Quinone diazide

Quino[3,2-c][l,8]naphthyridine — see 4,5,12-Triazabenz[a]anthracenes Quinone, a-tocopheryl-synthesis, 3, 734 o-Quinone allides synthesis, 3, 741 o-Quinone diazides reactions... 

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. 

In the 1980 s three monographs were published that cover parts of the present book, namely Quinone Diazides, by Ershov, Nikiforov, and de Jonge (1981), Aromatic Diazo Compounds, by Saunders and Allen (1985), and Williams Nitrosa-tion (1988). The book of Saunders and Allen which is actually the third edition of Saunders original book (1936, 1949), focuses on synthesis and preparative methods. The other two books emphasize rather the mechanistic and physical organic aspects of their subjects. 

Anion-catalyzed phase transfer catalysis in a dichloromethane-aqueous sulfuric acid two-phase system was successfully applied to the diazotization of pen-tafluoroaniline by Iwamoto et al. (1983 a, 1984). If this compound is diazotized in dilute aqueous acid, tetrafluoro-l,4-quinone diazide is obtained, indicating that the diazotization proper is followed by a hydroxy-de-fluorination (Brooke et al., 1965). 

It was previously mentioned in Section 1.2 that the products of diazotizing o- and /7-aminophenols exist in neutral aqueous solutions as zwitterions (1.7 b) which are mesomeric with the corresponding quinone diazides (1.7 a). They can therefore be... 

On the other hand, there is at least one case of an aromatic amine without a hydroxy group in the 2-position, namely 1-aminophenazine (2.29) which, after the initial diazotization, is oxidized within minutes by air or additional nitrous acid to the quinone diazide 2.31 (Olson, 1977). 

There is no direct experimental evidence for the intermediate 2.30 in the reaction sequence of Scheme 2-19. In the corresponding diazotization of 2-aminophenazine the proportion of the quinone diazide (isomer of 2.31) amounted to only 16%, but 30% unsubstituted phenazine was also found. The phenazine may have resulted from the overall redox reaction. 

The general applicability of this type of synthesis of quinone diazides is nevertheless limited since, depending on the type and number of substituents in the 2-, 4-, and 6-positions of benzenediazonium ions, either hydroxy-de-diazoniation (reaction A in Scheme 2-20) or nucleophilic substitution of one of the groups in the 2-, 4-, or 6-position (reaction B) will predominate. It is difficult to predict the ratio of the two reactions in a specific case. This is exemplified by two investigations carried... 

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). 

Imino analogues of quinone diazides were studied quite early by Morgan and his coworkers (Morgan and Upton, 1917, and references cited therein). A-monoacylated 1,4-diaminobenzenes were successfully diazotized starting with 4-benzenesulfon-... 

The other major route to quinone diazides is based on the alkaline hydrolyses of mono-4-toluenesulfohydrazones of quinones, which will be discussed in Section 2.6. In the same section other synthetic methods are briefly discussed. 

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 can also be obtained by the diazo group transfer reaction of 4-tosyl azide. For example, 9-diazo-10-anthrone (2.55) is formed from anthrone (2.54) if the reaction is carried out in an ethanol-piperidine mixture. On the other hand, if ethanol is replaced by pyridine, dimerization with loss of molecular nitrogen takes place and the azine 2.56 is isolated (Scheme 2-32 Regitz, 1964 Cauquis et al., 1965). In the preceding discussion tosyl azide was shown to be an electrophilic reagent. It therefore seems likely that it is not the anthrone 2.54 but its conjugate base which reacts with tosyl azide. 

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). 

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. 

In conclusion, with regard to the structure of benzenediazonium compounds with electron donor substituents in the 2- or 4-position, the most recent experimental data, mainly X-ray analyses and 13C and 15N NMR data, are consistent with 4.4 as the dominant mesomeric structure of quinone diazides, as proposed by Lowe-Ma et al. (1988). For benzenediazonium salts with a tertiary amino group in the 4-position the data are consistent with the quinonoid structure 4.20 as the dominant mesomeric form. 

We have to emphasize, however, that this is only a qualitative differentiation of weights of mesomeric structures, and therefore we do not propose that the IUPAC or CA nomenclature (quinone diazides and diazo-cyclohexadien-ones, respectively) should be changed. 

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). 

Photo-de-diazoniation has found relatively little application in organic synthesis, as is clearly evident from the annual Specialist Periodical Reports on Photochemistry published by the Royal Society of Chemistry. Since the beginning of these reports (1970) they have contained a section on the elimination of nitrogen from diazo compounds, written since 1973 by Reid (1990). In the 1980s (including 1990), at least 90% of each report is concerned with dediazoniations of diazoalkanes and non-quinon-oid diazo ketones, the rest being mainly related to quinone diazides and only occasionally to arenediazonium salts. 

In this section we first discuss photolytic reactions of arenediazonium salts and report on quinone diazides at the end of the section in the context of imaging technology. Diazoalkenes, non-quinonoid diazo ketones, and the Wolff rearrangement are treated in the book on aliphatic diazo compounds (Zollinger, 1995, Chap. 8). 

The photolysis of o-quinone diazides was carefully investigated by Stis in 1944, many years before the development of photoresists. Scheme 10-102 shows the photolysis sequence for the diazoquinone 10.75 formed in the diazotization of 2-amino-1-naphthol. The product of the photolytic step is a ketocarbene (10.76), which undergoes a Wolff rearrangement to a ketene (10.77). In the presence of water in-dene-3-carboxylic acid (10.78) is formed this compound is highly soluble in water and can be removed in the development step. The mechanism given in Scheme 10-102 was not postulated as such by Stis, because in 1944 ketocarbenes were unknown (for a mechanistic discussion of such Wolff rearrangements see review by Zollinger, 1995, Sec. 8.6, and Andraos et al., 1994). 

Tsuda and Oikawa (1989) investigated the photolysis of the 1,2-isomer of 10.89 (1,2-benzoquinone diazide) by means of MINDO/3 molecular orbital calculations with configurational interaction. These authors came to the conclusion that no ketocarbene of the type of 10.90 is formed, but that the rearrangement into the cyclopentadienyl ketene 10.94 is a concerted reaction in which the elimination of nitrogen and the rearrangement take place simultaneously. In the opinion of the present author the theoretical result for 1,2-quinone diazide is not necessarily in contradiction to the experimental investigations of Sander, Yankelevich et al., and Nakamura et al., as the reagents used were not exactly the same. 

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. 

The reactivities of 1,2-quinone diazides are lower than those of the corresponding... 

The monograph by Ershov et al. (1981) on quinone diazides includes more detailed information on azo coupling reactions of this group of diazo components. 

Naphthoquinone diazides 32, 284ff., see also Quinone diazides 2,3-Naphthotriazole, formation 132 f. Negations, psycholinguistics of 215 Nesmeyanov reactions 273 ff. Nicotinamide-adenine nucleotide (NAD+) 328 f. 

Oxocyclohexadienylidene (la) and derivatives are highly reactive, electrophilic carbenes. Suitable precursors of these carbenes are quinone diazides... 

---