1,2,3-Thiadiazoles with Unsaturated Side Chains; Synthesis, Polymerization, and Photocrosslinking

Abstract

1,2,3-Thiadiazoles with polymerizable functionalities in the 4-position were synthesized as potential negative photoresists. The polymerization to soluble, film-forming materials must leave the heterocyclic rings intact, because they are needed for photocrosslinking reactions to give insoluble materials. 1,2,3-Thiadiazoles 1 cycloeliminate N₂ on irradiation. The resulting 1,3-diradicals 2 have various options for stabilization processes leading to alkynes 3 or to higher heterocycles 5-12. The generation of atomic sulfur and its involvement in these subsequent reactions must be avoided. Therefore, systems like model compound 1a, in which the 1,3-diradicals form 2-methylene-1,3-dithioles (dithiafulvenes) 9 were selected here. Optimization gave ultimately two materials for application as photoresists. Monomer 1c could be polymerized in the presence of boron trifluoride to soluble 1c′, which on irradiation formed 1c′′ as a cross-linked insoluble polymer. Furthermore, thiadiazole 1f was attached to polystyrene 26. The resulting soluble polymer 1i′ yielded the insoluble material 1i′′ on irradiation.

Key words

cyclodimerization - cycloelimination - heterocycles - photochemistry - photoresists

References

• 1a Wilkins DJ. Bradley PA. In Science of Synthesis   Vol. 13:  Shinkai I. Georg Thieme Verlag; Stuttgart: 2004.  p.253 
• 1b Morzherin YY. Glukhareva TV. Bakulev VA. Chem. Heterocycl. Compd. Engl. Transl.  2003,  39:  679 
• 1c Stanetty P. Turner M. Mihovilovic MD. Targets Heterocycl. Syst.  1999,  3:  265 
• 1d Thomas EW. In Comprehensive Heterocyclic Chemistry II   Vol. 4:  Katritzky AR. Rees CW. Scriven EFV. Pergamon; Oxford: 1996.  p.289 
• 1e Meier H. Hanold N. In Houben Weyl   Vol. E8c:  Schaumann E. Georg Thieme Verlag; Stuttgart: 1994.  p.59 
• 1f Thomas EW. In Comprehensive Heterocyclic Chemistry   Vol. 6:  Katritzky AR. Rees CW. Pergamon; Oxford: 1984.  p.447 
• See also:
• 1g Spanka C. Schaumann E. Science of Synthesis   Vol. 23:  Danheiser RL. Georg Thieme Verlag; Stuttgart: 2006.  p.735 
• 2 Schaumann E. Ehlers J. Mrotzek H. Liebigs Ann. Chem.  1979,  1734 
• 3 Bühl H. Timm U. Meier H. Chem. Ber.  1979,  112:  3728 
• 4 Winter W. Bühl H. Meier H. Z. Naturforsch., B: Chem. Sci.  1980,  35:  1015 
• 5 Kirmse W. Horner L. Justus Liebigs Ann. Chem.  1958,  614:  4 
• 6 Zeller K.-P. Meier H. Müller E. Justus Liebigs Ann. Chem.  1972,  766:  32 
• 7 Zeller K.-P. Meier H. Müller E. Tetrahedron Lett.  1971,  12:  537 
• 8 Bühl H. Seitz B. Meier H. Tetrahedron  1977,  33:  449 
• 9 Timm U. Bühl H. Meier H. J. Heterocycl. Chem.  1978,  15:  697 
• 10 Timm U. Meier H. J. Heterocycl. Chem.  1979,  16:  1295 
• 11 Staudinger H. Siegwart J. Ber. Dtsch. Chem. Ges.  1916,  49:  1918 
• 12 Schaumann E. Ehlers J. Förster W.-R. Adividjaja G. Chem. Ber.  1979,  112:  1769 
• 13 Katritzky AR. Moyano EL. Yranzo G. Singh SK. ARKIVOC  2004,  (xi):  61 ; and references therein
• 14 Shafiee A. Vosooghi M. Lalezari L. J. Heterocycl. Chem.  1980,  17:  545 
• 15 Meier H. Zimmer O. J. Heterocycl. Chem.  1980,  17:  1639 
• 16 Zimmer O. Echter T. Merkle U. Meier H. Liebigs Ann. Chem.  1982,  683 
• 17 Hanold N. Kalbitz H. Pieper M. Zimmer O. Meier H. Liebigs Ann. Chem.  1986,  1344 
• 18 Aoyama T. Iwamoto Y. Shioiri T. Heterocycles  1986,  24:  589 
• 19 Pieper M. Teichert W. Meier H. Liebigs Ann. Chem.  1986,  1334 
• 20 Prass W, Zertani R, Lingnau J, Hanold N, and Meier H. inventors; DE  3,835,039. 
• 21 Prass W, Zertani R, Lingnau J, Hanold N, and Meier H. inventors; EP  363,817.  ; Chem. Abstr. 1990, 113, 181455
• 22 Hanold N. Kalbitz H. Al-Smadi M. Meier H. Z. Naturforsch., B: Chem. Sci.  1995,  50:  1121 
• 23 Al-Smadi M. Hanold N. Meier H. J. Heterocycl. Chem.  1997,  34:  605 
• 24 Attanasi O. Crescentini LDe. Favi G. Fillippone P. Giorgi G. Mantellini F. Santeusanio S. J. Org. Chem.  2003,  68:  1947 
• 25 Timm U. Merkle U. Meier H. Chem. Ber.  1980,  113:  2519 
• 26 Mereyala HB. Gurrala SR. Mohan SK. Tetrahedron  1999,  55:  11331 
• 27 Hurd CD. Mori RI. J. Am. Chem. Soc.  1955,  77:  5359 
• 29 Klebanov MS. J. Gen. Chem. USSR (Engl. Transl.)  1989,  59:  136 ; Chem. Abstr. 1989, 119, 226953
• 30 Hodd K. In Comprehensive Polymer Science   Vol. 5:  Al-len G. Berington JC. Pergamon; Oxford: 1989.  p.667 
• 32 Bonini BF. Franchini MC. Fochi M. Mangini S. Mazzanti G. Ricci A. Eur. J. Org. Chem.  2000,  2391 
• See also:
• 33a Shafiee A. Lalezari I. J. Heterocycl. Chem.  1973,  10:  11 
• 33b Benitez FM. Grunwell JR. J. Org. Chem.  1978,  43:  2914 
• 34 Naka S. Uemura T. Chujo Y. Macromolecules  1999,  32:  4641 
• 35 Naka S. Uemura T. Chujo Y. Macromolecules  1998,  31:  7570 
• 36 L’abbe G. Haelterman B. Dehaen W. Bull. Soc. Chim. Belg.  1996,  105:  419 
• 37 Al-Smadi M. Ratrout S. Molecules  2004,  9:  957 
• 38 Besombes JL. Cheminat B. Mousset G. Mousty C. Bull. Soc. Chim. Fr.  1992,  129:  513 
• 39 Sandrinelli F. Boudou C. Caupène C. Averbuch-Pouchot M.-T. Perrio S. Metzner P. Synlett  2006,  3289 

28

For the polymerization of related phenylglycidyl ethers see refs. 29 and 30.

31

The ^¹³C NMR signals of 9a published in ref. 32 cannot be correct, because they contain too many CH and too few C_q signals.