Fierz-David

Crude 5 -butyramldo-2 -(2,3-epoxypropoxy)acetophenone used as starting material was prepared as follows p-butyramidophenol (58 g prepared according to Fierz-David and Kuster, Helv. Chim. Acta 1939,2282), acetyl chloride (25.4 g) and benzene (500 ml) were heated together under reflux until a solution formed (12 hours). This solution was cooled and treated with water. The benzene layer was separated and the aqueous layer was again extracted with benzene. 

The only practical method for the preparation of anthra-quinone-a-sulfonates is that based upon the discovery 1 that in the presence of a small amount of mercuric salt anthraquinone is sulfonated chiefly in the a- rather than in the /3-position. Detailed procedures are described by Fierz-David,2 by Lauer,3 and by Groggins 4 the above directions are based largely upon the observations of Lauer.3... 

Table II 24) R. McGill, Evaluation of Explosives Submitted to the Explosives Research -Laboratory in 1941 , OSRD 830 (Aug 1942), 64 25) H.E. Fierz-David R. Sponagel, Helv...

Fierz-David, H Edward L= Blangey, Grundle-gende Operationen der Farbenchemie , Springer, Vienna (1943)... 

An increased hydrogen ion concentration, that is a considerably greater amount of acid than the theoretical two equivalents of Scheme 2-1, is necessary in the diazotization of weakly basic amines. The classic example of this is the preparation of 4-nitrobenzenediazonium ions 4-nitroaniline is dissolved in hot 5-10 m HC1 to convert it into the anilinium ion and the solution is either cooled quickly or poured onto ice. In this way the anilinium chloride is precipitated before hydrolysis to the base can occur. On immediate addition of nitrite, smooth diazotization can be obtained. The diazonium salt solution formed should be practically clear and should not become cloudy on standing in the dark. Some practice is necessary, and details can be found in the books emphasizing preparative aspects (Fierz-David and Blangey, 1952 Saunders and Allen, 1985 in Houben-Weyl, Vol. E 16a, Part II, the chapter written by Engel, 1990). These books give a series of detailed prescriptions for specific examples and a useful review of the principal variations of the methods of diazotization. Such reviews have also been written by Putter (1965) and Schank (1975). 

For these reasons there are limits to the extent to which the acid concentration can be increased gradually as the basicity of the amines decreases. Nevertheless, diazotization can be carried out without difficulty in 90-96% sulfuric acid. It has already been mentioned that nitrous fumes are given off as soon as nitrite is added to sulfuric acid of lower concentration, but solid sodium nitrite can be dissolved in 90-96% sulfuric acid at 0-10°C smoothly and without evolution of gas. Nitrosylsulfuric acid, N0+HS04, is formed. Directions for the preparation of 2 m nitrosylsulfuric acid are given by Fierz-David and Blangey (1952, p. 244), but sodium hydrogen sulfate crystallizes after some time from acid of this strength so that it is best to prepare a stock solution of 1 m sodium nitrite in 96% sulfuric acid, which is quite stable at room temperature. 

Fierz-David, H. E. (1952). Die Entwicklungsgeschichte der Chemie [The Development of Chemistry], Basel Birkhauser. 

Colonna. Francesco.The dream of Poliphilo related and interpreted by L. Fierz-David translated by Mary Hottinger. Forewod by C.G. Jung. Edited by Linda Fierz-David. Translated by Mary Hottinger. New York Pantheon, 1950. xv, 243 p Bollingen Series 25... 

Nitrobenzene can be chlorinated at 40-50° by the use of 1 per cent of iron with 0.1 per cent of iodine as a combined catalyst. Fierz-David, Naturwiss. 17, 13 (1929). 

Verkade, Rec. trav. chim., 62, 393 (1943) Fierz-David and Kuster, Helv. Chim. Acta, 22, 82 (1939). 

HE Fierz-David and L Blangey, Fundamental processes of dye chemistry, (New York Interscience, 1949). 

The most important technical azo-dyes are derived from naphthalene, and indeed there is hardly any branch of organic chemistry which has been so thoroughly investigated in all its details as that of the intermediate products which are here involved. The number of possible combinations is almost without limit, and we can only refer to the specialist works, particularly F. Mayer, Ghemie der organ. Farbstoffe, Berlin, 1924 Mohlau-Bucherer, Farbenchem. Prakt., Berlin, 1926 Fierz-David, Farbenchemie, Berlin, 1924 Ristenpart, Chem. Technol. der organ. Farbstoffe, Leipzig, 1925. 

H. E. Fierz-David and L. Blangey, Grundlegende Operationen der Farbenchemie, 8th ed., Springer, Vienna, 1952 (English edition Fundamental Processes of Dye Chemistry, Interscience, New York, 1959) (a) p. 244. 

H. E. Fierz-David andE. Merian,Abr. derChem. Tech. derTextilfasem 146 (1948). 

H. E. Fierz-David, Kbnst/khe Organic Farbstoffie, Julius Springer, Berlin, 1926. 

OrdSynth, CollVol 1(1941),332 3)H.E.Fierz-David L.Blangey/ Grundlegende Operationen der Farbenchemie,"w ien( 1943), 125 Kirk Othmer l(1947),48-52 4a)Ullmann 3, (1953), 653"4(under Aniline) 5)Cond Chem Diet (1956), 6 6)Sax(1957), 229 7)Faith,Keyes... 

H. E. Fierz-David,Farbenchemie, 8. Aufl., Springer Verlag, Wien, 1952. 

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