1,2- and 1,4-Quinone diazides

The problem of the structure of 1,2- and 1,4-quinone diazides was investigated by Le Fevre s group (1949, 1954) by measuring dipole moments. The observed moments in benzene are in the range 2.9 to 5.0 D, compared with calculated values of 1.6 to 4.0 D for the quinone diazide structure and 15.7 and 27.4 D respectively for the 1,2-and 1,4-zwitterionic forms. No attempts were made by Lowe-Ma et al. (1988) to calculate dipole moments for the mesomeric structure 4.4 that they proposed. 

The y-nitrogen atom of a sulfonic acid azide is electrophilic and reacts in an electrophilic aromatic substitution with an activated benzene or naphthalene derivative, e.g., a phenoxide ion, forming a l-tosyl-3-aryltriazene (2.47). The 1,4-quinone diazide is obtained by hydrolysis (Scheme 2-30, Tedder and Webster, 1960). The general applicability of this reaction seems to be doubtful. With 1-naphthol the 1,2-naphthoquinone diazide was obtained, not the 1,4-isomer. 

Quinone diazides (12.9) and their 1,2-isomers (Secs. 1.2, 2.4, and 4.2) simultaneously display the properties of both aliphatic and aromatic diazo components. They can be considered as analogues of conjugated diazoketones. On the other hand, a specific feature of many of their reactions is their conversion to hydroxyarenediazo-nium ions (12.8) in the presence of acids (Scheme 12-7). The p Ta-value of the 4-hydroxybenzenediazonium ion is 3.19 (Kazitsyna and Klyueva, 1972), so the reactivity of compounds of this type will depend considerably on the acidity of the reaction medium. Compound 12.8 is much more electrophilic than 12.9, and therefore the measured rate depends on the position of the equilibrium in Scheme 12-7. 

Herz s Explosives. Patented in 1923 CA 18, 1573-4 (1924) BritP 207563, several compositions, such as ortho-, and para-nitrated quinone diazides of the polymeric phenols or their metallic salts either (1) as a top charge over a main (base) charge such as Tetryl, TNT, or PETN, or (2) in admixtures with other compounds. Following are the primary and nitrating compounds proposed by von Herz ... 

Carbenes, generated by photolysis of di- and tetrachloro-o-quinone diazides, react with oxetane in a 1 3 ratio to afford 15-membered crown ethers. Benzocrown ether 675 was obtained in 16% yield (91CB1865). Derivatives of macrocyclic crown ethers with four or five oxygen atoms in a ring were synthesized by Cu(acac)2-catalyzed cyclization of a,polyethylene glycols. 20-26-Membered crown-4(5) ethers 676 were prepared from the above-mentioned diazo ketones with tri- or tetra-ethylene glycols in 7-26% yields. Treatment of l,8-bis(diazoacetyl)octane with dodecane-l,12-diol under the same conditions results in a mixture of 52-membered tetraether 646 (40%) and compound 645 (81CC616). 

In the modern formulation, but ignoring the quinone diazide mesomerism (see Sec. 4.2), his diazotization is shown in Scheme 1-1 yielding 1.2. For the centenary of the discovery of diazo compounds Wizinger (1958) and Cliffe (1959) wrote accounts of its history. More recently Zahn (1989) summarized the life and work of Peter Griess. 

In aromatic diazonium compounds containing an ionized hydroxyl group ( —O-) in the 2- or 4-position, it is necessary to consider delocalization of electrons and, therefore, two mesomeric structures (1.7a-1.7b) (see Sec. 4.2). This fact has implications for nomenclature compounds of this type are considered as quinone derivatives following IUPAC Rule C-815.3 (Exception) compounds of this class are called quinone diazides. As a specific compound 1.7a-1.7b is indexed in Chemical Abstracts as 4-diazo-2,5-cyclohexadien-l-one. If reference is made specifically to mesomeric structure 1.7b, however, it is called 4-diazoniophenolate. 

Compounds which correspond to 1,2-quinone diazides can also be obtained by diazotization of aromatic and nonaromatic heterocyclic amines with a hydroxy group in the ortho position. Examples include 3,4-quinolinequinone-3-diazide (2.35, Sus et al., 1953 Sus and Moller, 1955) and 3-diazochromane-2,4-dione (2.36, Arndt et al., 1951). Syntheses of more complex heterocyclic quinone diazides have been tabulated by Ershov et al. (1981, p. 105). More recent publications are cited in a paper by Tisler s group (Klotzer et al., 1984). 

Bis(diazo)-l,2,4,5-cyclohexanetetraone (4.5) may be regarded as a derivative of a double 1,2-quinone diazide. Its X-ray analysis was reported by Ansell (1969). The synthesis, properties, and structure of this interesting compound will be discussed in the forthcoming book on aliphatic diazo compounds (Zollinger, 1995, Secs. 2.3 and 5.2). 

For many decades intramolecular O-coupling was considered not to take place in the diazotization products of 2-aminophenol and its derivatives (for a contrary opinion see, however, Kazitsyna and Klyueva, 1972). The compounds were assumed to be present as one structure only, which can be represented as a mesomer of a phenoxide diazonium zwitterion 6.63 b and a diazocyclohexadienone 6.63 a (see reviews by Kazitsyna et al., 1966 Meier and Zeller, 1977 Ershov et al., 1981). In IUPAC nomenclature 6.63 is called 1,2-quinone diazide, in Chemical Abstracts 6-diazo-2,4-cyclohexadien-one (see Sec. 1.3). More recently, however, Schulz and Schweig (1979, 1984) were able to identify the intramolecular product of O-coupling, i.e., 1,2,3-benzooxadiazole (6.64) after condensation of 6.63 in vacuo at 15 K in the presence of argon (see Sec. 4.2). 

Quinone Diazides. E. von Herz (Ref 1) proposed the use of nitrated quinone diazides and tetra-zides of polyhydric phenols or their metallic salts in percussion caps and primers, either as a top charge over a main charge (Tetryl, PETN or TNT), or in mixts with usual primary expls such as LA, MF, etc. Typical compds were 4,6-dinitro-2-quinone diazide, the K salt of dinitro-3-hydroxy quin one diazide, metallic salts of dinitro-4-hydroxyquinone diazide, the Pb salt of dinitro-3,5-dihydroxyquinone diazide, and sym-tetra-nitrodihydroxydiphenylolquinone tetrazide J.E. Burns (Ref 2) proposed the use of nitrated quinone diazides, such as the 2,6-dinitro-2-diazide, with Pb pic rate, Na nitrate, Pb thio-... 

Bis(diazo)cyclohexane-l,2,4,5-tetraone (5.18) is an interesting borderline case between l,3-dicarbonyl-2-diazocycloalkanes and quinone diazides (5.19, also the 1,2-isomer). We discussed the latter compounds in the book on aromatic diazo com-... 

Methylquinoline-3,4-quinone-3-diazide heated in abs. xylene 2-(6-methyl-3-indolylidene)-7 -methylquinolino(3, 4 )-1,3-dioxole. Y 77%.—Similarly 9,10-Phenanthrenequinone diazide -> 2-fluorenylidene(9,10)phenanthro-l,3-dioxole. Y 73%. F. e. and reactions s. W. Ried and R. Dietrich, A, 639, 32 (1961). 

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