Diazidation

The process by which a solubility differential between exposed and unexposed areas occurs is well known (74). Photodegradation products of the naphthoquinone diazide sensitizer, eg, a l,2-naphthoquinonediazide-5-sulfonic acid ester (11), where Ar is an aryl group, to an indene carboxylic acid confers much increased solubility in aqueous alkaline developer solutions. 

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... 

Aluminium triazide Barium diazide Boron triazide Cadmium diazide Calcium diazide Chromyl azide Copper(l) azide Copper(ll) azide Lead(ll) azide Lead(IV) azide Lithium azide Lithium boroazide Mercury(l) azide Mercury(ll) azide Potassium azide Silicon tetraazide Silver azide... 

Hydrazine azide Hydrazine chlorate Hydrazine dicarbonic acid diazide Hydrazine perchlorate Hydrazine selenate Hydrogen cyanide, unstabilized Hydroxyl amine iodide Hyponitrous acid... 

Five possible isomers may coexist in the tautomeric equilibrium involving 2,6-diazidopurine 343 (Scheme 135). It was concluded (75UK1028) that diazide 343AA is the sole form in the solid state and in solutions in acetic and trifluoroacetic acids. In DMSO solution, two additional tautomers, 343AT and 343ATS were also observed. 

This conclusion is valid also for the isomerizations involving cyclization of diazides 344a (R = Na.Y = CH) [74JOC1778 76AHC(Sl),p. 498]. Thermodynamic and kinetic parameters of type 344a 344b interconversion... 

Krivopalov et al. investigated the formation of the ditetrazolo form 90TT and the dependence of equilibria on the solvent and on the substitution and benzoannelation in the diazides of type 90AA (86BAU1745 88MRC42 89BAU1839). 

Iodine azide, generated in situ from an excess of sodium azide and iodine monochloride in acetonitrile, adds to ethyl l//-azepine-l-carboxylate at the C4 — C5 and C2 —C3 positions to yield a 10 1 mixture of the rw-diazidodihydro-l//-azepines 1 and 2, respectively.278 The as stereochemistry of the products is thought to be the result of initial trans addition of the iodine azide followed by an SN2 azido-deiodination. The diazides were isolated and their stereochemistry determined by conversion to their bis-l,3-dipolar cycloadducts with dimethyl acetylene-dicarboxylate. 

An elegant extension of these ring expansions involving diazidonaphthalenes has been reported. Early results on the photolysis of 1,8-diazidonaphthalene (14) indicated the formation of benz[t d]indazole (17).176 However, it has since been found that photolysis of the diazide in sodium methoxide-methanol/dioxane solution for a short period (20 -40 min) yields, in addition to the benz[c,d]indazole (17, 40%), a mixture of 9-azido-l-methoxy-5//-2-benzazepine (15 15-20%) and l,10-dimethoxy-5,5a-dihydroazepino[3,4-c]azepine (16 10-15%).117... 

Methylaluminum Diazide. CH3A1(N3)2, mw 126.08, N 66.67%, white powd. When a frozen eth soln of A1(CH3)3 and excess HN3 is thawed, reaction begins at room temp with evolution of CH4 and pptn of a fine white powd, methyl-aluminum diazide. The reaction is completed... 

Neugen. Polyethylene glycol laurate used as an additive to prevent the expi reaction of Ba azide. See under Barium Diazide in Vol 1, A524-L... 

Isophthalic Acid Diazide (m-Phthalic Acid Diazide). C6H4(CO.N3)2, mw 216.18, N 38.88%. Prisms from acet, mp 56°, explds on further heating. Easily sol in acet or eth. Can be prepd by treating isophthalic acid hydrazide hydrochloride with Na nitrite in cold aq soln Refs 1) Beil 9,837 2) E. Davidis, JPrCh... 

Experimentally, Flynn (Ref 73a) has tested plastisol NC composite propints containing beryllium and triaminoguanidinium hydrazinium diazide in a closed bomb and measured the high specific impulses indicated in Table 23... 

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). 

A similar ambiguity concerning structure appears to arise for 1,4-imidoquinone diazides (4.6), which were synthesized many years ago by Dimroth et al. (1917) and by Morgan and Upton (1917), and were reinvestigated by Kazitsyna et al. (1965, 1967, 1968a). Such compounds are obtained by diazotization of 4-aminodiphenylamine and mono-acylated or -formylated 1,4-diaminobenzenes. Under the influence of the... 

---