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.

Role of foliar spray of plant growth regulators in improving photosynthetic pigments and metabolites in Plantago ovata (Psyllium) under salt stress–A field appraisal

Salinity is one of the major abiotic factors that limit the growth and productivity of plants.Foliar application of plant growth regulators(PGRs)may help plants ameliorate the negative impacts of salinity.Thus,a field experiment was conducted at the Botanical Garden University of Balochistan,Quetta,to explore the potential role of PGRs,i.e.,moringa leaf extract(MLE;10%),proline(PRO;1μM),salicylic acid(SA;250μM),and thiourea(TU;10 mM)in ameliorating the impacts of salinity(120 mM)on Plantago ovata,an important medicinal plant.Salinity hampered plant photosynthetic pigments and metabolites but elevated oxidative parameters.However,foliar application of PGRs enhanced photosynthetic pigments,including Chl b(21.11%),carotenoids(57.87%)except Chl a,activated the defense mechanisms by restoring and enhancing the metabolites,i.e.,soluble sugars(49.68%),soluble phenolics(33.34%),and proline(31.47%),significantly under salinity stress.Furthermore,foliar supplementation of PGRs under salt stress led to a decrease of about 43.02%and 43.27%in hydrogen peroxide and malondialdehyde content,respectively.Thus,PGRs can be recommended for improved photosynthetic efficiency and metabolite content that can help to get better yield under salt stress,with the best and most effective treatments being those of PRO and MLE to predominately ameliorate the harsh impacts of salinity.

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.

GRAFT COPOLYMERIZATION OF VINYL MONOMERS ONTO STARCH INITIATED BY TRANSITION METAL-THIOUREA REDOX SYSTEMS

In this paper, the capabilities of grafting acrylonitrile (AN) onto starch initiated by Fe(III)-TU, V(V)-TU, Cr(VI)-TU, Mn(VII)-TU redox systems were compared in the presence of sulfuric acid of different concentrations. It was shown that the grafting capability of Mn(VII)-TU is the highest in these initiating systems. Using Mn (VII-TU as initiator, the effects of various acids (HClO4, H2SO4, HNO3, HCl) on the graft copolymerization of acrylonitrile onto starch were discussed, and the capabilities of graft copolymerization of methyl methacrylate (MMA), acrylamide (AM), acrylic acid (AA) onto starch were investigated. The experimental results show that the order of the influences of different acids is HClO4 > H2SO4 > HNO3 > HCl, and the order of grafting capabilities of different monomers grafted onto starch is MMA > AN > AM > AA. The structure and morphology of graft, copolymers were studied with infrared spectroscopy and scanning electron microscopy. The size, shape and roughness of surface of the grafted starch granules are changed after grafting.

High adsorption of Cd(Ⅱ)by modification of synthetic zeolites Y,A and mordenite with thiourea

Zeolites Y,A and mordenite(ZY,ZA and ZM)were obtained from diatomite in a template-free system,and the products were modified by thiourea(TU).Characterization studies results indicated that the TU molecules were loaded onto the exterior surfaces of the synthetic zeolites as well as the channels.Elemental analysis and energy-dispersive X-ray spectrometer proved that the TU molecules loaded on to ZA were more than ZY and ZM.Removal of Cd(Ⅱ)was investigated,and itwas found that themodified zeolites have higher removal capacity,modified ZA is especially noticeable.In the adsorption experiments,the effects of various parameters such as sorbent content,contact time,concentration of cadmium solution,pH,selectivity and regeneration were discussed.At the best removal efficiency by modified zeolites,the maximum adsorption capacity is 94.3 mg·g^−1,103.2 mg·g^−1 and 89.7 mg·g^−1 at 25℃,respectively.The sorbents show good efficiency for the removal of Cd(Ⅱ)in the presence of different multivalent cations and have good regeneration effect.For the modified samples,removal experiments take place via ion exchange and complexation processes.

Optimization of efficient stable reagent of alkaline thiourea solution for gold leaching

Na2SiO3 and Na2SeO3 were chosen as stable reagents of alkaline thiourea solution substituting Na2SO3, according to the structure-property relationship between the stability of alkaline thiourea and the structure of thiourea and sulfite ion, and the effect of the stable reagents on stability of alkaline thiourea was investigated. The results show that contrary to Na2SeO3, Na2SO3 and Na2SiO3 affect the stability of alkaline thiourea solution remarkably. The stable effect of Na2SiO3 on alkaline thiourea is obviously better than that of Na2SO3. The stable reagents Na2SO3 and Na2SiO3 decrease the decomposition rate of alkaline thiourea solution greatly, and the decomposition rate of alkaline thiourea reduces from （72.5%） to （33.8%） with addition of (0.3 mol·L-1) Na2SiO3. Dissolution currents of gold in the alkaline thiourea solution containing Na2SO3 and Na2SiO3 are （2.0） (mA·cm-2) and （3.5） (mA·cm-2) at the potential of 0.42 V, respectively, and Na2SO3 is consumed excessively due to the oxidation reaction of Na2SO3 occurring in the studied potential range. Na2SiO3 is an efficient stable reagent of alkaline thiourea solution, and gold dissolution is accelerated much more obviously by Na2SiO3 than by Na2SO3.

Determination of the metastable zone and induction time of thiourea for cooling crystallization

The solubility,metastable zone width(MSZW),and induction time of thiourea for cooling crystallization were experimentally determined in the temperature range of 283-323 K.The solubility data could be well described by the Apelblat equation model as lnx=-99.55+1071.66/T+16.27 lnT.The determinations of the effects of various stirring and cooling rates indicated that the MSZW increased with increasing and decreasing cooling and stirring rates,respectively.Furthermore,the induction times at various temperatures and supersaturation ratios were also measured.The results indicated that homogeneous nucleation could occur at high supersaturation,whereas heterogeneous nucleation was more likely to occur at low supersaturation.Based on the classical nucleation theory and induction period data,the calculated solid-liquid interfacial tensions of thiourea in deionized water at 302.46 and 312.58 K were 2.86 and 2.94 mJ·m^(-2),respectively.

Synthesis and Herbicidal Activities of N'-(substituted pyrimidin-2-yl)-N-Substituted Phenoxyacetyl Thiourea Derivatives

Fifteen N'-(substituted pyrimidin-2-y1)-N-substituted phenoxyacetyl thioureas were synthesized and tested for biological activities. All of them are new compounds and their structures were confirmed by IR. IHNMR. MS and elemental analysis. Some of the target compounds showed excellent inhibitory activities against root and stalk of dicotyledon plant (such as radish). and selective on monoctyledon plant (such as rice).

Synthesis and Crystal structure of Bis- (thiourea)dichloroiron(II) Di(4,5-diazafluoren-9-one)

The title compound Fe(CH4N2S)2Cl22(C11H6N2O) (Mr = 643.35) has been prepared and its crystal structure was determined by X-ray diffraction method with the following data: triclinic, space group P1, a = 7.3742(10), b = 13.0427(12), c = 15.215(2) , a = 88.969(12), b = 78.004(12), g = 79.689(11)o, V = 1408.1(3) 3, Z = 2, Dx = 1.517 g/cm3, m = 0.912 mm-1 and F(000) = 656. The final R = 0.030 and wR = 0.078 for 4070 observed reflections (I > 2s(I)), and R = 0.064 and wR = 0.091 for 5516 independent ones. The crystal consists of tetrahedral Fe(II) complex and hydrogen bonded 4,5-diazafluoren-9-one (dafone). The carbonyl bridge in dafone distorts the bipyridine moiety and results in the longer N…N separation of 3.071(3) and 3.061(3) ? There exists an extensive intermolecular hydrogen bond network in the crystal, and p-p stacking is observed between the neighboring dafone rings.

Adsorption of Hg(Ⅱ) from aqueous solution using thiourea functionalized chelating fiber

A fast and selective adsorbent for Hg(II) from aqueous solutions using thiourea(TU) functionalized polypropylene fiber grafted acrylic acid(PP-g-AA),PP-g-AA-TU fibers,was characterized by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy.The adsorption behavior of the functionalized chelating fibers for Hg(II) was investigated by static adsorption experiments,and the effects of some essential factors on adsorption of Hg(II) were examined,such as pH,initial concentration,adsorption time,coexisting cations,and temperature.The results showed that the adsorptive equilibrium could be achieved in 10 min,and the equilibrium adsorption quantity of PP-g-AA-TU fibers was 20 times that of PP-g-AA fibers.The PP-g-AA-TU fibers showed a very high adsorption rate and a good selectivity for Hg(II) over a wide range of p H.The adsorption isotherm can be well described with Langmuir model,with the maximum adsorption capacity for Hg(II) up to52.04 mg·g^(-1)and the removal of Hg(II) more than 97%.The kinetic data indicate that the adsorption process is best-fitted into the pseudo-second-order model.