Synthesis,Crystal Structure and Anticancer Property of (Z)-N-(4-Bromo-5-ethoxy-3,5-dimethyl-furan-2(5H)-ylidene)-4-methylbenzenesulfonamide

The novel title compound（Z）-N-（4-bromo-5-ethoxy-3,5-dimethylfuran-2（5H）-yli-dene）-4-methylbenzenesulfonamide 1（C15H18BrNO4S） has been unexpectedly synthesized by the aminohalogenation reaction of ethyl 2-methylpenta-2,3-dienoate with TsNBr2,and characterized by mp,IR,1H NMR,EIMS,ESIHRMS and single-crystal X-ray diffraction.It crystallizes in mono-clinic,space group P21/c with a = 11.714（5）,b = 14.106（5）,c = 10.402（4） ,β = 97.298（8）°,V = 1704.9（12） 3,Mr = 388.27,Z = 4,Dc = 1.513 g/cm3,μ（MoKα） = 2.549 mm-1,F（000） = 792,the final R = 0.033 and wR = 0.062 for 3098 observed reflections（Ⅰ 〉 2σ（Ⅰ））.

Theoretical Study on the Reaction Mechanism of 2-Methoxybenzaldehyde,4-Bromo-indanone,Malononitrile and Ammonium Acetate One-pot to Form 6-(2-Methoxyphenyl)-2-amino-6-bromo-5H-indeno[1,2-b]pyridine-3-carbonitrile

The reaction mechanism of 2-methoxybenzaldehyde, 4-bromo-indanone, malononitrile and ammonium acetate one-pot to form 6-（2-methoxyphenyl）-2-amino-6-bromo-5 Hindeno[1,2-b]pyridine-3-carbonitrile was studied by density functional theory. The geometries of the reactants, transition states, intermediates and products were optimized at the PW91/DNP level. Vibration analysis was carried out to confirm the transition state structure. Reaction pathways were investigated in this study. The result indicates that the reaction Re→ TSB1→IMB1→ TSB2→ IMB2→TSB3→IMB3→TSB4→IMB4→TSB5→IMB5→TSB6→IMB6→TSB7→IMB7→ TSB8→IMB8→TSB9→IMB9→P2 is the main pathway, the activation energy of which is the lowest. The dominant product predicted theoretically is in agreement with the experiment results.

Synthesis, Crystal Structure and Biological Activities of 3-Bromo-5-(4-chlorophenyl)-4-cyanopyrrole-N,N-dimethyl-2-carboxamide

The title compound 3-bromo-5-（4-chlorophenyl）-4-cyanopyrrole-N,N-dimethyl-2-amide（3） was synthesized with 4-bromo-2-（4-chlorophenyl）-5-（trifluoromethyl）-1H-pyrrole-3-carbonitrile（1） and N,N-dimethylformamide（2） by the α-C acylation reaction catalyzed by potassium t-butoxide, and characterized by IR, 1H-NMR and X-ray single-crystal diffraction. It crystallizes in monoclinic, space group P2（1/n）with a = 12.789（2）, b = 13.783（2）, c = 17.980（3） °, β = 109.230（3）°, V = 2992.5 A3, Mr = 352.62, Dc = 1.565 mg/m3, Z = 8, m = 2.924 mm-1, F（000） = 1408, the final R = 0.0424 and w R = 0.0973 for 3518 observed reflections with I 〉 2σ（I）. A total of 23559 reflections were collected, of which 6242 were independent（Rint = 0.0566）. The insecticidal, herbicidal and antibacterial activities of compound 3 were determined, and the experimental results showed that the mortality of 3 at the concentration of 100 ppm on the Fipronil against Linnaeus was 76.6%, the growth inhibition rate of 3 against Cynodon Dactylon under the condition of 100 ppm was 35.8% and the inhibitory activity of 3 at the concentration of 25 ppm against Fusarium graminearum reached 50.9%. Hence, the title compound has the value of further research and application prospect.

Synthesis and Crystal Structure of 4-Bromo-5-ethoxy-3-methyl-5- (naphthalen-1-yl)-1-tosyl-1H-pyrrol-2(5H)-one

The title compound 4-bromo-5-ethoxy-3-methyl-5-（naphthalen-l-yl）-l-tosyl-lH- pyrrol-2（5H）-one 1 （C24H22BrNO4S, Mr = 500.40） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 8.8562（15）, b = 18.118（3）, c = 14.055（2）A, β = 99.855（3）^o, V= 2221.9（6）A3, Z = 4, Dc = 1.496 g/cm^3,μ= 1.975 mm^-1, 2 = 0.71073A, F（000） = 1024, R = 0.0607 and wR = 0.1371.

Synthesis and Crystal Structure of N1-(2-(4-Bromo-2-nitrophenoxy)-2-dimethyl acyloxymethyl)-5-fluorouracil

The title compound N1-（2-（4-bromo-2-nitrophenoxy）-2-dimethyl acyloxymethyl）-5-fluorouracil（C15H13BrFN3O7, Mr = 446.19） was synthesized and structurally characterized by ^1H-NMR, -（13）C-NMR, ESI-MS and single-crystal X-ray diffraction. The compound crystallizes in triclinic, space group P1, with a = 8.3325（6）, b = 10.1808（13）, c = 11.8194（16） A, α = 73.194（12）, β= 72.351（9）, γ = 89.509（8）o, V = 911.2（2） A^3, Z = 2, T = 300.79（10） K, μ（Cu Kα） = 3.578 mm^-1, Dc = 1.626 g/cm3, F（000） = 448.0, GOF = 1.060, 5723 reflections measured（8.232≤2θ≤139.592°）, 3339 unique（Rint = 0.0184, Rsigma = 0.0254） which were used in all calculations. The final R = 0.0517（I 〉 2s（I）） and wR = 0.1494（all data）. Hydrogen bonds and π-π interactions together stabilize the structure of the molecule. The preliminary biological test shows that the title compound has good antitumor activity against A549 in vitro and lower toxicity to normal cells.

Synthesis, Structure and Photophysical Properties of Silole-Oxadiazole Copolymers

A new conjugated copolymer （PTST-DyOXD） derived from 1,1-dimethyl-3,4-diphenyl-2,5-bis（5-bromo-2- thienyl）-silole （TST） and 2,5-bis（4-ethynylphenyl）-l,3,4-oxadiazole （DyOXD） was synthesized by Pd（0）-catalyzed Sonogashira coupling reaction. For comparison, another copolymer without acetenyl group （PTST-OXD） was also synthesized by Pd（0）-catalyzed Suzuki coupling reaction. Chemical structures and optoelectronic properties of the copolymers were characterized by IH NMR, 13C NMR, IR, UV-vis absorption, photoluminescence and cyclic voltammetry. The number-average molecular weight （Mn） is 4010 Da for PTST-DyOXD and 3890 Da for PTST-OXD, respectively. The thermogravimetric analysis （TGA） measurements show that they have good thermal stability with decomposition temperature at 312 and 318 ~C, respectively. The optical band gap is 2.21 eV for PTST-DyOXD and 2.10 eV for PTST-OXD based on the absorption onset. CV analysis revealed the LUMO level of PTST-DyOXD is -3.04 eV, lower than that of PTST-OXD （about -2.89 eV）, which is attributed to the introduction of acetylene group in PTST-DyOXD, increasing the system of the conjugate chain length.