- C-substituted cyclams from cyclotetrapeptides [1]
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The reduction of cyclotetrapeptides cyclo(X-β-Ala-X-β-Ala) (X = Gly, (S)-Ala, (S)-Leu, (S)-Val, (S)-Phe) 1a - 1e with LiAlH4 in THF gives the C-substituted cyclams 2a - 2e.
- Lang, Markus A.,Beck, Wolfgang
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- ARENE CONNECTED POLYAMINE MACRORING DERIVATIVES, PREPARATION METHODS AND PHARMACEUTICAL USES THEREOF
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Abstract: The present invention relates to arene connected polyamine macrocyclic derivatives represented by general formula I, pharmaceutically acceptable salts or hydrates thereof which have anti-HIV activities, in which the definitions of substituents are as defined in the description; to preparation methods of the compounds of formula I; to pharmaceutical compositions containing the compounds of formula I or their pharmaceutically acceptable salts or hydrates; to the use of the compounds of formula I or their pharmaceutically acceptable salts or hydrates for the preparation of a medicament for the treatment and prevention of HIV-associated diseases.
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Page/Page column 18-19
(2010/04/24)
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- Cyclohexanedione bisaminals as intermediates for cyclen, homocyclen, and cyclam synthesis
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A new easy-to-run route to cyclen, homocyclen, and cyclam is proposed, based on the cyclization with dibromo- or ditosyloxy-derivatives of bisaminal intermediates obtained by condensation of the appropriate linear tetraamine with cyclohexanedione. In the cyclization step, the use of cesium carbonate instead of potassium carbonate as proton trapper caused a remarkable increase of yields. Copyright Taylor & Francis Group, LLC.
- Prokhorov, Anton,Le Bris, Nathalie,Bernard, Helene,Claudon, Geraldine,Handel, Henri
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p. 3271 - 3282
(2007/10/03)
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- Selective protection of 1,4,8,11-tetraazacyclotetradecane (cyclam) in position 1,4 with the phosphonothioyl group and synthesis of a cyclam-1,4-bis(methylphosphonic acid). Crystal structures of several cyclic phosphonothioamides
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A new cyclam-based ligand, 1,4,8,11-tetraazacyclotetradecane-1,4- bis(methylphosphonic acid) (1,4-H4te2p), was synthesized. Cyclam was protected by the reaction with PhP(S)Cl2 to form exclusively five-membered cyclic phenylphosphonothioic diamide 2 in a moderate yield. The solid-state structures of 2 and several by-products were determined. Compound 2 was isolated as two stable conformers differing in a mutual position of benzene ring and sulfur atom with respect to the cyclam ring. Compound 2 was used for the synthesis of 1,4-dibenzylcyclam. However, the deprotection of the thiophosphoryl-protected bis(methyl-phosphonate diester) with aqueous HCl under non-optimized conditions led to a mixture of cyclam derivatives differently substituted with methylphosphonic acid groups. The crystal structures of the target product, 1,4-H4te2p, and also 1,4,8,11- tetraazacyclotetradecane-1,4,8,11-tetrakis(methylphosphonic acid) (H 8tetp) were determined. A similar reaction with cyclen (1,4,7,10-tetraazacyclododecane) led only to hardly purifiable mixtures.
- Vitha, Tomas,Kotek, Jan,Rudovsky, Jakub,Kubicek, Vojtech,Cisarova, Ivana,Hermann, Petr,Lukes, Ivan
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p. 337 - 367
(2007/10/03)
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- Coloring agent comprising transition metals
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The present invention relates to a composition for coloring keratin fibers and a method of using the same. The composition of the present invention contains at least one dye precursor, and one or more clathrate compounds that contain transition metal complexes.
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- Phenylglyoxal for polyamines modification and cyclam synthesis
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The bis-aminals obtained by tetraamine and phenylglyoxal condensation display various behaviours such as equilibrium between different configurations, rearrangements that lead to lactam derivatives, or amine deprotection. Our investigations about them were focused on three different linear amines, and then extended to polyazacycloalkanes cyclen and cyclam. Cyclam was also synthesised with the bis-aminals issued from condensation of linear polyamines with phenylglyoxal. The lactam derivatives described here were moreover, employed for the mono-N-functionalisation of tetraamines by phenyl-acetic acid group.
- Tripier, Rapha?l,Chuburu, Fran?oise,Le Baccon, Michel,Handel, Henri
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p. 4573 - 4579
(2007/10/03)
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- Studies on biologically potent tetraazamacrocyclic complexes of bivalent tin
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Fourteen- to eighteen-membered tetraamide macrocyclic ligands N4L1-N4L4 have been prepared by the condensation of 1,2-diaminoethane or 1,3-diaminopropane with malonic or succinic acid in the presence of condensing reagents dicyclohexylcarbodiimide and 4-dimethylaminopyridine. On reduction, these macrocyclic ligands give a new series of tetraazamacrocycles MacL1-MacL4 which form complexes with tin(II) chloride. The ligands and their complexes were characterized by elemental analyses, molecular weight determinations, infrared and 1H NMR spectral studies. The hexacoordinated state for tin has been confirmed by spectral studies. An octahedral geometry for these complexes has been proposed as the binding sites are the nitrogen atoms of the macrocycles. On the basis of the chemical composition the representation of the complexes as [Sn(MacLn)Cl2] (n = 1-4) has been established. The ligands and their complexes also have been screened for their antifungal and antibacterial activities and the findings have been reported and explained.
- Chaudhary, Ashu,Singh
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p. 615 - 626
(2007/10/03)
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- Process for preparing 1,4,8,11-tetraazacyclotetradecane
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An improved process for preparing 1,4,8,11-tetraazacyclotetradecane comprising the bisacylation of an acyclic diamine to obtain a dichlorodiamide compound in a first step, the cyclization of said diamide compound to obtain dioxocyclam in a second step, and the reduction of dioxocyclam in a third step to obtain the desired 1,4,8,11-tetraazacyclotetradecane.
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- Studies on the interaction of iron(II), nickel(II), copper(II) and zinc(II) with tetraazamacrocycles
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The condensation of aliphatic diamines H2N(CH2)nNH2 (n = 2-3) with dicarboxylic acid HOOC - (CH2)n - COOH (n=1-2) in the presence of dicyclohexyl-carbodiimide and 4-(dimethylamino)pyridine results in new types of 14-18 membered tetraamide macrocyclic ligands 1a-1d. These compounds on reduction with LiAlH4 yield a series of tetraazamacrocycles 2a-2d which form complexes with Fe(II), Ni(II), Cu(II) and Zn(II). The ligands and their complexes have been characterized by elemental analyses, mass, IR, 1H NMR, UV/Vis, EPR spectroscopic, molar conductance and magnetic moment data. An octahedral geometry around the metal ion is suggested for [M2aCl2][M2dCl2], where M = Fe(II) and Ni(II) while a square-planar and a tetrahedral geometry is proposed for [M2a]Cl2-[M2d]Cl2 for M = Cu(II) and Zn(II).
- Shakir, Mohammad,Varkey, Saji P.,Nasman, Omar S. M.
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p. 671 - 676
(2007/10/03)
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- Process for the synthesis of cyclic polynitrogenated compounds
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A method for the synthesis of cyclic polyamines preceeds by reaction of a diamine with the acrylonitrile wherein the reduction steps are carried out with Raney alloy instead of using hydrogen under pressure in the presence of Raney nickel. Compounds so prepared have the formula: STR1 wherein A and B are: an alkyl chain --(CH2)-- in which x is an integer of 2 to 4, substituted or not by an alkyl group of 1 to 5 carbon atoms, which may be substituted or not by an aromatic ring, heterocyclic ring, amine ketone, carboxylic acid, amide, cyano, alkyl, alkoxy, hydroxy, nitro or halogen and R1 and R2 are the same moieties as those substituting the alkyl claim above.
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- Synthesis and characterization of various unsubstituted and mono-N-substituted tetraazamacrocycles
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Syntheses of tetraazamacrocycles have been carried out by using p-toluenesulfonyl chloride as protective group.The and were also obtained by the template synthesis.Mono-N-functionalization of tetraazamacrocycles was accomplished by reaction of a fivefold excess of the free macrocycles with 1 equivalent of a suitable alkylating or arylating reagent.The key point of the synthesis lies in the use of an excess of the macrocycle over the substituting reactants to reduce the formation of polysubstituted derivatives, and in the easy separation of the excess of unreacted macrocycle.All the products were characterized on the basis of spectral studies (1H and 13C NMR, including 2D NMR and NOE difference studies) and mass spectrometry.Key words: tetraazamacrocycles, improved synthesis, protective group, N-tosylation, template synthesis, NOE difference spectroscopy.
- Meunier, I.,Mishra, A. K.,Hanquet, B.,Cocolios, P.,Guilard, R.
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p. 685 - 695
(2007/10/02)
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- Polyazamacrocyclic compounds for complexation of metal ions
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The present invention relates to a new polyazamacrocyclic compound or a salt thereof and its uses. The compound has the formula STR1 where x is 2, 3 or a combination of p 2(s) and q 3(s) where p+q=y; y is 3 or 4; R is (CH2)z P(=0)R1 R2 ; R1 is R3 or OR3 where R3 is alkyl, cycloalkyl or aryl; R2 is H, alkyl or STR2 where R4 is alkyl, cycloalkyl or aryl; and z is 1 to 3. In one important embodiment, this compound may be complexed with a metal to be a polyazamacrocyclic compound-metal complex having the formula STR3 where r is 2 or 3; and Me is a metal ion.
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- Cascade polymer bound chelating compounds, their chelates and conjugates, processes for their production, and pharmaceutical agents containing them
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Cascade polymers, containing complex-forming ligands, optionally at least five ions of an element of atomic numbers 21-29, 39, 42, 44 or 57-83, as well as, if desired, cations of inorganic and/or organic bases, amino acids or amino acid amides, are valuable complexing compounds and complexes for diagnostics and therapy.
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- Triflamides for protection and cyclization of tetraamines to tetraazamacrocycles
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A facile two-step synthesis of tetraazamacrocycles is reported starting from trifluoromethanesulfonyl derivatives of linear tetraamines. After cyclization, the macrocycle was deprotected using sodium in liquid ammonia.
- Panetta,Yaouanc,Handel
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p. 5505 - 5508
(2007/10/02)
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- MACROHETEROCYCLES. 15.* SYNTHESIS OF MACROCYCLIC POLYAMINES IN A BIPHASIC SYSTEM
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Macrocyclic polyamines are conveniently synthesized by condensation of bissulfonamides with ditosylates or dibromides of glycols in the biphasic system toluene(xylene)-aqueous sodium hydroxide.
- Luk'yanenko, N. G.,Basok, S. S.,Filonova, L. K.,Kulikov, N. V.,Pastushok, V. N.
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p. 346 - 349
(2007/10/02)
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- MACROHETEROCYCES. XXXVI. A CONVENIENT METHOD FOR SYNTHESIS OF DI- AND POLYAZACROWN ETHERS
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A method is proposed for the production of di- and polyazacrown ethers by the condensation of bissulfonamides with dibromides or ditosyloxy derivatives in a two-phase aqueous alkali-toluene (benzene) system.The optimum concentration range for the substrate and the alkylating agent is 0.017-0.1 M.The catalytic activity of the quaternary ammonium salts decreases in the order (Bu)4NI > (Bu4)NBr > (Bu4)NCl > (Bu4)NHSO4 > (C2H5)3C6H5CH2NCl >> (Et)4NI > (Et)4NBr.The highest yields of te 12-membered azacrown ethers are obtained in the presence of lithium hyroxide, and the largest yields of the crown ethers with larger ring sizes are obtained in the presence of sodium or potassium hydroxide, and this is probably due to the matrix effects of the cation.
- Luk'yanenko, N.G.,Basok, S.S.,Filonova, L.K.
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p. 1562 - 1571
(2007/10/02)
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- Characterization of 2,2'-Bi-(1,4,8,11-tetra-azacyclotetradecane): X-Ray Structure and Properties of the Dinuclear Complex 4
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2,2'-Bi-(1,4,8,11-tetra-azacyclotetradecane) has been isolated as minor product from the nickel(II)-assisted synthesis of 1,4,8,11-tetra-azacyclotetradecane (cyclam) and its structure confirmed by X-ray structural analysis of the dinuclear complex 4.
- Barefield, E. Kent,Chueng, Duncan,Derveer, Donald G. Van,Wagner, Frank
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p. 302 - 304
(2007/10/02)
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