1,5-Diphenyl-carbohydrazide

Several methods have been introduced which express the degree of oxidation deterioration in terms of hydroperoxides per unit weight of fat. The modified Stamm method (Hamm et at 1965), the most sensitive of the peroxide determinations, is based on the reaction of oxidized fat and 1,5-diphenyl-carbohydrazide to yield a red color. The Lea method (American Oil Chemists Society 1971) depends on the liberation of iodine from potassium iodide, wherein the amount of iodine liberated by the hydroperoxides is used as the measure of the extent of oxidative deterioration. The colorimetric ferric thiocyanate procedure adapted to dairy products by Loftus Hills and Thiel (1946), with modifications by various workers (Pont 1955 Stine et at 1954), involves conversion of the ferrous ion to the ferric state in the presence of ammonium thiocyanate, presumably by the hydroperoxides present, to yield the red pigment ferric thiocyanate. Newstead and Headifen (1981), who reexamined this method, recommend that the extraction of the fat from whole milk powder be carried out in complete darkness to avoid elevated peroxide values. Hamm and Hammond (1967) have shown that the results of these three methods can be interrelated by the use of the proper correction factors. However, those methods based on the direct or indirect determination of hydroperoxides which do not consider previous dismutations of these primary reaction products are not necessarily indicative of the extent of the reaction, nor do they correlate well with the degree of off-flavors in the product (Kliman et at. 1962). 

The ferric thiocyanate method for peroxide value is based on the oxidation of ferrous to ferric ions, which are determined colorimetrically as ferric thiocyanate. This method is more sensitive and requires a smaller sample (about 0.1 g) than does the iodometric method (Table 5.3). However, the values obtained by the ferric thiocyanate method are higher by a factor of 1.5 to 2 relative to those of the iodometric method. The peroxide values obtained by both methods are of only relative significance. The ferric thiocyanate method is commonly applied to dairy products, which undergo oxidative deterioration at relatively low peroxide values. Other colorimetric methods for peroxide values include the determination of the blue starch-iodine complex in the iodometric method, the red color developed with 1,5-diphenyl-carbohydrazide, the color developed with ferric ions and xylenol orange, ferrous chloride and 2,6-dichlorophenolindophenol, titanium dichloride, and xylenol orange. 

Trifluoromethyl-l,8-naphthyridine-3-carbohydrazide (34) with benzoyls-tyrene gave 3-(3,5-diphenyl-3-pyrazolin-1 -yl)carbonyl-2-trifluoromethyl-1, 8-naphthyridine (35) (BzCH=CHPh, trace TsOH, AcOH, reflux 70%).1356... 

Carbohydrazide has been prepared by the reaction between diphenyl carbonate and hydrazine hydrate1 and also by the action of dilute acid on tris(benzalamino)guan-idine.2 Curtius and Heidenreich3 synthesized carbohydrazide by long refluxing of a mixture of diethyl carbonate and hydrazine hydrate. Kesting4 increased the yield by distilling off volatile products and unreacted materials after the 48-hour reflux period. 

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