898-22-6Relevant articles and documents
Formation of cocrystals between alkali triazine tricarboxylates and cyanuric acid - Reactivity considerations and structural characterization of the adduct phases M3[C3N3(CO2) 3][C3N3O3H3] ·H2O (M = K, Rb)
Makowski, Sophia J.,Calta, Evelyn,Lacher, Monika,Schnick, Wolfgang
, p. 88 - 93 (2012)
The reactivity of cyanuric acid towards alkali triazinetricarboxylates was investigated and the first triazine-triazine adduct phases comprising alkali metal ions were synthesized and characterized by single-crystal X-ray diffraction and thermal analysis. An investigation of the reaction between the alkali triazine tricarboxylates M3[C3N3(CO 2)3]·xH2O (M = Li, Na, K, Rb, Cs) and cyanuric acid showed that the degree of ion transfer from triazine tricarboxylate to cyanuric acid increases gradually from the lithium to the cesium salt reflecting an increasing basicity of the triazine tricarboxylates.The reaction of potassium and rubidium triazine tricarboxylate dihydrate with cyanuric yielded the novel co-crystalsK3[C 3N3(CO2)3][C3N 3O3H3]·H2O (3a) and Rb 3[C3N3(CO2)3][C 3N3O3H3]·H2O (3b). In comparison to metal free triazine-triazine adduct phases in these compounds the assembly of molecules in the crystal is mainly determined by Coulomb interactions and only to a certain degree by hydrogen bonds and dispersive interactions. In the crystal the s-triazine units exhibit a layered structure with triazine tricarboxylate and isocyanuric acid being arranged in zigzag strands within the layers and stacked in columns perpendicular to the layers. Thermal analysis revealed a quite weak cohesion between triazine tricarboxylate and cyanuric acid upon heating. Copyright
K3[C3N3(COO)3]·2H 2O - Crystal structure of a new alkali derivative of the multidentate ligand triazine tricarboxylate
Makowski, Sophia J.,Hoermannsdorfer, Michael,Schnick, Wolfgang
, p. 2584 - 2588 (2010)
Potassium-1,3,5-triazine-2,4,6-tricarboxylate dihydrate K 3[C3N3(COO)3]·2H 2O was obtained by saponification of the respective ethyl ester in aqueous solution under mild conditions and subsequent crystallization at 4 °C. The crystal structure of the molecular salt was elucidated by single-crystal X-ray diffraction [Pβar{1}$, a = 696.63(14), b = 1748.5(3), c = 1756.0(3) pm, α = 119.73(3), β = 91.96(3), Iγ = 93.84(3)°, V = 1847.6(6)·106 pm3, Z = 6, T = 200 K]. Perpendicular to [100] the triazine tricarboxylate and potassium ions are arranged in layers alternating with layers of crystal water molecules. Two thirds of the triazine tricarboxylate units form hexagonal channels being filled with the remaining triazine tricarboxylate molecules. K3[C 3N3(COO)3]·2H2O was additionally investigated by means of FTIR spectroscopy, TG and DTA measurements. Copyright
Exploring the route to 1,3,5-triazine-2,4,6-triisocyanate (C 6N6O3), a hydrogen-free molecular precursor for polymeric C-N-(O) materials
Schmidt, Carsten Ludwig,Jansen, Martin
, p. 5649 - 5657 (2013/02/22)
We report on the synthesis of 1,3,5-triazine-2,4,6-triisocyanate [C 3N3(NCO)3]. The hydrogen-free compound, a new molecular precursor for the realisation of C-N-(O) networks (e.g., C 2N2O, C3N4), has been obtained in a five-step reaction sequence with well-defined intermediates. Starting from cyanoformiate, triethyl 1,3,5-triazine-2,4,6-tricarboxylate (C 12O6N3H15) was prepared and identified by means of spectroscopic and thermal methods. In addition, the crystal structures of two modifications were solved [high temperature (HT): P63/m (no. 176), a = 11.07(2) A, c = 6.83(4) A, γ = 120°, V = 725.80(2) A3, Z = 2; low temperature (LT): P21/n (no. 14), a = 21.75(2) A, b = 6.54(5) A, c = 21.81(0) A, β = 119.81(0)°, V = 2693.98(6) A3, Z = 8]. Hydrolysis of the ester under alkaline conditions (KOH) yielded the corresponding salt of 1,3,5-triazine-2,4,6-tricarboxylic acid, C 3N3(COO)3K3·2H2O [P1 (no. 2), a = 6.95(0) A, b = 17.45(8) A, c = 17.54(1) A, α = 119.76(0)°, β = 92.04(0)°, γ = 93.92(0) °A; V = 1837.63(0) A3, Z = 6]. The dried salt was converted into 1,3,5-triazine-2,4,6-tricarbonyl trichloride [C3N 3(COCl)3] by reaction with POCl3. The trichloride was also studied by means of single-crystal structure analysis [P21/c (no. 14), a = 9.73(6) A, b = 11.21(1) A, c = 17.03(1) A, β = 91.91(1)°, V = 1857.87(23) A3, Z = 8]. Further reaction of the molecular acid chloride with AgN3 gave the acyl azide, which was converted in situ into the product 1,3,5-triazine-2,4,6-triisocyanate by means of a thermally induced Curtius rearrangement. The final product was studied by thermal and spectroscopic methods. Owing to the high chemical reactivity of the isocyanate groups, oligomerisation/polymerisation of the molecular compound occurred immediately at room temperature, thus forming amorphous uretdione-type coordination compounds. The uretdione-based network has been converted into the corresponding molecular carbamates (R-NH-CO-OR) by reaction with ethanol [P63/m (no. 176), a = 14.873(12) A, c = 6.605(7) A, γ = 120°, Z = 2, V = 1265(2) A3] and 2-propanol [P43 (no. 78), a = 13.526(8) A, c = 12.956(2) A, Z = 4, V = 2370.5(3) A3]. The potential of this new precursor in the field of carbon nitrides as well as carbon oxynitrides is discussed briefly.
Nucleic acid related compounds. 136. Synthesis of 2-amino- and 2,6-diaminopurine derivatives via inverse-electron-demand Diels-Alder reactions
Lin, Xiaoyu,Robins, Morris J.
, p. 1029 - 1041 (2008/02/07)
Thermal inverse-electron-demand Diels-Alder reactions of 5-aminoimidazoles and 2,4,6-tris-(ethoxycarbonyl)-1,3,5-triazine (2) with spontaneous retro-Diels-Alder loss of ethyl cyanoformate and elimination of ammonia give 2,6-bis(ethoxycarbonyl)purines. A report that selective alkaline hydrolysis followed by acid-catalyzed decarboxylation gave 6-(ethoxycarbonyl)purine products was not in harmony with known reactions in purine chemistry. Our reinvestigation has shown that the 6-(ethoxycarbonyl) group undergoes preferential base-promoted hydrolysis, as expected, but regioselectivity for attack of hydroxide at the carbonyl group at C6 is not high (relative to hydrolysis of both C2 and C6 esters). The structure of 9-benzyl-2- (ethoxycarbonyl)purine was determined by X-ray crystallography and confirmed by Curtius rearrangement of the azidocarbonyl analogue to give 2-amino-6- benzylpurine. Acid-catalyzed decarboxylation of the 2,6-dicarboxylate formed during hydrolysis gave 9-benzylpurine, and Curtius rearrangement of 2,6-bis(azidocarbonyl)-9-benzylpurine gave 2,6-diamino-9-benzylpurine. Attempted applications of inverse-electron-demand Diels-Alder reactions of 2 with nucleoside derivatives were problematic.
Preparation of 5-amino-6-oxo-1,6-dihydro[1,2,4]triazine-3-carboxylic acid derivatives and synthesis of compound libraries thereof
Gambert, Romain,Kuratli, Christoph,Martin, Rainer E.
, p. 2791 - 2795 (2007/10/03)
Treatment of [1,3,5]triazine-2,4,6-tricarboxylic acid triethyl ester (4) with arylhydrazines provided 5-amino-6-oxo-1,6-dihydro[1,2,4]triazine-3- carboxylic acid ethyl esters 5a-g in moderate to good yields. Hydrolysis under basic conditions gave the corresponding free carboxylic acids 6a-d. Despite the relatively high number of heteroatoms present the amido as-triazine compounds 6a-d showed good solubility in phosphate buffer as determined by a lyophilization solubility assay. Building block 5a served as starting point for the syntheses of two discrete exocyclic 5-amido and 3-amido compound libraries 7 and 8, respectively.
Compounds having a plurality of nitrogenous substitutents
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, (2008/06/13)
Novel compounds having the formula: STR1wherein the constituent variables are defined herein. The compounds are constructed to include a central aromatic, aliphatic, or heterocyclic ring system. Attached to the central ring system are two linear groups having nitrogenous moieties that are derivatized with chemical functional groups. The ring system can include further nitrogenous moieties, either as ring atoms or on pendant groups attached to the ring, that may also be derivatized with chemical functional groups. The totality of the chemical functional groups imparts certain conformational and other properties to the these compounds. In accordance with certain embodiments of the invention, libraries of such compounds are prepared utilizing permutations and combinations of the chemical functional groups and the nitrogenous moieties to build complexity into the libraries.
SUBSTITUTED HETEROCYCLIC COMPOUNDS
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, (2008/06/13)
Novel compounds having the formula: STR1 wherein the constituent variables are defined herein. The compounds are constructed to include a central aromatic, aliphatic, or heterocyclic ring system. Attached to the central ring system are two linear groups having nitrogenous moieties that are derivatized with chemical functional groups. The ring system can include further nitrogenous moieties, either as ring atoms or on pendant groups attached to the ring, that may also be derivatized with chemical functional groups. The totality of the chemical functional groups imparts certain conformational and other properties to the these compounds. In accordance with certain embodiments of the invention, libraries of such compounds are prepared utilizing permutations and combinations of the chemical functional groups and the nitrogenous moieties to build complexity into the libraries.
Nitrogenous macrocyclic compounds
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, (2011/08/10)
PCT No. PCT/US96/04215 Sec. 371 Date Sep. 19, 1997 Sec. 102(e) Date Sep. 19, 1997 PCT Filed Mar. 27, 1996 PCT Pub. No. WO96/30377 PCT Pub. Date Oct. 3, 1996Novel macrocyclic compounds are constructed to include large cyclic structures that are interrupted by at least one ring system. Each interrupting ring system includes two bridgehead atoms. Bridgehead atoms are bonded to one or more bridges that interconnect one or more ring systems thereby forming a large cyclic structure. Located in each bridge are two or more nitrogenous moieties that are derivatized with chemical functional groups. The ring systems can include further nitrogenous moieties, either as ring atoms or on pendant groups attached to the ring. These can also be derivatized with chemical functional groups. The totality of the chemical functional groups imparts certain conformational and other properties to the macrocyclic compounds. In accordance with certain embodiments of the invention, libraries of such macrocyclic compounds are prepared utilizing permutations and combinations of the chemical functional groups and the nitrogenous moieties to build complexity into the library.
Inverse Electron Demand Diels-Alder Reactions of Heterocyclic Azadienes: Cycloaddition Reaction of Amidines with 1,3,5-Triazines
Boger, Dale L.,Kochanny, Monica J.
, p. 4950 - 4955 (2007/10/02)
A detailed study of the scope of the amidine Diels-Alder reaction with 1,3,5-triazines is described.The thermal reaction of amidines with symmetrical 1,3,5-triazines proceeds with in situ amidine to 1,1-diaminoethene tautomerization, cycloaddition with the 1,3,5-triazine, loss of ammonia from the initial Diels-Alder adduct with imine generation, imine to enamine tautomerization, and retro Diels-Alder loss of ethyl cyanoformate to provide substituted 4-aminopyrimidines in excellent conversions.The reaction proceeds best with the amidine hydrochloride salts at intermediate reaction temperatures (90-100 deg C) in polar, aprotic solvents, is rather invariant to the ratio of dienophile-diene used (1:12:1), and is subject to triazine substituent effects characteristic of an inverse electron demand Diels-Alder reaction (R = CO2Et > R = H >> R = SCH3).Notably, the generality of the amidine cycloaddition reaction with 1,3,5-triazines which has been extended to include cyclic amidines effectively addresses the limitations of the alternative ynamine or N,O-ketene acetal dienophiles.A comparative examination of amidines, thioimidates, and imidates revealed that amidines are uniquely suited for use in this reaction cascade.
Synthesis of 4-Alkoxy-1,3-oxazol-5(2H)-ones, Precursors of 1-Alkoxy-Substituted Nitrile Ylides
Bozhkova, Nina,Heimgartner, Heinz
, p. 825 - 837 (2007/10/02)
4-Alkoxy-1,3-oxazol-5(2H)-ones of type 4 and 7 were synthesized by two different methods: oxidation of the 4-(phenylthio)-1,3-oxazol-5(2H)-one 2a with m-chloroperbenzoic acid in the presence of an alcohol gave the corresponding 4-alkoxy derivatives 4, presumably via nucleophilic substitution of an intermediate sulfoxide (Scheme 2).The second approach is the BF3-catalyzed condensation of imino-acetates of type 6 and ketones (Scheme 3).The yields of this more straightforward method were modest due to the competitive formation of 1,3,5-triazine tricarboxylate 8.At 155 deg C, 1,3-oxazol-5(2H)-one 7b underwent decarboxylation leading to an alkoxy-substituted nitrile ylide which was trapped in a 1,3-dipolar cycloaddition by trifluoro-acetophenone to give the dihydro-oxazoles cis- and trans-9 (Scheme 4).In the absence of a dipolarophile, 1,5-dipolar cyclization of the intermediate nitrile ylide yielded isoindole derivatives 10 (Schemes 4 and 5).
