Synthesis, Crystal Structure, Docking and Antifungal Activity of a New Pyrazole Acylurea Compound

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.

Synthesis,Crystal Structure and Biological Activity of 2-(1-(3-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyl)piperidin-4-yl)-N-isopropyl-1,3-thiazole-4-carboxamide

The title compound 2-（1-（3-bromo-1-（3-chloropyridin-2-yl）-1H-pyrazole-5-carbonyl）piperidin-4-yl）-N-isopropylthiazole-4-carboxamide（C21H22Br Cl N6O2 S,Mr = 536.04） has been synthesized,and its structure was characterized by IR spectra,1H-NMR,13C-NMR,EA,and single-crystal X-ray diffraction.The crystal of the title compound belongs to monoclinic system,space group P/c with a = 15.146（3）,b = 11.573（2）,c = 26.937（5） A,β = 103.64（3）°,V = 1839.0（6） A^3,Z = 4,Dc = 1.557 g/cm^3,μ（Mo Ka） = 0.71073 mm^-1,F（000） = 2192,R = 0.0601 and w R = 0.1392.There exist one intramolecular hydrogen bond at N–H···N and four intermolecular weak interactions at O（2）···H（1）,Cl（1）···H（12）,O（1）···Cl（1） and S（1）···O（2）.Bioassay results indicated that the title compound had good fungicidal and antiviral activities against tobacco mosaic virus.

Synthesis,Crystal Structure and Insecticidal Activity of N-(pyridin-2-ylmethyl)-1-phenyl-1,4,5,6,7,8-hexahydrocyclohepta[c]pyrazole-3-carboxamide

The title compound N-（pyridin-2-ylmethyl）- 1-phenyl- 1,4,5,6,7,8-hexahydrocy-clohepta[c]pyrazole-3-carboxamide 5 （C21I-I22N40, Mr = 346.42） has been synthesized andstructurally characterized by IR, 1H NMR, 13C NMR, H RMS and single-crystal X-raydiffraction. The crystal crystallizes in monoclinic system, space group P21/n with a = 8.668（2）,b = 22.236（4）, c = 9.539（2） A, β = 108.68（3）°, V = 1786.4（7）/k3, Z = 4, Dx= 1.288 g/cm3,F（000） = 736,μ（MoKa） = 0.649 mm^-1, the final R = 0.0354 and wR = 0.0933 with 3234observed reflections with I 〉 2σ（/）. The benzene and pyrazole rings are nearly coplanar with adihedral angle of 50.977（46）°. The dihedral angle between the central pyrazole and pyridinerings is 11.688（46）°. No classical hydrogen bonds were found in the molecules. Two adjacentmolecules in crystal packing of compound 5 were linked by two intramolecularhydrogen-bonding interactions C（15）-H（15）…O（1） to generate a stable structure. Compound 5had weak insecticidal activity against the diamondback moth （Plutella xylostella）, butexhibited good activity against cotton bollworm （Helicoverpa armigera）.

Synthesis,Crystal Structure and Antifungal Activity of N-((2,6-Difluorophenyl)carbamoyl)-1,3-dimethyl-1H-pyrazole-4-carboxamide

The title compound N-（（2,6-difluorophenyl）carbamoyl）-1,3-dimethyl-1 H-pyrazole-4-carboxamide（C13H12F2N4O2） was synthesized, and its structure was confirmed by ^1H NMR,HRMS and X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a = 9.50（2）, b = 10.11（2）, c = 14.07（3） A^°, β = 102.15（3）°, Dc = 1.480 g/cm^3, Z = 4, V = 1320（5） A^°3, the final R = 0.0789 and wR = 0.1860 for 1054 observed reflections with I 〉 2σ（I）. The preliminary biological test shows that the title compound has weak antifungal activities.

Synthesis, X-ray Crystallographic Analysis and Bioactivities of α-Aminophosphonates Featuring Pyrazole and Fluorine Moieties

A series of novel -aminophosphonates containing pyrazole and fluorine moieties was designed and synthesized through ultrasonic-assisted condensation and solvent-free addition reactions. Their structures were verified by IR, ^1H NMR, ^13C NMR and elemental analysis. The crystal structure of diethyl[（4-cyano-1H-pyrazol-3-ylamino）（3,5-difluorophenyl）methyl]phosphonate（4a, C15H17F2N4O3P） was determined by single-crystal X-ray diffraction. Compound 4a crystallizes in the triclinic system, space group P1 with a = 8.381（3）, b = 10.103（5）, c = 11.268（3） A, α= 83.772（19）, β= 74.726（19）, γ= 70.964（18）, V = 869.9（6） 3, Mr = 370.30, Dc = 1.414 g/cm^3, Z = 2, F（000） = 384, = 0.200 mm^-1, MoKa radiation（ = 0.71073 ）, the final R = 0.0487 and w R = 0.0823 for 1582 observed reflections with I 〉 2（I）. X-ray diffraction analysis reveals that there are two planes in 4a, and the dihedral angle is 71.51°. Two intermolecular hydrogen bonds and a face-to-face … stacking interaction are observed in the crystal structure. The compounds were evaluated for their antifungal, antiviral and antitumor activities, respectively. Among them, 4b, 4c, 4g and 4h exhibit good activities on Sclerotium rolfsii Sacc at 200 μg/m L, while 4b, 4c, 4f and 4g possess good anti-TMV activities at 500 μg/m L. Unfortunately, all of the compounds showed weak antitumor activities.

Synthesis,Crystal Structure and Antitumor Activity of 6-Chloro-1-((6-chloropyridin-3-yl)methyl)-3-phenyl-1H-benzofuro[3,2-c]pyrazole

The title compound 6-chloro-l-（（6-chloropyridin-3-yl）methyl）-3-phenyl-lH-benzofuro[3,2-c]pyrazole（5,C21H13Cl2N3O,Mr = 394.26） was synthesized and characterized by elemental analysis,^1H NMR,^13C NMR and X-ray single-crystal diffraction.The structure reveals that the crystal belongs to the triclinic system,space group P1 with a = 7.8829（8）,b = 10.3281（10）,c = 11.7615（12）A°,α = 83.5552（2）,β = 79.921（2）,γ = 70.189（2）°,V= 885.54（15） A°3,Z = 2,Dc =1.479 g/cm^3,μ = 0.383 mm^-1,F（000） = 404,R = 0.0538 and wR = 0.1335 for 2453 observed reflections with I 〉 2σ（I）.The result reveals that the crystal structure of the title compound 5 is stabilized by three C-Cl…π interactions and π…π stacking interaction.In addition,the preliminary investigation showed that 5 exhibits remarkably good antitumor activity against the MCF-7 and A549 cell lines.

Synthesis, Crystal Structure and Fungicidal Activity of 3-(Difluoromethyl)-1-methyl-N-((2-(trifluoromethyl)phenyl) carbamoyl)-1H-pyrazole-4-carboxamide

The title compound 3-（difluoromethyl）-1-methyl-N-（（2-（trifluoromethyl）phenyl）-carbamoyl）-1 H-pyrazole-4-carboxamide(C14 H11 F5 N4 O2) was synthesized, and its structure was confirmed by 1 H NMR, H RMS and X-ray diffraction. It crystallizes in monoclinic system, space group P21/n with a = 6.994（3）, b = 13.860（6）, c = 15.308（7） ?, β = 97.632（6）°, V = 1470.8（11） ?3,Z = 4, the final R = 0.0692 and wR = 0.2108 for 3989 observed reflections with Ⅰ > 2σ（Ⅰ）. The preliminary biological test shows that the title compound has moderate fungicidal activities against Pseudomonas syringae.

Syntheses,Crystal Structures and Antibacterial Activities of 5-Chloro-3-methyl-1-phenyl-1H-pyrazole-4-carboxylic Acid and Its Copper(Ⅱ) Compound

The title compounds 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carboxylic acid（C11H9Cl N2O2, HL）（1） and [Cu（L）2（H2O）]（2） were prepared and structurally characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compound 1（C11H9Cl N2O2） crystallizes in the monoclinic system, space group P21/n with a = 7.249（3）, b = 20.515（10）, c = 7.249（3）,β= 96.30°, V = 1071.6（9） ？3, Z = 4, Mr = 236.65, Dc = 1.467 g/cm3, F（000） = 488, GOOF = 1.029, μ= 0.341 mm-1, the final R = 0.0736 and w R = 0.1966 for 1500 observed reflections with I 〉 2σ（I）. Compound 2（C22H18Cl2Cu N4O5） crystallizes in the monoclinic system, space group P21/c with a = 7.2931（6）, b = 24.548（2）, c = 13.2726（11）, β= 99.4040（10）°, V = 2344.2（3） ？3, Z = 4, Mr = 552.84, Dc = 1.566 g/cm3, F（000） = 1124, GOOF = 1.050, μ= 1.201 mm-1, the final R = 0.0376 and w R = 0.1000 for 3626 observed reflections with I 〉 2σ（I）. 1 and 2 are connected through hydrogen bonding interactions to generate 2D and 3D supramolecular structures, respectively. Moreover, the preliminary antibacterial activities of 1 and 2 against the gram positive bacteria（S. aureus, C. albicans and B. subtilis） and gram negative bacteria（E. coli and P. aeruginosa） have been tested by using the microdilution method, and the results indicate that 2 is more active than 1 against the tested bacteria.

Synthesis,Crystal Structure and Antifungal Activities of 3-Methyl-1-(4-methylphenyl)-4-(N-4-trifluoromethylphenyl)-aminomethyl-5-(4-methoxyphenylthio)-1H-pyrazole

The title compound 3-methyl-l-（4-methylphenyl）-4-（N-4-trifluoromethylphenyl） aminomethyl-5-（4-methoxyphenylthio）-lH-pyrazole has been synthesized via a four-step reaction and characterized by IR, 1H NMR, elemental analysis and X-ray crystallography. The compound crystallizes in monoclinic, space group P21/c with a = 8.7170（15）, b = 18.355（3）, c = 15.292（3） A, fl = 103.445（3）°, V= 2379.7（7） A3, Dc = 1.350 g/cm3, Z = 4, p = 0.184, F（000） = 1008, and the final R = 0.0491 and wR = 0.1339 for 4160 observed reflections （I 〉 2a（/））. The results demonstrate that there is a face-to-face π-π stacking interaction between one benzene ring （C（19）-C（24）） and another （C（I 3）-C（! 8）） at a plane-plane distance of 3.3539 A. The ring normal and vector between the ring centroids form an angle of 18.2° up to the centroid-to-centroid distance of 3.5273 A. The crystal structure is stabilized by the intermolecular hydrogen bond of N（3）-H（3A）...N（2） （symmetry code： A -x＋l, -y＋l, -z）. The preliminary biological test shows that the title compound has a moderate antifungal activity.

Syntheses, Crystal Structures and Antifungal Activities of Two Compounds Containing Pyrazole and Pyrethroid Units

Compounds 1 （C15H17C1F3N303, Mr = 379） and 2 （C14H14C1F3N4OS, Mr = 378） have been synthesized and their crystal structures were determined by single-crystal X-ray diffraction. Crystal 1 belongs to the triclinic system, space group P1 with a = 6.0223（19）, b = 9.324（3）, c = 15.936（5） A, a = 80.687（5）, β= 87.289（5）, ）, = 86.097（5）°, V= 880.4（5） A3, Z = 2, Dc = 1.433 g/cm3,μ（MoKa） = 0.266 mm^-1, F（000） = 392, R = 0.0861 and wR = 0.1999 for 2022 observed reflections with I 〉 2o（/）. Crystal 2 belongs to the triclinic system, space group PI with a = 7.7029（15）, b = 8.3371（16）, c = 14.410（3） A, a = 100.672（3）, β= 103.168（3）, ？ = 98.726（3）°, V = 876.1（3） A3, Z = 2, Dc= 1.451 g/cm^3,μ（MoKa） = 0.379 mm^-1, F（000） = 388, R = 0.0672 and wR = 0.2105 for 2725 observed reflections with I 〉 2σ（I）. Although the two compounds are similar with the same pyrazole and pyrethroid units, X-ray analysis reveals that their structures are completely different.

Synthesis and Crystal Structureof Ethyl 5-Amino-1-[(5′-methyl-1′-t-butyl-4′-pyrazolyl)carbonyl]-3-methylthio-1H-pyrazole-4-carboxylate

The title compound, ethyl 5-amino-1-[(5?-methyl-1?-t-butyl-4?-pyrazolyl)carbonyl] -3-methylthio-1H-pyrazole-4-carboxylate 5, has been synthesized by the treatment of 4 with ethyl 2-cyano-3,3-dimethylthioacrylate, and its crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic, space group P21/c with a = 12.194(4), b = 12.909(4), c = 11.607(4) ?, β = 90.183(5)°, V = 1827.2(10) ?3, Mr = 365.45, Z = 4, Dc = 1.328 g/cm3, μ = 0.203 mm-1, F(000) = 776, R = 0.0586 and wR = 0.1558. Preliminary bioassays indicated that the title compound shows fungicidal and plant growth regulation activities.

Synthesis and Crystal Structure of 3-{[(1E)1-(2-Hydroxyphenyl) methylidene]amino}-4-cyanopyrazole

The title Schiff base compound （C11H8N4O）, a derivative of pyrazole, has been synthesized by the reaction of salicylaldehyde and 3-amino-4-cyanopyrazole in absolute ethanol and characterized by elemental analyses, IR, ^1H NMR and X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/n, with a = 7.5594（7）, b = 18.3342（19）, c = 22.461（2） A^°, β = 98.419（2）°, V = 3079.5（5） A^°3, Mr = 212.21, Z = 12, F（000） = 1320, Dc = 1.373 g/cm^3, T = 298（2） K, 2 = 0.71073 A^°, the final R = 0.0571 and wR = 0.0493. A total of 5412 unique reflections were collected, of which 1612 with I 〉 2σ（I） were observed. The molecular structure adopts a trans configuration about the C=N double bond. The preliminary biological tests show that the compound has high antibacterial activities.

Synthesis,Bioactivity and Crystal Structure Analysis of Diisopropyl[(4-cyanopyrazol-3-ylamino)(2-hydroxyl-phenyl) methyl]phosphonate

The title compound,diisopropyl[（4-cyanopyrazol-3-ylamino）（2-hydroxylphenyl） -methyl] phosphonate was synthesized by the addition reaction of diisopropyl phosphite and N-（4-cyanopyrazole-3-yl） -2-hydroxylphenyl-imine. Its structure was characterized by IR,1H NMR,elemental analysis and single-crystal X-ray diffraction. The crystal belongs to the triclinic system,space group P1^- with a = 9.1840（13） ,b = 9.2278（13）,c = 12.1952（17） A,α = 93.846（2） ,β = 90.947（2） ,γ = 111.289（2） °,V = 959.9（3） A^3,Dc = 1.309 g/cm^3,Z = 2,μ（MoKa） = 0.173,F（000） = 400,the final R = 0.0414 and wR = 0.1196 for 2985 observed reflections（I 〉 2σ（I）） . The pyrazole and benzene moieties are approximately coplanar in each case. The dihedral angle between planes 1 and 2 is 82.99°. The crystal structure is stabilized by three intermolecular hydrogen bonds of O（1） -H（1） …O（2） ,N（2） -H（2） …N（3） and N（2） -H（2） …O（1） . Preliminary bioassay indicated that the title compound possessed antiviral activity to some extent.

Synthesis, Crystal Structure and Biological Activity of 2-Chloro-5-(((5-(1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl)-4-phenyl-4H-1,2,4-triazol-3-yl)thio)methyl)thiazole

The title compound 5-chloro-2-（（（5-（1-methyl-3-（trifluoromethyl）-1H-pyrazol-4-yl）- 4-phenyl-4H-1,2,4-triazol-3-yl）thio）methyl）thiazole （C17H12ClF3N6S2） was synthesized, and its structure was confirmed by 1H NMR, 13C NMR, HRMS and X-ray diffraction. It crystallizes in the triclinic system, space group P with a = 8.214（5）, b = 10.188（6）, c = 12.378（7） , α = 81.679（8）, β = 87.994（8）, γ = 70.351（8）°, Dc = 1.572 g/cm3, Z = 2, V = 965.2（9） ？3, the final R = 0.0591 and wR = 0.1113 for 3005 observed reflections with I 〉 2σ（I）. The preliminary biological test shows that the title compound possesses good herbicidal activities （80%） against rape at 200 μg/mL.

Synthesis, Crystal Structure and Fungicidal Activity of 3-(4-Chloro-3-ethyl-1-methyl-1H-pyrazol-5-yl)-6-(E)phenylvinyltriazolo[3,4-b]-1,3,4-thiadiazole

The crystal structure of the title compound 3 (4 Chloro 3 ethyl 1 methyl 1H pyrazol 5 yl) 6 (E)phenylvinyltriazolo[3,4 b] 1,3,4 thiadiazole (C 17 H 15 ClN 6S, M r =370.87) was determined by single crystal X ray diffraction. The crystal is monoclinic, space group P2 1/n , a=10.862(2), b=11.541(2), c=14\^994(3), β=108.41(3)°, V=1783(1), Z=4, D x =1.381 g/cm -3 , μ =0.3361 mm -1 , and F (000)=768. The results confirmed that the title compound belongs to type E of stereochemistry. The dihedral angle between triazole and 1,3,4 thiadiaole ring is 3° and the torsion angle between 1,3,4 thiadiazole and pyrazole ring is 134.0°.

Synthesis, Crystal Structure and Biological Activity of 2-((2,2-Dimethyl-2,3-dihydrobenzofuran-7-yl)oxy)-N-(3-(furan-2-yl)-1-phenyl-1H-pyrazol-5-yl)acetamide

The title compound 2-（（2,2-dimethyl-2,3-dihydrobenzofuran-7-yl）oxy）-N-（3-（furan-2-yl）-1-phenyl-1H-pyrazol-5-yl） acetamide（C25H23N3O4, Mr = 429.46） has been synthesized, and its structure was characterized by 1H-NMR, 13C-NMR, H RMS, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 20.6205（18）, b = 5.2930（5）, c = 18.9282（17） A, β = 94.089（2）°, V = 2060.6（3） A^3, Z = 4, Dc = 1.384 g/cm^3, μ（Mo Ka） = 0.71073 mm^-1, F（000） = 904, R = 0.0345 and w R = 0.0930. The intramolecular hydrogen bond at N（1）–H（1）…O（2）, intermolecular weak interactions at O（3）…H（4） and weak π-π interactions connected the molecules to lead to one-dimensional tapes. Bioassay results indicated that the title compound had moderate herbicidal and fungicidal activities.

Synthesis and Crystal Structure of 2-Ethoxycarbonylmethyl-8-chloro-3a,4-dihydro-3a-methyl-chromeno[4,3-c]pyrazol-3(2H)-one

The crystal structure of the title compound 2-ethoxycarbonylmethyl-8-chloro-3a,4-dihydro-3a-methyl-chromeno[4,3-c]pyrazol-3（2H）-one（C15H15ClN2O4,Mr = 322.74） has been prepared and determined by single-crystal X-ray diffraction.The crystal is of orthorhombic,space group Pccn with a = 16.7246（10）,b = 19.6626（12）,c = 9.3013（6） ,V = 3058.7（3） 3,Z = 8,Dc = 1.402 g/cm3,μ = 0.269 mm-1,F（000） = 1344,the final R = 0.0506 and wR = 0.1464 for 2568 reflections with I 〉 2σ（I）.In addition,disordered C（14） and C（15） atoms exist in the crystal structure.

Synthesis and Crystal Structure of S-(+)-N′-Tertbutylaminocarbonyl-N-[3-methyl-2-(4-chlorophenyl)butyryl] Thiourea

The title compound S-（＋）-N＇-tertbutylaminocarbonyl-N-[3-methyl-2-（4-chlorophenyl）butyryl] thiourea has been synthesized and its crystal structure was determined by singlecrystal X-ray diffraction analysis. There exist intramolecular N（2）-H（2A）…O（1）, C（17）-H（17A）… O（2） and N（3）-H（3A）…S（1） hydrogen bonds as well as intermolecular N-H…O interaction between the carbonyl and amidogen groups. Crystallographic data： CITH24ClN3O2S, Mr = 369.90, monoclinic, space group C2/c with a = 22.9922（19）, b = 14.4844（12）, c = 12.4618（11） A, β = 92.608（2）°, V = 4145.8（6） ]k3, Z = 8, Dc = 1.185 g/cm^3, F（000） = 1568, g（MoKa） = 0.298 mm^-1, R = 0.0578 and wR = 0.1308.

吡唑锌配合物的合成、晶体结构及抗肝癌细胞活性

通过溶剂挥发法合成了锌配合物[Zn(Hppo)2(ppo)Cl](1),Hppo=5-苯基-3-羟基吡唑,利用元素分析、FTIR以及X射线衍射法对配合物1进行表征。晶体结构显示配合物属于单斜晶系,P21空间群。检测了配合物1对肝癌细胞HepG2、Hep3B和Huh7的细胞形态与细胞毒性的影响,结果表明配合物1对肿瘤细胞具有明显的抑制作用。

吡唑-3-甲酸配合物的合成、结构及性质研究

选用吡唑-3-甲酸为主配体,通过溶剂热法合成出两种配合物{[Ag3(3-PCA)3][Ag(DMAP)2]3}·10H2O(1)和[Cu2(3-PCA)2(DMAP)4]·2H2O(2)(3-PCA=pyrazole-3-carboxylic acid,DMAP=4-Dimethylaminopyridine).用X射线单晶衍射仪测定了它们的晶体结构,并进行了红外表征.结果显示,配合物(1)为单斜晶系,空间群为Pc,晶胞参数为a=0.9409(8)nm,b=1.3411(8)nm,c=2.8699(2)nm,Z=2,V=3.6215(5)nm^3;配合物(2)属于三斜晶系,空间群为Pī,晶胞参数为a=0.8999(14)nm,b=1.0870(18)nm,c=1.1050(17)nm,α=78.426(14)°,β=68.732(15)°,γ=87.237(13)°,Z=1,V=0.9865(3)nm 3.对配合物(1)进行了固态荧光测试,结果表明其具有荧光性质;对配合物(2)进行了生物活性研究,结果表明该配合物可与BSA相互作用.