Synthesis and characterization of substituted 2‐diazo‐1 ‐oxo‐1,2‐dihydzonaphthalenes and their products of photolysis and thermolysis

Abstract

Several 2‐diazo‐1‐oxo‐1,2‐dihydronaphthalene{ (1, 2) have been synthesized by reaction of selected hydroxy compounds and 2‐diazo‐1‐oxo‐1,2‐dihydzonaphthalene‐5‐ and ‐4‐sulfonylchloride, respectively. Photolysis as well as thermolysis of 1 and 2 leads to final products, the nature of which depends on the position of substitution. So, reactions of 5‐substituted derivatives (1) yield the corresponding indene‐3‐carboxylic acids 3 and their esters 5, respectively. In contrast, reactions of 4‐substituted derivatives (2) lead to the formation of the 1‐sulfo‐indene‐3‐carboxylic acid derivatives 4 and 6. Prepared compounds have been characterized by means of mass, ultraviolet, infrared, 1H‐n.m.r. ind 13C‐n.m.r. {pectroscopy.

100 Years of the Wolff Rearrangement

“…Good yields of indenecarboxylic acids 697 were obtained in aqueous acetic acid. [494] After irradiation of 696 in a novolac matrix at 77 K, both ketenes and ketene hydrates were detected by infrared spectroscopy. [495] Reaction of the intervening ketenes with hydroxyl groups of the novolac was modeled by decomposition of 696 in the presence of p-cresol to give 699.…”

“…[495] Reaction of the intervening ketenes with hydroxyl groups of the novolac was modeled by decomposition of 696 in the presence of p-cresol to give 699. [494] This undesired side-reaction is minimized by maintaining a sufficient concentration of water in the resist. Aqueous alkaline developers (pH 11.5Ϫ12.8) are used to dissolve the exposed areas of the resist where 696 was converted into 697 (positive photoresist).…”

“…In contrast to 696, ring contraction of aryl 2-diazonaphthalen-1-one-4-sulfonates 700 is followed by light-induced hydrolysis of 701 to give sulfonic acids 702. [494,495] In combination with an acid-dependent crosslinking agent, 700 provides negative photoresists.…”

3.19 The Wolff Rearrangement

“…In combination with an acid-dependent crosslinking agent, aryl 2-diazonaphthalen-1-one-4-sulfonates provide negative photoresists (Scheme 59, top). 173,175 Other resists are available like, two-component resists bearing up to three diazo quinones linked in the same core 177 and a one-component system where the diazo quinone is directly linked to fragments of Novolac 178 (Scheme 59, below). The 2-diazo-1(2H)-naphthalenone has been recently explored as potential UV-phototriggered releasing agents.…”

“…The ring contraction and ketene hydrolysis provides 1H-indene-3-carboxylic acids 205, which displays a very distinct solubility in aqueous basic solutions compared with the parent diazo quinone 204 (Scheme 56). 173 The change in solubility in diazo quinones on irradiation allowed the exploration of these compounds as photoresists in the field of photolitography. 10 …”