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.

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 Structure of 7-Ethoxycarbonyl-2-methyl-6-methylthio-1H-imidazo[1,2-b]pyrazole

The title compound 7-ethoxycarbonyl-2-methyl-6-methylthio-lH-imidazo[1,2-b]- pyrazole （Mr = 239.29） was synthesized and structurally characterized by IR, ^1H NMR and single-crystal X-ray diffraction. It belongs to the triclinic system, space group P1, with a =8.0461（10）, b = 8.5534（11）, c = 9.5605（12）А,α= 64.804（2）,β= 74.231（2）, γ= 76.885（2）°, V = 568.27（12）А^3, Z = 2,Dc= 1.398 g/cm^3,μ= 0.274 nunl, F（000） - 252, the final R = 0.0454 and wR = 0.1261. A total of 3360 reflections were collected, of which 2466 were independent （R_int = 0.0138） and 2154 were observed with I〉2σ（I）.

Synthesis and Crystal Structure of Ethyl 1-(2-bromoethyl)-3-(4-meth-oxyphenyl)-1H-pyrazole-5-carboxylate

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.

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)A,β= 97.632(6)°, V = 1470.8(11) A^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.

Synthesis and Crystal Structure of 1-(1'- t- Butyl-5'-methyl-4-pyrazolyl-carbonyl)- 3,5-dimethyl-1H-yl-pyrazole

The crystal structure of 1-(1-t-butyl-5-methyl-4-pyrazolylcarbonyl)-3,5-dimeth- yl-1H-yl-pyrazole ([C14H20N4O]2, Mr = 520.68) has been determined by single-crystal X-ray diffraction analysis. The crystal belongs to triclinic, space group P with a = 11.049(4), b = 11.313(4), c = 13.964(5) , ?= 69.085(6), b = 75.962(6), = 62.245(6), V = 1436.7(9) 3, Z = 2, Dc = 1.204 g/cm3, m = 0.079 mm-1, F(000) = 560, R = 0.0790 and wR = 0.1416 for 4729 unique reflections with 2635 observed ones (I > 2(I)). The results indicate that the pyrazole rings display aromaticity. The four pyrazole moieties are approximately coplanar in each case. The dihedral angles between planes 1 and 2, 3 and 4 are 40.99 and 10.77? respectively.

Crystal Structures of Two Compounds from a Rapid and One-pot Synthesis Method

Compounds 1 （C17H22N2,Mr =254.37） and 2 （C13H16N2,Mr=200.28） have been synthesized and their crystal structures were determined by single-crystal X-ray diffraction.Crystal 1 belongs to triclinic,space group P（1） with a =6.524（2）,b =8.987（3）,c =12.746（5） A,α =95.220（7）,β =90.055（6）,γ =104.431（6）°,V =720.5（4） A^3,Z =2,Dc =1.173 g/cm^3,μ（MoKα） =0.069 mm1,F（000） =276,R =0.0578 and wR =0.1221 for 1487 observed reflections Ⅰ 〉 2o（Ⅰ）.Crystal 2 is of tetragonal system,space group Ⅰ41/a with a =20.763（10）,b =20.763（10）,c =11.427（6） A,V=4926（4） A3,Z =16,Dc =1.080 g/cm^3,μ（MoKα） =0.065 mm-1,F（000） =1728,R =0.0581 and wR =0.1288 for 1408 observed reflections with Ⅰ 〉 2σ（Ⅰ）.Although the two compounds are similar with the same pyrazole and benzene ring units,X-ray analysis reveals that their structures are completely different maybe caused by steric effects.

Synthesis and Crystal Structure of [Cu_3(dmpzm)_4(μ-1,3-dca)_2(dca)_4]·2H_2O (dmpzm=1,1'-Methylenebis-(3,5-dimethyl-1H-pyrazole),dca=dicyanamide)

The title compound, [Cu3（dmpzm）4（μ-1,3-dca）2（dca）4]·2H2O （dmpzm = 1,1＇-methylenebis（3,5-dimethyl-lH-pyrazole）, dca = dicyanamide） 1·2H2O, was synthesized via the reaction of CuCl2·2H2O with dmpzm and Na（dca）, and characterized by elemental analysis and IR spectra. 1·2H2O crystallizes in the monoclinic system, space group C2/m with a = 13.578（3）, b = 16.769（3）, c = 14.769（3） A, β = 104.10（3）° V = 3261.4（11） A^3, Z = 2, Dc = 1.466 g/cm^3, T = 153（2） K, C56H68N34O2Cu3, Mr = 1440.09, F（000） = 1490,μ（MoKa） = 1.040 mm^-1, S = 1.150, R = 0.0553 and wR = 0.1123 for 2744 observed reflections with I 〉 2σ（I）. The central copper atom is chelated by two dmpzm ligands and coordinated by two bridging dca anions, forming a slightly distorted octahedral geometry. The two external copper atoms adopt a square-pyramidal coordination geometry, coordinated by one chelating dmpzm ligand and one bridging and two terminal dca anions. Two intermolecular hydrogen bonding interactions result in the formation of a 2D （4,4） hydrogen-bonded network.

Synthesis and Crystal Structure of 2[1-(1,1-Dimethylethyl)-5-methyl-1-H-pyrazol- 4-ylcarbonyl]-N-phenyldrazinecarbothioamide

The crystal structure of 2[1-(1,1-dimethylethyl)-5-methyl-1-H-pyrazol-4-ylcar- bonyl]-N-phenyldrazinecarbothioamide ([C16H21N5OS]CH3COCH3, C19H27N5O2S, Mr = 389.52) has been determined by single-crystal X-ray diffraction. The crystal belongs to tetragonal, space group I41/a with a = 23.960(4), b = 23.960(4), c = 16.120(5) , V = 9254(4) 3, Z = 16, Dc = 1.118 g/cm3, m = 0.161 mm-1, F(000) = 3328, R = 0.0660 and wR = 0.1305 for 3878 unique reflections with 1653 observed ones (I > 2(I)). The intermolecular hydrogen bond between N(3)H(3B)…O(1), N(5) H(5A)…S(1) and N(4)H(4D)…O(2) has been observed.

Synthesis and Crystal Structure of 2(1-Phenyl-3-methyl-5-chloro-1H-pyrazol- 4-yl)-3-(1-naphthoylamido)-4-thiazolidinone

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.

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 and Crystal Structure of 3,7,7-Trimethyl-1-phenyl-4-(3-nitrophenyl)-4,5,6,7,8,9-hexahydro-1H-pyrazolo[3,4-b]quinoline-5(6H)-one

The title compound (C25H24N4O3) has been prepared by the cyclocondensation of 5-amino-3-methyl-1-phenypyrazol, m-nitrobenaldehyde and dimedone in glycol under microwave irradiation without catalyst. The crystal structure was determined by single-crystal X-ray diffraction to be orthorhombic, space group Pbca with a = 16.3331(10), b = 13.8329(9), c = 19.4163(12) ?, V = 4386.8(5) ?3, Z = 8, Dc = 1.298 g/cm3, μ = 0.087 mm-1, F(000) = 1808, Mr = 428.48, the final R = 0.0519 and wR = 0.1019. X-ray analysis revealed that the pyridine ring is of boat conformation and the six-membered ring fused with it adopts twist boat conformation.② Corresponding author. Tu Shu-Jiang, born in 1957, professor, majoring in the synthesis of organic and heterocycle compounds. E-mail: laotu2001@ 263.net

Synthesis, Bioactivity and Crystal Structure Analysis of 2-(Benzo[d]isothiazol-3-yloxy)-N-(3-cyano-1-(4-fluorophenyl)-1H-pyrazol-5-yl) Acetamide

A novel benzisothiazolin-3-one derivative, 2-（benzo[d]isothiazol-3-yloxy）-N-（3- cyano-l-（4-fluorophenyl）-lH-pyrazol-5-yl） acetamide （8）, was synthesized from the initial compound benzo[d]isothiazol-3（2H）-one （BIT） 1 and 4-fluoroaniline 3. The structure of the target compound 8 was determined by elemental analyses, IR and 1H NMR. The single crystals of intermediate compound 6 and the target compound 8 were obtained and determined by X-ray diffraction analysis. The preliminary biological activity was also evaluated and the results showed tile target compound exhibited a good anti-microbial activity.

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 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 Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.

Synthesis and Crystal Structure of 3-(5-Amino-4-ethoxycarbonyl-3-methylthio- 1-H- pyrazolyl)-5-phenyl-1,2,4-triazine

The crystal structure of 3-（5-amino-4-ethoxycarbonyl-3-methylthio-l-H-pyrazolyl）-5-phenyl- 1,2,4-triazine （C16H16N6O2S, Mr = 356.41） has been determined by single-crystal X-ray diffraction. It belongs to monoclinic, space group P2（1/c） with a = 16.961（14）, b = 7.297（6）, c = 13.857（11）A^°, β = 109.803（13）°, V = 2237（2）A^°3, Z = 4, Dc = 1.467 g/cm^3,μ = 0.225 mm^-1, F（000） = 744, R=0.0477 and wR = 0.1156 for 2847 unique reflections with 1713 observed ones （I 〉2σ（I））. X-ray analysis reveals that there exist both intra- and intermolecular hydrogen bonds in the crystal lattice.

Synthesis and Crystal Structure of 4-Phenyl-5-(1't-butyl-5'-methyl-4'-pyrazolyl)-1,2,4-triazol-3-thione

The crystal structure of 4-phenyl-5-(1-t-butyl-5-methyl-4-pyrazolyl)-1,2,4-triazol- 3-thione 5 (C16H19N5S, Mr = 313.42) has been determined by single-crystal X-ray diffraction analysis. The crystal belongs to monoclinic, space group P21/c with a = 6.680(2), b = 27.44(1), c = 9.388(4) ? b = 106.738(6), V = 1648(1) 3, Z = 4, Dc = 1.263 g/cm3, m = 0.200 mm-1, F(000) = 664, R = 0.0608 and wR = 0.1176. The results confirmed that 5 can be assigned to the thione tautomeric form.

Syntheses,Crystal Structures and Herbicide Activities of Two Pyrazole Derivatives

Two novel N-acyl-3-phenylpyrazol benzophenones were designed and synthesized via cyclization and acylation with 1,3-diphenylpropane-1,3-dione and dimethylformamide dimethylacetal as the starting materials.Both of the newly synthesized compounds were characterized with IR,~1H NMR,^（13）C NMR,HRMS and single-crystal X-ray diffraction.3-Phenyl-1-o-methylbenzoyl-pyrazole-4-benzophenone（5 a） and 3-phenyl-1-p-fuorobenzoyl-pyrazole-4-benzophenone（5 b） crystallize in triclinic system,space group P1.The existence of p-π conjunction effect resulted in correlative bond length shorter than the typical bond length in both of the crystals.The presence of van der Waals forces leads to the stability of the compounds.

Syntheses and Crystal Structures of Two Nickel(Ⅱ) Complexes [Ni(dmpzm)_2(L)]Cl·nH_2O (L=HCO_2,OAc;n=2,3;dmpzm=1,1'-Methylenebis(3,5-dimethyl-1H-pyrazole))

Reactions of NiCl2-6H2O with dmpzm and formic or acetic acid at PH = 7 produced the two title compounds, [Ni（dmpzm）2（HCO2）]Cl·2H2O 1 and [Ni（dmpzm）2（OAc）]C2·H2O 2 （dmpzm = 1,1 ＇-methylenebis（3,5-dimethyl-lH-pyrazole））. 1 and 2 were characterized by elemental analysis, IR spectra, and thermogravimetric analysis. 1 crystallizes in the orthorhombic system, space group Pcca with a = 18.700（2）, b = 8.6843（9）, c = 18.098（2）A, V= 2939.1（5）A^3, Z = 4, Dc = 1.319 g/cm^3, T = 193 K, C23H37CINsNiO4, Mr = 583.75, F（000） = 1232, p（MoKa） = 0.792 cm^-1, S = 1.079, R = 0.0772 and wR = 0.1958 for 2265 observed reflections with I〉 2σ（I）. 2 crystallizes in the orthorhombic system, space group Pcca with a = 17.011（3）, b = 18.630（4）, c = 19.300（4）A, V = 6117（2）A^3, Z = 8, Dc = 1.337 g/cm^3, T= 193（2） K, C24H41C1N8NiO5, Mr = 615.79, F（000） = 2608, μ（MoKa） = 0.768 cm^-1, S = 1.059, R = 0.0518 and wR = 0.1109 for 5124 observed reflections with I 〉 2σ（I）. The Ni atoms in 1 or 2 are chelated by two dmpzm ligands and one formate or acetate anion, forming slightly distorted octahedral geometries. In the crystals of 1 or 2, intermolecular hydrogen bonding interactions result in the formation of 2D hydrogen-bonded frameworks.