Synthesis and Crystal Structure Analysis of 2-Amino-4,6-bis(diphenoxyl phosphoramide)-1,3,5-triazine

A disubstituted triazine compound, namely, 2-amino-4,6-bis（diphenoxyl phosphorramide）-1,3,5-triazine, which is an inherent flame retardant monomer, was synthesized specifically, and its structure was characterized by using NMR spectrum and X-ray single-crystal diffraction. Unit cell parameters： space group P21/c, Z=4, a=8.7494（15）, b=27.518（5）, c=12.511（2）,β=109.323（16） , Z=4, V=2842.7（9）β3 , Dc=1.380 g/cm3 , F（000）=1224 and Mr=590.46. All the atoms are in the general positions.

Synthesis and Crystal Structure of 3-(5-Amino-4-ethoxycarbonyl-3-methylthio- 1-H- pyrazolyl)-5-phenyl-1,2,4-triazine

The crystal structure of 3-（5-amino-4-ethoxycarbonyl-3-methylthio-l-H-pyrazolyl）-5-phenyl- 1,2,4-triazine （C16H16N6O2S, Mr = 356.41） has been determined by single-crystal X-ray diffraction. It belongs to monoclinic, space group P2（1/c） with a = 16.961（14）, b = 7.297（6）, c = 13.857（11）A^°, β = 109.803（13）°, V = 2237（2）A^°3, Z = 4, Dc = 1.467 g/cm^3,μ = 0.225 mm^-1, F（000） = 744, R=0.0477 and wR = 0.1156 for 2847 unique reflections with 1713 observed ones （I 〉2σ（I））. X-ray analysis reveals that there exist both intra- and intermolecular hydrogen bonds in the crystal lattice.

Synthesis and Crystal Structure of 3-Phenyl-6-(4-methylphenyl)-1,2,4-triazolo[4,3-b]-1,2,4-triazine

The crystal structure of the title compound 3-phenyl-6-（4-methylphenyl）-1,2,4- triazolo[4,3-b]-1,2,4-triazine （C17H13N5, Mr = 287.32） was synthesized and determined by singlecrystal X-ray diffraction. It belongs to monoclinic, space group P21/c, with α = 11.4038（18）, b = 11.7675（18）, c = 11.0904（18） A, β = 108.439（7）°, V = 1411.9（4） A^3, Z = 2, Dc = 1.352 g/cm^3, p = 0.085 mm^-1, F（000） = 600, R = 0.0445 and wR = 0.1041 for 2888 unique reflections with 1501 observed ones （I 〉20（I））. In the crystal structure, the triazine moiety is almost coplanar with the triazole ring, and the largest deviation for atom C（4） is -0.026 A. The intermolecular hydrogen bond in the crystal lattice plays an important role in stabilizing the structure.

Synthesis of New Fluorinated Amino-Heterocyclic Compounds Bearing 6-Aryl-5-Oxo-1,2,4-Triazin-3-Yl Moiety as Antimicrobial Agents

Some more new fluorine substitutedamino compounds bearing 6-aryl-5-oxo-1,2,4-triazin-3-yl moieties and its derivatives 3 - 7 have been synthesised successfully from aroylation of 6-(2’-aminophenyl)-3-thioxo-1,2,4-triazin-5-one (1), followed by fluoro amination with 4-fluoroanilinein Abs EtOH and then treated with ammonia/EtOH and finally acylation/aroylation or cyclocondensation reactions with malonic acid in AcOH. Structure of the products has been established upon elemental analysis and their spectral measurements. All the obtained compounds evaluated as antimicrobial agents were the compounds which contained both nitro and fluorine elements and exhibited a highly activity the other derivatives.

Synthesis, Structure and Luminescent Property of a New Zn(Ⅱ) Coordination Polymer Based on 1,3,5-Benzenetricarboxylate and 4,4'-Bipyridine Ligands

A new Zn（II） coordination polymer [Zn3（BTC）2（4,4＇-bpy）（CO）2]n （1, H3BTC = 1,3,5-benzenetricarboxylic acid, 4,4＇-bpy = 4,4＇-bipyridine） has been prepared through urothermal reaction of zinc nitrate hexahydrate with 1,3,5-benzenetricarboxylic acid and 4,4＇-bipyridine, and characterized by elemental analysis, IR spectroscopy, TGA and powder XRD, and its crystal structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in the monoclinic system, space group C2/c, with a = 10.262（3）, b = 18.838（5）, c = 15.083（4）/k, fl = 99.203（4）°, V = 2878.3（14） A3, C30H14Zn3N2O14, Mr= 822.54, Z = 4, Dc = 1.898 g/cm3,μ = 2.561 mm-1,F（000） = 1640, R = 0.0363 and wR = 0.0932 for 2828 observed reflections （I 〉 2σ（I））. X-ray analysis shows that the asymmetric unit of the title compound contains two crystallographically unique Zn（lI） atoms which are connected by BTC3- ligands and 4,4＇-bpy coligands to form a 3D framework with 1D channels. The solid luminescence of ligand and the title complex was also studied at room temperature.

Eu(Ⅲ) complexes involving 1,3,5-triazine diphosphine oxides

The 1,3,5-triazine diphosphine oxide ligands with donor-acceptor properties formed strong complexes with europium（Ⅲ） ion in acetonitrile. Spectrophotometric titrations and mass spectra indicated that two ligands coordinated to one europium ion. The stability constants varied from 11.64 to 14.60 （log 13）. Binary complexes exhibited rather weak luminescence in solution. 1,3,5-triazine diphosphine oxides engaged as co-ligands in Eu（Ⅲ） （2-thenoyltrifluoroacetonate）3 complex contributed to the overall photoluminescence and allowed for excitation with longer wavelengths than the parent complex.

Asymmetric Synthesis of (-)-(4R, 5R)-4-[5-(Benzo[1, 3]dioxol-5-yl)-4- hydroxyl-1-(pyridin-2-yl)-4, 5-dihydro-1H-pyrazol-3-yl]benzamide

The asymmetric synthesis of （-）-（4R, 5R）-4-[5-（benzo[1, 3]dioxol-5-yl）-4-hydroxyl-1- （pyridin-2-yl）-4,5-dihydro-lH-pyrazol-3-yl]-benzamide with improved Juliá-Colonna asymmetric epoxidation procedure as key step was described.

4-methoxy-2,6-bis(3,5-dimethylpyrazoyl)-1,3,5-triazine modified carbon paste electrode for trace Cu(Ⅱ) determination by differential pulse volt-ammetry

A differential pulse voltammetric method was developed for the sensitive andselective determination of Cu(II) at 4-methoxy-2,6-bis(3,5-dimethylpyrazoyl)-l,3,5-triazine modifiedcarbon paste electrode in 0.05 mol/L KHC_8H_4O_4 solution (pH = 4.02). The oxidation peak of Cu(II)was observed at 0.065 V(vs Ag/AgCl) by scanning the potential in positive direction. The analysisprocedure consisted of an open circuit accumulation step in stirred sample solution. It was followedby medium exchange to a clean solution and subsequently an anodic potential scan was affected toobtain the voltammetric peak. The current was proportional to the concentration of the Cu(II) ion ina range of 1 X 10^(-7) -1 X 10^(-4) mol/L for 6 min accumulation; the most of metal ions did notinterfere with the determination. The developed method was applied to Cu (II) determination incoal-ash sample, the results agreed with that of atomic adsorption spectroscopy (AAS).

Synthesis, Crystal Structure and Biological Activity of 6-Arylmethyl-7H-thiazolo[3,2-b]-1,2,4-triazin-7-one Derivatives as Antitumor Agents

In order to explore the novel anti-tumor agents,ten 6-arylmethyl-3-aryl-777-thiazolo[3,2-b],2,4-triazin-7-ones were designed and synthesized,and the structures were characterized by ^1H-NMR,MS,IR and X-ray single-crystal diffraction analysis.The biological activity results showed that the target compounds exhibited certain inhibitory activity of osteosarcoma cells U2OS-EGFP.Compounds 6a,6g and 6j exhibited more than 70%inhibition ratio at the concentration of 50μmol·L^-1,and especially,the IC5o value of compound 6j was 11.58μmol·L^-1.The crystal of 6h was obtained and analyzed;some related weak interactions were discussed.The molecular docking results showed that the target compounds were supposed to be ERK1/2 inhibitors.

A 1D Double Stranded Chain Complex Based on Barium Ion and 1,3,5-Triazine

A new coordination compound [Ba（OBPT）2（H2O）2]·H2O was obtained at room temperature by the reaction of 4,6-bis（2-pyridyl）-1,3,5-triazin-2-ol（HOBPT） with BaCl2.It was characterized by elemental analysis,FTIR,TG analysis,powder X-ray diffraction analysis and single-crystal X-ray diffraction analysis.The complex crystallizes in the monoclinic P21/n space group,with a = 16.325（1）,b = 6.7977（5）,c = 24.164（2） ,β = 104.009（1）,V = 2601.8（3） 3,Z =4,C26H22BaN10O5,Mr = 691.88,Dc = 1.766 g/cm3,F（000） = 1376 and μ（MoKα） = 1.587 mm-1.The final R = 0.0282 and wR = 0.0724 for 5095 observed reflections with I 〉 2σ（I） and R = 0.0312 and wR = 0.0744 for all data.In the complex,the barium ion is ten-coordinated with six nitrogen atoms from two ligands,two deprotonated hydroxyl oxygen atoms from another two ligands and two coordinated water molecules to form a double stranded chain.The extensive supramolecular interac-tions lead to the formation of an infinite 2D framework.

2，6-二氨基-3，5-二硝基吡啶-1-氧化物的合成新方法

研究了2,6-二氨基-3,5-二硝基吡啶-1-氧化物(ANPyO)的合成新方法.以2,6-二氨基吡啶为起始原料,经酰基化、N-氧化、硝化三步反应得到ANPyO,总收率为75%.测试了ANPyO的爆速、爆压、DSC,以及电火花感度和落锤感度,同1,3,5-三氨基-2,4,6-三硝基苯(TATB)的性能进行了对比,结果表明ANPyO综合性能和TATB基本相当.用1HNMR,MS和红外光谱对ANPyO及其中间体结构进行了表征.

2,4,6-三(芳基氨基)-1,3,5-三嗪衍生物的合成方法和微波效应研究

用碳酸氢钠作扑酸剂 ,将芳香胺和氰尿酰氯在 1,4 二氧六环中回流状态下反应合成了 7个 2 ,4,6 三 (芳基氨基 ) 1,3 ,5 三嗪衍生物 ,其中 6个是新化合物 .与已有文献报道的方法相比 ,条件温和 ,易于操作 ,收率高 .所合成化合物的结构通过元素分析 ,FAB MS ,IR确定 .在二氧六环∶DMF为 10∶3 (V∶V)的混合溶剂中 ,研究了在微波照射下和常规加热下反应速率的差异 .结果表明 ,微波加热比常规加热下的反应速率至少高 10倍以上 .

新型阻燃剂1,3,5-三(5,5-二溴甲基-1,3-二氧杂己内磷酰氧基)苯的热分解动力学研究

以TG-DTG为手段,研究了1,3,5-三(5,5-二溴甲基-1,3-二氧杂己内磷酰氧基)苯(TDDB)在氮气气氛中的热分解动力学,利用K issinger法、F lynn-W all-Ozawa(FWO)法对TDDB进行热分解动力学分析,求出该物质的热分解动力学参数,利用Coast-Redfen法研究该物质的热分解机理。结果表明:K issinger法所求得的活化能为344.48 kJ/mol,指前因子lnA为66.02;F lynn-W all-Ozawa法所求得的活化能为337.61 kJ/mol。TDDB的热分解的动力学方程为g(α)=α2,反应级数n=2。

1,3,5-三甲氧基苯的合成

以 1 ,3,5-三溴苯为原料 ,二甲基甲酰胺 (DMF)和甲醇为溶剂 ,Cu Cl为催化剂 ,通过甲氧基化反应高收率地制备有机中间体 ,1 ,3,5-三甲氧基苯 ,收率可达 92 .3%。反应的适宜条件为 :甲醇钠 /1 ,3,5-三溴苯摩尔比为 6,DMF/甲醇的体积比为 2 .5,反应时间

一锅法合成1,3,5-三甲基-2,4,6-间苯三醛

1,3,5-三甲基-2,4,6-间苯三醛是重要的有机合成中间体,可用于制备药物、农药、有机材料等。本文报道了采用"一锅法",以1,3,5-三甲基苯为原料,经氯甲基化反应,亲核取代反应,水解反应及氧化反应制得,并且其结构经1H NMR和13C NMR表征。

1，3，5-三甲基-2，4，6-三(3，5-二叔丁基-4-羟基苄基)苯的常压合成新工艺

以2,6-二叔丁基苯酚、多聚甲醛和均三甲苯为原料,经两步常压反应合成了1,3,5-三甲基-2,4,6-三(3, 5-二叔丁基-4-羟基苄基)苯(即抗氧剂330)。通过正交设计,分别对两步合成反应的影响因素进行了考察,最优条件为:第一步,以甲醇为溶剂,n(2,6-二叔丁基苯酚):n(多聚甲醛)=1:1.6,反应时间为8 h,以二甲胺水(w=33%)溶液为催化剂,收率可达83.8%;第二步,以二氯甲烷为溶剂,n(均三甲苯):n(3,4-二叔丁基-4-羟基苄基甲基醚)=1:3.9,以H_2SO_4(w=80%)为催化剂,反应时间为1 h,收率可达90.4%。对产物进行了IR、元素分析、熔点及透光率测定,确定产物为目标产物。该工艺所得产物纯度高、成本低、三废少。

光稳定剂中间体2-氯-4,6-二(N-丁基-1-环己氧基-2,2,6,6-四甲基-4-哌啶胺基)-1,3,5-三嗪的合成研究

采用单因素法,以2-氯-4,6-二(N-丁基-2,2,6,6-四甲基-4-哌啶胺基)-1,3,5-三嗪、环己烷、叔丁基过氧化氢为原料,三氧化钼为催化剂合成2-氯-4,6-二(N-丁基-1-环己氧基-2,2,6,6-四甲基-4-哌啶胺基)-1,3,5-三嗪。结果表明,最佳工艺条件为反应温度95℃,反应时间14 h,原料物质的量比n(2-氯-4,6-二(N-丁基-2,2,6,6-四甲基-4-哌啶胺基)-1,3,5-三嗪)∶n(环己烷)∶n(叔丁基过氧化氢)为0.01∶0.45∶0.2,催化剂三氧化钼用量为0.4 g (相对0.01 mol2-氯-4,6-二(N-丁基-2,2,6,6-四甲基-4-哌啶胺基)-1,3,5-三嗪),产品收率为93.50%。

3-甲基-4-硝基亚胺基全氢化-1,3,5-二嗪的合成

3-甲基-4-硝基亚胺基全氢化-1,3,5-二嗪是合成第二代烟碱类杀虫剂噻虫嗪的重要中间体。介绍并评价了文献中所报道的合成3-甲基-4-硝基亚胺基全氢化-1,3,5-二嗪的方法。以硝基胍为起始原料成功的合成了3-甲基-4-硝基亚胺基全氢化-1,3,5-二嗪,总收率为68.2%。

功能性1,3,5-三芳基苯的合成

以苯乙酮为原料 ,氯化亚砜 无水乙醇为催化剂 ,合成了三苯基苯 (产率 80 %～ 85 % ) ,并在此基础上进一步合成了功能性的三芳基苯分子———对称性取代的三 (4 乙酰基苯基 )苯 ,总产率 72 %～ 77%。

新型1,3,5-三嗪衍生物的合成

以二甲双胍盐酸盐和氯乙酸乙酯为起始原料,经环合反应制得2-二甲胺基-4-氯甲基-6-氨基-1,3,5-三嗪(1);1分别与吗啉(2a),N-甲基哌嗪(2b),1-苯基-5-巯基四氮唑(2c)和乙醇胺(2d)反应,合成了4个1,3,5-三嗪衍生物(3a^3d),其中3b^3d为新化合物,其结构经1H NMR和IR表征。