Schiff bases with

The reaction between 4-aminothiazole and paranitrobenzaldehyde, followed by the cydization of the Schiff base with PfOEtfs, provides 2-(4-thiazolyl)indazole (84a) (1576) (Scheme 59). 

Another viable method for the synthesis of L-foUc acid (1) starts from 6-formylpterin (23). The diester of L-glutamic acid (24) is condensed with 6-formylpterin (23). Reduction of the Schiff base with sodium borohydride is followed by hydrolysis to yield L-foUc acid (37). 

The observations that heteroaromatic amino compounds are not easily diazotized, are quite readily hydrolyzed,and often do not form Schiff bases with aldehydes have all been incorrectly interpreted as indications that these compounds exist principally in the imino form, whereas these observations can reasonably be attributed to the fact that the amino groups in compounds of the type of 4-aminopyridine are electron deficient as a result of the contribution of structures of type 36. ... 

A very simple and elegant alternative to the use of ion-exchange columns or extraction to separate the mixture of D-amino add amide and the L-amino add has been elaborated. Addition of one equivalent of benzaldehyde (with respect to die D-amino add amide) to the enzymic hydrolysate results in the formation of a Schiff base with die D-amino add amide, which is insoluble in water and, therefore, can be easily separated. Add hydrolysis (H2SQ4, HX, HNO3, etc.) results in the formation of die D-amino add (without racemizadon). Alternatively the D-amino add amide can be hydrolysed by cell-preparations of Rhodococcus erythropolis. This biocatalyst lacks stereoselectivity. This option is very useful for amino adds which are highly soluble in die neutralised reaction mixture obtained after acid hydrolysis of the amide. 

The kinetic stereoselection of this process is rationalized in terms of the formation of Schiff bases with anti configuration. 

In 1996, Cavell described the synthesis of neutral P(VI) compound 37 containing a divalent tridentate diphenol imine ligand and three chlorine atoms by the reaction of a bis silylated Schiff base with PCI5 to give 37 after elimination of two equivalents of Me3SiCl (Scheme 7) [51]. 

Affinity microparticles (AMPs) were obtained by cross-linking the S-layer lattice on S-layer-carrying cell wall fragments with glutaraldehyde, reducing Schiff bases with sodium borohydride, and immobilizing protein A as an IgG-specific ligand [92]. Thus, AMPs rep-... 

We succeeded in showing that recycling of the enzyme was indeed possible in our IL solvent system, though the reaction rate gradually dropped with repetition of the reaction process. Since vinyl acetate was used as acyl donor, acetaldehyde was produced hy the hpase-catalyzed transesterification. It is well known that acetaldehyde acts as an inhibitor of enzymes because it forms a Schiff base with amino residue in the enzyme. However, due to the very volatile nature of acetaldehyde, it easily escapes from the reaction mixture and therefore has no inhibitory action on the lipase. However, this drop in reactivity was assumed to be caused by the inhibitory action of acetaldehyde oligomer which had accumulated in the [bmim][PFg] solvent system. In fact, it was confirmed that the reaction was inhibited by addition of acetaldehyde trimer. =... 

Scheme 8.34 Hydrogenation of a Schiff base with tetrasulfonated diphosphine ligand.

Other examples of this synthetic strategy are known for example, a recent zirconium polymer by Illingsworth and Burke (8), who joined amine side groups of a zirconium bis(quadridentate Schiff-base) with an acid dianhydride to give amide linkages. Once again, caution is necesary, as Jones and Power (2) learned when they attempted to link metal bisO-diketonates) with sulfur halides that is, they obtained insoluble metal sulfides because the p-diketone complexes which they used were fairly labile and the insolubility drove the reactions to completion in the wrong direction. 

With RNH2 the products are also imines these, too, are usually unstable unless one of the substituents on the carbonyl carbon atom is aromatic, e.g. ArCH=NR—the stable products are then known as Schiff bases. With R2NH, the initial adduct (74) cannot lose water in the normal way some such species have been isolated but they are not particularly stable. If, however, the adduct has any a-H atoms then a different dehydration can be made to take place yielding an enamine (75) ... 

The preparation of quinoline and tetrahydroquinoline derivatives from metal carbonyl-catalyzed reactions of Schiff bases with alkyl vinyl ethers in... 

Hapten molecules containing aldehyde residues may be crosslinked to carrier molecules by use of reductive animation (Chapter 3, Section 4). At alkaline pH values, the aldehyde groups form intermediate Schiff bases with available amine groups on the carrier. Reduction of the resultant Schiff bases with sodium cyanoborohydride or sodium borohydride creates a stable conjugate held together by secondary amine bonds. 

Aminoanthracene forms a Schiff base with dimethylacetaldehyde (isobutyral-dehyde). This compound can be oxidized by peroxide under basic conditions to form 9-formamidoanthracene and acetone in dimethylformamide as a solvent [54, 55], CL from this system can be observed in other aprotic solvents as well. A limited amount of work has been done with the CLs of Schiff bases or anthracene derivatives. Presumably, this will change in the future. 

In contrast to the flavin-dependent monoamine oxidases, SSAO/VAP-1 has evolved to hydroxylate a tyrosine residue in the active site which is further oxidized to the quinone state by oxygen in the presence of copper ion releasing hydrogen peroxide [28-30]. The primary amine in the substrate (R-NH2, Scheme 1) forms a Schiff-base with the quinone carbonyl group, which through a series of steps ultimately releases the aldehyde product. 

Schiff bases with intramolecular charge transfer complexes such as 2,3-bis[(4-diethylamino-2-hydroxybenzylidene)amino]but-2-enedinitrile zinc (II) (BDPMB-Zn, 187) emit red fluorescence with fluorescent quantum yields up to 67%. OLEDs with a structure of ITO/TPD/ TPD BDPMB-Zn/Alq3 BDPMB-Zn/Alq3/Mg-Ag showed very bright saturated red emission with CIE (0.67, 0.32) with a luminance of 2260 cd/m2 at 20 V and a current efficiency of 0.46 cd/A (at 20 mA/cm2). In addition, the EL spectra do not change with the doping concentration in the range of 0.5—3% [229]. 

The anion B12H11NH22 can form Schiff bases with aldehydes, which in turn can be reduced to amines, opening the way to both secondary amine derivatives of the B12H122 cluster and tertiary amines and quaternary ammonium salts after further alkylation [61]. 

A further remarkable finding in the hydrolysis of aflatoxin B1 exo-8,9-epoxide is the relative instability of the dihydrodiol, which under basic conditions exists in equilibrium with an aflatoxin dialdehyde, more precisely a furofuran-ring-opened oxy anionic a-hydroxy dialdehyde (10.134, Fig. 10.30). The dihydrodiol is the predominant or exclusive species at pH < 7, whereas this is true for the dialdehyde at pH >9, the pK value of the equilibrium being 8.2 [204], The dialdehyde is known to form Schiff bases with primary amino groups leading to protein adducts. However, the slow rate of dialdehyde formation at physiological pH and its reduction by rat and human aldo-keto reductases cast doubts on the toxicological relevance of this pathway [206]. 

Parmar et al have developed a method for resolving racemic mixtures of a variety of natural and nonnatural amino acids using the ethyl ester of the amino acid protected at the amino position hy the formation of a Schiff base with an aromatic aldehyde such as /)-chlorobenzaldehyde. Both chymotrypsin and Lip such as porcine Lip gave good yields of the L-amino acid which precipitates out of solution as the amino acid ester released from the imine is cleaved by the hydrolase. 

In the S-peptide design, the Pal residue was introduced at position 8, replacing the native phenylalanine (Fig. 9) [22]. Lysine residues, which have the potential to form Schiff bases with the pyridoxal functionahty, and a potentially oxidatively unstable methionine residue were replaced with either norleucine or glycine. These changes resulted in a modified S-peptide that associated with S-protein at levels comparable to the original S-peptide. 

Isoniazid, carbidopa, and hydralazine are hydrazine derivatives with therapeutic uses. They form Schiff bases with pyridoxal 5 -phosphate, and rate constants for their formation and hydrolysis have been measured in aqueous solution pH-rate profiles are reported and compared with that of hydrazine itself. 

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