N,N''-双苯基-3,6-二甲基-1,4-二氢- S -四嗪-1,4-二甲酰胺的晶体结构

苯基异氰酸酯与3,6-二甲基-1,6-二氢-S-四嗪反应生成标题化合物（C18H18N6O2,Mr=350.38）。经X-射线单晶结构分析表明此晶体属于单斜晶系,P21/c空间群,a=9.348（2）,b=6.860（6）,c=27.929（7） A,β=94.57（2）°,V=1785.3A3,Z=4,μ=0.090mm-1,Dc=1.304g/cm3,F（000）=736。结果表明该化合物的2个酰胺基接在S-四嗪环的1,4位,而四嗪环本身呈船式构象,不具有同芳香性,分子间存在氢键相互作用。     

N,N'-双苯基-3,6-二甲基-1,4-二氢-S-四嗪-1,4-二甲酰胺的晶体结构

苯基异氰酸酯与3,6-二甲基-1,6-二氢-S-四嗪反应生成标题化合物（C18H18N6O2,Mr=350.38）。经X-射线单晶结构分析表明此晶体属于单斜晶系,P21/c空间群,a=9.348（2）,b=6.860（6）,c=27.929（7） A,β=94.57（2）°,V=1785.3A3,Z=4,μ=0.090mm-1,Dc=1.304g/cm3,F（000）=736。结果表明该化合物的2个酰胺基接在S-四嗪环的1,4位,而四嗪环本身呈船式构象,不具有同芳香性,分子间存在氢键相互作用。     

N,N(-双(邻甲苯基)-3,6-二甲基-1,4-二氢-S-四嗪-1,4-二甲酰胺的晶体结构

邻甲苯基异腈酸酯与3,6-二甲基-1,6-二氢-S-四嗪在催化剂4-二甲胺基吡啶存在下反应,生成标题化合物( C20H22N6O2, Mr = 378.43 )。经X-射线单晶结构分析表明此晶体属单斜晶系,P21/c空间群,a = 11.151(4),b = 15.318(2),c = 11.352(2)?,β=103.85(2)°,V = 1882.7? 3,Z = 4,μ= 0.093mm-1,Dc = 1.413g/cm3,F(000) = 800。结果表明,该化合物的两个酰胺基处于S-四嗪环的1,4位,而四嗪环本身呈船式构象。     

N,N′-二-(3,5-二甲基苯基)-3,6-二甲基-1,4-二氢-1,2,4,5-四嗪-1,4-二甲酰胺的合成

1,2,4,5-四嗪衍生物具有抗肿瘤,杀菌,杀虫等活性,我们曾合成了具有抗肿瘤活性的N,N′-二苯基-3,6-二甲基-1,4-二氢-1,2,4,5-四嗪-1,4-二甲酰胺(3a)[1,2,3],合成路线见图1.研究它们的抗肿瘤活性时发现该化合物的苯环间位若以N,N-二甲基取代,对小鼠白血病细胞(P-388)和人肺腺癌细胞(A-549)有很强的抗肿瘤活性.     

3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪及其衍生物的合成和晶体结构

以乙腈和芳基腈为原料, 经过醚化、环化和还原三步方便且有效地合成了3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪, 并在此基础上合成了一系列新的3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪衍生物, 通过元素分析, ¹H NMR, IR和HRMS对这些化合物进行了表征. 对化合物N-邻甲基苯-3-苯基-6-甲基-1,6-二氢-1,2,4,5-四嗪-1-甲酰胺(5a)的X射线晶体衍射研究表明: 其属于单斜晶系, P2_{1 /c空间群, 晶胞参数a＝1.3941(6) nm, b＝0.5675(2) nm, c＝2.0614(8) nm; α＝γ＝90°, β＝102.055(6)°; V＝1.5949(11) nm³, 此类化合物的四嗪环采用不对称船式结构, 且具有同芳香性.}     

四嗪衍生物的合成及其抗癌性能研究

标题化合物是一类结构新颖,具有一定生物活性的新化合物(Ⅰ_1-7)。它由3,6-二甲基-1,6-二氢-1,2,4,5-四嗪(Ⅱ)在对二甲胺基吡啶(DMAP)催化下,与取代苯异氰酸酯(Ⅲ)反应生成。     

N,N′-双间甲苯基-3,6-二甲基-1,4-二氢-s-四嗪-1,4-二甲酰胺的合成和晶体结构

间甲苯基异氰酸酯与 3 ,6 二甲基 1,6 二氢 s 四嗪反应生成标题化合物 (C2 0 H2 2 N6O2 ,Mr=3 78 44 ) .经X射线单晶结构分析表明 ,此晶体属正交晶系 ,P2 12 12 1空间群 ,晶胞参数分别为 :a =1 160 2 ( 2 )nm ,b =1 5 92 1( 3 )nm ,c=1 3 918( 3 )nm ,V =1 9874( 10 )nm3 ,Z =4,Dc=1 2 65g/cm3 ,μ(MoKα) =0 0 86mm-1,F( 0 0 0 ) =80 0 ,R和wR分别是 0 0 619和 0 14 95 .结果表明该化合物的两个酰胺基接在s 四嗪环的 1,4 位 ,而四嗪环呈船式构象 ,不具有同芳香性 ,分子中存在氢键 .     

3,6-二苯基-1,2-二氢-1,2,4,5-四嗪-1,2-二甲酸乙酯的合成和晶体结构

氯甲酸乙酯和3,6-二苯基-1,2-二氢-1,2,4,5-四嗪反应生成的是标题化合物3,6-二苯基-1,2-二氢-1,2,4,5-四嗪-1,2-二甲酸乙酯,而不是预期的3,6-二苯基-1,4-二氢-1,2,4,5-四嗪-1,4-二甲酸乙酯,其结构通过X射线单晶结构分析得以证实.此晶体属三斜晶系,P-1空间群,晶胞参数分别为:a=0.8915(2)nm,b=1.0444(2)nm,c=1.1509(3)nm,α=103.268(3)°,β=102.844(3)°,y=100.765(3)°,Z=2,R1=0.0593和wR2=0.1691.结果表明该化合物中心六元环的2,3-二氮杂丁二烯基团不共平面,没有很好地共轭.且该化合物中心六元环呈扭式构象,N(1)和N(2)原子分别偏离环平面-0.03611(41)和0.02944(40)nm.     

烟酰胺辅酶反应中心结构选择1,4-二氢烟酰胺的热力学和动力学根源

合成了对位取代的1-苯基-1,4-二氢烟酰胺和对位取代的1-苯基-1,2-二氢烟酰胺作为烟酰胺辅酶两种模型物, 分别测定了它们与N-甲基吖啶正离子反应热和活化吉布斯自由能. 通过对其热力学参数和动力学参数的比较发现, 虽然1,2-二氢烟酰胺辅酶模型物与吖啶正离子反应热力学驱动力大于相应的1,4-二氢烟酰胺辅酶模型物与吖啶正离子反应热力学驱动力, 但前者具有很高的活化熵, 从而导致其活化吉布斯自由能反而大于后者. 表明烟酰胺辅酶NADH反应中心结构在其氧化还原循环进化过程中选择1,4-二氢烟酰胺而不是1,2-二氢烟酰胺的根本原因是烟酰胺辅酶反应中心结构二氢吡啶环2位上的氢原子较4位上的氢原子有较大的空间位阻.     

含(1-芳乙酰胺基-2-叔胺基)乙烷结构的六氢-1H-1,4-二氮革类新化合物的合成(Ⅱ)

设计并合成了2-[1-(4-(N-苯基-N-丙酰基)氨基)哌啶基]甲基-六氢-1H-1,4-二氮 7.由3经还原、氯取代、胺取代、胺脱苄反应得到了7.7经单酰化反应得到了8.8经酰化反应后得到了11个带有(1-芳乙酰胺基-2-叔氨基)乙烷结构的六氢-1H-1,4-二氮类目标化合物(9a～9g,10a～10d).     

Synthesis and Crystal Structure of (3,6-Dichloro-2-nitrophenyl)(3-nitrophenyl)methanone

Novel compounds, (3,6-dichloro-2-nitrophenyl)(3-nitrophenyl)methanone(2), (2-amino-3,6-dichloro- phenyl)(3-aminophenyl)methanone(3) and 1-[3-(2-amino-3,6-dichlorobenzoyl)phenyl]-1H-pyrrole-2,5-dione(4), were synthesized from the initial compound 2,5-dichlorobenzophenone(1) and characterized by 1H NMR, 13C NMR, IR, mass spectrum and element analysis, respectively. The single crystal of compound 2 was obtained and determined by X-ray diffraction analysis. The single crystal data illustrates that it belongs to...     

矩形多环芳烃的合成

本文用3,4-二苯基-2,5-二(3,5-二溴苯基)环戊二烯酮(4a)与二苯乙炔(5a)通过Diels-Alder环加成反应得到1,2,4,5-四苯基-3,6-二(3,5-二溴苯基)苯(6a)。化合物6a通过经典的Suzuki偶联反应得到1,2,4,5-四苯基-3,6-二(3,5-二(4-十二烷基噻吩))苯基苯(8a),再利用Fe Cl3作为氧化剂发生Scholl氧化脱氢关环反应,得到目标化合物1a。采用类似合成方法,得到目标化合物1b。化合物的结构均通过1H NMR和MALDI-TOF MS表征,并对其光谱特征、热性能及电学性能进行了初步研究。     

Acid-Base Equilibrium of 5-Methoxy-6-methyluracil in Solutions: Evaluation of Content of Anionic Forms in Aqueous Alkaline Solution

Dissociation constants of 5-methoxy-6-methyluracil, 5-methoxy-1,6-dimethyluracil and 5-methoxy-3,6-dimethyluracil in water are determined. Basing on the obtained рK_а1 values, the content of anions in aqueous alkaline solution of 5-methoxy-6-methyluracil was calculated. The results were confirmed by the use of model compounds: 5-methoxy-1,6-dimethyluracil and 5-methoxy-3,6-dimethyluracil using the NMR spectroscopy.     

Highly selective photoreactions of α-oxoamides and α-tropolone alkyl ethers in crystalline inclusion complexes

Control of photocyclization of three α-oxoamides in crystalline inclusion complexes with three kinds of host compounds was studied. In all cases, β-lactams were obtained exclusively. In two cases, cis-β-lactams were formed selectively. By an enantioselective control using an optically active host compound, 1,6-di(o-chlorophenyl)-1,6-diphenylhexa-2, 4-diyne-l,6-diol, optically active β-lactams of high enantiomeric excess were obtained. Irradiation of complexes of α-tropolone alkyl ethers with the above optically active host compound in a solid state, gave the [2+2] photoreaction product, 1-alkoxybicyclo[3.2.0]hepta-3,6-dien-2-one, and its ring-opened derivative, alkyl 4-oxo-2-cyclopentene-1-acetate, in 100 and 72–91% enantiomeric excess, respectively.     

New Substituted 1‐Aryl‐4,4,6‐Trimethyl‐3,4‐Dihydropyrimidine‐2‐(1H)Thiones; A Metal‐Free and Solvent‐Free Synthesis,Characterization, and Lymphoid Tyrosine Phosphatase Inhibition Studies

A series of fourteen 3,4‐dihydropyrimidine‐2‐thiones ( 3a–n ) were synthesized by a green protocol, and their structures were characterized by spectroanalytical data. The compounds were obtained in high yields by efficient annulation of mesityl oxide (4‐methylpent‐3‐en‐2‐one) with anilines in the presence of potassium thiocyanate. The reaction is essentially metal‐catalyst‐ and solvent‐free, as mesityl oxide itself is the solvent as well as the reactant. The compounds were tested for their ability to inhibit the lymphoid tyrosine phosphatase PTPN22, and 5 of the 14 compounds exhibited IC₅₀ values in the mid‐micromolar range, with the most potent hit being the compound 3d , having a methoxy substituent at the 2‐position of the phenyl ring with an IC₅₀ = 18 ± 1 μM, and second most potent compound ( 3c ) with an IC₅₀ value of 45 ± 3 μM, having methyl substituents at both 2‐ and 4‐position of the phenyl ring.     

Application of Phase Transfer Catalysis in Heterocyclic Synthesis: Synthesis of Some New Polyfunctional Thiophenes,Thiopyrans, Pyridines and Oxazines

The reaction of compound 1 with CS 2 and different active halo compounds gave the corresponding thiophene derivatives 2a,b-4a,b , whereas treatment of compound 1 with CS 2 and active methylene compounds afforded the corresponding thiopyran derivatives 5a,b , 6a,b , 7 , and 8 . Also, 1,3-thioxane derivatives 9 and 10 were obtained by reacting compound 1 with CS 2 and different cycloalkanones. Thiophene and pyrrolidene derivatives 11 , 12a,b , and 13a,b were obtained by reacting compound 1 with phenyl isothiocyanate and different halo compounds. The active methylene compounds and/or cycloalkanones were treated with compound 1 in the presence of phenyl isothiocyanate to give pyridines, thiopyran and oxazine derivatives 14a,b-16a,b , 17a-19a , and 19b , respectively.     

手性方酰化双取代哒嗪的合成及荧光性研究

哒嗪衍生物是一类重要的芳香杂环化合物,哒嗪环常出现于农药、医药等具有生物活性的化合物中,研究哒嗪化合物的结构和性能的关系具有重要的科学意义和潜在的应用价值.作为中心桥联基的有机液晶化合物我们已有过系列报道[1-4].     

Synthesis and Photophysical Properties of 3,6-Diphenyl-9-hexyl-9<Emphasis Type="Italic">H</Emphasis>-carbazole Derivatives Bearing Electron Withdrawing Groups

Summary. 3,6-Diphenyl-9-hexyl-9H-carbazole derivatives bearing electron withdrawing groups, such as the formyl or the nitro-group in 4-positions of the phenyl substituents, were prepared and characterized. Their photophysical properties were evaluated and compared with those of the unsubstituted counterpart 3,6-diphenyl-9-hexyl-9H-carbazole. The electron withdrawing groups bearing compounds exhibited considerable red shifts of the absorption and the emission maxima. While 3,6-di(4-nitrophenyl)-9-hexyl-9H-carbazole emitted in the orange region of the visible spectrum with its emission maximum peaking at 585 nm, 3,6-di(4-formylphenyl)-9-hexyl-9H-carbazole gave a pure blue emission with a luminescence quantum yield of 95% peaking at 450 nm. Observed features were explained using quantum mechanical calculations and organic light emitting diodes using the formylphenyl substituted compound as emissive layer were built demonstrating the practical applicability of this class of compounds.     

1 - 烃基异喹啉Reissert Compounds 的合成及其氢化研究

1-苄基异喹啉Reissertcompound经RaneyNi(w-2)催化氢化,分离得到二个未见报道的氢化产物,经化学和波谱分析推定其结构为:1-亚氨基-1-苄基-2-苯甲酰基-1,2-二氢异喹啉(4)和3-苯基-10b-苄基-1,10b-二氢咪唑骈[5,1-a]异喹啉(5)。据此提出了一条1-苄基异喹啉Reissertcompound高压催化氢化的途径,并对异喹啉eissertcompound高压催化氢化反应中酰基转位进行了讨论。试图以环已基溴作为烷化剂,在氢化钠条件下,与异喹啉Reissertcompound作用来制备1-环已基异喹啉Reissertcompound,结果只得到了1-氰基异喹啉,产率达75%,为制备1-氰基异喹啉提供了一个新方法。     

1-芳基-2-丙酮的合成研究

以芳香胺为原料, 经重氮化和改进的Meerwein芳基取代反应, 合成了一系列的1-芳基-2-丙酮, 其中1-(3,5-二三氟甲基苯基)-2-丙酮是一个新化合物. 改进后的方法简化了合成步骤, 提高了收率, 可方便地用于在苯环上具有不同取代基的芳基丙酮的合成.