The novel title compound 1-（4-methoxybenzylidene）-2-（1-phenyl-6-trifluoromethyl- 1H-pyrazolo[3,4-d]pyrimidin-4-yl）hydrazine monohydrate （C20HisF3N60-H20, Mr = 430.40） has been synthesized by a four-step procedure including the cyclization, chlorination, hydrazinolysis and condensation reaction, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space groupPbca with a = 8.3779（13）, b = 17.607（3）, c = 26.774（4） A, V= 3949.2（11） A3, Z=8, Dc = 1.448 g/cm3, μ = 0.117 mm-l, F（000） = 1776, the final R = 0.0553 and wR = 0.1516 for 2354 observed reflections with 1 〉 2σ（/）. X-ray diffraction analysis reveals that the title compound is almost coplanar except for the trifluoromethyl and phenyl moieties. In the crystal packing, the molecules are linked by intermolecular O（lW）-H（1WA）-＂N（2）, O（1W）-H（1WA）.--N（4） and N（5）-H（5A）...O（lW） hydrogen bonds via water molecules and stacked through π-π stacking interactions. The preliminary bioassay suggested that the title compound exhibits relatively good antitumor activity against HepG2 and BCG-823.
The title compound N-[5-（benzylthio）-1,3,4-thiadiazol-2-yl]-4-chlorobenzamide（C（16）H（12）ClN3OS2, Mr = 361.86） was designed and synthesized as anticancer agent, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1 with a = 5.7417（10）, b = 9.8057（17）, c = 14.330（3） A, a = 91.987（3）, b = 97.154（3）, γ = 93.402（3）°, V = 798.4（2） A3, Z = 2, Dc = 1.505 g/cm^3, μ = 0.507 mm-1） F（000） = 372, the final R = 0.0481 and wR = 0.1290 for 2064 observed reflections with I 〉 2s（I）. In the crystal packing, the molecules form stacks by a three-dimensional framework, which results from intermolecular N（1）-H（1）···N（2） and C（5）-H（5）···N（3） hydrogen bonds together with π-π stacking interactions between the thiadiazole and chlorobenzene rings. The title compound was found to exhibit more potent in vitro antitumor activities against the four tested cancer cell lines than sorafenib.
The novel title compound 4-chlorobenzaldehyde （2-trifluoromethyl-5,6,7,8- tetrahydro- benzo[4,5]thieno[2,3-d]pyrimidin-4-yl）hydrazone monohydrate （C18H14C1F3N4S.H20, Mr = 428.86） has been synthesized by a condensation reaction of 4-chlorobenzaldehyde with （2-trifuoromethyl-5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-4-yl）hydrazine, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 7.4252（7）, b = 26.344（2）, c = 10.3095（9） A, /3 = 109.407（2）~, V= 1902.0（3） A3, Z = 4, Dc = 1.498 g/cm^3, p = 0.356 mm-1, F（000） = 880, the final R = 0.0564 and wR = 0.1681 for 2343 observed reflections with I 〉 2o（/）. X-ray diffraction analysis reveals that the title hydrazone molecule is nearly planar except for the cyclohexene and trifluoromethyl moieties. In the crystal packing, the molecules form stacks by a three-dimensional framework, which results from intermolecular N（3）-H（3）...O（1）, O（1）-H（1B）...N（2）, O（1）- H（1B）...N（4） and O（1）-H（1A）...F（1） hydrogen bonds via water molecules together with π-π stacking interactions. Molecular geometry of the title compound in the ground state optimized by B3LYP functional with 6-311G＊＊ basis sets indicates that the calculations are in agreement with the experimental data. The preliminary bioassay suggested that the title compound exhibits relatively good fungicidal activity against Fusarium oxysporium fsp.vasinfectum and Dothiorella gregaria.
A series of novel 2-trifluoromethylthieno[2,3-d]pyrimidine derivatives were synthesized by a facile three-step procedure that afforded advantages of mild reaction conditions, simple protocol and good yields. The structures of the final compounds were confirmed by 1R, NMR, El-MS, elemental analysis, and X-ray diffraction. Preliminary bioassay results showed that some of the analogs exhibit excellent antitumor activity against MCF-7 and HepG2, especially compounds 3a, 3b, 3e and 3h exhibited higher activity than the positive control gefitinib.
Xin-Jian SongPing YangHui GaoYan WangXing-Gao DongXiao-Hong Tan
Two enantiomeric 2-trifluoromethyl-6,7-dihydro-5H-cyclopenta[4,5]thieno[2,3-d] pyrimidin-4-amine derivatives were synthesized by nucleophilic substitution of two chiral amines with 4-chloro-2-trifiuoromethyl-6,7-dihydro-5H-cyclopenta[4~5]thieno[2-3-d]pyrimidine, which started from 2-amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile, trifluoroacetic acid （TFA） and phosphoryl trichloride via one-pot procedure. Their structures were determined by single-crystal X-ray diffraction. Enantiomer （R）-3,（R）-N-（1-phenylethyl）-2-trifluoromethyl-6,7- dihydro-5H-cyclopenta[4,5]thieno[2,3-d]pyrimidin-4-amine crystallizes in the tetragonal system, space group P43 with a = 8.6847（6）, b = 8.6847（6）, c = 22.419（2） A, V= 1690.9（3） A3, Z = 4, Dc = 1.428 g/cm^3, p = 0.228 mm-1, F（000） = 752, the final R = 0.0463 and wR = 0.1257 for 3442 observed reflections with 1〉 20（/）. Enantiomer （S）-3,（S）-N-（1-phenylethyl）-2-trifluoromethyl-6,7-dihydro- 5H-cycloperita[4,5]thieno[2,3-d]pyrimidin-4-amine crystallizes in the tetragonal system, space group P41 with a = 8.688, b = 8.688, c = 22.421 A, V = 1692.4 A3, Z = 4, Dc = 1.426 g/cm^3, μ= 0.227 mm^-1, F（000） = 752, the final R = 0.0682 and wR = 0.1806 for 3182 observed reflections with ≥20（I）. The preliminary bioassay indicated that the R-enantiomer exhibits higher antitumor activity against MCF-7 than gefitinib.
N-(5-Aryl-1,3,4-thiadiazol-2-yl)-N?-((E)-styryl)ureas 4 a～4 i were designed and synthesized as antitumor agents, and their structures were characterized by IR, 1 H NMR, 13 C NMR,MS and elemental analysis. The single crystal of compound 4 a, C17 H13 FN4 OS, was also determined by X-ray crystallography. Crystal data: monoclinic, space group P21/n, a = 4.9401(8), b= 8.7100(15), c = 36.604(6) ?, β = 93.320(3)°, V = 1572.4(5) ?3, Z = 4, F(000) = 704, Dc = 1.438 g/cm3, μ = 0.228 mm-1, R = 0.0600 and wR = 0.1448 for 2743 independent reflections(Rint =0.0418) and 2174 observed ones(I > 2σ(I)). The in vitro antitumor activities of compounds 4 a～4 i were preliminarily evaluated by the standard MTT assay.
SONG Xin-JianWANG Xu-MeiSUN QiHUANG Sheng-TianWANG Yan
The title compound 4-(5-(2,6-difluorophenyl)-1,3,4-oxadiazol-2-ylthio)-2-(trifluoromethyl)thieno[2,3-d]pyrimidine(C15H5F5N4OS2, Mr = 416.35) was designed and synthesized as antitumor agent, and its structure was determined by 1H NMR, 13C NMR, MS, elemental analysis and single-crystal X-ray diffraction. The crystal belongs to monoclinic system, space group P21/c with a = 9.904(2), b = 10.057(2), c = 16.595(3) ?, β = 100.000(3)°, V = 1627.9(6) ?3, Z = 4, F(000) = 832, Dc = 1.699 g/cm3, μ = 0.395 mm-1, R = 0.0468 and wR = 0.1255 for 4726 independent reflections(Rint = 0.0336) and 2847 observed ones(I > 2σ(I)). The in vitro antitumor activity of the title compound was preliminarily evaluated by the standard MTT assay.
SONG Xin-JianLI Chen-ChenWANG Xu-MeiSUN QiYANG Ping
