1,2,3-Thiadiazole mit ungesättigten Seitenketten - Monomerbausteine für Photoresist-Materialien / 1,2,3-Thiadiazoles with Unsaturated Side Chains - Monomeric Building Blocks for Photoresists

Abstract

The phosphonium salts 4 are versatile reagents for the synthesis of 1,2,3-thiadiazoles 6 with unsaturated side chains. The preparation starts with the α-chloroketones 1 which are transformed in a stepwise process to the phosphonium salts 2 and 3. The reaction with SOCl2 leads to a regioselective ring closure 3 → 4 . Subsequent Wittig reactions yield the monomers 6, which exhibit with the exception of 6ac a high tendency for a thermal polymerization. Cleavage of the ester groups in 6ca and 6 cd generates the carboxylic acids 7ca and 7 cd which possess a higher stability.

A New Type of Synthesis of 1,2,3‐Thiadiazole and 1,2,3‐Diazaphosphole Derivatives Via‐Hurd‐Mori Cyclization

“…In the present study, new 1,2,3-thiadiazole and 1,2,3-diazaphosphole derivatives were obtained started from a variety of ketones (1-5) containing -methylene group (scheme 1) that were first converted into their corresponding semicarbazones and then further converted into 1,2,3-thiadiazole by reaction of thiosemicarbazide with thionyl chloride [33][34][35][36][37] and into 1,2,3-diazaphosphole ring derivatives by triphenyl phosphine reductive ring closure of these thiosemicarbazide derivatives.…”

New 1,2,3-Selenadiazole and 1,2,3-Thiadiazole Derivatives

“…Our synthetic procedure for new 1,2,3-selenadiazole and 1,2,3-thiadiazole derivatives started from a variety of ketones 1-5 containing α-methylene groups (Scheme 1) that were first converted into their corresponding tosyl or acyl hydrazones or semicarbazones and then further converted into 1,2,3-selenadiazole ring derivatives by the selenium dioxide oxidative ring closure of these semicarbazone or hydrazone derivatives [8][9][10][11] and into 1,2,3-thiadiazoles by reaction of the hydrazones or semicarbazones with thionyl chloride [12][13][14][15][16]. Scheme 1.…”

“…dried over magnesium sulphate and the solvent was removed under vacuum to afford the crude title compounds, which were further purifed as indicated under each heading. [13].…”

Thiadiazoles

“…4-and 5-Amino- [1,3,41,42], 5-halo- [3,42], 5-mercapto- [36], and 5-and 4-alkenyl 1,2,3-thiadiazoles [60][61][62] have been prepared following the same synthetic approach.…”