Phospha-s-triazines. IV. Degradation studies of 1-diarylphospha-3,5-bis(perfluoroaliphatic)-2,4,6-triazines and 1,3,-bis(diarylphospha)-5-perfluoroaliphatic-2,4,6-triazines

Thermal and thermal oxidative stability evaluations were performed on mono- and diphospha-s-triazines at 235 and 316°C using sealed Pyrex ampoules. The specific compounds studied were: 1-diphenylphospa-3,5-bis(perfluoro-n-heptyl)-2,4,6-triazine, 1-diphenylphospha-3,5-bis(perfluoro-alkylether)-2,4,6-triazines, their respective pentafluorophenyl analogues, 1,3-bis(diphenylphospha)-5-perfluoro-n-heptyl-2,4,6-triazine and 1,3-bis(diphenylphospha)-5-perfluoroalkylether-2,4,6-triazine. All the compounds wherein phenyl groups were present on the phosphorous exhibited good thermal stability up to 316°C; the analogous pentafluorophenyl substituted materials were degraded extensively at these temperatures. The oxidative stability of both the mono- and diphospha-s-triazines was excellent at 235°C, but at 316°C some degradation was observed. This was more pronounced in compounds containing the perfluoroalkyl moiety on carbon than in the perfluoroalkylether substituted members of the series.     

Phospha-s-triazines. I. Syntheses and properties of mono(diarylphospha)-s-triazines

A series of monophospha-s-triazines, namely l-diphenylphospha-3,5-bis(perfluoro-n-heptyl)-2,4,6-triazine, 1-diphenylphospha-3,5-bis[C₃F₇-[OCF(CF₃)CF₂]_xOCF(CF₃)]-2,4,6-triazine (x = 1 and 2), and the penta-fluorophenyl-substituted analogues were prepared, in yields of 50-75%, from the respective imidoylamidines and trichlorophosphoranes. The physical properties of the corresponding phenyl and pentafluorophenyl monophospha-s-triazines did not differ significantly; the perfluoroalkyl-substituted materials were low melting solids whereas the perfluoroalkyl-ether-containing compositions were liquids. Preliminary degradative studies showed these compounds to be thermally and oxidatively stable. The l-diphenylphospha-3,5-bis[C₃F₇OCF(CF₃)CF₂OCF(CF₃)]-2,4,6-triazine was found to be an effective anti-corrosion additive for perfluoroalkylether type fluids.     

Phospha-s-triazines II. Mass spectra of mono(diarylphospha)-s-triazines

Electron impact fragmentation patterns were obtained for 1-dephenylphospha-3,5-bis(perfluoro-n-heptyl)-2,4,6-triazine, 1-diphenylphospha-3,5-bis[C₃F₇(OCF(CF₃)CF₂)_xOCF(CF₃]-2,4,6-triazine (x=1 and 2) and their pentafluorophenyl analogues. In each instance the ion R₂PN₂C⁺ (RC₆H₅ or C₆F₅) constituted the base peak. Based on the observed metastable peaks, fragmentation pathways leading to the formation of this and other significant ions are postulated and similarities to s-triazine and diphenyl phosphazene trimer breakdown patterns are discussed.     

Phospha-S-triazines. VIII. Chloro-substituted diphospha-S-triazines

1,3-Bis(phenylchlorophospha)-5-perfluoroalkyl-2,4,6- triazine and the corresponding perfluoroalkylether analogue were synthesized by interaction of equimolar amounts of the respective amidines and imido-diphenyl-diphosphinic acid pentachloride. With additional quantities of amidine, 1,3-bis(phenylperfluoro-$\text{n}$-octanoylamidinophospha)-5-perfluoro- $\text{n}$-heptyl-2,4,6-triazine was obtained. The replacement of the chloro- by azido-groups in 1,3-bis(phenylchlorophospha)-5- perfluoro-$\text{n}$-heptyl-2,4,6-triazine proceeded readily. The mass spectral breakdown patterns of the chloro- and the amidino- substituted compounds were directly comparable to those of the bis(diphenylphospha)-s-triazines.     

Syntheses and degradations of fluorinated heterocyclics

Tris (perluoro-n-heptyl)-s-triazine, the perfluoroether substituted-s-triazine [C₃F₇OCF(CF₃)CF₂OCF(CF₃]₃C₃N₃, 1,4-bis[(5-perfluoro-n-heptyl)-1, 2,4-oxadiazolyl]benzene, its perfluoroalky ether substituted analogue, and 3,5-bis(perfluoro-n-heptyl)-1,2,4-oxadiazole were synthesized and characterized. Each of these compounds was subjected to thermal and oxidative degradation at 235 and 325°C and to hydrolytic degradation at 235°C. Two benzene derivatives decomposed completely during heating in nitrogen or air at 325°C, tris(perfluoro-n-heptyl)-s-triazine was quantitatively hydrolyzed at 235°C. The perfluoroalkyl ether substituted triazine and 3,5-bis(perfluoro-n-heptyl)-1,2,4- oxadiazole were found to be stable under all conditions employed as evidenced by practically quantitative recovery of the test samples.     

Syntheses and degradations of fluorinated heterocyclics II. Perfluoroalkyl and perfluoroalkylether-1,2,4-oxadiazoles

3-Perfluoroalkylether-5-perfluoro-n-heptyl-1,2,4-oxadiazole and 3,5-bis(perfluoroalkylether)-1,2,4-oxadiazole were synthesized and characterized. The 3,5-bis(perfluoroalkylether)-1,2,4-oxadiazole was subjected to thermal, thermal oxidative, and hydrolytic degradations at 235 and 325°C and was found to be stable under these conditions as evidenced by practically quantitative recovery of the test samples. In the presence of Jet-A-fuel at 235°C a low degree of degradation,～4%, was observed. 3,5-Bis(perfluoro-n-heptyl)-1,2,4-oxadiazole was found to be stable to attack by water at 325°C; however in air in the presence of Jet-A at 235°C the extent of degradation was in excess of 10%.     

Nucleophilic Substitution Reactions of 2,4,6-Tris(trinitromethyl)-1,3,5-triazine. 3. Reaction of 2,4,6-Tris(trinitromethyl)-1,3,5-triazine with Azides and Hydrazine

As a result of nucleophilic substitution of the trinitromethyl groups in 2,4,6-tris(trinitromethyl)-1,3,5-triazine, the corresponding monoazido and diazido derivatives have been synthesized. The reaction of the starting triazine with hydrazine acetate in the presence of trifluoroacetic acid leads to 1-acetyl-2,2-bis[4,6-bis(trinitromethyl)-1,3,5-triazin-2-yl]hydrazine.     

Synthesis and polymerization of 1-(2,4,6-tricyanophenylthio)-3-[3,5-bis(n,n-dimethylamino)phenoxy]-2-propyl methacrylate; polymer effect on intramolecular charge–transfer interaction

1-[3,5-Bis(N,N-dimethylamino)phenoxy]-ω-(2,4,6-tricyanophenylthio)alkanes ( 1a–c ), where an electron-accepting 2,4,6-tricyanophenylthio group and an electron-donating 3,5-bis(N,N-dimethylamino)phenoxy one are linked with a spacer such as ethylene, trimethylene, and tetramethylene, were prepared in order to examine an effect of the spacer chain length on intramolecular charge–transfer interaction between the 2,4,6-tricyanophenylthio and 3,5-bis(N,N-dimethylamino)phenoxy groups. From the UV-vis spectra measurements of 1a–c , 1-[3,5-bis(N,N-dimethylamino)phenoxy]-3-(2,4,6-tricyanophenylthio)Propane ( 1b ) carrying the trimethylene chain as a spacer was found to have the strongest intramolecular charge–transfer interaction. A new methacrylate-type monomer carrying the 1b unit as a side chain, 1-(2,4,6-tricyanophenylthio)-3-[3,5-bis(N,N-dimethylamino)phenoxy]-2-propyl methacrylate ( 2 ), was prepared successfully in 9.2% total yield in seven steps. The monomer 2 homopolymerized in benzene, tetrahydrofuran, acetone, and dimethyl sulfoxide in the presence of 2,2′-azobis(isobutyronitrile) at 60°C to give polymers [poly( 2 )] with molecular weights of 6,000 to 98,000. An intramolecular charge–transfer interaction in the poly( 2 ) was found to be larger than that in the monomer 2 and to increase with an increase in the degree of polymerization of the poly( 2 ), suggesting that there is an existence of polymer effect other than the polymer effect due to the high local concentration of the donor-acceptor pair. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of new soluble fluorinated seco-porphyrazines

Magnesium porphyrazinate substituted with eight 3,5-bis(trifluoromethyl)phenyl groups on the peripheral positions has been synthesized by the cyclotetramerization of 3,4-[3,5-bis(trifluoromethyl)phenyl]pyrroline-2,5-diimine in the presence of magnesium butanolate. Acid-mediated demetallation of the magnesium porphyrazine resulted in peripheral oxidation of one pyrrole ring to reveal the seco-porphyrazine, octakis[3,5-bis(trifluoromethyl)phenyl]-2-seco-porphyrazine-2,3-dione. Further reaction of this product with copper (II) acetate, zinc (II) acetate and cobalt (II) acetate has led to the metallo-derivatives, {octakis[3,5-bis(trifluoromethyl)phenyl]-2-seco-2,3-dioxoporphyrazinato} M(II) [M = Cu(II), Zn(II), Co(II)]. These new soluble complexes were characterized by elemental analysis, together with FT-IR, ¹H NMR, ¹³C NMR, ¹⁹F NMR, UV-Vis and mass spectral data.     

Decoupling optical and potentiometric band gaps in pi-conjugated materials

Syntheses, optical spectroscopy, potentiometric studies, and electronic structural calculations are reported for two classes of conjugated (porphinato)metal oligomers that feature a meso-to-meso ethyne-bridged linkage topology. One set of these systems, bis[(5,5'-10,20-bis[3,5-bis(3,3-dimethyl-1-butyloxy)phenyl]porphinato)zinc(II)]ethyne (DD), 5,15-bis[[5'-10',20'-bis[3,5-di(3,3-dimethyl-1-butyloxy)phenyl]porphinato)zinc(II)]ethynyl]-10,20-bis[3,5-di(9-methoxy-1,4,7-trioxanonyl)phenyl]porphinato)zinc(II) (DDD), and 5,15-bis[[15' '-(5'-10',20'-bis[3,5-bis(3,3-dimethyl-1-butyloxy)phenyl]porphinato)zinc(II)]-[(5' '-10' ',20' '-bis[3,5-di(9-methoxy-1,4,7-trioxanonyl)phenyl]porphinato)zinc(II)]ethyne]ethynyl]-10,20-bis[3,5-di(9-methoxy-1,4,7-trioxanonyl)phenyl]porphinato)zinc(II) (DDDDD), constitute highly soluble analogues of previously studied examples of this structural motif having simple 10,20-diaryl substituents, while a corresponding set of conjugated oligomers, [(5-10,20-bis[3,5-bis(3,3-dimethyl-1-butyloxy)phenyl]porphinato)zinc(II)]-[(5'-15'-ethynyl-10',20'-bis[10,20-bis(heptafluoropropyl)porphinato)zinc(II)]ethyne (DA), 5,15-bis[[5'-10',20'-bis[3,5-di(3,3-dimethyl-1-butyloxy)phenyl]porphinato)zinc(II)]ethynyl]-10,20-bis(heptafluoropropyl)porphinato]zinc(II) (DAD), and 5,15-bis[[15' '-(5'-10',20'-bis[3,5-bis(3,3-dimethyl-1-butyloxy)phenyl]porphinato)zinc(II)]-[(5' '-(10' ',20' '-bis(heptafluoropropyl)porphinato)zinc(II)]ethyne]ethynyl]-10,20-bis[3,5-di(9-methoxy-1,4,7-trioxanonyl)phenyl]porphinato)zinc(II) (DADAD), features alternating electron-rich and electron-poor (porphinato)zinc(II) units. Electrooptic and computational data for these species demonstrate that it is possible to engineer conjugated oligomeric structures that possess highly delocalized singlet (S1) excited states yet manifest apparent one-electron oxidation and reduction potentials (E1/20/+ and E1/2-/0 values) that are essentially invariant with respect to those elucidated for their constituent monomeric precursors.     

Condensed imidazo-1,2,4-azines. 14. Synthesis and reactivity of 3-chlorine-substituted imidazo[1,2-b]-1,2,4-triazines

When boiled with phosphorus pentachloride in phosphorus oxychloride, 2-methyl-6-phenyl-imidazo[1,2-b]1,2,4-triazin-4H-3-one gives a mixture of mono- and dichloro derivatives, whereas the action of thionyl chloride in chloroform with a catalytic amount of DMFA gives only the monosubstituted product 2-methyl-3-chloro-6-phenylimidazo[1,2-b]-1,2,4-triazine. The reactivity of the 3-chloro derivatives of imidazo[1,2-b]-1,2,4-triazine in reactions with diethylamine, piperidine, morpholine, aniline, hydrazine hydrate and thiourea was investigated.For Communication 13, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 981–985, July, 1986.     

Synthesis, Crystal Structure and Hydrogenation Catalysis of a CF3-BINAP（O）-Rh-COD Complex

The complex [(CF3-BINAP(O))Rh(COD)][ClO4]·Et2O(2,CF3-BINAP(O)=2-{bis[3,5-bis(trifluoromethyl)phenyl]phosphino}-2-{bis[3,5-bis(trifluoromethyl)phenyl]phosphinyl}-1,1-binaphthyl, COD=1,5-cyclooctadiene) was obtained directly from the reaction of CF 3-BINAP(O) ligand with [Rh(COD)][ClO4]. Complex 2 has been characterized by single-crystal X-ray diffraction. The crystal adopts space group P21/n with a=19.0727(4), b=15.6275(4), c=22.3039(6), β=112.3570(10)°, V=6148.2(3)3 , Z=4, Dc=1.693 g/cm3 , F(000)=3144, μ(MoKα)=0.500 mm-1 , the final R=0.0947 and wR=0.2501. Structural studies reveal that Rh(I) is coordinated by one oxygen and one phosphorus in the same ligand. Asymmetric hydrogenation of acetami- docinnamic acid with compound 2 was also evaluated.     

2,4,6-Tri[(S)-1′-methylbenzylamino]-1,3,5-triazine: a new NMR chiral solvating agent for 3,5-dinitrophenyl derivatives; an attempt at a chiral discrimination rationale

The use of 2,4,6-tri[(S)-1′-methylbenzylamino]-1,3,5-triazine as a chiral solvating agent for the NMR evaluation of the enantiomeric excess of 3,5-dinitrophenyl derivatives is reported along with an investigation into the origin of the enantiodiscrimination process.     

Trisubstituted 1,3,5-Triazines. 5. Reaction of 2,4,6-Tris[di(tert-butoxycarbonyl)nitromethyl]-1,3,5-triazine with Nucleophiles

The reaction of 2,4,6-tris[di(tert-butoxycarbonyl)nitromethyl]-1,3,5-triazine with ammonia, amines, and hydrazine has been studied. It was possible to substitute one of the di(tert-butoxycarbonyl)nitromethyl groups in this compound in the presence of ammonia, primary aliphatic amines, dimethylamine, and morpholine. The reaction with hydrazine leads to both mono- and disubstituted products. A double dealkoxylation occurs in the presence of diethylamine to give the bis(dimethylammonium) salt of 2,4-bis(tert-butoxycarbonylnitromethyl)-6-[di(tert-butoxycarbonyl)nitromethyl]-1,3,5-triazine.     

meso-三嗪取代苯基卟啉的简单一锅合成

报道一种以羟基卟啉与三嗪和其它亲核试剂为原料一锅法高产率合成不对称多取代三嗪卟啉化合物的简单方法. 研究了2,4,6-三氯三嗪与羟基卟啉、醇和胺通过分级亲核取代反应合成不对称2,4,6-取代三嗪卟啉的方法和反应条件. 以2,4,6- 三氯三嗪和5-(4-羟基)苯基-10,15,20-三苯基卟啉反应生成卟啉单取代二氯三嗪, 然后进一步与醇或胺反应合成了7个三嗪卟啉新化合物, 产物经元素分析, MS, 1H NMR和UV-Vis进行结构表征.     

Malonic ester derivatives of s-Triazine

Reaction of cyanuric chloride with solutions of sodium diethyl malonate led to three products, 2,4,6-tris(dicarbethoxymethylene)hexahydro-s-triazine, 2,4-bis(dicarbethoxymethylene)-6-oxohexahydro-s-triazine, and 2-dicarbethoxymethylene-4,6-dioxohexahydro-s-triazine. The preferred structures (IV,V,VI) are stabilized by chelated N-H-O protons in six membered rings. The assignment of structures was made on the basis of ir, nmr, uv and mass spectral data.     

Formation of two (6,3) networks showing structural diversity, Borromean topology and conformational chirality in the same crystal

Reaction of two tripodal ligands, 2,4,6-tris(4-((2-methyl-benzimidazol-1-yl)methyl)phenyl)-1,3,5-triazine (L1) and 1,3,5-tris(4-((2-methyl-benzimidazol-1-yl)methyl)phenyl)benzene (L2), with AgSbF6 led to formation of two types (6,3) networks in one single crystal, of which one is three-fold Borromean topologically entangled while the other is independent, showing the same chirality and sandwiched Borromean stacking.     

Assembly of CdI2-type coordination networks from triangular ligand and octahedral metal center: topological analysis and potential framework porosity

Reaction of a rigid triangular ligand 2,4,6-tris[4-(1H-imidazole-1-yl)phenyl]-1,3,5-triazine (TIPT) with Cd2+ ions affordedrare non-interpenetrating CdI2-type networks which display high thermostability and potential porosity; the topological character of the CdI2-type networks have been analyzed in comparison with three common uniform (4,4), (6,3) and (3,6) plane nets.     

Three-coordinate organoboron compounds BAr2R (Ar = mesityl, R = 7-azaindolyl- or 2,2'-dipyridylamino-functionalized aryl or thienyl) for electroluminescent devices and supramolecular assembly

Eight novel three-coordinate boron compounds with the general formula BAr(2)L, in which Ar is mesityl and L is a 7-azaindolyl- or a 2,2'-dipyridylamino-functionalized aryl or thienyl ligand, have been synthesized by Suzuki coupling, Ullmann condensation methods, or simple substitution reactions (L = p-(2,2'-dipyridylamino)phenyl, 1; p-(2,2'-dipyridylamino)biphenyl, 2; p-(7-azaindolyl)phenyl, 3; p-(7-azaindolyl)biphenyl, 4; 3,5-bis(2,2'-dipyridylamino)phenyl, 5; 3,5-bis(7-azaindolyl)phenyl, 6; p-[3,5-bis(2,2'-dipyridylamino)phenyl]phenyl, 7; 5-[p-(2,2'-dipyridylamino)phenyl]-2-thienyl, 8). The structures of 1, 3, and 5-7 have been determined by X-ray diffraction analyses. These new boron compounds are bright blue emitters. Electroluminescent devices using compound 2 or 8 as the emitter and the electron-transport layer have been successfully fabricated. Molecular orbital calculations (Gaussian 98) have established that the blue emission of compounds 1-8 originates from charge transfer between the pi orbital of the ligand L and the p(pi) orbital of the boron center. The ability of these boron compounds to bind to metal centers to form supramolecular assemblies was demonstrated by treatment of compound 2 with Zn(O(2)CCF(3))(2), which generated a 1:1 chelate complex [2.Zn(O(2)CCF(3))(2)] (10), and also by treatment of compound 4 with AgNO(3), yielding a 2:1 coordination compound [(4)(2).Ag(NO(3))] (11). In the solid state, compounds 10 and 11 form interesting head-to-head and tail-to-tail extended structures that host solvent molecules such as benzene.     

Infrared and Raman spectra of 3,5-diamino-6-(o-C6H4X)-1,2,4-triazines [X = F,Cl, Br,CH3

Raman and infrared spectra of four substituted 3,5-diamino-6-(ortho-substituted phenyl)-1,2,4-triazines, having ortho-fluoro, -chloro, -bromo and -methyl groups on the phenyl ring, are reported and discussed. Bands due to substituent sensitive phenyl vibrations are observed in both the Raman and infrared spectra. The Raman spectra of all four compounds have strong bands near 770 and 1330 cm(-1) which are assigned to the ring breathing vibration of the 1,2,4-triazine ring and an asymmetric triazine C-NH2 stretching vibration, respectively. A medium/strong band near 800 cm(-1) in the infrared spectra is attributed to an out-of-plane bending vibration of the substituted 1,2,4-triazine ring.