2,4,6-三萘基-1,3,5-三嗪的合成与光谱行为

本文通过Suzuki偶联反应高效合成了两种三萘基三嗪化合物,即2,4,6-三(1-萘基)-1,3,5-三嗪(T1NT)和2,4,6-三(2-萘基)-1,3,5-三嗪(T2NT). 考察了介质的极性、温度以及THF-H₂O二元溶剂体系中的溶解性等因素对它们吸收和发射光谱行为的影响.研究发现, 由于T1NT比T2NT具有更好的分子平面性,其激发态下分子内电荷转移的程度较大,导致其在溶液中吸收光谱、发射光谱比T2NT呈现显著红移.冻结态下,分子平面性较差的T2NT显示出较短波长的发光.     

Synthesis of Some New 2-(4-Methoxybenzothiazol-2′-yl amino)-4-(2-chloro-4-trifluoromethylanilino)-6-(substituted thioureido)-1,3,5-triazine as Antifungal Agents

2,4,6-Trichloro 1,3,5-triazine was selectively reacted with new nucleophilic reagents such as 4-methoxy-2-aminobenzothiazole, 2-chloro-4-trifluoromethyl-aniline, and phenylsubstituted thiourea in alkaline medium to give 2-(4-methoxybenzothiazol-2′-ylamino)-4-(phenylthioureido)-6-(substitutedthioureido)-1,3,5-triazines. The structures of these compounds were confirmed by IR, ¹H NMR, ¹⁹F NMR, mass spectral data, and elemental analysis. The compounds show fungicidal activity against Alternaria alternata, Aspergillus niger, and Macrofomina.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

<Emphasis Type="Italic">sym</Emphasis>-triazines. 8. Synthesis and some reactions of 4,6-disubstituted 2-(1H-pyrrolyl)-1,3,5-triazines

We have studied the reaction of 2,5-dimethoxytetrahydrofuran with 4,6-disubstituted 2-amino-1,3,5-triazines with the aim of obtaining novel coupled polyheterocyclic systems with potential bioactivity. Reaction conditions were optimized. A series of novel 4,6-disubstituted 2-(1H-1-pyrrolyl)-sym-triazines was obtained. It was found that the product yields depended on the nature of the substituent in the 4 and 6 positions of the triazine ring and on the reaction conditions. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 440–451, March, 2008.     

Trisubstituted 1,3,5-Triazines. 6. Synthesis of 2,4,6-Tris(acetonyl)-1,3,5-triazine

Acylation of 2,4,6-tris(tert-butoxycarbonylmethyl)-1,3,5-triazine with acetic anhydride in the presence of lithium hydride with subsequent removal of the tert-butoxycarbonyl groups with trifluoroacetic acid leads to 2,4,6-tris(acetonyl)-1,3,5-triazine, the cyclic analog of -cyanoacetone. The special spectral features of this compound compared with triazines obtained previously are discussed.     

4-(9-蒽基)-6-十六烷氧基-2-氨基-1,3,5-三嗪的合成及光谱行为的研究

从三氯均三嗪出发通过三步反应合成了4-(9-蒽基)-6-十六烷氧基-2-氨基-1,3,5-三嗪(AHTA),并通过红外、核磁、质谱、高分辨质谱对目标产物进行了表征.研究表明AHTA分子在基态下分子的蒽环与三嗪环不共平面,激发态下表现为ICT的荧光发射.由于分子间氢键作用的存在,AHTA在自组装膜和LB膜中均形成H-聚集体.     

离子色谱法测定1,3,5-三(3-二甲基氨丙基)六氢三嗪含量

建立了环状有机多胺类化合物1,3,5-三(3-二甲基氨丙基)六氢三嗪(PC41)的离子色谱测定法。研究表明,采用Ionpac CS12A阳离子交换柱,抑制电导模式,以25 mmol/L硫酸溶液为淋洗液,可对1,3,5-三(3-二甲基氨丙基)六氢三嗪进行定量测定。多胺类化合物在抑制电导下为非线性响应,故采用二次抛物线方法定量,线性范围为0~17.84 mg/L,线性方程为y=–0.001 8x2+0.231 3x+0.011 5,相关系数为0.999 8,测量结果的相对标准偏差小于1%(n=5),3水平加标回收率为99.3%~100.2%。该方法操作简单,测定结果准确可靠,可用于测定合成聚亚胺酯原料1,3,5-三(3-二甲基氨丙基)六氢三嗪的含量。     

由氢键连接的三个金属-有机网状化合物的合成、结构及半导体性质

以2,4,6-三(1-吡唑基)-1,3,5-三嗪(TPTz)与不同金属离子进行溶剂热反应,得到了3个氢键连接的金属-有机网状化合物。实验发现TPTz的水解产物6-(1-吡唑基)-1,3,5-三嗪-2,4-二酚(H₂L)在反应中起到了实际的配位作用。单晶结构分析表明,它们是同构化合物,分子式为[M(HL)₂]·2H₂O(M=Zn,1;Co,2;Mn,3)。每个中心金属原子分别与2个吡唑基上的N、2个吡嗪环上的N和2个水分子中的O形成六配位的结构。2个HL-与1个中心金属配位形成一个零维的金属-有机配合物小分子,这些小分子通过氢键连接进一步拓展为二维层状结构。紫外-可见漫反射(UV-VisDRS)分析结果表明,这3种化合物都是宽系半导体材料,其带隙宽度分别为3.80(Zn),3.30(Co),3.27(Mn)eV,其半导体性质同中心金属原子表现出明显的相关性。     

由氢键连接的三个金属-有机网状化合物的合成、结构及半导体性质

以2,4,6-三（1-吡唑基）-1,3,5-三嗪（TPTz）与不同金属离子进行溶剂热反应,得到了3个氢键连接的金属-有机网状化合物。实验发现TPTz的水解产物6-（1-吡唑基）-1,3,5-三嗪-2,4-二酚（H₂L）在反应中起到了实际的配位作用。单晶结构分析表明,它们是同构化合物,分子式为[M（HL）₂]·2H₂O（M=Zn,1;Co,2;Mn,3）。每个中心金属原子分别与2个吡唑基上的N、2个吡嗪环上的N和2个水分子中的O形成六配位的结构。2个HL-与1个中心金属配位形成一个零维的金属-有机配合物小分子,这些小分子通过氢键连接进一步拓展为二维层状结构。紫外-可见漫反射（UV-Vis DRS）分析结果表明,这3种化合物都是宽系半导体材料,其带隙宽度分别为3.80（Zn）,3.30（Co）,3.27（Mn） eV,其半导体性质同中心金属原子表现出明显的相关性。     

Conformational behavior of dithia[n.3.3](1,3,5)cyclophanes and dithia[n.3.3](1,2,6)cyclophanes

The conformational behavior of a series of crown-fused dithia[n.3.3](1,2,6)cyclophanes (126-CPs) and dithia[n.3.3](1,3,5)cyclophanes (135-CPs) was investigated by variable-temperature ¹H and ¹³C NMR spectroscopy, X-ray crystallography and density functional theory (DFT) calculations. Single crystal X-ray structure analysis showed that two thia-bridges in 126-CPs adopted a pseudochair-pseudochair (cc) conformation and the cyclophane decks underwent a ring-tilting motion in the case of [10.3.3](1,2,6)cyclophane (1a). In contrast, the thia-bridges in 135-CPs took both cc and pseudoboat-pseudochair (bc) conformations, and the ring-tilting process was also found in [10.3.3](1,3,5)cyclophane (2a). Variable temperature ¹H NMR study revealed that there was no wobbling-motion for two thia-bridges in 126-CPs while thia-bridges in 135-CPs experienced a wobbling-process with a conformational barrier of 9.21 and 8.80 kcal mol⁻¹, respectively, for 2a and [13.3.3](1,3,5)cyclophane (2b). DFT calculations for the two cyclophanes series revealed that 126-CPs preferred a cc conformation which was consistent with the experimental observation; similarly, 135-CPs took a preferential cc conformation, agreeing with 2a having a predominant cc conformer (cc:bc ratio=70:30), but not 2b having a predominant bc conformer (cc:bc ratio=15:85) in the solid state.     

Synthesis of substituted 2-amino-4,6-bis(nonafluoro-tert-butyl)-1,3,5-triazines

A procedure was developed for the synthesis of substituted 2-amino-4,6-bis(nonafluoro-tert-butyl)-1,3,5-triazines from 2-chloro-4,6-bis(nonafluoro-tert-butyl)-1,3,5-triazine and aliphatic and aromatic amines. The data of¹⁹F NMR spectroscopy are indicative of the presence of a barrier to internal rotation. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1568–1572, August, 1999.     

4-(9-蒽基)-6-辛氧基-1,3,5-三嗪-2-胺的合成及其在酸性介质中的光谱行为研究

以2,4-二氯-6-辛氧基-1,3,5-三嗪为原料,经Kumada偶联及胺化两步反应合成了三嗪胺衍生物:4-(9-蒽基)-6-辛氧基-1,3,5-三嗪-2-胺(AOOTA),总产率为38%.通过紫外-可见吸收光谱及荧光光谱研究了氯仿溶液中AOOTA在乙酸(HOAc)及三氟乙酸(TFA)作用下的光谱行为.研究发现AOOTA与HOAc在基态及激发态下均不能发生双氢键作用,而AOOTA与TFA相互作用基态下形成双氢键复合物,激发态下由于分子中蒽基及辛氧基与三嗪环间的C-C单键以及C-O单键的自由旋转,从而使得AOOTA与TFA分子间不能形成有效的氢键相互作用.     

Syntheses,characterizations and crystal structures of triorganotin(IV) complexes with amine derivatives of 6-amino-1,3,5-triazine-2,4-dithiol

Four new triorganotin(IV) complexes: Me₃SnL¹SnMe₃ (1), Ph₃SnL¹SnPh₃ (2), [Me₃SnL²] _n (3), Ph₃SnL²SnPh₃ (4) have been synthesized from 6-anilino-1,3,5-triazine-2,4-dithiol (L¹H₂) and 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol (L²H₂). All were characterized by elemental analyses, IR and NMR spectra and X-ray diffraction analyses. Crystal structures show that 1, 2 and 4 are monomers with one ligand coordinated to two triorganotin moieties; complex 3 is a helical chain. Significant C–H ··· π, N–H ··· π interactions and intermolecular hydrogen bonds stabilize these structures.     

A 3D Supramolecular Pd（Ⅱ） Complex via Hydrogen-bonding and Weak M…M Interactions

The reaction of 2,4,6-tris（2-pyridyl）-1,3,5-triazine （tptz） and K2PdCl4 in THF/H2O （10：1） results in the hydrolysis of tptz to bis（2-pyridylcarbonyl）amide anion （bpca）, and affords complex Pd（bpca）Cl 1, which is the first example of Pd（Ⅱ）-promoted hydrolysis of ligands. Crystal data for 1： orthorhombic, space group Pbcn, a = 12.0136（17）, b = 14.180（2）, c = 6.9747（11）A, V= 1188.2（3） A3, Z = 4, Mr = 368.06, Dc = 2.058 g/cm3, F（000） = 720,μ = 1.786 mm^-1, λ（MoKα） = 0.71073 A, T= 293（2） K, 2θmax = 54.9°, GOOF = 1.085, the final R= 0.0647 and wR = 0.1051 for 1234 observed reflections with I 〉 2σ（I） （refinement on F2）. Complex 1 is connected through hydrogen bonding to give a 2D network. And weak Pd...Pd interactions are also found between adjacent molecules with the distance of 3.6074（5） A, so the complex is further extended into a 3D supramolecular structure. Thermal gravity analysis （TGA） shows that 1 exhibits high thermal stability below 310℃. X-ray powder diffraction （XRD） and UV/Vis spectrum of 1 are also discussed.     

Condensed tetrazolo-1,3,5-triazines. 4. Synthesis of salts of 5-aminotetrazolo[1,5-a]-1,3,5-triazin-7-one

2-Amino-4-azido-1,3,5-triazin-6(1H)-ones were synthesized by successive substitution of the trinitromethyl groups in 2-amino-4,6-bis(trinitromethyl)-1,3,5-triazines under the influence of azide and nitrite ions. Interaction of 2-amino-4-azido-1,3,5-triazin-6(1H)-ones with bases led to the azido-tetrazole tautomeric conversion give salts of 5-aminotetrazolo[1,5-a]-1,3,5-triazin-7-one. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1211–1219, August, 2006.     

1,3,5-三硝基-六氢化-1,3,5-三嗪-2(1H)-酮(Keto-RDX)新法合成、晶体结构和热性能研究

研究了1,3,5-三硝基-六氢化-1,3,5-三嗪-2(1H)-酮(Keto-RDX)的合成新方法,以乌洛托品和硝基胍为原料,通过Mannich反应得到2-硝亚胺基-六氢化-1,3,5-三嗪盐酸盐(NIHT·HCl),用HNO3/AC2O硝化可得Keto-RDX,并采用核磁共振、红外、质谱以及元素分析等进行了结构表征.培养了Keto-RDX单晶,晶体结构解析表明:晶体属于正交晶系,空间群Pnma,晶胞参数a=1.0057(17)nm,b=1.3483(2)nm,c=0.5982(10)nm,V=0.8112(2)nm3,Z=4,Dc=1.933 g/cm3,μ=0.188 mm-1,F(000)=480.差示扫描量热(DSC)法和热失重(TG/DTG)法分析表明,Keto-RDX分解峰温为211.4℃(DSC),在185.00～202.79℃为固相分解阶段,峰温为198.61℃,质量损失为21.45%,在202.79～230.00℃为液相分解阶段,质量损失为77.83%,峰温为213.78℃,热稳定性较RDX差.     

Copper(II)-assisted thorough hydrolysis of 2,4,6-tris(2-pyridyl)1,3,5-triazine (tptz). Crystal structures of bis(2-pyridylcarboxylato)-copper(II) dihydrate and bis(2-pyridylcarbonyl)-amido-2,4,6-tris(2-pyridyl)-1,3,5-triazine-copper(II) dicyanamide heptahydrate

2,4,6-Tris(2-pyridyl)-1,3,5-triazine (tptz) undergoes hydrolysis in the presence of copper(II) acetate affording bis(2-pyridylcarbonyl)amido-copper(II) and free 2-pyridylcarboxylic anion. Two compounds of formulas [Cu(NC₅H₄COO)₂]·2H₂O (1) and [Cu(NC₅H₄CO)₂N(tptz)](N(CN)₂)·7H₂O (2), where NC₅H₄COO^? and (NC₅H₄CO)₂N^? are 2-pyridylcarboxylate and bis(2-pyridylcarbonyl)amido-anion, respectively, were obtained from methanol/ethanol solution of tptz with copper acetate; they were characterized by element analysis and single crystal X-ray diffraction method. Single crystal XRD analysis shows that in complex 1 coordination number around Cu atom is 4 with distorted square-planar coordination geometry and in complex 2 coordination number around Cu atom is 6 with distorted octahedral geometry. Crystal data for 1: a = 5.1359(10) Å, b = 7.6471(15) Å, c = 9.2303(18) Å, α = 74.90(3)°, β = 84.36(3)°, γ = 71.37(3)°, space group P1, crystal system triclinic, Z = 1, V = 331.6(1) ų, d _calc = 1.721 g/cm³. Crystallographic data for 2: space group C2/c, crystal system monoclinic, a = 23.976(5) Å, b = 15.465(3) Å, c = 18.649(4) Å, β = 92.66(3)°, V = 6907(2) ų, d _calc = 1.0448 g/cm³, Z = 4.     

High yielding microwave-assisted synthesis of 2-(arylmethyl)amino-4-arylamino-6-alkyl-1,3,5-triazines

An efficient and practical procedure was developed to prepare novel 2-(arylmethyl)amino-4-arylamino-6-alkyl-1,3,5-triazines, starting from dicyandiamide and the corresponding arylamines under microwave irradiation and its scope is demonstrated with a number of examples. The valuable feature of this procedure included the short reaction times, high yields, and easy operation.     

Condensed Tetrazolo-1,3,5-triazines. 1. Synthesis of 5-Polynitromethyltetrazolo[1,5-<Emphasis Type="Italic">a</Emphasis>]-1,3,5-triazin-7-one Salts

The aziridation of 2-R-4,6-bis(trinitromethyl)-1,3,5-triazines containing electron-donor substituents has been studied. It was found that the corresponding 4-azido-2-dialkylamino-6-trinitromethyl-1,3,5-triazines are formed when R = NMe₂, NEt₂. When R = O^–NMe₄ ⁺ a novel reaction route was discovered leading to the tetramethylammonium salt of 5-polynitromethyltetrazolo[1,5-a]-1,3,5-triazin-7-one which is formed as a result of azido-tetrazole and lactim-lactam tautomeric conversion. Denitration of this salt at the trinitromethyl group occurs with retention of the tetrazolo-1,3,5-triazine structure. An X-ray analysis was carried out for the denitration product which was the dipotassium salt of 5-dinitromethyltetrazolo[1,5-a]-1,3,5-triazin-7-one.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 259–266, February, 2005.     

TLC of steroids VII. Comparative TLC properties of hydroxy-estrones,hydroxy-estradiols and their synthetic intermediates

Thin-layer Chromatographic behavior of 22 steroids were compared in five systems of different compositions and polarities. Some of the steroids studied are new: mainly aromatic steroid derivatives substituted with hydroxy on carbon-2 or carbon-4, or both carbon-2 and carbon-4 of the aromatic ring: from a biological point of view they are of importance as metabolic intermediates.