4,6-二硝基苯并氧化呋咱的制备、晶体结构及热分解机理

通过2,4,6-三硝基叠氮苯(TNAB)在冰醋酸中的关环反应,制备了4,6-二硝基苯并氧化呋咱(DNBF)、并培养出了DNBF的单晶.利用X射线单晶衍射、元素分析和红外光谱对其进行了结构表征.测试结果表明:DNBF晶体属单斜晶系,空间群为P21, a=0.7408(2) nm, b=0.6185(1) nm, c=0.9796(2) nm, β=107.99(2)°, V=0.4269(16) nm3, Z=2, Dc=1.759 g·cm-3, F(000)=228, μ(Mo Kα)=0.161 mm-1, R1=0.0483, wR2=0.1240, DNBF分子呈平面构型,其晶体为层状晶体.用TG-DTG和DSC研究了DNBF的热分解过程,在5 K·min-1的升温条件下,其熔点为173 ℃,在206～246 ℃之间发生剧烈分解反应,至429 ℃分解完全.     

两个基于二噻吩乙烯结构单元双核钌乙烯配合物的合成,表征和性质

合成了2个含二噻吩乙烯结构单元双核钌乙烯配合物[RuCl(CO)(PMe3)3]2(μ-2,2′-(CH=CH)2-DTE)(1a)和[RuCl(CO)(PMe3)3]2(μ-2,5-(CH=CH)2-DTE)(1b),利用元素分析、红外、核磁共振谱和电化学对它们的结构进行了表征,X-射线单晶衍射分析表明,配合物1a晶体属单斜晶系,C2/c空间群,晶胞参数为:a=3.445 75(6)nm,b=1.459 45(2)nm,c=2.321 91(5)nm,β=110.977 0(10)°,V=10.902 8(3)nm3,Z=8,Dc=1.467 g·cm-3,λ=0.071 073 nm,μ(Mo Kα)=0.956 mm-1,F(000)=4 912。测定了它们光照前后的紫外-可见吸收光谱变化图,并对其光致变色性质进行了讨论。     

多波长HPLC内标法同时测定姜黄油树脂中5种成分的含量

建立了HPLC内标法同时测定姜黄油树脂中双去甲氧基姜黄素、去甲氧基姜黄素、姜黄素、芳香姜黄酮、α-姜黄酮含量的方法。采用Thermo C₁₈色谱柱(250 mm×4.6 mm, 5.0μm),流动相为含0.1%冰醋酸的乙腈(A)-0.1%冰醋酸水溶液(B),梯度洗脱,流速1.0 mL·min^-1,柱温35℃,检测波长分别为420 nm(0～8 min)、238 nm(8～15 min)、262 nm(15～40 min)。双去甲氧基姜黄素、去甲氧基姜黄素、姜黄素、芳香姜黄酮、α-姜黄酮分别在1.388×10^-2～3.553μg(r=0.9999)、1.395×10^-2～3.570μg(r=1.0000)、1.382×10^-2～3.539μg(r=0.9998)、1.388×10^-2～3.554μg(r=0.9999)、1.719×10^-2～4.400μg(r=0.9997)的范围内与色谱峰峰面积呈良好的的线性关系;平均回收率(n=9)...     

两个基于二噻吩乙烯结构单元双核钌乙烯配合物的合成,表征和性质（英文）

合成了2个含二噻吩乙烯结构单元双核钌乙烯配合物[RuCl(CO)(PMe3)3]2(μ-2,2′-(CH=CH)2-DTE)(1a)和[RuCl(CO)(PMe3)3]2(μ-2,5-(CH=CH)2-DTE)(1b),利用元素分析、红外、核磁共振谱和电化学对它们的结构进行了表征,X-射线单晶衍射分析表明,配合物1a晶体属单斜晶系,C2/c空间群,晶胞参数为:a=3.445 75(6)nm,b=1.459 45(2)nm,c=2.321 91(5)nm,β=110.977 0(10)°,V=10.902 8(3)nm3,Z=8,Dc=1.467 g·cm-3,λ=0.071 073 nm,μ(Mo Kα)=0.956 mm-1,F(000)=4 912。测定了它们光照前后的紫外-可见吸收光谱变化图,并对其光致变色性质进行了讨论。     

Tm，Ho∶BaY2F8晶体光谱性能与能量传递

采用提拉法,生长钬铥双掺氟化钇钡[分子式:Tm3+,Ho3+∶BaY2F8,简称Tm,Ho∶BYF]激光晶体。工艺参数:拉速0.5 mm.h-1,转速5 r.min-1,冷却速率10℃.h-1。XRD表明:属于单斜晶系,空间群C12/m1。计算出晶格参数:a=0.69973 nm,b=1.05293 nm,c=0.427 84 nm,β=99.71°。测试了晶体的吸收及荧光光谱,同时计算了784 nm处吸收峰的半高宽、吸收系数及吸收截面,分别为3.2 nm,2.23 cm-1,7.44×10-21 cm2。该吸收峰对应于Tm3+离子从基态3H6到激发态3H4的跃迁。Tm,Ho∶BYF晶体在2.06μm附近有很强的荧光发射峰,在该荧光峰的发射截面和荧光寿命分别为4.96×10-21 cm2,10.1 ms。Tm3+→Ho3+的正向、反向能量转换系数之比是10.4。     

3,4-二氨基呋咱基氧化呋咱的制备及晶体结构研究

首次通过3-氨基-4-氯肟基呋咱在热作用下脱HCl、[4 2]关环反应制备了新型呋咱(氧化呋咱)类含能化合物3,4-二氨基呋咱基氧化呋咱(DAFF),并培养出了DAFF单晶.用X射线单晶衍射、元素分析和红外光谱对其分子结构进行了表征.测试结果表明:DAFF晶体属三斜晶系,空间群P1,a=0.6400(4)nm,b=1.0609(8)nm,c=1.4634(7)nm,α=83.53(5)°,β=87.27(4)°,γ=77.74(5)°,V=0.9645(11)nm3,Z=4,Dc=1.737g?cm-3,F(000)=512,μ(MoKα)=0.149mm-1;R1=0.0568,wR2=0.1137.DAFF分子不共面,三环面扭曲,面间夹角为27.18(1.99)°和30.48(2.07)°,晶体中存在分子内和分子间氢键.     

二(1-环戊烯基茚基)四羰基二钌的合成、晶体结构及热稳定性研究

由6,6-四亚甲基苯并富烯C9H6C(CH2)4与Ru3(CO)12在二甲苯中加热回流,合成了一个钌配合物[((η5-C9H6)C(C4H7))2Ru2(μ-CO)2(CO)2]。通过元素分析、红外、热重、核磁共振进行了表征及研究。用X射线单晶衍射法测定了[((η5-C9H6)C(C4H7))2Ru2(μ-CO)2(CO)2]的结构,结果表明:晶体属于单斜晶系,P21/c空间群,a=0.757 1(13)nm,b=1.577 7(3)nm,c=1.107 3(19)nm,β=90.07(2)°,V=1.322 6(4)nm3,Dc=1.699 g.cm-3,μ=1.179 mm-1,F(000)=676,Z=2,R1=0.030 5,wR2=0.072 4。     

双环[2.2.2]辛-7-烯-2，3，5，6-四羧酸铜配合物的合成和晶体结构研究

以双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸(H4L)为配体,采用水热法合成了个铜配合物[Cu2L2(H2O)2](2),并得到单晶,同时在水热条件下得到了化合物H4L.2H2O(1)的晶体。分别对化合物1和2进行了元素分析、红外光谱等分析,并用X-射线单晶衍射测定了化合物的单晶结构。化合物1属于三斜晶系,P1空间群,化合物1的晶体学数据为:a=0.88554(15)nm,b=0.95566(16)nm,c=1.043 88(17)nm,α=110.863(3)°,β=91.127(3)°,γ=91.429(3)°,V=0.824 9(2)nm3,Z=2,Mr=366.32,Dc=1.475 g.cm-3,F(000)=388,μ=0.129,R1=0.067 0,wR2=0.189 3;配合物2属于正交晶系,Pnnm空间群,配合物2的晶体学数据为:a=2.766 8(6)nm,b=0.638 75(14)nm,c=0.737 32(16)nm,V=1.303 1(5)nm3,Z=4,Mr=442.31,Dc=2.254 g.cm-3,F(000)=884,μ=3.324,R1=0.059 4和wR2=0.191 7。化合物1通过氢键形成三维网状结构,配合物2中的中心离子有3种配位方式,通过不同的配位方式也形成三维结构。     

二(o-溴苄基)锡双(二乙基二硫代氨基甲酸)酯和二(o-氯苄基)锡双(吡咯啶二硫代氨基甲酸)酯的合成、结构及体外抗癌活性研究

二(o-溴苄基)二溴化锡和二(o-氯苄基)二氯化锡分别与N,N-二乙基二硫代氨基甲酸钠和吡咯啶二硫代氨基甲酸钠反应,合成了二(o-溴苄基)锡双(二乙基二硫代氨基甲酸)酯(1)和二(o-氯苄基)锡双(吡咯啶二硫代氨基甲酸)酯(2)。用X-射线单晶衍射测定了两个化合物的晶体结构,测试结果表明:化合物1的晶体为单斜晶系,空间群P21/c,晶体学参数a=1.827 36(4)nm,b=0.900 60(2)nm,c=1.988 41(5)nm,β=114.878 0(10)°,V=2.968 71(12)nm3,Z=4,Dc=1.690 g·cm-3,μ(Mo Kα)=38.50 cm-1,F(000)=1 496,R1=0.051 6,wR2=0.154 6。化合物2的晶体为单斜晶系,空间群C2/c,晶体学参数a=2.241 28(4)nm,b=0.818 78(2)nm,c=1.542 69(3)nm,β=106.787 0(10)°,V=2.710 37(10)nm3,Z=4,Dc=1.623 g·cm-3,μ(Mo Kα)=14.65 cm-1,F(000)=1 336,R1=0.022 9,wR2=0.056 5。晶体中锡原子呈六配位畸变八面体构型。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。测定了配合物的热稳定性和体外抗癌活性。     

超分子化合物[M(4,4''''-bipy)2(H2O)4]·(4,4''''-bipy)2·(3,5-diaba)2·8H2O](M=Co,Ni,Cd)的合成及晶体结构

合成了3个超分子化合物[M(4,4'-bipy)2(H2O)4]·(4,4'-bipy)2·(3,5-diaba)2·8H2O(M=Co(1),Ni(2),Cd(3);4,4'-bipy=4,4'-联吡啶;3,5-diaba=3,5-二氨基苯甲酸阴离子),用红外光谱、元素分析及X-射线单晶衍射进行了表征。3个化合物的晶体都属于单斜晶系,空间群为P2/c。晶体学参数:化合物1:a=0.9389(2)nm,b=0.7751(1)nm,c=3.9284(6)nm,β=90.14(2)°,V=2.85880(69)nm3,Z=4,Dc=1.397g·cm-3,F(000)=1266,μ=0.380mm-1,R1=0.0349,wR2=0.0829;化合物2:a=0.9383(2)nm,b=0.7753(1)nm,c=3.9218(6)nm,β=90.09(1)°,V=2.85280(68)nm3,Z=2,Dc=1.399g·cm-3,F(000)=1268,μ=0.420mm-1,R1=0.0366,wR2=0.0805;化合物3:a=0.94091(13)nm,b=0.77885(11)nm,c=3.9712(5)nm,β=90.10°,V=2.9102(7)nm3,Z=2,Dc=1.433g·cm-3,F(000)=1308,μ=0.454mm-1,R1=0.0468,wR2=0.0964。3,5-diaba未参与配位,在配位阳离子[M(4,4'-bipy)2(H2O)4]2 中,金属离子M髤与来自2个4,4'-bipy的2个氮原子和4个水分子的氧原子配位,呈八面体的几何构型。分子中还存在未配位的4,4'-bipy。通过配位阳离子、游离4,4'-bipy及未配位的3,5-diaba间的丰富氢键,构建成具有三维结构的超分子化合物。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.