Hydrazide derivatives

Reactions involving quinoline hydrazide derivatives have been noted in the pyridazino-[4,3-c]- (64MI21500), -[4,5-f ]- (31M(58)238) and -[4,5-c]-quinoline (71CB3341) series, whilst the double cyclization of (358) to the pyridazino[4,5-f ]quinoline (359) (80CPB3457) and related cyclizations in the same series (80H(14)267) are of a basically similar type. A lone cyclization of this type from cinnoline intermediates involves the o-acetonylcarboxamide type formation of the pyridine ring to give the pyrido[3,4-c]cinnoline (360) (76JCS(Pl)592). 

Dehydrogenation of the hydrazide derivative 33 with mercuric oxide in the presence of ethylene diamine tetraacetic acid (EDTA) gave 34 and 35 (77AP588). The latter (35) was prepared from a reaction of ester 36 with the appropriate lactam 37 (Scheme 11). 

An auxiliary controlled enantioselective route to generate seven-membered ring lactams 75 used the a-alkylation of cyclic hydrazide derivatives 74. Initially, 6-chloro hydrazides 73,bearing the chiral information in the M-amino-pyrrolidine function underwent amidocyclization in the presence of a base. A subse-... 

Hurwitz et al. [256] used a hydrazide derivative of poly(glutamic acid) as a carrier for daunamycin. This was less toxic than free drug against mouse lymphoma in vitro, but it was as effective, or more effective, against the same lymphoma in vivo. 

Figure 1.108 Glycoproteins that have been treated with sodium periodate to produce aldehyde groups can be further modified with adipic acid dihydrazide to result in a hydrazide derivative.

Figure 1.109 Carboxylate groups on proteins may be modified with adipic acid dihydrazide in the presence of a carbodiimide to produce hydrazide derivatives.

Bis-hydrazide-containing molecules also can be used to activate soluble polymeric sub-stances-containing aldehyde groups. For instance, dextran may be periodate oxidized to create numerous formyl functionalities on each molecule. Subsequent reaction with a homobifunctional hydrazide in large excess results in a hydrazide-activated polymer having multivalent-binding capability toward aldehydes or ketones (Chapter 25, Section 2.2). Insoluble support matrices suitable for affinity chromatography have been activated in a similar fashion to create the hydrazide derivative (O Shannessy and Wilchek, 1990). 

Lissamine rhodamine B sulfonyl hydrazine is a hydrazide derivative of sulforhodamine B that can spontaneously react with aldehyde- or ketone-containing molecules to form a covalent,... 

The hydrazide derivative of AMCA can be used to modify aldehyde- or ketone-containing molecules, including cytosine residues using the bisulfite activation procedure described in Chapter 27, Section 2.1. AMCA-hydrazide reacts with these target groups to form hydrazone bonds (Figure 9.26). Carbohydrates and glycoconjugates can be labeled specifically at their polysaccharide portion if the required aldehydes are first formed by periodate oxidation or another such method (Chapter 1, Section 4.4). 

Aldehyde particles are spontaneously reactive with hydrazine or hydrazide derivatives, forming hydrazone linkages upon Schiff base formation. Reactions with amine-containing molecules, such as proteins, can be done through a reductive amination process using sodium cyanoborohydride (Figure 14.21). 

Figure 23.9 Reaction of adipic acid dihydrazide with (strept)avidin produces a hydrazide derivative that is highly reactive toward periodate-oxidized polysaccharides.

Hydrazide derivatives also may be prepared from a periodate-oxidized dextran polymer or from a carboxyl-containing dextran derivative by reaction with te-hydrazidc compounds (Chapter 4, Section 8). A hydrazide terminal spacer provides reactivity toward aldehyde- or ketone-containing molecules. Thus, the hydrazide-dextran polymer can be used to conjugate specifically glycoproteins or other polysaccharide-containing molecules after they have been oxidized with periodate to form aldehydes (Chapter 1, Section 4.4). 

Preparation of Amine or Hydrazide Derivatives by Reductive Amination... 

Ghosh, S.S., Kao, P.M., and Kwoh, D.Y. (1989) Synthesis of 5 -oligonucleotide hydrazide derivatives and their use in preparation of enzyme-nucleic acid hybridization probes. Anal. Biochem. 178, 43-51. 

Leteux, C., Childs, R.A., Chai, W., Stoll, M.S., Kogelberg, H., and Feizi, T. (1998) Biotinyl-L-3-(2-naph-thyl)-alanine hydrazide derivatives of N-glycans Versatile solid-phase probes for carbohydrate-recognition studies. Glycobiology 8, 227-236. 

Hydrazide chemiluminescence has been investigated very intensively during recent years (for reviews, see 1>, p. 63, 2>, 90>). Main topics in this field are synthesis of highly chemiluminescent cyclic diacyl hydrazides derived from aromatic hydrocarbons, relations between chemiluminescence quantum yield and fluorescence efficiency of the dicarboxylates produced in the reaction, studies concerning the mechanism of luminol type chemiluminescence, and energy-transfer problems. 

L-glyceronic acid. The formula XXXIV had also been proposed from the results of the application of the hydrazide rule28 to the hydrazide derivative of dihydrostreptosonic acid prepared by Folkers and coworkers.66... 

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