Chiral recognition of Schiff bases by 15N NMR spectroscopy in the presence of a dirhodium complex. Deuterium isotope effect on 15N chemical shift of the optically active Schiff bases and their dirhodium tetracarboxylate adducts

Optically active Schiff bases, derivatives of ortho-hydroxyaldehydes and their adducts with dirhodium tetracarboxylate complexes have been studied by (15)N NMR spectroscopy. The position of the equilibrium of Schiff bases, as well as their adducts, has been established on the basis of measurements of deuterium isotope effects on (15)N chemical shifts. At the equilibrium state, the formation of the adducts with dirhodium complexes shifted the proton-transfer equilibrium towards the NH-form.     

Deuterium isotope effect on 13C chemical shifts of tetrabutylammonium salts of Schiff bases amino acids

Deuterium isotope effects on 13C chemical shift of tetrabutylammonium salts of Schiff bases, derivatives of amino acids (glycine, L-alanine, L-phenylalanine, L-valine, L-leucine, L-isoleucine and L-methionine) and various ortho-hydroxyaldehydes in CDCl3 have been measured. The results have shown that the tetrabutylammonium salts of the Schiff bases amino acids, being derivatives of 2-hydroxynaphthaldehyde and 3,5-dibromosalicylaldehyde, exist in the NH-form, while in the derivatives of salicylaldehyde and 5-bromosalicylaldehyde a proton transfer takes place. The interactions between COO- and NH groups stabilize the proton-transferred form through a bifurcated intramolecular hydrogen bond.     

Deuterium isotope effects on 15N chemical shifts of double Schiff bases in the solid state and solution

The proton transfer equilibrium in a series of double Schiff base derivatives of trans‐1,2‐diaminocyclohexane in solution and the solid state was studied by means of ¹⁵N NMR spectroscopy and analysis of the deuterium isotope effect on the chemical shifts Δ¹⁵N(D). The presence of a proton transfer equilibrium in the N‐2‐hydroxynaphthylidene moieties of the Schiff bases studied in the solid state at room temperature was evidenced. The results confirmed the interrelation of the two hydrogen bonds in double Schiff base derivatives of trans‐1,2‐diaminocyclohexane. Copyright © 2003 John Wiley & Sons, Ltd.     

Chemistry and applications of organotin(IV) complexes of Schiff bases

Schiff bases are the most widely used versatile ligands, able to coordinate many elements and to stabilize them in various oxidation states. Recently, this class of compounds has been employed as models for biological systems, and in control of stereochemistry in six-coordinate transition metal complexes. Recently, the chemistry of organotin(IV) complexes of Schiff bases has also stemmed from their antitumour, antimicrobial, antinematicidal, anti-insecticidal and anti-inflammatory activities. Furthermore, organotin(IV) complexes of Schiff bases present a wide variety of interesting structural possibilities. Both aliphatic and aromatic Schiff bases in their neutral and deprotonated forms have been used to yield adducts and chelates with variable stoichiometry and different modes of coordination. This critical review (>155 references) focuses upon the chemistry and biological applications of organotin(IV) complexes of Schiff bases reported in the past 15 years. Thermal behavior of these complexes is also discussed.     

AIM analysis of intramolecular hydrogen bonding in O-hydroxy aryl Schiff bases

AIM analysis was applied to study the changes in such topological parameters as the electron density at critical points of all the bonds of the molecule during the so-called nonadiabatic proton transfer in intramolecular hydrogen bonding in o-hydroxy aryl Schiff bases. Proton transfer is presented by a stepwise elongation and fixing of the hydroxyl bond with complete optimization of the rest of the parameters of the molecule by the B3LYP/6-311++G(d,p) method. A more detailed study of electron density changes at the critical points of the chelate and phenol rings in the stepwise proton-transfer process is presented. It was shown that the dependency of the electron density at the critical point of the chelate ring on tautomeric equilibrium is of a complicated character, whereas it is linear for the phenol ring. A complex study of the changes in the total electron density at the hydrogen bond, the quasi-aromatic ring, and in the whole molecule has been accomlished. The calculations of the intramolecular hydrogen bond by means of conformational and topological methods are discussed.     

Spectroscopic and photophysical studies of the hydroquinone family of photochromic Schiff bases analyzed over a 17-orders-of-magnitude time scale

The hydroquinone family of photochromic Schiff bases has been studied by means of stationary and time-resolved spectroscopic absorption and emission techniques in the UV-Vis spectral range in the temporal range from 100 fs to 1 h. The studies have revealed that besides the ultrafast excited state intramolecular proton transfer reaction there is also another deactivation channel from the initially excited state. For the symmetric molecule with two intramolecular hydrogen bonds, the efficiency of the proton transfer reaction has been found to be at least ten times reduced when compared to that of the asymmetric molecule with one intramolecular hydrogen bond. The long-lived transient species absorbing in the UV range and coexisting with the photochrome have been observed in differently interacting solvents. Evidence for different conformers of almost all of the tautomers involved in the photochromic cycle has been also found.     

Reaction of dihydrosylvan with Schiff bases

Summary In the presence of Lewis acids (BF₃, AlCl₃, AlBr₃), dihydrosylvan (2-methyl-4,5-dihydrofuran) reacts with Schiff bases, like o-nitrobenzylideneaniline, o-hydroxybenzylideneaniline, benzylidene-o-aminophenol, cinnamaldehyde anil, citral anil and cyclohexanone anil, to give tetrahydrofuranotetrahydroquinoline derivatives as adducts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1693–1695, September, 1964     

三种水杨醛类席夫碱的合成与性质研究

以取代水杨醛和3-氨基噻吩为原料合成了三种水杨醛类席夫碱,探讨了水杨醛结构中酚羟基对位取代基结构变化对于该席夫碱探针的激发态内质子转移过程、pH响应和金属离子响应的影响。研究结果表明,改变取代基团的推、吸电子能力,可调节酚氧负离子对活泼氢的束缚能力,进而影响这些席夫碱分子的激发态内质子转移性能。同时,酚氧负离子的电荷密度也决定了其与阳离子的配位能力,从而表现出不同结构的席夫碱对金属离子的选择性和灵敏性差异。     

A flash photolysis study of the formation of retinal Schiff bases in a native photoreceptor cell

It is believed that the accumulation of all-trans-retinal (ATR) in retinal cells is responsible for photoinduced damage to the retina. However, ATR is formed within a photoreceptor cell disk in the process of photolysis and transferred to the cell cytoplasm, where it is converted in a high yield into the nonphototoxic compound retinol. Within the disk where ATR can be accumulated, retinol can form Schiff bases, which are also nonphototoxic compounds, with the amino groups of proteins and lipids. Thus, it is unclear in which concentrations free ATR can be accumulated inside a cell. In this study, it has been proposed to evaluate the concentration of free ATR in the cell from the yield of an excited triplet state because neither Schiff bases nor retinol can be transformed into an excited triplet state. It has been found that 70% ATR forms Schiff bases in the native cell in the equilibrium state, thereby, a considerably decreasing the probability that ATR is the main inducer of photodamage.     

Interconversion of host–guest components in supramolecular assemblies of polycarboxylic acids and reduced Schiff bases

Eight supramolecular assemblies of benzene-1,3,5-tricarboxylic acid (H₃BTC) and benzene-1,2,4,5-tetracarboxylic acid (H₄BTtC) with reduced Schiff base of flexible backbone having phenolic and pyridyl groups, i.e., 1,2-bis(2-hydroxybenzylamino)ethane, 1,3-bis(2-hydroxybenzylamino)propane, 1,4-bis(2-hydroxybenzylamino)butane and 1,4-bis(4-pyridinylmethylamino)butane have been constructed by proton transfer reaction. H₃BTC forms host–guest type assemblies with amines having phenolic functionality, while a layered structure was obtained with pyridyl functionalized amine. H₄BTtC also formed host–guest assemblies with the diamines where reduced Schiff base acts as host and acid moiety acts as the guest. Different conformations of the diamines were observed in these assemblies. Theoretical studies were performed to analyze the effect of varied chain lengths of diamines on hydrogen bond interaction energy of the adducts.     

Diastereoselectivity in addition of nitrile-stabilized carbanions to Schiff bases and in subsequent alkylation reactions

The stereochemical course in the addition of lithiated benzylcyanide and propionitrile to aromatic Schiff bases, as well as of the subsequent alkylation reaction has been investigated. The stereochemical ratios in the condensation reaction are proved to result from the intermediacy of a prochiral carbanionic intermediate, produced by a fast proton shift in the initially formed azanion. Subsequent one-pot alkylation reaction with a variety of electrophiles leads in high to moderate yields to diastereoselective formation of a second carbon-carbon bond at the same carbon center. Diastereoselectivity in alkylation, which varies from outstanding to high and poor is rationalized in terms of open-chain, product-like or reactant-like transition state models.     

Reaction mechanisms between methylamine and a few Schiff bases: Ab initio potential energy surfaces of a catalytic step in semicarbazide sensitive amino oxidases (SSAO)

The potential energy surfaces for the transamination reaction catalyzed by SSAO were explored for some of the possible reactants considered in a preliminary investigation (Comput Chem 2000, 24 , 311). The proton transfer to methylamine (as a model of the catalytic base belonging to the enzyme active site)—either from the keto or enol form of the reactant Schiff bases with one of the possible cofactors, pyridoxal phosphate, PLP (using as a model the pyridoxal ring protonated at N)—was investigated. The enol form seems to be preferred in the region of the neutral intermediate, because even the keto form undergoes a spontaneous rearrangement to the enol form once the C_α proton is delivered to methylamine, producing methylammonium. When the proton is returned back to the Schiff base (on C₁), the adduct is about 1.4 kcal/mol more stable than the reactants, while a canonical electron distribution is obtainable only for the enol form. The proton transfer to methylamine was also studied in the presence of the other possible cofactor (para or ortho) topaquinone, TQ. A steep uphill pathway, similar to the keto‐pyridoxal Schiff base one, is obtained using the Schiff base with pTQ, which requires a rearrangement to the final intermediate. On the contrary, using the oTQ structures with the quinonoid O on the same side of methylamine, the proton abstracted from the Schiff base goes spontaneously onto the other quinonoid oxygen. The effect on the barrier heights produced by the presence of a variety of functional groups in the vicinity of the pyridoxal ring nitrogen was also examined. © 2001 John Wiley & Sons, Inc. Int J Quant Chem, 2001     

Charge-transfer complexes of pyrimidine Schiff bases with aromatic nitro compounds

Charge-transfer (CT) complexes of pyrimidine Schiff bases, derived from condensation of 2-aminopyrimidine and substituted benzaldehydes, with some aromatic polynitro compounds were prepared and investigated using IR, UV, visible and (1)H NMR spectroscopy. For all solid complexes, the main interaction between the donor and acceptor molecules takes place through the π-π* interaction. Strong and some weak acidic acceptors, in addition interact through proton transfer from the acceptor molecule to the basic centre of the electron donor. Also, an n-π* transition was detected in some complexes.     

Synthesis, characterization, and spectroscopic investigation of benzoxazole conjugated Schiff bases

Two Schiff bases were synthesized by reaction of 2-(4'-aminophenyl)benzoxazole derivatives with 4-N,N-diethylaminobenzaldehyde. UV-visible (UV-vis) and steady-state fluorescence in solution were applied in order to characterize its photophysical behavior. The Schiff bases present absorption in the UV region with fluorescence emission in the blue-green region, with a large Stokes' shift. The UV-vis data indicates that each dye behaves as two different chromophores in solution in the ground state. The fluorescence emission spectra of the dye 5a show that an intramolecular proton transfer (ESIPT) mechanism takes place in the excited state, whereas a twisted internal charge transfer (TICT) state is observed for the dye 5b. Theoretical calculations were performed in order to study the conformation and polarity of the molecules at their ground and excited electronic states. Using density functional theory (DFT) methods at theoretical levels BLYP/Aug-SV(P) for geometry optimizations and B3LYP/6-311++G(2d,p) for single-point energy evaluations, the calculations indicate that the lowest energy conformations are in all cases nonplanar and that the dipole moments of the excited state relaxed structures are much larger than those of the ground state structures, which corroborates the experimental UV-vis absorption results.     

Rapid photodynamics of vitamin B6 coenzyme pyridoxal 5'-phosphate and its Schiff bases in solution

The active form of vitamin B6, pyridoxal 5'-phosphate (PLP), is an important cofactor for numerous enzymes in amine and amino acid metabolism. Presented here is the first femtosecond transient absorption study of free PLP and two Schiff bases, PLP-valine and PLP-alpha-aminoisobutyric acid (AIB), in solution. Photoexcitation of free PLP leads to efficient triplet formation with an internal conversion rate that increases with increasing pH. The measured excited-state kinetics of the PLP-valine Schiff base exhibits a dramatic deuterium dependence as a result of excited-state proton transfer (ESPT) of the Calpha hydrogen in the amino acid substrate. This is consistent with formation of the key reaction carbanionic intermediate (quinonoid), which is resonance stabilized by the electron-deficient, conjugated pi system of the Schiff base/pyridine ring. The transient absorption signals of the PLP-Schiff base with alpha-methylalanine (2-aminoisobutyric acid), which does not have a Calpha proton, lack an observable deuterium effect, verifying ESPT formation of the quinonoid intermediate. In contrast to previous studies, no dependence on the excitation wavelength of the femtosecond kinetics is observed with PLP or PLP-valine, which suggests that a rapid (<250 fs) tautomerization occurs between the enolimine (absorbing at 330 nm) and ketoenamine (absorbing at 410 nm) tautomers in solution.     

Orientational effects of hydrogen bonding in liquid-crystalline solutions containing Schiff bases

Intermolecular hydrogen bonding in binary mixtures containing nematogenic Schiff bases as solvents and proton-donating non-mesomorphic solutes has been considered. Reasons for the anomalous concentration dependences of solute order parameters are discussed. A solution structure model of acetic acid in nematic solvents is proposed; constants of complex-dimer equilibrium and coefficients of the orientational correlation of the non-mesogenic solute are calculated on the basis of this model. Hydrogen bonded complex structure using ¹³C NMR has been studied and stability constants in isotropic solutions in chloroform have been calculated. The influence of the solvent orientational ordering on the complex stability is discussed. Data on the solvation isotopic effects in the solutions investigated, which confirm the adequacy of the model are given.     

Solvent extraction of metal ions by use of Schiff bases

Schiff bases are aldehyde or ketone like compounds in which the carbonyl group is replaced by imine or azomethine group. They are widely used for industrial purposes and also exhibit a broad range as extractants. A general view of solvent extraction applications of complexes is discussed in this review. The family of Schiff bases and their extraction of various transition metals such as Co, Cu, Cr, Fe, Ga, Hg, Mn, Mo and Ni are discussed. A brief history of the synthesis and reactivity of Schiff bases will be presented. Factors on solvent extraction will be illustrated and discussed.     

Syntheses and structural studies of Schiff bases involving hydrogen bonds

New Schiff bases have been prepared by reacting 3-hydroxy-4-pyridine- carboxaldehyde with various amines. NMR spectroscopic methods provided clear evidence that the Schiff bases exist in the solid state and in solution as hydroxyimino tautomers with the E-configuration. A study of the stabilities of the tautomeric forms and the different conformers has been carried out using density functional calculations at the B3LYP/6-31G** level.     

The reactions of dihydropyran and 2-methyldihydropyran with some Schiff bases

Summary Schiff bases such as benzylideneaniline, benzylidene-p-anisidine, benzylidene--naphthylamine, and thienylideneaniline react in the presence of BF₃ with dihydropyran and 2-methyl-4,5-dihydrofuran by diene addition to form 1,2,3,4-tetrahydroquinoline derivatives as adducts.     

Synthesis and spectroscopic studies of new Schiff bases

Five novel Schiff bases have been prepared from o-formylphenoxyacetic acid and a series of aminothiazoles to form a number of potentially biologically active compounds. The structures of these Schiff bases have been characterized using IR and (1)H-and (13)C-NMR spectroscopy.