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．     

Synthesis of 2,4,6-triphenyl-1,3,5-triazine

Conclusions A study was made of the cyclotrimerization of benzonitrile in chlorosulfonic acid and the optimum conditions were ascertained for the formation of 2,4,6-triphenyl-1,3,5-triazine.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2105, September, 1972.     

sym-triazine derivatives. 6. Conversion of 2,4,6-triethoxycarbonyl-1,3,5-triazine with acylhydrazines into 3,5-diethoxycarbonyl-1,2,4-triazole

The reaction of 2,4,6-triethoxycarbonyl-1,3,5-triazine with acylhydrazines leads to fragmentation with the formation of 3,5-diethoxycarbonyl-1,2,4-triazole, 1-acyl-ethoxycarbonylformamidrazones N,N-diacylhydrazines, and the amines of the corresponding carboxylic acids.For Communication 5, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 700–704, May, 1985.     

Generation and photoreactions of 2,4,6-trinitreno-1,3,5-triazine, a septet trinitrene

We have studied the matrix photolysis of 2,4,6-triazido-1,3,5-triazine (cyanuric triazide, 1). Stepwise generation of the corresponding mononitrene, dinitrene, and trinitrene was observed by matrix IR and electron paramagnetic resonance (EPR) spectroscopy. The generated species were identified by comparison of their matrix IR spectra with density functional theory (DFT) computational results. The generation of 2,4,6-trinitreno-1,3,5-triazine with a septet ground state was confirmed for the first time by matrix EPR spectroscopy. The trinitrene readily decomposed into three NCN molecules upon further photoirradiation. This process was also confirmed by matrix EPR spectroscopy.     

利用二氢吡啶光诱导芳香化反应合成3,5-二氰基-2,4,6-三甲基吡啶

3,5-二氰基-2,4,6-三甲基吡啶在新型光电功能材料的合成中有重要的应用价值.本文在CCl₄中光照1,4-二氢-3,5-二氰基-2,4,6-三甲基吡啶,高产率地合成了3,5-二氰基-2,4,6-三甲基吡啶.     

Photochemical magnetism of crystalline 2,4,6-triazido-3,5-dichloropyridine

The magnetic properties and the buildup kinetics of the photolysis products of crystalline 2,4,6-triazido-3,5-dichloropyridine at temperatures of 2–300 K were studied with the use of a superconducting quantum interference device (SQUID). Under UV irradiation, the azide groups of the triazide decompose to afford high-spin nitrenes. The diamagnetic sample is converted into a paramagnetic with an average spin of 1.8 after 30 min of irradiation. The rate of triazide photolysis increases with a decrease in temperature down to 2 K.     

Nucleophilic substitution reactions of 2,4,6-tris(trinitromethyl)-1,3,5-triazine. 1. Interaction of 2,4,6-tris(trinitromethyl)-1,3,5-triazine with alcohols,diols, ammonia,and secondary amines

A study has been made of nucleophilic substitution reactions of 2,4,6-tris(trinitromethyl)-1,3,5-triazine with certain nucleophiles. The possibility of replacing one, two, or three trinitromethyl groups in this compound has been demonstrated.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 674–678, May, 1995. Original article submitted February 28, 1995.     

含不同水溶性基团的三聚氰氯衍生物的合成

木质纤维素制备乙醇最关键的步骤是使纤维素水解成可发酵糖,但目前纤维素水解效率很低,是生物质能源化利用的瓶颈。依据活性染料染色纤维素类织物具有"活性脆损"的性质提出一种新思路——以化学改性的方法改变纤维素的结晶结构从而提高其水解效率。采用三聚氰氯与氨基丙酸、氨基乙磺酸中的-NH2发生亲核取代反应,制备含有不同水溶性基团的三聚氰氯衍生物作为木质纤维素化学改性的改性剂。通过红外光谱、高效液相色谱质谱联用、13C NMR谱对其进行结构验证。     

Mild,efficient Fischer indole synthesis using 2,4,6-trichloro-1,3,5-triazine (TCT)

Mild and efficient protocol for the Fischer indole synthesis using TCT has been described. TCT serves as a mild and inexpensive catalyst. Under these conditions several functional groups such as ester, cyano, sulfone, amides, and ethers are tolerated. By this method, many functionalized analytically pure indoles were prepared easily without the need of purification.     

2,4,6-Trichloro-1,3,5-triazine Catalyzed Chemoselective Transthioacetalization of Aldehyde Acetals and Oxathioacetals

Summary. A mild and efficient transthioacetalization of aldehyde acetals and oxathioacetals was carried out using 2,4,6-trichloro-1,3,5-triazine as a mild and inexpensive catalyst. Chemoselective transacetalization is impressive as aldehyde O,O- and O,S-acetals are converted into the corresponding S,S-acetals in the presence of ketones or their acetals and oxathiocetals in nearly quantitative yields.     

Coordination chemistry of 2,4,6-tri(pyridyl)-1,3,5-triazine ligands

This review covers the rich coordination chemistry of 2,4,6-tri(pyridyl)-1,3,5-triazine ligands. These polypyridyl derivatives have been coupled to transition metals and lanthanides, and the complexes obtained have been used in various fields such as luminescent materials, for the preparation of coordination polymers and networks as well as for the synthesis of discrete metalla-assemblies. The synthetic and structural aspects of the different isomers of 2,4,6-tri(pyridyl)-1,3,5-triazine are presented, and a survey of their coordination chemistry is given.     

Kinetics and mechanism of the addition of benzylamines to benzylidene-3,5-heptadione in acetonitrile

The addition reaction of benzylamine (XC6H4CH2NH2) to benzylidene-3,5-heptadione (BHD; YC6H(4-)CH=C(COEt)(2)) in acetonitrile is investigated. The rate is slower than the corresponding rate for benzylidenediethylmalonate (YC6H4CH=C(OOEt)(2)) as the result of a greater steric hindrance in the planar dicarbonyl transition state. The kinetic isotope effects (k(H)/k(D)) involving deuterated amine nucleophiles (XC6H4CH2ND2) are greater than 1 (1.37-2.04), indicating N-H bond stretching with concurrent N-C(alpha) and H-C(beta) bond formation in the TS. The trend of change in k(H)/k(D) with variation of substituent X in the nucleophile conforms to the Bell-Evans-Polanyi principle. It has been stressed that the dicarbonyl group activated olefins exhibit insignificant charge imbalance in the TS for the benzylamine additions in acetonitrile as a result of the two strong n(c) --> pi*(C=O) vicinal charge-transfer interactions.     

2,4,6-Trichloro-1,3,5-triazine Catalyzed Chemoselective Transthioacetalization of Aldehyde Acetals and Oxathioacetals

A mild and efficient transthioacetalization of aldehyde acetals and oxathioacetals was carried out using 2,4,6-trichloro-1,3,5-triazine as a mild and inexpensive catalyst. Chemoselective transacetalization is impressive as aldehyde O,O- and O,S-acetals are converted into the corresponding S,S-acetals in the presence of ketones or their acetals and oxathiocetals in nearly quantitative yields.     

Formation of the perfluoro-2,6-dimethyl-2,4,6-triaza-hept-3,4-dienium ion by trimerization of perfluoro-azapropene

The reaction of CF₃NCF₂ with SbF₅, from which previously a cyclotrimer has been obtained, can be directed to selectively yield the acyclic trimeric cation (III) if carried out in SO₂ as a solvent. The derivatives (V) and (VII) were obtained when (III) was treated with F^Θ and (C₂H₅)₂O, respectively, while (VIII) and (IX) were formed by hydrolysis of (III). (VI) was obtained from (V) and BCl₃. All compounds were isolated, characterized analytically and investigated by infrared, Raman, mass and NMR spectroscopy.[(CF₃)₂NCFNCFN(CF₃)₂]⁺ (III) (CF₃)₂NCFNCF₂N(CF₃)₂ (V)(CF₃)₂NCClNCCl₂N(CF₃)₂ (VI) (CF₃)₂NC(OC₂H₅)NCF₂N(CF₃)₂ (VII)(CF₃)₂NCFNCON(CF₃)₂ (VIII) (CF₃)₂NCONH₂ (IX)     

3,5-二氯-2,4,6-三硝基苯胺及其衍生物的合成

分别以3,5-二氯苯胺为原料,经N保护、硝化、水解以及以1,3,5-三氯-2,4,6-三硝基苯(TCTNB)为原料,经叔丁胺化,再在三氟乙酸中脱叔丁基2种方法合成了3,5-二氯-2,4,6-三硝基苯胺。 与甲胺反应,合成了3,5-二甲氨基-2,4,6-三硝基苯胺,收率85%,再用混酸硝化合成了3,5-二甲硝胺基-2,4,6-三硝基苯胺的硝酸盐,收率70%。 采用核磁共振、质谱、红外和元素分析等进行了结构表征。 探讨了不同参数下TCTNB的氨化结果。 优化的条件为：n(TCTNB)∶n(叔丁胺)=1∶2,CuO为催化剂,KHCO3为碱。     

High-pressure vibrational spectroscopy of energetic materials: hexahydro-1,3,5-trinitro-1,3,5-triazine

Vibrational spectroscopy has been used to investigate the room-temperature high-pressure phases of the energetic material hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). The pressure-induced alterations in the spectral profiles were studied in a compression sequence to 30.2 GPa using Raman spectroscopy and to 26.6 GPa using far-infrared spectroscopy. At pressures near 4.0 GPa, several changes become immediately apparent in the Raman spectrum, such as large frequency shifts, mode splittings, and intensity changes, which are associated with a phase transition from alpha-RDX to gamma-RDX. Our study extends the kinetic stability of gamma-RDX to pressures near 18.0 GPa. Evidence for a new phase was found at pressures between 17.8 and 18.8 GPa and is based on the appearance of new vibrational bands and associated changes in intensity patterns. The new phase has vibrational characteristics that are similar to those of beta-RDX, suggesting the two polymorphs share a related crystal structure.