Amino 3,5-dinitrophenyl

Heating 4-(4-acetamidophenyl) imidazole with 3 M nitric acid at 85°C forms the dinitrate salt of the corresponding amine, but the use of 5 M acid gives 4-(4-amino-3,5-dinitrophenyl) imidazole (41) (79AKZ475). 

Analytical screens are performed with both reverse-phase RP-HPLC and SFC isolation techniques. Analytical SFC should be screened first unless instrumentation availability or project background specifics dictate otherwise. Screening achiral column bonded phases varying in polarity and functionality against different mobile-phase solvent choices is effective for identifying analytical methods for the purpose of impurity isolation. There are currently many unique achiral SFC bonded phase column choices commercially available (2-ethyl pyridine, diethyl amino, dinitrophenyl, pyridine urea, diol, cyano, etc.). SFC column choice provides the most impact in manipulation of relative selectivity for individual... 

Appllca.tlons. Various A/-derivatives of amino acids (qv) are resolvable on BSA columns. These /V-amino acid derivatives include ben2enesulfonyl-, phthalimido-, S-dimethylarnino-l-naphthalenesulfonyl- (DANSYL-), 2,4-dinitrophenyl- (DNP-), and 2,3,6-trinitrophenyl- (TNP-) derivatives (30). Amines such as Prilocain, ( )-2-(prop5lamino)-(9-propiono-toluidide, a local anesthetic (Astra Pharm. Co.), are also resolved on BSA. The aromatic amino acids DL-tryptophan, 5-hydroxy-DL-tryptophan, DL-kynurenine [343-65-7] C qH 2N 2 3 3-hydroxy-DT.-kynurenine [484-78-6] and dmgs... 

The dinitrophenyl group has been used to protect the imidazole — NH group in histidines (45% yield)" by reaction with 2,4-dinitrofluorobenzene and potassium carbonate. Imidazole —NH groups, but not a-amino acid groups, are quantitatively regenerated by reaction with 2-mercaptoethanol (22°, pH 8, 1 h)." The 2,4-... 

Acid hydrolysis cleaves the amide bonds of the 2,4-dinitrophenyl-labeled peptide, giving the 2,4-dinitrophenyl-labeled N-teiminal amino acid and a mixture of unlabeled anino acids. 

Tetrahydrocarboline derivatives have recently been synthesized from 2-o-nitroarylated cyclohexanone derivatives. Thus, reductive cyclization of 3-(2,4-dinitrophenyl)-l-methyl-4-piperidone (68) (prepared by the reaction of 2,4-dinitrochlorobenzene with l-methyl-4-A-pyrrolidmo-3-piperideine) gave 7-amino-2-methyl-l,2,3,4-tetrahydro-y-carboline (69). Neither catalytic nor chemical reduction of the... 

A regioselective synthesis of 2-amino[l, 2,4]triazinones 708 was reported (82JHC1583 83JHC1671) by reaction of 706 with 0-(2,4-dinitrophenyl)-hydroxylamine 707 as an amino transfer agent. Subsequent reaction of 708 with ammonia or amines, followed by ring closure with formic acid, provided 709. 

We recently synthesized cationic polymers containing imidazole (e g. 68 (SZ811) and 69 (SZ11—3—3)] by reacting poly [N-(2,4-dinitrophenyl)-4-vinyl-pyridinium chloride] with histamine or histamine mixed with other amino derivatives ll8 The hydrolyses of neutral and anionic esters with the models followed saturation kinetics in alkaline media. 

New Methods for the Synthesis of 2-Amino-2-deoxyglucosides Utilizing N-2, 4-Dinitrophenyl (DNP) Derivatives. P. F. Lloyd and M. Stacey, Chem. Ind. (London), (1955) 917. 

Reactions of 2-(2, 4 -Dinitrophenyl)-amino-2-deoxy-r>-glucose, (DNP-D-glucosamine), and derivatives, P. F. Lloyd and M. Stacey, Tetrahedron, 9 (1960) 116-124. 

A simple and rapid method of separating optical isomers of amino acids on a reversed-phase plate, without using impregnated plates or a chiral mobile phase, was described by Nagata et al. [27]. Amino acids were derivatized with /-fluoro-2,4-dinitrophenyl-5-L-alanine amide (FDAA or Marfey s reagent). Each FDAA amino acid can be separated from the others by two-dimensional elution. Separation of L- and D-serine was achieved with 30% of acetonitrile solvent. The enantiomers of threonine, proline, and alanine were separated with 35% of acetonitrile solvent and those of methionine, valine, phenylalanine, and leucine with 40% of acetonitrile solvent. The spots were scraped off the plate after the... 

Sugars and Amino Acids, Using the AT-(2 4-dinitrophenyl) Derivatives. Science [Washington] 113, 354 (1951). 

Though y-CD was found to form complexes also with PEG, the yields were too small for their characterization. Thus, Harada et al. turned to two PEG deriva-tives-bis(3,5-dinitrobenzoyl)-PEG (PEG-DNB2) and bis(2,4-dinitrophenyl-amino)-PEG (PEG-DNP2)-, which were found to complex with this CD at high yields. Using a fluorescent probe technique the resulting complexes were shown to include four ethylene glycol units in one y-CD cavity. However, these PEG derivatives formed no complex with a-CD. This is attributable to the fact that their chains are too thick to enter the slim a-CD cavity. 

Shaltiel, S. (1967) Thiolysis of some dinitrophenyl derivatives of amino acids. Biochem. Biophys. Res. Comm. 29, 178. 

In earlier studies the in vitro transition metal-catalyzed oxidation of proteins and the interaction of proteins with free radicals have been studied. In 1983, Levine [1] showed that the oxidative inactivation of enzymes and the oxidative modification of proteins resulted in the formation of protein carbonyl derivatives. These derivatives easily react with dinitrophenyl-hydrazine (DNPH) to form protein hydrazones, which were used for the detection of protein carbonyl content. Using this method and spin-trapping with PBN, it has been demonstrated [2,3] that protein oxidation and inactivation of glutamine synthetase (a key enzyme in the regulation of amino acid metabolism and the brain L-glutamate and y-aminobutyric acid levels) were sharply enhanced during ischemia- and reperfusion-induced injury in gerbil brain. 

Amines, amino acids, peptides 2,4-dinitrophenyl hydrazone PRE-CD with +1.10 217... 

Figure 10.13 The reaction of FDNB with compounds containing a free amino group. The reaction at pH 9.5 between FDNB and amino acids or peptides results in the formation of yellow-coloured dinitrophenyl derivatives.

An easily accessible DA CSP derived from L-A-(2-naphthyl)valine (80) was used to separate appropriately derivatized amines, amino alcohols and thiols, derivatization consisting of N-, O- and 5-acylation with 3,5-dinitrobenzoyl chloride or 3,5-dinitrophenyl... 

N-(4-nitrophenyl)-amino acids N-(2,4-dinitrophenyl)-amino acids 8) and 3-nitro-2-pyridyl amino acids have been of considerable interest. A generally applicable mechanistic scheme does not exist so far, and except for 3-nitrophenyl acetate in ortho and/or -para position of the phenyl (pyridyl) ring seems to be a prerequisite for efficient decarboxylation. 

Dinitrofluorobenzene (DNFB) reacts with phenols and, which is not of interest here, with amino groups. Hydrogen fluoride is eliminated. DNFB does not react w ith carboxylic acids. Alcohols, if they react at all, form dinitrophenyl ethers very slowly. Very weakly dissociated phenolic hydroxyl groups, e.g., in salicylic acid (pK = 13.4), are inert towards DNFB. 

Other interesting examples of these amino-exchange reactions are the conversion of 3-aminocarbonyl-4-R-l-(2,4-dinitrophenyl)pyridinium salt (2) into 3-aminocarbonyl-4-R-l-cbutylpyridinium salt by Cbutylamine (82RTC342) and the preparation of l-(pentadeuteriophenyl)-3-amino-carbonyl-4-deuteriopyridinium salt from 3-aminocarbonyl-l-(2,4-dinitro-phenyl)-4-deuteriopyridinium salt (2, R = D) with pentadeuterioaniline (84T433) (Scheme IIL2). 

Example 7 the bis(2,4-dinitrophenyl)phosphoroamidite which can be prepared by a standard procedure reacts with alcohols in a non-selective way which leads to a mixture of products [28]. From a mechanistic point of view this result is consistent with spontaneous displacement of a 2,4-dinitro-phenoxy group in the reaction with alcohol which liberates free DNP. The latter activates the amino group allowing further ligand exchange. However if phosphitylation by the bis(2,4-dinitrophenyl)phosphoroamidite is performed in the presence of one equivalent of triethylamine, high chemoselec-tivity is observed, and the nucleoside (2,4-dinitrophenyl)phosphoramidite is formed in over 92% yield. 

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