Carbohydrazides

Concern for personnel exposure to hydrazine has led to several innovations in packaging to minimize direct contact with hydrazine, eg, Olin s E-Z dmm systems. Carbohydrazide was introduced into this market for the same reason it is a soHd derivative of hydrazine, considered safer to handle because of its low vapor pressure. It hydrolyzes to release free hydrazine at elevated temperatures in the boiler. It is, however, fairly expensive and contributes to dissolved soHds (carbonates) in the water (193). In field tests, catalyzed hydrazine outperformed both hydrazine and carbohydrazide when the feedwater oxygen and iron levels were critical (194). A pubUshed comparison is available (195) of these and other proposed oxygen scavengers, eg, diethyUiydroxylarnine, ydroquinone, methyethylketoxime, and isoascorbic acid. 

Hydrazine reacts with phosgene yielding carbohydrazide ... 

In recent years, possible alternatives to hydrazine have been suggested, and some have been used on plant. These include carbohydrazide (NH2NHCONHNH2), derivatives of hydroxylamine, e.g. diethyl hydroxy-lamine (HONfCiHjIi), ketoximes, and erythrobic acid (iso corbic acid). These are usually faster scavengers than hydrazine or activated hydrazine . 

Hydroquinone is a good oxygen scavenger, even in cold water, so much so that it is commonly employed as a catalyst for hydrazine, DEHA, and carbohydrazide. 

Carbohydrazide was the first novel oxygen scavenger of any significance to provide a safe handling replacement for hydrazine it was patented as an oxygen scavenger as Nalco ELIMIN-OX in 1981. 

Carbohydrazide is a derivative of hydrazine that hydrolyzes in the boiler to produce hydrazine, although CHZ is an oxygen scavenger in its own right. Other derivations of this oxygen-scavenging chemistry now exist, including polyacrylic hydrazide. 

Carbohydrazide itself is of very low volatility, but it decomposes at relatively low temperatures to produce volatile carbon dioxide and ammonia. In theory, the combined corrosive effects of these two materials should be negated in the condensate system, but in practice, this is not always so and both steel and copper corrosion transport problems may develop, primarily as the result of corrosion-enhancement reactions resulting from oxygen in-leakage. It is presumed, therefore, that (similar to hydrazine) some deliberate after-desuperheating line addition of CHZ is necessary if post-boiler section corrosion is to be avoided. 

Ammonia/hydrazine passivator An alkaline hydrazine solution (pH over 9.0, 0.5% N2H2) provides a useful passivator. If there are concerns over the use of hydrazine, diethylhydroxylamine (DEHA), erythorbate, or carbohydrazide may be substituted. Air blowing improves the passivating effect. 

Wiltsey, D G. Carbohydrazide as a Hydrazine Replacement. Missouri Valley Electric Association Conference 86. Nalco Chemical Company, USA, April 1986. 

AVT Barg BD BDHR BF BOF BOOM BOP BS W BSI BTA Btu/lb BW BWR BX CA CANDUR CDI CFH CFR CHA CHF CHZ Cl CIP CMC CMC CMC COC All-Volatile treatment bar (pressure), gravity blowdown blowdown and heat recovery system blast furnace basic oxygen furnace boiler build, own, operate, maintain balance of plant basic sediment and water British Standards Institution benzotriazole British thermal unit(s) per pound boiler water boiling water reactor base-exchange water softener cellulose acetate Canadian deuterium reactor continuous deionization critical heat flux Code of Federal Regulations cyclohexylamine critical heat-flux carbohydrazide cast iron boiler clean-in-place carboxymethylcellulose (sodium) carboxy-methylcellulose critical miscelle concentration cycle of concentration... 

This chapter covers not only nuclear and extranuclear quinoxahnecarboxylic acids (and anhydrides) but also the carboxylic esters, acyl halides, carboxamides, carbohydrazides, carbonitriles, carbaldehydes, and (ketonic) acyl derivatives of quinoxaline a few related speceis are also included. To avoid repetition, the interconversions of these quinoxaline derivatives are discussed only at the first opportunity thus the esterification of quinoxalinecarboxylic acids in covered as a reaction of carboxylic acids rather than as a preparative route to carboxylic esters, simply because the section on carboxylic acids precedes that on carboxylic esters. To minimize any confusion, appropriate cross-references have been inserted. 

There is an extensive recent literature on quinoxalinecarboxylic acids and anhydrides, much of it in connection with their role as intermediates for derivatives such as carbohydrazides. 

The IR spectra of carbohydrazide 9 showed absorption bands at 3317 cm (OH,Hydrazide NH2), 3269 cm (aromatic CH), 1711 cm (CO stretching), and 1621-1640 cm (CO-NH-NH2 groups). The H NMR spectra exhibited a singlet due to the CONHNH2, NH proton at 9.32 ppm. Methylene protons resonated as a singlet at 4.23 ppm. The structures of the products lOa-1 were inferred from their analytical and spectral data. Thus, their IR spectra showed characteristic absorption bands at 3400-3240 cm (NH,OH), 1710-1700 cm (lactone CO), and NHCO at 1650-1600 cm . ... 

Add a quantity of adipic acid dihydrazide or carbohydrazide (Aldrich) to the protein solution to obtain at least a 10-fold molar excess over the amount of aldehyde functionality present. High molar ratios are necessary to avoid protein conjugation during the reaction process. If the concentration of aldehydes is unknown, the addition of 32mg adipic acid dihydrazide per ml of the protein solution to be modified should work well. 

Carboxylic acids may be covalently modified with adipic acid dihydrazide or carbohydrazide to yield stable imide bonds with extending terminal hydrazide groups. Hydrazide functionalities don t spontaneously react with carboxylate groups the way they do with aldehyde groups (Section 4.5, this chapter). In this case, the carboxylic acid first must be activated with another compound that makes it reactive toward nucleophiles. In organic solutions, this may be accomplished by using a water-insoluble carbodiimide (Chapter 3, Section 1.4) or by creating an intermediate active ester, such as an NHS ester (Chapter 2, Section 1.4). 

Most proteins contain an abundance of carboxylic acid groups from C-terminal functionalities and aspartic and glutamic acid side chains. These groups are readily modified with bis-hydrazide compounds to yield useful hydrazide-activated derivatives. Both carbohydrazide and adipic acid dihydrazide have been employed in forming these modifications using the carbodi-imide reaction (Wilchek and Bayer, 1987). 

Add to the tube 7.5 pi of RNA or DNA containing a 5 -phosphate group. The concentration of the oligonucleotide should be 7.5-15 nmol or total of about 57-115.5 pg. Also, immediately add 5 pi of 0.25 M adipic acid dihydrazide or carbohydrazide dissolved in 0.1 M imidazole, pH 6.0. Because EDC is labile in aqueous solutions, the addition of the oligo and fezs-hydrazide/imidazole solutions should occur quickly. 

Figure 4.30 Carbohydrazide can be used to transform an aldehyde residue into a hydrazide group.

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