Two primitive metal-organic frameworks(MOFs),Ni L1 and Ni L2,based on Ni_(8)O_(6)-cluster and ditopic pyrazolate linkers,L1(with rigid alkyne arms)and L2(with flexible alkyne chains),were prepared.The proton conductiv...Two primitive metal-organic frameworks(MOFs),Ni L1 and Ni L2,based on Ni_(8)O_(6)-cluster and ditopic pyrazolate linkers,L1(with rigid alkyne arms)and L2(with flexible alkyne chains),were prepared.The proton conductivities of these MOFs in pristine form and imidazole-encapsulated forms,Im@Ni L1 and Im@Ni L2,were measured and compared.Upon introduction of imidazole molecules,the proton conductivity could be increased by 3 to 5 orders of magnitude and reached as high as 1.72×10^(-2)S/cm(at 98%RH and 80℃).Also,whether imidazole molecules were introduced or not,Ni_(8)O_(6)-based MOFs with L2 in general gave better proton conductivity than those with L1 signifying that flexible side arms indeed assist proton conduction probably via establishment of efficient proton-conducting channels along with formation of highly ordered domains of water/imidazole molecules within the network cavities.Beyond the active Ni_(8)O_(6)-cluster,tuning flexibility of linker pendants serves as an alternative approach to regulate/modulate the proton conductivity of MOFs.展开更多
A series of clip-shaped cationic molecular corners C1~C4(C1=[(bpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C2=[(dmbpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C3=(bpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),C4=(dmbpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),bpy=2,2-bi...A series of clip-shaped cationic molecular corners C1~C4(C1=[(bpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C2=[(dmbpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C3=(bpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),C4=(dmbpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),bpy=2,2-bipyridine,dmbpy=4,4΄-dimethyl-2,2-bipyridine)were synthesized through dipalladium complexes[(bpy)_(2)Pd_(2)(NO_(3))_(2)](NO_(3))_(2),[(dmbpy)_(2)Pd_(2)(NO_(3))_(2)](NO_(3))_(2)and bifunctional pyrazole ligands 4-(3,4-dimethoxyphenyl)-3,5-dimethyl-1H-pyrazol(HL^(1))and 4,4΄-(5-(^(1)H-pyrazol-4-yl)-1,3-phenylene)dipyridine(HL^(2)).Complexes C1~C4 were characterized by^(1)H and^(13)C NMR,electrospray ionization mass spectrometry(ESI-MS),elemental analysis,and IR spectroscopy.The X-ray diffraction analysis of C1∙2NO_(3)−revealed a Pd_(2)dimetallic clip-shaped structure which was synthesized by two bifunctional ligands doubly bridged by the[(bpy)Pd]_(2)dimetal units.Additionally,all of the complexes with NO_(3)−as counter anions exhibited high-efficiency catalytical performance in the Suzuki-coupling reaction attributed to the tunable impact and weak dinuclear Pd(Ⅱ)···Pd(Ⅱ)intramolecular bonding interaction.展开更多
3-Trifluoromethyl-pyrazoles containing strong fluorophore groups:triphenylamine(TPAPz)and carbazole(CarbPz),and their trinuclear silver(Ⅰ)complexes are found to be emissive in solution and the solid state,giving the ...3-Trifluoromethyl-pyrazoles containing strong fluorophore groups:triphenylamine(TPAPz)and carbazole(CarbPz),and their trinuclear silver(Ⅰ)complexes are found to be emissive in solution and the solid state,giving the first example of silver pyrazolate adducts emissive in solution at room temperature.The electronic coupling was observed for pyrazole with a structurally flexible triphenylamine substituent,determining the intraligand charge-transfer(ILCT)nature of the excited states.The association-dissociation of the trinuclear complex core with the heavy atom effect leads to the intense phosphorescence of the triphenylamine-containing complex.The structural rigidity of the N-ethyl carbazole substituent allows only twisting via the bond to the pyrazolate core leading to typical carbazole-centered(LC)fluorescence in solution.In the solid-state,aggregation plays the primary role in emission properties.The observed behavior is in good agreement with the theoretical calculations.展开更多
Trivalent group 3 and 13 light metal pyrazolates were synthesised and their reactivity towards CO_(2)was investigated.The homoleptic complex Al(pz^(tBu_(2)))_(3)reversibly inserts two molecules of CO_(2)to afford Al(C...Trivalent group 3 and 13 light metal pyrazolates were synthesised and their reactivity towards CO_(2)was investigated.The homoleptic complex Al(pz^(tBu_(2)))_(3)reversibly inserts two molecules of CO_(2)to afford Al(CO_(2)·pz^(tBu_(2)))_(2)(pz^(tBu_(2))),exhibiting CO_(2)release only at elevated temperatures(>100℃).In contrast,donorstabilised Sc(pz^(tBu_(2)))_(3)(thf)forms mono-inserted species[Sc(μ-CO_(2)·pz^(tBu_(2)))(pz^(tBu_(2)))_(2)]_(2),which already releases CO_(2)at ambient temperature and pressure and hence is isolable only at low temperature.For the yttrium complex Y(pz^(tBu_(2)))_(3)(thf)_(2),insertion of CO_(2)is not observable at ambient temperature.The new homoleptic aluminium diisopropyl pyrazolate complex[Al(pziPr2)_(3)]_(2) shows exhaustive CO_(2)insertion,while dimethyl pyrazolate could be isolated as the separated ion pair[Al(N,N’,N’’-Al{pz^(Me_(2))}_(3)Me)_(2)][Al(pz^(Me_(2)))_(3)Me].The scandium complex Sc(pz^(tBu_(2)))_(3)(thf)performed best in the catalytic cycloaddition reaction of CO_(2)and epoxides,unveiling an inverse correlation of carboxophilicity(vCO_(2)affinity)and catalytic activity.Carboxophilicity is assessed using CO_(2)-release temperature(via VT ^(1)H NMR spectroscopy and thermogravimetric analysis).展开更多
Pyrazole derivatives have made impressive achievements in the discovery of new pesticides,especially novel fungicides,insecticides,and herbicides.The pyrazole ring containing two adjacent nitrogen atoms is an importan...Pyrazole derivatives have made impressive achievements in the discovery of new pesticides,especially novel fungicides,insecticides,and herbicides.The pyrazole ring containing two adjacent nitrogen atoms is an important active fragment,which showed broad-spectrum and efficient biological activities.With the great interest and focus on pyrazoles,it is necessary to keep up-to-date with the latest research progress on pyrazole derivatives in the discovery of new pesticides.Based on this,we reviewed the progress and applications of pyrazole derivatives in the discovery of fungicides,antibacterial agents,insecticides,herbicides,antiviral agents,and nematicides in the past decade,summarized the fungicidal,antibacterial,insecticidal,herbicidal,antiviral,and nematicidal activities of pyrazoles,as well as the synthetic methods of the representative compounds.We also discussed the structure-activity relationship(SAR) and mechanism of action of the active compounds,aiming to provide new clues and ideas for the search of new pyrazole pesticides with high efficiency,low toxicity,and unique mechanism of action.展开更多
Chemically engineered extracts represent a promising source of new bioactive semi-synthetic molecules.Prepared through direct derivatization of natural extracts,they can include constituents enriched with elements and...Chemically engineered extracts represent a promising source of new bioactive semi-synthetic molecules.Prepared through direct derivatization of natural extracts,they can include constituents enriched with elements and sub-structures that are less common in natural products compared to drugs.Fourteen such extracts were prepared through sequential reactions with hydrazine and a fluorinating reagent,and their α-glucosidase inhibition properties were compared.For the most bioactive mixture,a chemically modified propolis extract,enzyme inhibition increased 22 times due to the reaction sequence.Bio-guided fractionation led to the isolation of a new fluorinated pyrazole produced within the extract by chemical transformation of the flavonoid chrysin.The inhibitor results from the action of the two reagents used on four common functional groups present in natural products(carbonyl,phenol,aromatic carbon,and a double bond).The reactions led to the opening of a 6-member oxygenated heterocycle to produce a 5-member nitrogenated one,as well as the dehydroxylation and fluorination in two different positions of one of the aromatic rings of the natural starting material,all within a complex mixture of natural products.Overall,these transformations led to an approximately 20-fold increase in the α-glucosidase inhibition by the isolated inhibitor compared to its natural precursor.展开更多
Multistimuli-responsive luminescent materials,showing obvious alteration of emission colours or intensity toward multiple external stimuli,have attracted extensive interest from researchers for decades,but the tailore...Multistimuli-responsive luminescent materials,showing obvious alteration of emission colours or intensity toward multiple external stimuli,have attracted extensive interest from researchers for decades,but the tailored synthesis of such materials with a single phase remains a tough challenge.Herein,we investigate a Cu(I)cyclic trinuclear complex with the pyridyl-substituted pyrazolate ligand(denoted as complex 1).展开更多
The complexation of 4,4’-halogen-substituted biphenyls(BPs)with a trinuclear silver(I)3,5-bis(trifluoromethyl)pyrazolate adduct([AgL]_(3))is observed in the solution and solid states.Infinite stacks are formed by alt...The complexation of 4,4’-halogen-substituted biphenyls(BPs)with a trinuclear silver(I)3,5-bis(trifluoromethyl)pyrazolate adduct([AgL]_(3))is observed in the solution and solid states.Infinite stacks are formed by alternating BPs and[AgL]_(3) molecules via multiple metal-πinteractions in a crystal.Encapsulation of the biphenyl derivatives between the[AgL]_(3) units allows room-temperature phosphorescence in the solid state.Furthermore,the intercalation of BPs results in the formation of planar geometry,which allows the reduction of non-radiative relaxation and enhances luminescence due to the planar geometry of the excited states.Another crucial factor in efficient light emission is the asymmetry of the intermolecular complexes.The obtained complexes exhibited both phosphorescence and fluorescence bands spanning a wide spectral range.Furthermore,fine-tuning of emissions by varying excitation energy could produce white light.展开更多
A three-dimensional(3D)metal–organic framework constructed from unprecedented Zn_(9)O_(2)(OH)_(2)(pyz)_(12)(pyz=pyrazolate)clusters and Ni(salen)-derived linkers was reported.The MOF exhibits high catalytic activity ...A three-dimensional(3D)metal–organic framework constructed from unprecedented Zn_(9)O_(2)(OH)_(2)(pyz)_(12)(pyz=pyrazolate)clusters and Ni(salen)-derived linkers was reported.The MOF exhibits high catalytic activity for CO_(2)cycloaddition reactions with excellent stability.The MOF catalyst can be recycled at least 15 times without loss of activity and the turnover number(TON)per Ni site can reach as high as 2887.展开更多
A range of pyrazolate-based ligands have been used to balance the multidentate-chelating feature and the magnetic axiality in“destroyed”pentagonal-bipyramidal(DPB)dysprosium(III)single-molecule magnets(SMMs).This fa...A range of pyrazolate-based ligands have been used to balance the multidentate-chelating feature and the magnetic axiality in“destroyed”pentagonal-bipyramidal(DPB)dysprosium(III)single-molecule magnets(SMMs).This family of complexes are air-stable and share the general formulae of[DyX^(1)X^(2)(L_(eq))_(5)][BPh_(4)],where X^(1)and X^(2)are the anionic axial ligands,including pyrazolate-based ligands and chloride;L_(eq)is the equatorial solvent molecule such as tetrahydrofuran(THF),pyridine(py)and thiazole(NS).展开更多
We have developed an iron（III） phthalocyanine chloride‐catalyzed oxidation–aromatization ofα,β‐unsaturated ketones with hydrazine hydrate. Various 3,5‐disubstituted 1H‐pyrazoles were obtained in good to excel...We have developed an iron（III） phthalocyanine chloride‐catalyzed oxidation–aromatization ofα,β‐unsaturated ketones with hydrazine hydrate. Various 3,5‐disubstituted 1H‐pyrazoles were obtained in good to excellent yields. This method offers several advantages, including room‐tem‐perature conditions, short reaction time, high yields, simple work‐up procedure, and use of air as an oxidant. The catalyst can be recovered and reused five times without loss of activity.展开更多
A new neutral ternary samarium complex Sm（Phen）HL3 in which Phen is 1,10-phenanthroline and HL is （1,3-bis（1,3-dimethyl-1H-pyrazol-4-yl）-1,3-propanedione） was synthesized. Molecular structure of this complex was...A new neutral ternary samarium complex Sm（Phen）HL3 in which Phen is 1,10-phenanthroline and HL is （1,3-bis（1,3-dimethyl-1H-pyrazol-4-yl）-1,3-propanedione） was synthesized. Molecular structure of this complex was determined by X-ray diffraction. Under UV-light this complex is demonstrated bright red luminescence （λmax=647 nm）, which was corresponding to the electric dipole 4G5/2→6H9/2 transition in Sm3＋ ion. UV-absorption, excitation and emission spectra of the title compound were investigated.展开更多
A series of chromone derivatives containing substituted pyrazole were designed and synthesized.Preliminary bioassays showed that most of the synthesized compounds exhibited good nematicidal activity in vivo against Me...A series of chromone derivatives containing substituted pyrazole were designed and synthesized.Preliminary bioassays showed that most of the synthesized compounds exhibited good nematicidal activity in vivo against Meloidogyne incognita at 10 mg/L. Among the tested compounds, A10 and A11 exhibited 100% inhibition rates. In addition, the molecular docking results indicated that both compound A10 and A11 interacts with amino acid residue Tyr121, Trp279, Tyr70, Trp84 and Phe330 of ACh E via hydrogen bond and p–p stacking. This investigation suggested that the chromone containing substituted pyrazole scaffold could be further optimized to explore novel, high-bioactivity nematicidal leads.展开更多
Based on the similarities in the conformation of VS008（N-（4-methylphenyl）-3-（tert-butyl）-1-（phenylmethyl）-1H-pyrazole-5-carboxamide） and BYIO6830（N＇-（3,5-dimethylbenzoyl）-N＇-tert-butyl-5-methyl-2,3-dihydr...Based on the similarities in the conformation of VS008（N-（4-methylphenyl）-3-（tert-butyl）-1-（phenylmethyl）-1H-pyrazole-5-carboxamide） and BYIO6830（N＇-（3,5-dimethylbenzoyl）-N＇-tert-butyl-5-methyl-2,3-dihydro-l,4-benzodioxine-6-carbohydrazide） bound to the active site of the EcR subunit of the ecdysone receptor（EcR）-ultraspiracle protein（USP） heterodimeric receptor,a series of new pyrazole amide derivatives were designed and synthesized.Their structures were confirmed by IR,~1H NMR,^（13）C NMR and elemental analysis.Results from a preliminary bioassay revealed that two of the pyrazole derivatives exhibited promising insecticidal activity.Specifically,compounds 6e and 6i exhibited good activity against Helicoverpa armigera（cotton bollworm） at low concentration.Symptoms displayed by tebufenozide-treated H.armigera were identical with those displayed by its treated counterpart.6i showed the same poisoning symptoms as those of tebufenozide.In addition,results from molecular docking result indicated that the binding modes of 6e and 6i at the active site of the EcR subunit of the heterodimeric receptor were similar to that of the bound tebufenozide.展开更多
The title compound N-（（3,5-dimethylphenyl）carbamoyl）-1-methyl-3-（trifluoromethyl）-1 H-pyrazole-4-carboxamide（C（15）H（15）F3N4O2） was synthesized, and its structure was confirmed by 1 H NMR, H RMS and X-ray d...The title compound N-（（3,5-dimethylphenyl）carbamoyl）-1-methyl-3-（trifluoromethyl）-1 H-pyrazole-4-carboxamide（C（15）H（15）F3N4O2） was synthesized, and its structure was confirmed by 1 H NMR, H RMS and X-ray diffraction. It crystallizes in the triclinic system, space group P1 with a = 11.7147（5）, b = 11.7935（5）, c = 13.6620（5） A, α = 69.755（7）°, β = 66.182（6）°, γ = 72.100（7）°, Dc = 1.423 g/cm^3, Z = 4, V = 1588.88（11） A^3, the final R = 0.0347 and wR = 0.1005 for 7171 observed reflections with I 〉 2σ（I）. The preliminary biological test showed that the title compound has antifungal activities against Fusarium oxysporum, Pseudomonas syringae, Corynespora mazei and Botrytis cinerea at 100 μg/mL as 5.19%, 53.50%, 88.55% and 70.62%, respectively. The docking results indicated the hydrogen bonds formed between the compound and SHD.展开更多
A series of new pyrazole oximes bearing substituted thiazole ring were designed and prepared. The structures of the title compounds were identified by spectral analyses, The results of primary bioassay indicated that ...A series of new pyrazole oximes bearing substituted thiazole ring were designed and prepared. The structures of the title compounds were identified by spectral analyses, The results of primary bioassay indicated that some targeted compounds exhibited promising insecticidal activity besides acaricidal activity, particularly; compounds 8c and 8d were more potent against Tetranychus cinnabarinus and Plutella xylostella than other analogues.展开更多
In order to discover highly active ecdysone analogs, a series of new substituted pyrazole amide derivatives were obtained using structure-guided optimization method and further screened for their insecticidal activiti...In order to discover highly active ecdysone analogs, a series of new substituted pyrazole amide derivatives were obtained using structure-guided optimization method and further screened for their insecticidal activities, in the basis of the core structures of the two active compounds N-（3-methoxyphenyl）-3-（tert-butyl）-1-phenyl-1H-pyrazole-5-carboxamide（6e） and N-（4-（tert-butyl）phenyl）-3-（tert-butyl）-1-phenyl-1H-pyrazole-5-carboxamide（6i）, previously presented by us. The chemical structures of the title compounds were identified by spectral analyses. The preliminary bioassay results indicated that one among the synthesized pyrazole derivatives, compound 34, endowed with good activity against Mythimna Separata at 10 mg/L, which was equal to that displayed by the positive control tebufenozide. In addition, examples of molecular docking and molecular dynamics studies demonstrated that 34 may be the potential inhibitor to Ec R and its docking conformation was similar to that of tebufenozide. In addition, increasing the hydrophobic effect and considering the suitable bulk effect on pyrazole ring are beneficial to the inhibiting activity to Ec R and activity in vivo.展开更多
The crystal structure of 2(1-phenyl-3-methyl-5-chloro-1H-pyrazol-4-yl)-3-(1- naphthoylamido)-4-thiazolidinone (C24H19ClN4O2S, Mr = 462.94) has been determined by single- crystal X-ray diffraction method. The crystal b...The crystal structure of 2(1-phenyl-3-methyl-5-chloro-1H-pyrazol-4-yl)-3-(1- naphthoylamido)-4-thiazolidinone (C24H19ClN4O2S, Mr = 462.94) has been determined by single- crystal X-ray diffraction method. The crystal belongs to monoclinic, space group P21/c with a = 11.623(5), b = 11.579(5), c = 16.619(7) ? b = 90.112(8), V = 2237(2) 3, Z = 4, Dc = 1.375 g/cm3, m = 0.294 mm-1, F(000) = 960, R = 0.0492 and wR = 0.0768 for 3932 unique reflections with 1897 observed ones (I > 2s(I)). X-ray analysis reveals that there exist both intra-and intermolecular hydrogen bonds in the crystal lattice.展开更多
A series of 1,3,4-oxadiazole or 1,3,4-thiadiazole-substituted pyrazole derivatives were synthesized from 4-pyrazole formhydrazide; their biological activities were studied. The structures of all the new compounds were...A series of 1,3,4-oxadiazole or 1,3,4-thiadiazole-substituted pyrazole derivatives were synthesized from 4-pyrazole formhydrazide; their biological activities were studied. The structures of all the new compounds were confirmed by means of spectroscopic methods and microanalyses. The preliminary bioassay results indicate that some compounds of them have a good fungicidal activity against Phoma asparagi and Physalospora piricola Nose.展开更多
The title compound ethyl 1-（2-bromoethyl）-3-（4-methoxyphenyl）-1H-pyrazole-5-carboxylate 1 has been synthesized and structurally characterized by single-crystal X-ray diffraction.The crystal is of monoclinic（C15H1...The title compound ethyl 1-（2-bromoethyl）-3-（4-methoxyphenyl）-1H-pyrazole-5-carboxylate 1 has been synthesized and structurally characterized by single-crystal X-ray diffraction.The crystal is of monoclinic（C15H17BrN2O3,Mr = 353.22）,space group C21 with a = 24.691（7）,b = 6.7678（17）,c = 17.884（5） ,β = 97.184（5）o,V = 2965.1（13） 3,Z = 8,Dc = 1.583 g.cm-3,F（000） = 1440,μ = 2.784 mm-1,the final R = 0.0260 and wR = 0.0596 for 2684 observed reflections with I 2σ（I）.All the carbon atoms in the molecule are nearly coplanar except C（15）,with a large conjugated system among the carbonyl group,pyrazole ring and the benzene ring.Three non-classical intermolecular hydrogen bonds help to stabilize the crystal lattice.The regioselectivity was rationalized based on the coordination of potassium ion with the N-anion and the carbonyl oxygen atom.展开更多
基金the National Natural Science Foundation of China(No.21871061)the Foundation of Basic and Applied Basic Research of Guangdong Province(No.2021A1515010274)+2 种基金the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT01Z032)the Science and Technology Planning Project of Guangdong Province(No.2021A0505030066)the Science and Technology Program of Guangzhou(No.201807010026)。
文摘Two primitive metal-organic frameworks(MOFs),Ni L1 and Ni L2,based on Ni_(8)O_(6)-cluster and ditopic pyrazolate linkers,L1(with rigid alkyne arms)and L2(with flexible alkyne chains),were prepared.The proton conductivities of these MOFs in pristine form and imidazole-encapsulated forms,Im@Ni L1 and Im@Ni L2,were measured and compared.Upon introduction of imidazole molecules,the proton conductivity could be increased by 3 to 5 orders of magnitude and reached as high as 1.72×10^(-2)S/cm(at 98%RH and 80℃).Also,whether imidazole molecules were introduced or not,Ni_(8)O_(6)-based MOFs with L2 in general gave better proton conductivity than those with L1 signifying that flexible side arms indeed assist proton conduction probably via establishment of efficient proton-conducting channels along with formation of highly ordered domains of water/imidazole molecules within the network cavities.Beyond the active Ni_(8)O_(6)-cluster,tuning flexibility of linker pendants serves as an alternative approach to regulate/modulate the proton conductivity of MOFs.
基金the Beijing Natural Science Foundation of China(2212002)National Natural Science Foundation of China(21906002,21471011)+2 种基金the Beijing Municipal Science and Technology Project(KM202010005010)the Beijing Municipal High Level Innovative Team Building Program(IDHT20180504)the Beijing Outstanding Young Scientist Program(BJJWZYJH01201910005017)。
文摘A series of clip-shaped cationic molecular corners C1~C4(C1=[(bpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C2=[(dmbpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C3=(bpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),C4=(dmbpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),bpy=2,2-bipyridine,dmbpy=4,4΄-dimethyl-2,2-bipyridine)were synthesized through dipalladium complexes[(bpy)_(2)Pd_(2)(NO_(3))_(2)](NO_(3))_(2),[(dmbpy)_(2)Pd_(2)(NO_(3))_(2)](NO_(3))_(2)and bifunctional pyrazole ligands 4-(3,4-dimethoxyphenyl)-3,5-dimethyl-1H-pyrazol(HL^(1))and 4,4΄-(5-(^(1)H-pyrazol-4-yl)-1,3-phenylene)dipyridine(HL^(2)).Complexes C1~C4 were characterized by^(1)H and^(13)C NMR,electrospray ionization mass spectrometry(ESI-MS),elemental analysis,and IR spectroscopy.The X-ray diffraction analysis of C1∙2NO_(3)−revealed a Pd_(2)dimetallic clip-shaped structure which was synthesized by two bifunctional ligands doubly bridged by the[(bpy)Pd]_(2)dimetal units.Additionally,all of the complexes with NO_(3)−as counter anions exhibited high-efficiency catalytical performance in the Suzuki-coupling reaction attributed to the tunable impact and weak dinuclear Pd(Ⅱ)···Pd(Ⅱ)intramolecular bonding interaction.
基金financially supported by the Russian Science Foundation(project no.19-73-20262).
文摘3-Trifluoromethyl-pyrazoles containing strong fluorophore groups:triphenylamine(TPAPz)and carbazole(CarbPz),and their trinuclear silver(Ⅰ)complexes are found to be emissive in solution and the solid state,giving the first example of silver pyrazolate adducts emissive in solution at room temperature.The electronic coupling was observed for pyrazole with a structurally flexible triphenylamine substituent,determining the intraligand charge-transfer(ILCT)nature of the excited states.The association-dissociation of the trinuclear complex core with the heavy atom effect leads to the intense phosphorescence of the triphenylamine-containing complex.The structural rigidity of the N-ethyl carbazole substituent allows only twisting via the bond to the pyrazolate core leading to typical carbazole-centered(LC)fluorescence in solution.In the solid-state,aggregation plays the primary role in emission properties.The observed behavior is in good agreement with the theoretical calculations.
文摘Trivalent group 3 and 13 light metal pyrazolates were synthesised and their reactivity towards CO_(2)was investigated.The homoleptic complex Al(pz^(tBu_(2)))_(3)reversibly inserts two molecules of CO_(2)to afford Al(CO_(2)·pz^(tBu_(2)))_(2)(pz^(tBu_(2))),exhibiting CO_(2)release only at elevated temperatures(>100℃).In contrast,donorstabilised Sc(pz^(tBu_(2)))_(3)(thf)forms mono-inserted species[Sc(μ-CO_(2)·pz^(tBu_(2)))(pz^(tBu_(2)))_(2)]_(2),which already releases CO_(2)at ambient temperature and pressure and hence is isolable only at low temperature.For the yttrium complex Y(pz^(tBu_(2)))_(3)(thf)_(2),insertion of CO_(2)is not observable at ambient temperature.The new homoleptic aluminium diisopropyl pyrazolate complex[Al(pziPr2)_(3)]_(2) shows exhaustive CO_(2)insertion,while dimethyl pyrazolate could be isolated as the separated ion pair[Al(N,N’,N’’-Al{pz^(Me_(2))}_(3)Me)_(2)][Al(pz^(Me_(2)))_(3)Me].The scandium complex Sc(pz^(tBu_(2)))_(3)(thf)performed best in the catalytic cycloaddition reaction of CO_(2)and epoxides,unveiling an inverse correlation of carboxophilicity(vCO_(2)affinity)and catalytic activity.Carboxophilicity is assessed using CO_(2)-release temperature(via VT ^(1)H NMR spectroscopy and thermogravimetric analysis).
基金the National Key R & D Program of China(No.2023YFD1400400) for supporting the project。
文摘Pyrazole derivatives have made impressive achievements in the discovery of new pesticides,especially novel fungicides,insecticides,and herbicides.The pyrazole ring containing two adjacent nitrogen atoms is an important active fragment,which showed broad-spectrum and efficient biological activities.With the great interest and focus on pyrazoles,it is necessary to keep up-to-date with the latest research progress on pyrazole derivatives in the discovery of new pesticides.Based on this,we reviewed the progress and applications of pyrazole derivatives in the discovery of fungicides,antibacterial agents,insecticides,herbicides,antiviral agents,and nematicides in the past decade,summarized the fungicidal,antibacterial,insecticidal,herbicidal,antiviral,and nematicidal activities of pyrazoles,as well as the synthetic methods of the representative compounds.We also discussed the structure-activity relationship(SAR) and mechanism of action of the active compounds,aiming to provide new clues and ideas for the search of new pyrazole pesticides with high efficiency,low toxicity,and unique mechanism of action.
基金support by Universidad Nacional de Rosario(80020180300114UR and 80020180100128UR)CONICET(PIP No 11220200102423)FONCYT(PICT2019-02232 and PICT2021-1034)for the development of this work.
文摘Chemically engineered extracts represent a promising source of new bioactive semi-synthetic molecules.Prepared through direct derivatization of natural extracts,they can include constituents enriched with elements and sub-structures that are less common in natural products compared to drugs.Fourteen such extracts were prepared through sequential reactions with hydrazine and a fluorinating reagent,and their α-glucosidase inhibition properties were compared.For the most bioactive mixture,a chemically modified propolis extract,enzyme inhibition increased 22 times due to the reaction sequence.Bio-guided fractionation led to the isolation of a new fluorinated pyrazole produced within the extract by chemical transformation of the flavonoid chrysin.The inhibitor results from the action of the two reagents used on four common functional groups present in natural products(carbonyl,phenol,aromatic carbon,and a double bond).The reactions led to the opening of a 6-member oxygenated heterocycle to produce a 5-member nitrogenated one,as well as the dehydroxylation and fluorination in two different positions of one of the aromatic rings of the natural starting material,all within a complex mixture of natural products.Overall,these transformations led to an approximately 20-fold increase in the α-glucosidase inhibition by the isolated inhibitor compared to its natural precursor.
基金supported by the National Natural Science Foundation of China(21731002,21975104,and 22150004)the Guangdong Major Project of Basic and Applied Research(No.2019B030302009)+1 种基金the Fundamental Research Funds for the Central Universities(11621035)Jinan University.
文摘Multistimuli-responsive luminescent materials,showing obvious alteration of emission colours or intensity toward multiple external stimuli,have attracted extensive interest from researchers for decades,but the tailored synthesis of such materials with a single phase remains a tough challenge.Herein,we investigate a Cu(I)cyclic trinuclear complex with the pyridyl-substituted pyrazolate ligand(denoted as complex 1).
基金supported by the Russian Science Foundation(project№19-73-20262)NMR investigations were performed with the financial support of the Ministry of Science and Higher Education of the Russian Federation employing the equipment of Center for molecular composition studies of INEOS RAS.The crystal structures of 1Ag,2Ag and 3Ag were established using the equipment of St.Petersburg University Research Park(Center of X-ray Diffraction).
文摘The complexation of 4,4’-halogen-substituted biphenyls(BPs)with a trinuclear silver(I)3,5-bis(trifluoromethyl)pyrazolate adduct([AgL]_(3))is observed in the solution and solid states.Infinite stacks are formed by alternating BPs and[AgL]_(3) molecules via multiple metal-πinteractions in a crystal.Encapsulation of the biphenyl derivatives between the[AgL]_(3) units allows room-temperature phosphorescence in the solid state.Furthermore,the intercalation of BPs results in the formation of planar geometry,which allows the reduction of non-radiative relaxation and enhances luminescence due to the planar geometry of the excited states.Another crucial factor in efficient light emission is the asymmetry of the intermolecular complexes.The obtained complexes exhibited both phosphorescence and fluorescence bands spanning a wide spectral range.Furthermore,fine-tuning of emissions by varying excitation energy could produce white light.
基金financially supported by the National Key Research and Development Program of China(2017YFA0700103)the National Natural Science Foundation of China(Grant No.22005306)The authors greatly thank Prof.Li-Xin Wu(FJIRSM,CAS)for the help with contact angle measurements,Prof.Xin-Qiang Fang(FJIRSM,CAS)for the help with ee determination,and Bai-Tong Liu(FJIRSM,CAS),Jia-Wei Chen(XMU)and Shi-Rui Zhang(SNNU)for the help with crystallography and N2 sorption analysis.
文摘A three-dimensional(3D)metal–organic framework constructed from unprecedented Zn_(9)O_(2)(OH)_(2)(pyz)_(12)(pyz=pyrazolate)clusters and Ni(salen)-derived linkers was reported.The MOF exhibits high catalytic activity for CO_(2)cycloaddition reactions with excellent stability.The MOF catalyst can be recycled at least 15 times without loss of activity and the turnover number(TON)per Ni site can reach as high as 2887.
基金supported by the NSFC(21773130)the Key Laboratory Construction Program of Xi’an Municipal Bureau of Science and Technology(201805056ZD7CG40)+3 种基金the China Postdoctoral Science Foundation(2019T120892 and 2018M631138)the Shaanxi Postdoctoral Science Foundation,the Natural Science Basic Research Plan in Shaanxi Province of China(Program No.2019JQ-292)the Shenzhen Science and Technology Program(JCYJ20180306170859634)the Cyrus Chung Ying Tang Foundation and the Fundamental Research Funds for Central Universities.
文摘A range of pyrazolate-based ligands have been used to balance the multidentate-chelating feature and the magnetic axiality in“destroyed”pentagonal-bipyramidal(DPB)dysprosium(III)single-molecule magnets(SMMs).This family of complexes are air-stable and share the general formulae of[DyX^(1)X^(2)(L_(eq))_(5)][BPh_(4)],where X^(1)and X^(2)are the anionic axial ligands,including pyrazolate-based ligands and chloride;L_(eq)is the equatorial solvent molecule such as tetrahydrofuran(THF),pyridine(py)and thiazole(NS).
基金supported by the Industrial Research Project of Shaanxi Science and Technology Department(2014K08-29)Science and Technology Plan Project of Xi’an(CXY1511(7))Scientific Research Foundation of Northwest University~~
文摘We have developed an iron（III） phthalocyanine chloride‐catalyzed oxidation–aromatization ofα,β‐unsaturated ketones with hydrazine hydrate. Various 3,5‐disubstituted 1H‐pyrazoles were obtained in good to excellent yields. This method offers several advantages, including room‐tem‐perature conditions, short reaction time, high yields, simple work‐up procedure, and use of air as an oxidant. The catalyst can be recovered and reused five times without loss of activity.
文摘A new neutral ternary samarium complex Sm（Phen）HL3 in which Phen is 1,10-phenanthroline and HL is （1,3-bis（1,3-dimethyl-1H-pyrazol-4-yl）-1,3-propanedione） was synthesized. Molecular structure of this complex was determined by X-ray diffraction. Under UV-light this complex is demonstrated bright red luminescence （λmax=647 nm）, which was corresponding to the electric dipole 4G5/2→6H9/2 transition in Sm3＋ ion. UV-absorption, excitation and emission spectra of the title compound were investigated.
基金financial supported by the National Natural Science Foundation of China (No. 21672061)National Key Research Program of China (No. 2017YFD0200505)Fundamental Research Funds for the Central Universities (No. 222201718004)
文摘A series of chromone derivatives containing substituted pyrazole were designed and synthesized.Preliminary bioassays showed that most of the synthesized compounds exhibited good nematicidal activity in vivo against Meloidogyne incognita at 10 mg/L. Among the tested compounds, A10 and A11 exhibited 100% inhibition rates. In addition, the molecular docking results indicated that both compound A10 and A11 interacts with amino acid residue Tyr121, Trp279, Tyr70, Trp84 and Phe330 of ACh E via hydrogen bond and p–p stacking. This investigation suggested that the chromone containing substituted pyrazole scaffold could be further optimized to explore novel, high-bioactivity nematicidal leads.
基金supported by the National Natural Science Foundation of China (No. 21272265)the National High Technology Research and Development Program of China (No. 2011AA10A204)
文摘Based on the similarities in the conformation of VS008（N-（4-methylphenyl）-3-（tert-butyl）-1-（phenylmethyl）-1H-pyrazole-5-carboxamide） and BYIO6830（N＇-（3,5-dimethylbenzoyl）-N＇-tert-butyl-5-methyl-2,3-dihydro-l,4-benzodioxine-6-carbohydrazide） bound to the active site of the EcR subunit of the ecdysone receptor（EcR）-ultraspiracle protein（USP） heterodimeric receptor,a series of new pyrazole amide derivatives were designed and synthesized.Their structures were confirmed by IR,~1H NMR,^（13）C NMR and elemental analysis.Results from a preliminary bioassay revealed that two of the pyrazole derivatives exhibited promising insecticidal activity.Specifically,compounds 6e and 6i exhibited good activity against Helicoverpa armigera（cotton bollworm） at low concentration.Symptoms displayed by tebufenozide-treated H.armigera were identical with those displayed by its treated counterpart.6i showed the same poisoning symptoms as those of tebufenozide.In addition,results from molecular docking result indicated that the binding modes of 6e and 6i at the active site of the EcR subunit of the heterodimeric receptor were similar to that of the bound tebufenozide.
基金funded by Zhejiang Provincial Science Foundation of China(No.LY16C140007)
文摘The title compound N-（（3,5-dimethylphenyl）carbamoyl）-1-methyl-3-（trifluoromethyl）-1 H-pyrazole-4-carboxamide（C（15）H（15）F3N4O2） was synthesized, and its structure was confirmed by 1 H NMR, H RMS and X-ray diffraction. It crystallizes in the triclinic system, space group P1 with a = 11.7147（5）, b = 11.7935（5）, c = 13.6620（5） A, α = 69.755（7）°, β = 66.182（6）°, γ = 72.100（7）°, Dc = 1.423 g/cm^3, Z = 4, V = 1588.88（11） A^3, the final R = 0.0347 and wR = 0.1005 for 7171 observed reflections with I 〉 2σ（I）. The preliminary biological test showed that the title compound has antifungal activities against Fusarium oxysporum, Pseudomonas syringae, Corynespora mazei and Botrytis cinerea at 100 μg/mL as 5.19%, 53.50%, 88.55% and 70.62%, respectively. The docking results indicated the hydrogen bonds formed between the compound and SHD.
基金financial supported by the National Natural Science Foundation of China(No.21202089)China Postdoctoral Science Foundation(No.2013M531145)the Research Foundation of the Six People Peak of Jiangsu Province(No.2013-SWYY-013)
文摘A series of new pyrazole oximes bearing substituted thiazole ring were designed and prepared. The structures of the title compounds were identified by spectral analyses, The results of primary bioassay indicated that some targeted compounds exhibited promising insecticidal activity besides acaricidal activity, particularly; compounds 8c and 8d were more potent against Tetranychus cinnabarinus and Plutella xylostella than other analogues.
基金supported by the National Natural Science Foundation of China (No. 21272265)the National High Technology Research and Development Program of China (No.2011AA10A204)
文摘In order to discover highly active ecdysone analogs, a series of new substituted pyrazole amide derivatives were obtained using structure-guided optimization method and further screened for their insecticidal activities, in the basis of the core structures of the two active compounds N-（3-methoxyphenyl）-3-（tert-butyl）-1-phenyl-1H-pyrazole-5-carboxamide（6e） and N-（4-（tert-butyl）phenyl）-3-（tert-butyl）-1-phenyl-1H-pyrazole-5-carboxamide（6i）, previously presented by us. The chemical structures of the title compounds were identified by spectral analyses. The preliminary bioassay results indicated that one among the synthesized pyrazole derivatives, compound 34, endowed with good activity against Mythimna Separata at 10 mg/L, which was equal to that displayed by the positive control tebufenozide. In addition, examples of molecular docking and molecular dynamics studies demonstrated that 34 may be the potential inhibitor to Ec R and its docking conformation was similar to that of tebufenozide. In addition, increasing the hydrophobic effect and considering the suitable bulk effect on pyrazole ring are beneficial to the inhibiting activity to Ec R and activity in vivo.
文摘The crystal structure of 2(1-phenyl-3-methyl-5-chloro-1H-pyrazol-4-yl)-3-(1- naphthoylamido)-4-thiazolidinone (C24H19ClN4O2S, Mr = 462.94) has been determined by single- crystal X-ray diffraction method. The crystal belongs to monoclinic, space group P21/c with a = 11.623(5), b = 11.579(5), c = 16.619(7) ? b = 90.112(8), V = 2237(2) 3, Z = 4, Dc = 1.375 g/cm3, m = 0.294 mm-1, F(000) = 960, R = 0.0492 and wR = 0.0768 for 3932 unique reflections with 1897 observed ones (I > 2s(I)). X-ray analysis reveals that there exist both intra-and intermolecular hydrogen bonds in the crystal lattice.
基金Supported by the National Natural Science Foundation of China(No.2 0 2 0 2 0 0 3) and the state's"86 3"Project(No.2 0 0 1AA2 35 0 11)
文摘A series of 1,3,4-oxadiazole or 1,3,4-thiadiazole-substituted pyrazole derivatives were synthesized from 4-pyrazole formhydrazide; their biological activities were studied. The structures of all the new compounds were confirmed by means of spectroscopic methods and microanalyses. The preliminary bioassay results indicate that some compounds of them have a good fungicidal activity against Phoma asparagi and Physalospora piricola Nose.
基金Supported by Scientific Technological project (2009GG20002027) in Shandong Province
文摘The title compound ethyl 1-（2-bromoethyl）-3-（4-methoxyphenyl）-1H-pyrazole-5-carboxylate 1 has been synthesized and structurally characterized by single-crystal X-ray diffraction.The crystal is of monoclinic（C15H17BrN2O3,Mr = 353.22）,space group C21 with a = 24.691（7）,b = 6.7678（17）,c = 17.884（5） ,β = 97.184（5）o,V = 2965.1（13） 3,Z = 8,Dc = 1.583 g.cm-3,F（000） = 1440,μ = 2.784 mm-1,the final R = 0.0260 and wR = 0.0596 for 2684 observed reflections with I 2σ（I）.All the carbon atoms in the molecule are nearly coplanar except C（15）,with a large conjugated system among the carbonyl group,pyrazole ring and the benzene ring.Three non-classical intermolecular hydrogen bonds help to stabilize the crystal lattice.The regioselectivity was rationalized based on the coordination of potassium ion with the N-anion and the carbonyl oxygen atom.
