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Different strategies for the synthesis of symmetrical and unsymmetrical macrocyclic Schiff bases in the absence of metal ions are considered. General methods for performing macrocyclisation under thermodynamic or kinetic control are analysed. The key factors influencing the structure of macrocyclic azomethines are discussed. The bibliography includ...
Citations
... World literature describes methods for the synthesis of N,N 0disubstituted trans-1,2-diaminocyclohexane derivatives [1][2][3][4] and their cyclic adducts, 5-7 including poly-8 and macroheterocycles. 9,10 Compounds containing the trans-1,2-diaminocyclohexane moiety in the molecule oen exhibit antitumor activities [11][12][13][14] and antiproliferative properties 15 and are also of interest as N-containing chiral ligands, 16 bifunctional organocatalysts, 17 and catalyst systems for enantioselective transformations. 18,19 Recently, 20 we demonstrated the possibility of one-pot synthesis of (3bS*,7aR*,10bR*,14aS*)-perhydro-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracenes involving the catalytic reaction of cis-1,6,7,12-tetraazaperhydrotetracene with cycloaminomethylating reagents. ...
... In trans-1,2-diaminocyclohexane, both amino groups are located in equatorial positions and the H 2 N-C-C-NH 2 dihedral angle is close to 60 ; therefore, trans-1,2-diaminocyclohexane behaves as a nearly planar building block. 10 Preliminary experiments demonstrated that, without a catalyst, N,N-bis(methoxymethyl)-N-propylamine, obtained in situ, 24 reacts with trans-1,6,7,12tetraazaperhydrotetracene (1) at 60 C to give 2,9-dipropyl-perhydro-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracene (2) in $20% yield. In order to increase the yield of the target heterocycle 2, the reaction of bis(methoxymethyl)propylamine with 1,6,7,12-tetraazaperhydrotetracene was conducted in the presence of 5 mol% SmCl 3 $6H 2 O, which was successfully used in our previous studies for heterocyclization reactions. ...
... wR 2 ¼ 0.1721 [2594 reections with I > 2s(I)] and R 1 ¼ 0.2600, wR 2 ¼ 0.2723 for all data (8968 reections). Atomic coordinates, bond lengths, bond angles and thermal parameters have been deposited at the Cambridge Crystallographic Data Centre as a CIF deposition with le number CCDC 1973770.(3bR*,7aR*,10bR*,14aR*)-2,9-Dicyclooctyl-octadecahydro-1H,8H-2,3a,7b,9,10a,14b-hexaazadibenzo[fg,op]tetracene(10).White powdery crystals; yield 0.47 g (85%); mp 184-186 C; R f 0.72 (MeOH). 1 H NMR (500.17 MHz, CDCl 3 ): d ¼ 0.93 (qd, 2 J ab ¼ 12 Hz, 3 J ¼ 3 Hz, 2H, CH 2 , H a -7,14), 1.15-1.25 (m, 4H, CH 2 , H a -5,6,12,13), 1.27-1.33 ...
Catalytic methods for the synthesis of previously unknown 2,9-disubstituted 3b R *,7a R *,10b R *,14a R *- cis -14c,14d-perhydro-2,3a,7b,9,10a,14b-hexaazadibenzotetracenes with pronounced antitumor activity have been developed.
... Macrocyclic compounds are natural or synthetic polydentate compounds, containing their donor atoms either incorporated in or less commonly attached to a cyclic backbone. Macrocyclic compounds having heteroatoms are important compounds with broad spectrum of biological activities [1][2][3][4][5][6][7] apart from their potential applications in supramolecular chemistry, catalysis and new materials. [8,9] Over the last few years, macrocyclic chemistry has attracted lot of interest and has become a growing area of research in inorganic and organic chemistry in view of its biological importance. ...
... [8,9] Over the last few years, macrocyclic chemistry has attracted lot of interest and has become a growing area of research in inorganic and organic chemistry in view of its biological importance. [1][2][3][4] Compared to linear peptide macromolecules, cyclic macromolecules provide improved stability and membrane permeability. These factors were clearly demonstrated in the development of hepatitis C virus (HCV) NS3 protease inhibitor, BILN2061. ...
Macrocyclic chemistry is one of the emerging research areas in the chemical science. Macrocyclic compounds continue to attract significant attention due to their numerous possible applications particularly in the areas like biology, catalysis and industry. This review article summarizes the developments and advances in synthesis and medicinal applications of macrocyclic compounds derived from (benz)imidazole- and indole-based heterocycles. Important medicinal applications of (benz)imidazole- and indole-based macrocycles include antimicrobial and anticancer activities. The representative lead compounds in each series of macromolecules have been discussed. All these initial lead breakthroughs help validate the great potential of (benz)imidazole- and indole-based macrocyclic compounds as a class of effective medicinal agents.
... For example DAMN has been used extensively as a precursor for reaction with aromatic aldehydes to producing mono-and/or bis-iminated organic dyes [5e7]. Contrary to the conventional reactions, where the first substitution activates additional substitution, Schiff base formation at one amine group of DAMN inactivates the second amine group and only mono-imine products form under mild condition [5,8]. However, bis-imine products may be form at hard condition and in the presence of an acid catalyst at high temperature [7,9]. ...
New unsymmetric diaminomaleonitrile-based azo receptors (H3Lⁿ, n = 1–3) have been synthesized via condensation reaction of 5-(4-X-phenyl)-azo-salicyladehyde (X = NO2, OMe and CH3) with 2-amino-3-(5-bromo-2-hydroxybenzylamino)maleonitrile. The solvatochromic behaviors of the molecules were probed by studying their UV–Vis spectra in five pure organic solvents of different polarities. The p-NO2 substituted receptor shows a dramatic color change from yellow to blue upon the addition of fluoride ion in CH3CN. This capability was studied by systematic TD-DFT calculations. These compounds were assayed for their in vitro antibacterial activities against Gram-positive (S. aureus, S. epidermidis and L. monocytogenes) and Gram-negative (E. coli, P. aeruginosa and K. pneumonia.) bacteria by disc diffusion method. The results indicated that the compounds show good inhibition against Gram positive bacteria namely L. monocytogenes as compared to standard drugs.
... The aspect of interest in ligands is raised from features such as the nature, number and arrangement of ligand donors, as well as ligand conjugation, substitution and flexibility, which produce different types of macrocyclic molecules suitable for specific uses P [5] P . Recently, there was great interest in the field of chemistry of metal complexes of Schiff bases containing O and N donorsP [6][7][8][9][10][11] P .This can be attributed to increased activity in this field to their remarkable structural features antimicrobial activity of these ties donor complexes derived from themP [12,13] P . The ligands chelating contain O and N donor atoms show broad biological activity and are particularly important in view of the variety of ways that are bonded to metal ions. ...
... ppm.The peak at (40.01) ppm. assigned to DMSO P [7][8] P . ...
A new tetradentate schiff-base derived from 2-benzoyl benzoic acid with O-phenylene diamine have namely[2,2'-(1E,1'Z)-
(1,2-phenylenebis(azan-1–yl-1-ylidene)bis(phenylmethan -1-yl-1-ylidene)dibenzoic acid].Tetradental Schiff base type (NNOO) have been
synthesized and characterized using IR, UV, P
1
PH & P
13
PC-NMR spectroscopy, elemental analysis.
The ligand used in the preparation of five transition metal complexes with CoP(II)P, NiP(II)P, MnP(II)P, HgP(II)P&CuP(II)P and characterized via elemental analysis, FT-IR, UV, magnetic susceptibility and molar conductivity from the above data the geometrical formula was the square planar has suggested for Cu , Ni and Hg complexes and the tetrahedral geometry has suggested for Co and Mn complexes and in vitro tests for antibacterial activity showed that most of the prepared compounds display a good activity to (Staphylococcus aureus), (Escherichia coli) , (Bacillus )and (Pseudomonas).
... In general, macrocyclic Schiff bases prepared by condensation reactions between equimolar amounts of diamines and aliphatic dicarbonyl compounds are commonly unstable [10,11]; nevertheless, these macrocyclic ligands can be synthesized by the template method [12]. On the contrary, Schiff bases prepared from aromatic diamines and aliphatic dicarbonyl compounds are more stable and can be isolated as free ligands. ...
... For example, the condensation of acetyl acetone with an equimolar amount of 2,6-diaminopyridine in methanol in the presence of catalytic amounts of hydrochloric acid affords the corresponding [2 ? 2] macrocycle [10,11]. ...
... The combined dichloromethane extract was dried, filtered, and concentrated. The product was re-precipitated by addition of ethanol to afford a pale yellow precipitate of diester 5 6,7,8,9,10,11,12,13,14,15,23,24,25,26-Tetradecahydrodinaphtho[2,3-b:2 0 ,3 0 -n] [1,16,5,12]dioxadiazacycloicosine (3, C 32 H 38 N 2 O 2 ) A solution of 4 % (v/v) 1,6-diaminohexane in ethanol (1.7 cm 3 ) was added at 0.3 cm 3 /h to a stirred solution of 0.10 g dialdehyde 7 (0.25 mmol) in 25 cm 3 chloroform and 25 cm 3 ethanol. The resultant mixture was heated under reflux for 2 h, then it was kept at room temperature for 0.5 h. ...
Three novel diazacrown ether ligands, namely 17-, 18-, and 20-membered O2N2-donor macrocycles derived from 3,3′-[butane-1,4-diylbis(oxy)]bis(2-naphthalenecarbaldehyde), were prepared and characterized by 1H and 13C NMR spectroscopy and mass spectra. Their host–guest interaction with Ni(II) was studied in DMSO-d
6 using 1H NMR spectroscopy. The stoichiometry of the complex in each case in the concentration range examined was determined to be 1:1 using the continuous variation method (Job’s plot). The 17-membered O2N2-donor macrocycle in which the two nitrogen atoms are tethered by three methylene units binds Ni(II) more strongly than the other two macrocycles do.
Graphical abstract
... The macrocyclic Schiff base obtained has been versatile in forming a series of complexes with Cr(III) 12,13 , Mn(II) 13 , Mn(III) 14 , Fe(II) 15 , Fe(III) 13 ,Co(II) 4,15,16 , Ni(II) 6, 16 , Cu(II) 3,15,16 , Zn(II) 15,16 , Ru(II) 9,10 , Ru(III) 13 , Rh(III) 5 , Ir(III) 13 , Pd(II) 8 and Pt(II) 13 ions under well defined conditions and these complexes have been investigated with particular reference to the structural aspects of the ligand moiety in the metal complexes. The coordination chemistry of macrocyclic ligands is a fascinating area of intense study for inorganic chemists 2,[17][18][19] . The aspect of interest in macrocyclic ligands is raised from features such as the nature, number and arrangement of ligand donors, as well as ligand conjugation, substitution and flexibility, which produce different types of macrocyclic molecules suitable for specific uses 2 . ...
The synthesis, structure, physico-chemical investigation and biological studies of some manganese (III) complexes of tetraaza Schiff base macrocycles are described. The ligands were obtained by condensation of ortho- phthalaldehyde with different diamines in methonal. The metal complexes of Mn (III) were synthesized and isolated as solid products and characterized by analytical means as well as by spectral techniques such as FT-IR, Mass and UV-Vis spectrometry. On the basis of these studies, a five coordinate square pyramidal geometry for all of these complexes have been proposed. These complexes were also tested for their in vitro antimicrobial activities against some bacterial strains to assess their inhibiting potential and the activities shown by these complexes were compared with standard drugs.
... Macrocyclic compounds possessing heteroatoms are valuable compounds with broad spectrum of pharmacological activities [1][2][3][4] apart from their potential application in the field of molecular catalysis. More importantly, macrocyclic Schiff bases and the relevant transition metal complexes are of great interest in coordination chemistry, although this subject has been extensively studied [5][6][7]. ...
A series of novel macrocyclic compounds were synthesized by the condensation of o-phthalaldehyde with aromatic amino alcohols followed by treatment with 1,2-dibromoethane or 1,3-dibromopropane in non-template method. The structural features of the isolated macrocycles have been determined from the microanalytical, IR, (1)H, (13)C NMR and mass spectral studies. Antimicrobial activities of these macrocyclic compounds were tested against the gram-positive (Bacillus subtilis, Staphylococcus aureus) and gram-negative (Escherichia coli, Klebsiella pneumoniae) bacteria and found to exhibit potential antibacterial activity. The macrocycles were also tested in vitro to evaluate their activity against fungi, namely, Aspergillus flavus (A. flavus) and Fusarium species.
The reactions of 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene with acetic and tetrafluorobenzoic acids halides produce C - and N -acyl-substituted 1,4-diazepines. Their structure was characterized by IR, 1H, and 13C NMR spectroscopy using two-dimensional experiments 1H-13C HMQC, HMBC, and 1H-1H COSY.
