(±)-3,5-二羟基-7,4′-二甲氧基二氢黄酮醇和(±)-3,5,7-三羟基-4′-甲氧基二氢黄酮醇的全合成

3,5 -二羟基 - 7,4′-二甲氧基二氢黄酮醇 ( 1 )从 Cephalanthus spathelliferus中分离得到后 [1] ,又在H aplopappus bayahuen[2 ] 和 L annea coromandelica[3] 等植物中被发现 ,在印度一直被用于治疗象皮病、阳痿、溃疡、阴道炎、口臭、痢疾和风湿病等 . 3,5 ,7-三羟基 - 4′-甲氧基二氢黄酮醇 ( 2 )首次从 Prunusdonestica[4 ] 中分离出来后 ,又从 Salix caprea L.,Brazilian propolis中得到 .研究表明 ,该化合物具有抗菌、抗肿瘤活性 .我们用与文献 [5 ]类似的方法以 2 ,4,6-三羟基苯乙酮和茴香醛为起始原料 ,经选择性保护、缩合、…     

5,7-二羟基-4''''-甲氧基二氢黄酮与牛血清白蛋白的相互作用研究

应用荧光光谱、紫外吸收光谱和核磁共振波谱研究了5,7-二羟基-4'-甲氧基二氢黄酮(ISO)与牛血清白蛋白(BSA)分子间的相互作用.研究表明:ISO对BSA内源性荧光的猝灭机制属于ISO和BSA形成化合物所引起的静态猝灭;二者的结合常数为7.41×1011L/mol,结合位点数为1.98.ISO与BSA作用的活性部位为其分子内的7-OH和5-OH,且7-OH活性强于5-OH,并且随着ISO浓度增大,BSA的构象发生了变化.     

(±)-3,5-二羟基-7,4′-二甲氧基二氢黄酮醇和(±)-3,5,7-三羟基-4′-甲氧基二氢黄酮醇的全合成

3,5-二羟基-7,4′-二甲氧基二氢黄酮醇(1)从Cephalanthus spathelliferus中分离得到后[1], 又在Haplopappus bayahuen[2]和Lannea coromandelica[3]等植物中被发现, 在印度一直被用于治疗象皮病、阳痿、溃疡、阴道炎、口臭、痢疾和风湿病等. 3,5,7-三羟基-4′-甲氧基二氢黄酮醇(2)首次从Prunus donestica[4]中分离出来后, 又从Salix caprea L., Brazilian propolis中得到. 研究表明, 该化合物具有抗菌、抗肿瘤活性. 我们用与文献[5]类似的方法以2, 4, 6-三羟基苯乙酮和茴香醛为起始原料, 经选择性保护、缩合、环氧化、关环首次完成了化合物(±)-1和(±)-2的全合成. 合成路线如下:     

藉聚2-丙烯胺缩-3-(4-甲酰基苯偶氮)-4,5-二羟基-2,7-萘二磺酸分光光度法测定生物体液、食品和饮品中的镁

聚2-丙烯胺缩3－（4-甲酰基苯偶氮）-4，5-二羟基-2，7-萘二磺酸（PA-FPNS）在pH11．5的磷酸盐介质中．与镁（Ⅱ）形成一蓝色络合物，其最大吸收位于604nm，表观摩尔吸光系数ε=5．7×104L·mol-1·cm-1，线性范围为0．01～0．35mg／L，至少稳定12h。考察了30多种共存离子的影响，在所测样品中它们不干扰，无需掩蔽或分离即可直接测得其中的镁。     

两种苯并二氢吡喃-4-酮衍生物的合成

分别以间甲氧基苯酚与间苯二酚为原料,经过3步合成了(E)-7-甲氧基-3(4-甲氧基苯哑甲基)与(E)-7-羟基-3-(3',4',5'-三甲氧基苯哑甲基)取代的苯并二氢吡喃-4-酮.合成路线简单,易于操作,两者的最终收率分别为20.1%和15.3%.     

通过α-重氮-β-二酮与醛酮的环加成反应合成4H-1,3-二噁环己-5-烯-4-酮衍生物

研究了α-重氮-β-二酮与各类羰基化合物的环加成反应,合成了一系列4H-1,3-二噁环己-5-烯-4-酮衍生物.     

4-(7-甲氧基-2,2-二甲基-2,3-二氢苯并呋喃-5-基)-2-芳氨基噻唑的合成、晶体结构与杀虫活性

以2-(2-甲基烯丙氧基)苯酚为原料, 经Claisen重排、呋喃环化、醚化、Friedel-Crafts乙酰化、α-溴代和噻唑环化等反应合成了22种4-(7-甲氧基-2,2-二甲基-2,3-二氢苯并呋喃-5-基)-2-芳氨基噻唑化合物. 化合物的结构经质谱、1H NMR和元素分析等确证. 采用单晶X射线衍射仪测定了化合物7j的晶体结构, 该晶体属于单斜晶系, 空间群为C2/c, 晶胞参数a=2.21140(12) nm, b=0.87602(5) nm, c=2.13911(12) nm, β=115.5380(10)°; V=3.7391(4) nm3, Z=8, Dc=1.375 g/cm3, F(000)=1616, S=1.046, μ=0.333 mm-1, 最终偏差因子R1=0.0390, wR2=0.1079. 杀虫活性实验结果表明, 化合物7a, 7b, 7h和7t在浓度为500 mg/L时对蚕豆蚜死亡率分别为95.12%, 62.60%, 57.53%和59.06%.     

天然产物5,7-二甲氧基-4′-羟基异黄酮的合成

以4-羟基苯乙酸和3,5-二甲氧基苯酚为原料,通过一条包括苄基化、酰氯化、酯化、氢化、Fries重排、以及Vilsmeier-Haack反应等6步反应的路线合成了天然产物5,7-二甲氧基-4′-羟基异黄酮,目标产物的总收率为33%.利用1HNMR、13C NMR及元素分析确证了化合物的结构.     

5-芳亚甲基-2,3-二芳基噻唑-4-酮类衍生物的合成及抑菌活性研究

本文以多个2,3-二芳基噻唑-4-酮为底物,利用微波辅助的方法合成了18个5-芳亚甲基-2,3-二芳基噻唑-4-酮类衍生物,并测定了它们对7种植物病原菌的抑菌活性。它们的结构经熔点、1H NMR和MS确证。抑菌活性试验显示,化合物4g和4n表现出潜在的抑菌活性。     

2,5-二甲基-3,4-二乙酰基-1-芳基吡咯的合成

多取代吡咯;二乙酰基己二酮;取代苯胺;2;5-二甲基-3;4-二乙酰基-1-芳基吡咯的合成     

Comparative study of vibrational spectra of Rb4LiH3(SO4)4, K4LiH3(SO4)4, K4LiH3(SeO4)4, Na5H3(SeO4)4.2H2O and Na2SeO4.H2SeO3.H2O crystals. Polarized infrared and Raman studies

Vibrational spectra of M4LiH3(XO4)4 family, where M=K, Rb, X=S, Se together with Na5H3(SeO4)4.2H2O and Na2SeO4.H2SeO3.H2O crystals were compared. Similarities and differences are described. The spectroscopic manifestation of the presence of hydrogen bonds is discussed. Position of the bands corresponding to bending type of vibrations (in-plane and out-of plane) of hydrogen bonds is analyzed in the function of temperature. Small dynamic splitting of the bands due to weak interactions between ions is noticed.     

Photoelectron spectroscopic and theoretical study of aromatics-Pb(m) anionic complexes (aromatics = C6H5, C5H4N, C4H3O, and C4H4N; m = 1-4): a comparative study

The reactions between lead vapored by laser ablation and different aromatic molecules (C6H6, C5H5N, C4H4O, or C4H5N) seeded in argon carrier gas were studied by a reflectron time-of-flight mass spectrometer (RTOF-MS) with a photoelectron spectrometer. The adiabatic electron affinities (EAs) of the dominant anionic products PbmC6H5(-), Pb(m)C5H4N(-) (m = 1-4) and Pb(m)C4H3 (-), Pb(m)C4H4N(-) (m = 1-3) dehydrogenated complexes are obtained from the photoelectron spectra with 308 and 193 nm photon, respectively. It is found that the EAs of Pb(m)C4H4N are higher than those of Pb(m)C6H5, Pb(m)C5H4N, and Pb(m)C4H3O with the same metal number m. The possible structures for Pb(m)C4H4N(-) complexes were calculated with density functional theory (DFT) and the most stable structure was confirmed. The adiabatic detachment energies for the most stable structure were in agreement with the experimental PES results. The calculated density of state (DOS) agrees with the experimental PES spectrum well. It was confirmed by the theoretical calculations that the C4H4N group bonds on lead clusters through the Pb-N sigma bond.     

4-氧代-3（4H）-喹唑啉-5-羧酸的合成

以2-氨基-6-甲基苯甲酸为起始原料,通过合环反应生成两种4-氧代-3(4H)-喹唑啉-5-羧酸衍生物(1a, 1b), 1a, 1b分别经高锰酸钾氧化合成了4-氧代-3(4H)-喹唑啉-5-羧酸（2a, 2b）,其结构经¹H NMR, ¹³C NMR和MS表征。研究了投料比｛r［n(高锰酸钾) :n(5-甲基-3(4H)-喹唑啉-4-酮)］｝和反应温度等对收率的影响。结果表明：在最佳反应条件（r=7:1,中性高锰酸钾氧化,于90 ℃反应）下合成2总收率可达66%。     

The unexpected desulfurization of 4-aminothiophenols

Thermolysis of 4-aminophenyl benzyl sulfide at 523 K in the hydrogen donor solvent (HDS), 9,10-dihydroanthracene (AnH2), gave 4-aminothiophenol and toluene as the predominant products of the homolytic S-C bond cleavage. Under these conditions, a portion of the 4-aminothiophenol was desulfurized to aniline with first-order kinetics and with a rate constant estimated by kinetic modeling to be 7.0x10(-6) s-1. Starting with 4-NH2C6H4SH at 523 K, it was found that sulfur loss was more efficient in the non-HDSs, anthracene and hexadecane, than in AnH2. Under similar (competitive) reaction conditions, YC6H4SHs with Y=H, 4-CN, and 3-CF3 were completely inert; with Y=4-CH3O, there was some very minor desulfurization, whereas with Y=4-N(CH3)2 and 4-N(CH3)(H), the sulfur extrusions were as fast as that for Y=4-NH2. We tentatively suggest that this apparently novel reaction is a chain process initiated by the bimolecular formation of diatomic sulfur, S2, followed by a reversible addition of ground state, triplet 3S2 to the thiol sulfur atom, 4-NH2C6H4S upward arrow(SS upward arrow)H, and insertion into the S-H bond, 4-NH2C6H4SSSH. In a cascade of reactions, aniline and S8 are formed with the chains being terminated by reaction of 4-NH2C6H4S upward arrow(SS upward arrow)H with 4-NH2C6H4SH. Such a reaction mechanism is consistent with the first-order kinetics. That this reaction is primarily observed with 4-YC6H4SH having Y=N(CH3)2, N(CH3)(H), and NH2 is attributed to the fact that these compounds can exist as zwitterions.     

4-Methoxy- and 4-cyano-substituted lithium aryloxides: electronic effects of substituents on aggregation

The para-substituted lithium aryloxides [{4-NC-C6H4OLi.(Pyr)2}2.Pyr] 1a, [{4-NC-C6H4OLi.(THF)2}2] 1b, [{4-MeO-C6H4OLi.Pyr}4] 2a, [4-MeO-C6H4OLi.(THF)n] 2b, [{4-NC-2,6-(t-Bu)2-C6H2OLi.(Pyr)2}infinity] 3a, [{4-NC-2,6-(t-Bu)2-C6H2OLi.(THF)2}infinity] 3b, [{4-MeO-2,6-(t-Bu)2-C6H2OLi.Pyr}2.(Pyr)2] 4a, and [4-MeO-2,6-(t-Bu)2-C6H2OLi.(THF)n] 4b were prepared by the direct deprotonation of the corresponding phenol with an alkyllithium base (BuLi or MeLi) in the appropriate solvent, either pyridine or THF. All compounds were characterized by 1H and 13C NMR spectroscopy, and the crystal structures of 1a, 1b, 2a, 3a, 3b and 4a were elucidated. The cyano derivatives 1a and 1b adopt discrete tetrasolvated Li2O2 ring dimers whereas the methoxy analogue 2a crystallizes as a tetrasolvated molecular tetramer with a pseudo cubic Li4O4 core. The sterically encumbered cyano derivatives 3a and 3b form isostructural 1D polymeric chains of monomers via bridging of the phenolate ligands through Li...NC and Li-O contacts. In comparison, the crystal structure of the methoxy counterpart 4a is a disolvated molecular Li2O2 ring dimer. Solution NMR spectroscopic studies of 1-4 in d5-pyridine and d8-THF indicate that the methoxy complexes are more highly aggregated than the cyano derivatives, consistent with the solid-state studies. Ab initio molecular orbital calculations at the HF/6-31G* level of theory indicate that the origin of the aggregation state variations between the cyano and methoxy complexes is due to electronic effects.     

用离子阱经H2++H2碰撞反应碰撞反应制备H4+

用Penning型离子阱经碰撞反应H2++H2→H4+产生稳定的H4+。主要的反应产物是H3+,但十分明显地观测到H4+信号。H4+在阱中稳定存在时间长达0.1s量级。远比Kirchner等人测量的10-6s量级长。最后讨论了生成H4+的反应过程机制。     

Efficient Synthesis of 2,6—Diphenyl—4—arylpyrylium Tetrafluoroborate

Four pyrylium salts,(2,6-diphenyl-4-arylpyrylium tetrafluoroborate,aryl=C6H5,4-MeO C6H4,4-Me2NC6H4,4-NO2C6H4) were synthesized efficiently and economically from acetophenone and substituted chalcones in the presence of borontrifluoride.     

2-Carbethoxy-4H-3,1-benzoxazin-4-one. 2. Hydrazinolysis

3-Amino-2-carboxymethylquinazolin-4(3H)-one was obtained by hydrazinolysis of 2-carbethoxymethyl-4H-3,1-benzoxazin-4-one. Its transformations into 2-hydroxypyrazolo[5,1-b]quinazolin-9(1H)-oneand3-amino-2-hydrazido-(orbenzylamido)carbonylmethylquinazoline-4(3H)-ones were studied.For Communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1128–1130, August, 1991.     

新型2-(4-甲硫苯氧基)-4H-咪唑啉-4-酮衍生物的合成与杀菌活性

由膦亚胺，芳基异氰酸酯和4-甲硫苯酚反应制得2-(4-甲硫苯氧基)-4H-咪唑啉-4-酮衍生物，该衍生物显示出杀菌活性。     

1, 4-氧硫杂萘-4, 4-二氧化物含氟衍生物的合成

以含氟的2-(2-氯-4-硝基苯磺酰基)-1-芳基乙酮为原料, 在K2CO3/TEBA/DMF体系中, 与烷基化试剂发生烷基化-环化反应。合成六种未经文献报道的1, 4-氧硫杂萘-4, 4-二氧化物的含氟衍生物,利用元素分析、IR、1H NMR、MS对其结构进行了表征。