A convenient synthetic route to 2,4,6-tris(chlorosulfonyl)- and 2,4,6-tris(fluorosulfonyl)phenol, aniline and chlorobenzene

Convenient and preparative synthetic procedures of 2,4,6-tris(chlorosulfonyl)- and 2,4,6-tris(fluorosulfonyl)phenol, -chlorobenzene and -aniline have been elaborated. Chlorine exchange for fluorine by KF interaction on 2,4,6-tris(chlorosulfonyl)aniline and especially 2,4,6-tris(chlorosulfonyl)phenol proceeds easily and selectively under anhydrous conditions in dioxane. Unlike, 2,4,6-tris(chlorosulfonyl)chlorobenzene transformation requires the presence of water. On the basis of 2,4,6-tris(fluorosulfonyl)phenol and some of its salts, XRD measurements demonstrated the structural similarity to picric acid and its derivatives in the solid state.     

Nucleophilic substitution reactions of 2,4,6-tris(trinitromethyl)-1,3,5-triazine. 2. interaction of 2,4,6-tris(trinitromethyl)-1,3,5-triazine with primary amines and hexamethyldisilazane

2-R-amino-4,6-bis (trinitromethyl)-1,3,5-triazines have been synthesized, and their structures have been established. Dynamic¹³C NMR spectroscopy has been used to measure the rotational barriers of the tertbutylamino group around the C₍₂₎-NHBu-t bond in 2-(tert-butylamino)-4,6-dichloro-1, 3, 5-triazine and 2-(tertbutylamino)-4,6-dimethoxy-1,3,5-triazine. X-ray diffraction was used to investigate the structure of 2-(tertbutylamino)-4,6-bis (trinitromethyl)-1,3,5-triazine. From the results obtained in this work it has been concluded that the bond between the NHBu-t group and the triazine ring has a partial double-bond character.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from ] Khimiya Geterotsikiicheskikh Soedinenii, No. 5, pp. 679–688 May, 1995. Original article submitted March 7, 1995.     

Crystal Structures and Packing of 2,4,6-tris(4-Fluorophenoxy)-1,3,5-triazine and 2,4,6-tris(3,4-Dimethylphenoxy)-1,3,5-triazine. New Materials for Octupolar Nonlinear Optics

The crystal structures and packing of 2,4,6-tris(4-fluorophenoxy)-1,3,5-triazine and 2,4,6-tris(3,4-dimethylphenoxy)-1,3,5-triazine are discussed. These structures have been determined as a continuation of a series of octupolar NLO materials we have been investigating. The crystal structures are characterized by C–H...F and C–H... hydrogen bonds, respectively. A characteristic of these triazine structures is the presence of dimeric Piedfort Units (PU) that are extended into more elaborate two-dimensional (2-D) networks. The structure of the fluoro derivative is compared with that of the corresponding unsubstituted and chloro/bromo-substituted derivatives. The structure of the dimethyl triazine is compared with that of the corresponding 4-methyl derivative. The noncentrosymmetric nature of the dimethyl derivative was confirmed by a powder SHG signal at 1.064 m of the order of 0.5 × KDP. Interestingly, the dimethyl derivative studied here is isostructural with the corresponding 4-methyl triazine. This H/Me isostructurality is shown to be an uncommon phenomenon by an analysis with the CSD.     

Synthesis of 5-fluoro-2,4,6-tris(perfluoroalkyl)pyrimidines

5-Fluoro-2,4,6-tris(perfluoroalkyl)pyrimidines were synthesized by reactions of polyfluorinated iminoenamines with perfluorocarboxylic acid anhydrides and perfluorobutanoyl chloride. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2195–2196, November, 1999.     

An efficient and facile one-pot synthesis of structurally unique 2,4,6-tris(arylchalcogeno)-1,3,5-triazine and 1,3,5-tris(arylchalcogeno)-2,4,6-trimethylbenzene

An efficient one-pot synthesis of a novel class of 2,4,6-tris(arylchalcogeno)-1,3,5-triazine (sulfur, selenium and tellurium) and 1,3,5-tris(arylchalcogeno)-2,4,6-trimethylbenzene (sulfur and selenium)-containing ligands has been developed based on the reaction of 2,4,6-trichloro-1,3,5-triazine and 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene with the corresponding arylchalcogenide anions generated in aqueous tetrahydrofuran.     

Syntheses of 2,4,6-tris(di-tetrahydrofurfuroxy)phosphinyl-s-triazine and its derivatives as fire-retardants for cellulose

The synthesis of 2,4,6-tris(di-tetrahydrofurfuroxy)phosphinyl-s-triazine (2) was achieved by the reaction of cyanuric chloride with tris(tetrahydrofurfuryl)-phosphite (1) or with sodium bis(tetrahydrofurfuryl)phosphite (5). 2 on treatment with anhydrous ammonia yielded ammonium salt of 2,4-diamino-6-tetrahydro-furfuroxy-phosphinyl-s-striazine (3), which on methylolation yielded (4). The reaction of 2 and 4 with cellulose powder under different experimental conditions was carried out and they were found to exhibit promising fire-retardant properties.     

2,4,6-三(对甲基苯乙烯基)均三嗪的合成、结构及其光学性质

合成了八极分子2,4,6-三(对甲基苯乙烯基)均三嗪[即2,4,6-tris(p—methylstyryl)-s-triazine,缩写为TMSTA],用四圆X衍射法测得该晶体属于正交晶系的Pmn21空间群,晶体结构非中心对称,分子构型为微弯曲的平面三角形,具有近似的D3h对称性．该化合物在氯仿中最长波长吸收峰位于337nm,在极性较强的溶剂乙腈中的荧光发射峰位于435nm．在1064nm皮秒脉冲基频光下,测得其粉末的倍频光强度为尿素的9．1倍．另外,TMSTA良好的热稳定性(熔点为235～237℃)增加了其作为1064nm Nd：YAG激光的倍频材料的应用价值．     

Synthesis and spectroscopic properties of 1,3,5-tris(arylalkynyl)-2,4,6-trimethoxybenzenes

A number of C₃-symetric 1,3,5-tris(arylalkynyl)-2,4,6-trimethoxybenzenes which carry electron withdrawing aryl substituents at the acetylenic periphery and donating methoxy groups on the central benzene ring are prepared via Sonogashira coupling. The utility of two different synthetic routes is evaluated as well as the effect of the nature of the aryl and ethynyl starting compounds in the coupling reaction. Finally, a correlation between the substitution pattern of the alkynyl compounds and their UV-vis and fluorescence spectroscopic properties is established.     

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.     

Nucleophilic substitution reactions of 2,4,6-tris(methylsulfonyl)-3.5-dichloropyridine

It was established that hard bases replace the methylsulfonyl groups and that soft bases replace the chlorine atoms in 2,4,6-tris(methylsulfonyl)-3,5-dichloropyridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii. No. 7, pp. 915–919, July, 1976.     

Synthesis and Characterization of 2,4,6-tris(hydrazino)-s-triazine and its Metal Complexes

A new multidentate ligand related to s-triazine herbicides 2,4,6-tris(hydrazino)-s-triazine (THSTZ) and its metal complexes was synthesized. The complexes were investigated by m.s., n.m.r., i.r., u.v.–vis and AA spectroscopic techniques. Furthermore, carbon, nitrogen, hydrogen, chloride, and metal analyses, conductivity, magnetic susceptibility measurements, and thermal analyses were carried out. The Co(II), Ni(II), Cu(I), and Zn(II) metal complexes were synthesized in methanolic media. Metal-to-ligand ratios were found to be 1:1 for Co(II) and Zn(II), 2:1 for Cu(I) and 3:2 for Ni(II) complexes. N.m.r. spectral and thermal analyses showed the presence of MeOH in all of the complexes. Conductivity measurements suggested that the complexes were 1:2 electrolytes. Ring nitrogens as well as the terminal nitrogens of hydrazine side chains in THSTZ were proposed as metal binding centres. Magnetic moments of Ni(II) (4.12μ_B) and Co(II) (4.2μ_B) indicate tetrahedral and octahedral geometry, respectively. Tetrahedral geometry for Cu(I) and Zn(II) complexes was suggested. V. J. T. Raju - Previously working as Professor of Chemistry, Osmania University, Hyderbad, India     

Trisubstituted 1,3,5-triazines 3. Synthesis of substituted 2,4,6-tris(hydroxyiminomethyl)-1,3,5-triazines

Previously undescribed substituted 2,4,6-tris(hydroxyiminomethyl)-1,3,5-triazines, including 2,4,6-(1,3,5-triazinetriyl)trinitrolic acid, have been synthesized.For Communication 2, see [1].N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 117913. Institute of Chemical Physics in Chernoglovka, Chernoglovka, Moscow Oblast, 142432, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 76–78, January, 1999.     

Synthesis and nonlinear optical properties of 1,3,5-methoxy-2,4,6-tris(styryl)benzene derivatives

[reaction: see text] Novel two-dimensional octupoles containing donors at the core and acceptors at the edge of peripheral groups were synthesized by Horner-Wittig reactions. These chromophores show very large first hyperpolarizability and good thermal stability and are attractive candidates for nonlinear optical materials.     

Two photon absorption properties of 1,3,5-tricyano-2,4,6-tris(styryl)benzene derivatives

Two-photon absorption (TPA) properties of 1,3,5-tricyano-2,4,6-tris(styryl)benzene derivatives have been investigated. Comparison of the absorption and fluorescence spectra reveals that these compounds show large Stokes shifts, which increase gradually as the conjugation length increases. One-photon absorption and excitation spectra are similar except that the latter exhibit several peaks near lambda(max). It is also found that the one- and two-photon-induced fluorescence excitation spectra are quite similar, which indicates that the one- and two-photon allowed-excited states are the same. The peak TPA cross section values (delta(max)) measured with nanosecond pulses by the two-photon-induced fluorescence method are in the range (50-2620) x 10(-50) cm4 s/photon. The delta(max) value increases as the donor strength and conjugation length increase. A linear relationship is observed between delta(max) and beta, and this delta-beta relationship is found to serve as a useful synthetic strategy for the design of novel TPA dyes with the octupolar structure.     

The 2,4,6-tris(trifluoromethyl)phenyl group: Methyl and vinyl ketones and related chemistry

2,4,6-Tris(trifluoromethyl)phenyllithium (1) reacts with acetaldehyde and acrolein to give the corresponding alcohols 5 and 8. Oxidation of the alcohols with the CrO₃-pyridine complex affords the acetophenone 3 and the vinyl ketone 7 respectively. The reactions of 1 with trifluoroacetic anhydride and trimethylsilyl trifluoroacetate give low to moderate yields of the trifluoroacetophenone 6.