Patai S., Rappoport Z. 1996 The chemistry of functional groups. The chemistry of amino, nitroso, nitro and related groups / 0627 663

the thermal or photochemical de-diazoniation of arenediazonium tetrafluoroborates in trifluoromethanesulfonic acid. The yields with 19 substituted benzenediazonium salts are, with two exceptions, in the range of 73 93% at the appropriate temperature (60 160 °C) or by using a high-pressure mercury vapor lamp at 12 °C.

Activity on new mercapto-de-diazoniations was small in the last two decades, except for a recent investigation of the use of thioglycolic acid forming arylthioglycolic acids167.

F. Substitutions of the Diazonio Group by Carbonyl and Sulfonyl Groups

It has been known for a long time that CO and SO2 react with aryl radicals and that the adducts formed are converted, in the presence of cupric halides as ligand transfer reagents, to arenecarboxylic halides and arenesulfonyl halides. The importance of a ligand transfer reagent was realized rather late, in 1977, by Doyle168. Even in a recent paper169, using highly pressurized CO as reagent and CuCl2, the yields are rather low (36 54% with seven diazonium salts). Higher yields (82 85%) are reported for the reaction of benzenediazonium tetrafluoroborate with CO (9 atm) in acetonitrile with 2 mol% Pd(II) acetate170.

The chlorosulfo-de-diazoniation was discovered by Meerwein171 in 1957, but little used, although in the experience of the present author it may give reasonably good yields.

Aldehydes and ketones are formed in reactions with carbonyl compounds, e.g. oximes, diacetyl and CO C tetraalkyltin172 (see also Zollinger7m).

G. Metallo-de-diazoniations and Related Reactions

The replacement of the diazonio group by metals and related transition elements was investigated intensively until the mid-20th century, particularly by Nesmeyanov and coworkers (reviews173). Most intensively studied were mercury-de-diazoniations. Since about 1970 there has been very little activity in the whole field of aryl-element chemistry as far as arenediazonium salts are involved. This decrease is probably due to the lack of interest for technological purposes, and to the environmental problem, which the synthesis and the use of the compounds cause.

H. Photolytic Dediazoniations

Although it has been known since the early days of diazo chemistry that arenediazonium salt solutions are sensitive to light, photolytic dediazoniations have only marginal importance in organic synthesis. The recent successful photolytic fluoro-de-diazoniations of Yoneda and coworkers132 were discussed in Section III.C.

Photolytic dediazoniations are, however, important in image technology. These applications can be divided into four groups, namely (1) the use of products of heterolytic photo-de-diazoniation as Lewis acid catalysts in cationic polymerization, (2) the use of the nitrogen gas for the formation of light-scattering vesicles in a polymer layer, (3) the use of the dediazoniation process for rendering an irradiated polymer layer more or less soluble than the unexposed material and (4) the use of unexposed and, therefore, nondecomposed diazo compounds for dye formation by azo coupling reactions.

Chemical aspects of all four technologies were recently reviewed7n; here we review only briefly group (4) technology because it has some interest for general organic chemistry.

In 1924 the German company Kalle & Co. in Wiesbaden began production of ‘blueprint’ paper, i.e. a diazo reprographic paper. In that process a sheet coated with a diazonium compound was exposed to an optical image and developed by diazo coupling using a mono-

or di-hydroxynaphthalene derivative at high pH under wet (later also dry) conditions. In the exposure step before development the diazonium compound was destroyed by photolytic dediazoniation; therefore the azo dye was formed only on those parts of the sheet which were not irradiated with visible light. Originally, 2-diazophenols were used as diazo components, later 1,2-naphthoquinone diazide (48). Nowadays, the most important compound is 2,5-diethoxy-4-morpholinobenzenediazonium tetrafluoroborate. Typical coupling components are acetoacetic anilide, 1-phenyl-3-carbamidopyrazolone-(5) and 2-hydroxy- 6-methoxy-3-naphthoic acid-20-toluidide for yellow, red and blue colors, respectively.

In the context of this technology Sus¨ investigated already in 1944174 the photolysis of o-quinone diazides. Equation 34 shows the photolysis sequence for 1,2-naphthoquinone diazide (48) formed in the diazotization of 2-amino-1-naphthol. The product of the photolytic step is a ketocarbene (49), which undergoes a Wolff rearrangement to a ketene (50). In the presence of water indene-3-carboxylic acid (51) is formed; this compound is highly soluble in water and can be removed in the development step. The reaction steps of equation 34 were investigated in recent years intensively, mainly by Canadian chemists175 (see also the monograph of Tidwell on ketenes176).

(34)

O

H2O

The Wolff rearrangement is well known as a reaction of diazo ketones, i.e. of diazoalkanes with a carbonyl group in ˛-position. Reaction 34 demonstrates that diazotized aminonaphthols are mesomeric with naphthoquinone diazides (48b) and that they have therefore also the character of quinonoid diazo ketones (see also Section II.C of this chapter). Wolff rearrangements take place also thermally and catalyzed by silver ions.

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