Convenient Preparation of Halo-1,3-thiazoles:
Important Building Blocks for Materials and Pharmaceutical Synthesis

Alan M. Grubb; Michael J. Schmidt; Alexander J. Seed; Paul Sampson

doi:10.1055/s-0031-1289710

RSS-Feed abonnieren

Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.

https://www.thieme-connect.de/rss/thieme/de/10.1055-s-00000084.xml

Teilen / Bookmarken

Facebook X Linkedin Weibo

PDF herunterladen

Synthesis 2012(7): 1026-1029
DOI: 10.1055/s-0031-1289710

PSP

Convenient Preparation of Halo-1,3-thiazoles: Important Building Blocks for Materials and Pharmaceutical Synthesis

Alan M. Grubb, Michael J. Schmidt, Alexander J. Seed, Paul Sampson*
Department of Chemistry and Biochemistry, Kent State University, Kent, OH 44242-0001, USA
e-Mail: psampson@kent.edu;

Weitere Informationen

Publikationsverlauf

Received 3 November 2011
Publikationsdatum:
16. Februar 2012 (online)

Abstract
Volltext
Referenzen

Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

Convenient, scalable and high-yielding approaches to 2,5- and 2,4-dibromo-1,3-thiazole are reported that offer significant improvements over previously reported approaches. 2,5-Dibromo-1,3-thiazole was generated in two steps from commercially inexpensive 2-amino-1,3-thiazole, whereas 2,4-dibromo-1,3-thiazole was generated in a single step from commercially inexpensive 1,3-thiazolidine-2,4-dione. As part of this study, convenient approaches to 2-bromo- and 2-iodo-1,3-thiazole were also developed.

Key words

halogenation - bromine - iodine - 1,3-thiazole - heterocycles

References

For reviews of applications involving thiophene-containing compounds, see, for example:
1a Campaigne E. In Comprehensive Heterocyclic Chemistry Vol. 4: Katritzky AR. Rees CW. Pergamon Press; Oxford: 1984. p.863

Google Scholar
1b Russell DK. Press JB. In Comprehensive Heterocyclic Chemistry II Vol. 2: Katritzky AR. Rees CW. Scriven EFV. Pergamon Press; Oxford: 1996. p.679

Google Scholar
1c Schatz J. In Science of Synthesis Vol. 9: Maas G. Thieme; Stuttgart: 2000. p.422

Google Scholar
For reviews of applications involving 1,3-thiazole-containing compounds, see, for example:
2a Dondoni A. Merino P. In Comprehensive Heterocyclic Chemistry II Vol. 3: Katritzky AR. Rees CW. Scriven EFV. Pergamon Press; Oxford: 1996. p.373

Google Scholar
2b Kikelj D. Urleb U. In Science of Synthesis Vol. 11: Schaumann E. Thieme; Stuttgart: 2000. p.627

Google Scholar
3 Limberakis C. Mullins RJ. Azman AM. In Palladium in Heterocyclic Chemistry 2nd ed.: Li JJ. Gribble GW. Elsevier; Oxford: 2007. p.251 (thiophenes) and 345 (1,3-thiazoles)

Google Scholar
4 For a recent review, see: Seed A. Chem. Soc. Rev. 2007, 36: 2046

Google Scholar
For a summary of available approaches to the preparation of halothiophenes, see, for example:
5a Rajappa S. In Comprehensive Heterocyclic Chemistry Vol. 4: Katritzky AR. Rees CW. Pergamon Press; Oxford: 1984. p.765

Google Scholar
5b Rajappa S. Natekar MV. In Comprehensive Heterocyclic Chemistry II Vol. 2: Katritzky AR. Rees CW. Scriven EFV. Pergamon Press; Oxford: 1996. p.502

Google Scholar
5c Gronowitz S. Hörnfeldt AB. Thiophenes: Best Synthetic Methods. Elsevier Ltd.; Oxford: 2004.

Google Scholar
6a Ganapathi K. Venkataraman A. Proc. Indian Acad. Sci., Sect. A 1945, 22: 362

Google Scholar
6b Others have obtained 70% yield using this procedure, see: van Zwieten PA. Huisman HO. Recl. Trav. Chim. Pays-Bas 1962, 554

Google Scholar
7 The most attractive literature approach to 2-iodo-1,3-thiazole proceeds from inexpensive 2-amino-1,3-thiazole in 40% yield, see: Neenan TX. Whitesides GM. J. Org. Chem. 1988, 53: 2489

Google Scholar
8a
2-Bromo-1,3-thiazole is an article of commerce (e.g., $118/mol from Oakwood Products, Inc. as of the submission date of this paper).
8b
The most attractive literature approach to 2-bromo-1,3-thiazole proceeds from commercially inexpensive 2-amino-1,3-thiazole ($17/mol from Alfa Aesar) in 75% yield.^6a Use of 2-amino-1,3-thiazole purchased from Acros Organics resulted in an isolated yield of only 40%, whereas 2-amino-1,3-thiazole purchased from Alfa Aesar gave 86% yield. Removal of the copper salts by filtration through Celite, followed by extraction of the filtrate, resulted in a 7% decrease in isolated yield of 2-bromo-1,3-thiazole compared to steam distillation of the crude material. Alternate approaches to 2-bromo-1,3-thiazole have also been reported. See, for example:
8c Boga C. Vecchio ED. Forlani L. Todesco PE.
J. Organomet. Chem. 2000, 601: 233 (80% GC-MS yield from expensive 1,3-thiazole)

Google Scholar
8d Wibaut JP. Jansen HE. Recl. Trav. Chim. Pays-Bas 1934, 53: 77 (20% yield from 2-amino-1,3-thiazole)

Google Scholar
9a
2-Iodo-1,3-thiazole does not appear to be commercially available
9b 2-Iodo-1,3-thiazole has also been prepared from 2-trimethylstannyl-1,3-thiazole in excellent yield (90%), see: Dondoni A. Mastellari AR. Medici A. Negrini E. Pedrini P. Synthesis 1986, 757

Google Scholar
9c Another high-yielding approach to 2-iodo-1,3-thiazole, proceeding from expensive 1,3-thiazole via an experimentally less convenient 2-metalation and iodination strategy has also been reported. See: Shilai M. Kondo Y. Sakamoto T.
J. Chem. Soc., Perkin Trans. 1 2001, 442

Google Scholar
10a Clark RF. Zhang T. Wang X. Wang R. Zhang X. Camp HS. Beutel BA. Sham HL. Gu YG. Bioorg. Med. Chem. Lett. 2007, 17: 1961

Google Scholar
10b Clark RF. Zhang T. Xin Z. Liu G. Wang Y. Hansen TM. Wang X. Wang R. Zhang X. Frevert EU. Camp HS. Beutel BA. Sham HL. Gu YG. Bioorg. Med. Chem. Lett. 2006, 16: 6078

Google Scholar
10c Gu YG. Weitzberg M. Clark RF. Xu X. Li Q. Lubbers NL. Yang Y. Beno DWA. Widomski DL. Zhang T. Hansen TM. J. Med. Chem. 2007, 50: 1078

Google Scholar
10d Gu YG. Weitzberg M. Clark RF. Xu X. Li Q. Zhang T. Hansen TM. Liu G. Xin Z. Wang X. Wang R. McNally T. Camp H. Beutel BA. Sham HL. J. Med. Chem. 2006, 49: 3770

Google Scholar
10e Berry CR. Zificsak CA. Gibbs AC. Hlasta DJ. Org. Lett. 2007, 9: 4099

Google Scholar
11a Lee C.-H. Yamamoto T. Mol. Cryst. Liq. Cryst. 2001, 363: 77

Google Scholar
11b Takihana Y. Shiotsuki M. Sanda F. Masuda T. Macromolecules 2004, 37: 7578

Google Scholar
12a Dondoni A. Fogagnolo M. Medidci A. Negrini E. Synthesis 1987, 185

Google Scholar
12b Mitschke U. Osteritz EM. Debärdemaeker T. Sokolowski M. Bäuerle P. Chem. Eur. J. 1998, 4: 2211

Google Scholar
12c Stanetty P. Schnurch M. Mihovilovic MD. J. Org. Chem. 2006, 71: 3754

Google Scholar
13a Gronowitz S. Peters D. Heterocycles 1990, 30: 645

Google Scholar
13b Bey E. Marchais-Oberwinkler S. Werth R. Negri M. Al-Soud YA. Kruchten P. Oster A. Frotscher M. Birk B. Hartmann RW. J. Med. Chem. 2008, 51: 6725

Google Scholar
13c Strotman NA. Chobanian HR. He J. Guo Y. Dormer PG. Jones CM. Steves JE. J. Org. Chem. 2010, 75: 1733

Google Scholar
14 Gol’dfarb YL. Gromova GP. Belen’kii LI. Chem. Heterocycl. Compd. (Engl. Transl.) 1986, 22: 663

Google Scholar
15a Beyerman HC. Berben PH. Bontekoe JS. Recl. Trav. Chim. Pays-Bas 1954, 73: 325

Google Scholar
15b Roussel P. Metzger J. Bull. Soc. Chim. Fr. 1962, 2075

Google Scholar
17 English JP. Clark JH. Clapp JW. Seeger D. Ebel RH. J. Am. Chem. Soc. 1946, 68: 453

Google Scholar
18 Nußbaumer T. Neidlein R. Heterocycles 2000, 52: 349

Google Scholar
19a Ammer C. Bach T. Chem. Eur. J. 2010, 16: 14083

Google Scholar
19b Dondoni A. Fantin G. Fogagnolo M. Medici A. Pedrini P. J. Org. Chem. 1988, 53: 1748

Google Scholar
19c Gebauer J. Arseniyadis S. Cossy J. Org. Lett. 2007, 9: 3425

Google Scholar
19d Huang S.-T. Gordon DM. Tetrahedron Lett. 1998, 39: 9335

Google Scholar
19e Karama U. Hoefle G. Eur. J. Org. Chem. 2003, 1042

Google Scholar
19f Kelly TR. Lang F. Tetrahedron Lett. 1995, 36: 9293

Google Scholar
19g Kovalenko VN. Sokolov NA. Kulinkovich OG. Russ. J. Org. Chem. 2010, 46: 1702

Google Scholar
19h Moulin E. Nevado C. Gagnepain J. Kelter G. Fiebig H.-H. Fürstner A. Tetrahedron 2010, 66: 6421

Google Scholar
19i Nickson TE.
J. Fluorine Chem. 1991, 55: 173

Google Scholar
19j Shao J. Panek JS. Org. Lett. 2004, 6: 3083

Google Scholar
19k Siméon FG. Brown AK. Zoghbi SS. Patterson VM. Innis RB. Pike VW.
J. Med. Chem. 2007, 50: 3256

Google Scholar
19l Ung AT. Pyne SG. Tetrahedron: Asymmetry 1998, 9: 1395

Google Scholar
19m Boudet N. Sase S. Sinha P. Liu C.-Y. Krasovskiy A. Knochel P. J. Am. Chem. Soc. 2007, 129: 12358

Google Scholar
19n Gross S. Heuser S. Ammer C. Heckmann G. Bach T. Synthesis 2011, 199

Google Scholar
19o Delgado O. Heckmann G. Müller HM. Bach T. J. Org. Chem. 2006, 71: 4599

Google Scholar
19p Spieß A. Heckmann G. Bach T. Synlett 2004, 131

Google Scholar
19q Nicolaou KC. He Y. Roschangar F. King NP. Vourloumis D. Li T. Angew. Chem. Int. Ed. 1998, 37: 84

Google Scholar
19r Nicolaou KC. King NP. Finlay MRV. He Y. Roschangar F. Vourloumis D. Vallberg H. Sarabia F. Ninkovic S. Hepworth D. Bioorg. Med. Chem. 1999, 7: 665

Google Scholar
19s Martin T. Laguerre C. Hoarau C. Marsais F. Org. Lett. 2009, 11: 3690

Google Scholar
20a Athmani S. Bruce A. Iddon B. J. Chem. Soc., Perkin Trans. 1 1992, 215

Google Scholar
20b Kienle M. Dunst C. Knochel P. Org. Lett. 2009, 11: 5158

Google Scholar
20c Dunst C. Kienle M. Knochel P. Synthesis 2010, 2313

Google Scholar
20d Nicolaou KC. Sasmal PK. Rassias G. Reddy MV. Altmann K.-H. Wartmann M. O’Brate A. Giannakakou P. Angew. Chem. Int. Ed. 2003, 42: 3515

Google Scholar
20e Palmer JT. Bryant C. Wang D.-X. Davis DE. Setti EL. Rydzewski RM. Venkatraman S. Tian Z.-Q. Burrill LC. Mendonca RV. Springman E. McCarter J. Chung T. Cheung H. Janc J. W. McGrath M. Somoza J. R. Enriquez P. Yu Z. W. Strickley R. M. Liu L. Venuti M. C. Percival M. D. Falgueyret J.-P. Prasit P. Oballa R. Riendeau D. Young R. N. Wesolowski G. Rodan S. B. Johnson C. Kimmel D. B. Rodan G. J. Med. Chem. 2005, 48: 7520

Google Scholar
20f Satoh A. Nagatomi Y. Hirata Y. Ito S. Suzuki G. Kimura T. Maehara S. Hikichi H. Satow A. Hata M. Ohta H. Kawamoto H. Bioorg. Med. Chem. Lett. 2009, 19: 5464

Google Scholar
21a Bach T. Heuser S. Tetrahedron Lett. 2000, 41: 1707

Google Scholar
21b Bach T. Heuser S. Angew. Chem. Int. Ed. 2001, 40: 3184

Google Scholar
21c Gebauer J. Arseniyadis S. Cossy J. Eur. J. Org. Chem. 2008, 2701

Google Scholar
22a Bach T. Heuser S. J. Org. Chem. 2002, 67: 5789

Google Scholar
22b Cosford NDP. Tehrani L. Roppe J. Schweiger E. Smith ND. Anderson J. Bristow L. Brodkin J. Jiang X. McDonald I. Rao S. Washburn M. Varney M. A.
J. Med. Chem. 2003, 46: 204

Google Scholar
23a Delgado O. Martin Müller H. Bach T. Chem. Eur. J. 2008, 14: 2322

Google Scholar
23b Hoffman TJ. Dash J. Rigby JH. Arseniyadis S. Cossy J. Org. Lett. 2009, 11: 2756

Google Scholar
24 Wellmar U. Hörnfeldt A.-B. Gronowitz S. J. Heterocycl. Chem. 1995, 32: 1159

Google Scholar
25 Le Flohic A. Meyer C. Cossy J. Tetrahedron 2006, 62: 9017

Google Scholar
27 Kato Y. Okada S. Tomimoto K. Mase T. Tetrahedron Lett. 2001, 42: 4849

Google Scholar
28 Katritzky AR. Laurenzo KS. Relyea DI. Can. J. Chem. 1988, 66: 1617

Google Scholar
29 L’Helgoual’ch J.-M. Seggio A. Chevallier F. Yonehara M. Jeanneau E. Uchiyama M. Mongin F. J. Org. Chem. 2008, 73: 177

Google Scholar
30 Klein G. Prijs B. Helv. Chim. Acta 1954, 37: 2057

Google Scholar
31 Reynaud P. Robba M. Moreau RC. Bull. Soc. Chim. Fr. 1962, 1735

Google Scholar

16

2-Amino-5-bromo-1,3-thiazole is commercially available ($3509/mol from Accela ChemBio, Inc.)

26

POBr₃ is commercially available ($766/mol from Alfa Aesar).