better selectivity against pyrite. The zeta potential of chalcopyrite was positively shifted after interacting with PECTU, which indicated that the collector PECTU was obviously adsorbed on chalcopyrite surface. The cyclic voltammetry and Tafel curves results indicated that the oxidation and corrosion rates of chalcopyrite surface were limited in the presence of PECTU, while the effect of PECTU on pyrite in weak alkaline solution can be neglected basically according to the results of zeta potential and electrochemical tests.