2,6-二氨基-3,5-二硝基吡嗪-1-氧化物的合成及其晶体结构

以三氟乙酸为溶剂和催化剂,2,6-二氨基-3,5-二硝基吡嗪与过氧化氢反应制备了2,6-二氨基-3,5-二硝基吡嗪-1-氧化物(LLM-105),其结构经1H NMR,IR,MS,元素分析和四圆单晶X-射线衍射仪表征。LLM-105属单斜晶系,空间群P21/n,晶胞参数:a=0.571 6(3)nm,b=1.593 5(5)nm,c=0.841 2(5)nm,α=90°,β=100.97(4)°,γ=90°,V=0.7522(6)nm3,Dc=1.908 g.cm-3,Z=4,μ=0.175 mm-1,F(000)=440,μ(MoKα)=1.047 mm-1;R1=0.053 2,wR2=0.137 9。LLM-105存在分子内和分子间氢键。     

3,3''''-二溴氧化偶氮苯的绿色合成及晶体结构

在β-环糊精、氢氧化钠的水介质中,由间溴硝基苯直接合成3,3'-二溴氧化偶氮苯(1),其结构经1H NMR表征.采用X-射线单晶衍射仪测定了1的晶体结构,属单斜晶系,P2(1)空间群,晶胞参数为:a=0.79596(11)nm,b=0.58620(8)nm,c=2.5968(4)nm,α=90°,β=95.781(2)°,γ=90°,V=1.2055(3)nm3,Z=4,F(000)=688,Mr=356.02,Dc=1.962 g·cm-3,μ=6.708 mm-1,R1=0.0311,wR2=0.0766.     

3,3′-二溴氧化偶氮苯的绿色合成及晶体结构

在β-环糊精、氢氧化钠的水介质中,由间溴硝基苯直接合成3,3′-二溴氧化偶氮苯(1),其结构经1H NMR表征。采用X-射线单晶衍射仪测定了1的晶体结构,属单斜晶系,P2(1)空间群,晶胞参数为:a=0.79596(11)nm,b=0.58620(8)nm,c=2.5968(4)nm,α=90°,β=95.781(2)°,γ=90°,V=1.2055(3)nm3,Z=4,F(000)=688,M r=356.02,Dc=1.962 g.cm-3,μ=6.708 mm-1,R1=0.0311,wR2=0.0766。     

RESEARCH ON CRYSTAL STRUCTURE AND OPTICAL PROPERTIES OF TRIHYDROXYL METHYL-AMINOMETHANE(TAM),H_2NC(CH_2OH)_3

<正> H2NC(CH2OH)3,Mr=121.14, orthorhombic, space group P21cn a= 7.786(2), b=8.785(1), c=8.835(1)A,V=604.4(3)A3, Do=1.326g.cm-3, Z=4. Dc= 1.331g.cm-3, F(000)=264e,λ(MoKα)=0.71073A, graphite monochromator, R= 0.049, Rw=0.057 for 651 observed reflections.     

含S,N的配体及其铜(Ⅱ)配合物的合成与晶体结构

肼基二硫代甲酸苄酯与丙酮在冰醋酸的催化下合成了丙酮-肼基二硫代甲酸苄酯配体(HL);HL与氯化铜反应合成了配合物CuL2,其结构经IR,元素分析及X-射线单晶衍射表征.HL属单斜晶系,P21/c空间群,晶胞参数:a=11.952 6(8)(A), b=6.155 8(4)(A), c=16.959 3(12)(A), V=1 243.68(15)(A)3, Z=4, Dc=1.273 g·cm-3, R1=0.032 2, wR2=0.084 1;CuL2属单斜晶系,P21/c空间群,晶胞参数:a=7.440(13)(A), b=18.286(3)(A), c=19.294(3)(A), V=2 607.1(8)(A)3, Z=4, Dc=1.376 g·cm-3, R1=0.044 5, wR2=0.081 7. CuL2的晶体是由孤立的分子所组成,四配位的铜离子呈畸变的四面体构型.CuL2通过分子间弱的C-H┈S氢键形成一维链状结构.     

三环己基锡吡咯啶二硫代氨基甲酸酯和三环己基锡邻苯二甲酰亚胺配合物的合成、结构和量子化学研究

三环己基氢氧化锡分别与吡咯啶二硫代氨基甲酸钠和邻苯二甲酰亚胺反应,合成了三环己基锡吡咯啶二硫代氨基甲酸酯(1)和三环己基锡邻苯二甲酰亚胺配合物(2)。化合物经IR、1H NMR、元素分析表征,用X射线衍射法测定了晶体结构,化合物1属正交晶系,空间群P212121,晶体学参数:a=1.228 06(3)nm,b=1.238 20(2)nm,c=1.662 54(3)nm,Z=4,V=2.528 03(9)nm3,Dc=1.351 g.cm-3,μ(Mo Kα)=1.184 mm-1,F(000)=1 072,R1=0.048 7,wR2=0.121 0;化合物2属正交晶系,空间群P212121,晶体学参数:a=1.244 70(19)nm,b=1.269 45(19)nm,c=1.587 7(2)nm,Z=4,V=2.508 7(6)nm3,Dc=1.362 g.cm-3,μ(Mo Kα)=1.039 mm-1,F(000)=1 064,R1=0.049 9,wR2=0.128 4,中心锡原子均为畸变四面体构型。对化合物进行了量子化学从头计算,探讨了化合物的稳定性、分子轨道能量以及前沿分子轨道的组成特征。     

聚对甲基苯胺的合成及其晶体结构

在水相中,FeCl3催化对甲基苯胺聚合合成了对甲基苯胺三分子聚合物——(N,N′E,N,N′E)-N,N′-(2-氨基-5-甲基-2,5-环己二烯-1,4-二亚基)二(4-甲基苯胺)(1),其结构经X-射线单晶衍射仪表征。1属六方晶系,R3空间群,晶胞参数:a=21.116(2),b=21.116(2),c=10.364(2),α=90°,β=90°,γ=120°,Mr=315.41,Z=9,V=4002.1(10)3,Dc=1.178 g.cm-3,μ=0.070 mm-1,λ=0.710 73,F(000)=1 512,R=0.067 8,wR=0.112 6。     

酰腙席夫碱铜单核配合物的合成、结构及性质

合成了一个铜单核配合物Cu(HL)2(H2L=(水杨酸乙酯缩水合肼)缩2-吡啶甲醛),利用红外光谱,紫外-可见光谱和X射线单晶衍射对这个配合物的结构和性质进行了表征.结果表明,该配合物属正交晶系,Aba2空间群,晶胞参数为a=1.292 0(2)nm,b=1.806 0(3)nm,c=1.092 4(2)nm,α=β=γ=90°,V=2.549 0(7)nm3,Z=4,Dc=1.418g·cm-3,μ=0.901 mm-1,F(000)=1 116,R1=0.074 9,wR2=0.164 9.配合物的结构是两个配体夹着一个金属铜原子的十字交叉结构.     

3-氯-4-二苄胺基-5-甲氧基-2(5H)-呋喃酮的合成与晶体结构

在THF溶液中合成了标题化合物3-氯-4-二苄胺基-5-甲氧基-2(5H)-呋喃酮,并用FT-IR、UV-Vis、1HNMR、13C NMR、MS、元素分析和X-射线衍射等进行了表征。结果表明此化合物属正交晶系,空间群为Pbca,晶胞参数为:a=15.891(16),b=11.126(11),c=19.778(19),α=β=γ=90°,V=3497(6)3,Z=8,Dc=1.306Mg/m3,μ=0.234 mm-1,F(000)=1440。在化合物的分子结构中,两个苯环几乎垂直于呋喃酮平面,且它们与呋喃酮平面的两面角分别为89.38°和88.19°。     

(Z)-1,3-二苯基-N,2-二对甲苯磺酰基-2,5-己二烯-1-胺的合成及其晶体结构

通过烯丙基溴化镁、1-苯基-2-对甲苯磺酰基乙炔和N-对甲苯磺酰基苯甲醛亚胺的三组分串联反应,立体及区域选择地合成了含1,4-二烯结构单元的多取代烯丙胺--(Z)-1,3-二苯基-N,2-二对甲苯磺酰基-2,5-己二烯-1-胺(1),其结构经1H NMR, IR, MS, 元素分析和X-射线单晶衍射表征.1为Z型结构,属单斜晶系,P2(1)/n空间群,晶胞参数为:a=11.388 1(2)(A), b=15.297 4(2)(A), c=17.123 8(3)(A), α=90.00°, β=107.62(10)°, γ=90.00°, V=2 843.16(8)(A)3, Z=4, Dc=1.303 g·cm-1, S=1.055.     

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%.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.