Intramolecular [4 + 2] Cycloaddition Reactions of Ketenimines: A New Synthesis­ of Benz[b]acridines

Mateo  Alajarín; Angel  Vidal; María-Mar  Ortín; Fulgencio  Tovar

doi:10.1055/s-2002-35234

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

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

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synthesis 2002(16): 2393-2398
DOI: 10.1055/s-2002-35234

PAPER

Intramolecular [4 + 2] Cycloaddition Reactions of Ketenimines: A New Synthesis of Benz[b]acridines

Mateo Alajarín*, Angel Vidal, María-Mar Ortín, Fulgencio Tovar
Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain
Fax: +34(968)364149; e-Mail: alajarin@um.es;

Further Information

Publication History

Received 18 July 2002
Publication Date:
04 November 2002 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

N-[2-(2-Propenyl)phenyl]-C,C-diphenyl ketenimines undergo a thermally induced intramolecular [4 + 2] cycloaddition to give 5,11,11a,12-tetrahydrobenz[b]acridines, which are converted into the fully aromatic benz[b]acridines by oxidation with Pd/C in refluxing ortho-xylene.

Key words

azides - acridines - cycloadditions - polycycles - ketenimines - phosphazenes

References

1a Barker MW. McHenry WE. In The Chemistry of Ketenes, Allenes and Related Compounds Part. 2: Patai S. Wiley; Chichester: 1980. p.701

Google Scholar
1b Alajarín M. Vidal A. Tovar F. Targets Heterocycl. Syst. 2000, 4: 293 ; and references cited therein.

Google Scholar
2a Molina P. Alajarín M. Vidal A. Tetrahedron Lett. 1991, 32: 5379

Google Scholar
2b Molina P. Alajarín M. Vidal A. J. Org. Chem. 1992, 57: 6703

Google Scholar
3 Alajarín M. Vidal A. Tovar F. Conesa C. Tetrahedron Lett. 1999, 40: 6127

Crossref Google Scholar
4 Alajarín M. Vidal A. Tovar F. Tetrahedron Lett. 2000, 41: 7029

Crossref Google Scholar
General syntheses of benz[b]acridines have been scarcely reported and usually yield oxidized derivatives. For examples, see:
5a Narasimhan NS. Ranade AC. Indian J. Chem. 1969, 7: 538

Crossref Google Scholar
5b Roushdi IM. Mikhail AA. Chaaban I. Pharmazie 1976, 31: 406

Crossref Google Scholar
5c Joos K. Pardo M. Schäfer W. J. Chem. Res., Synop. 1978, 406

Crossref Google Scholar
5d Hamdan AJ. Moore HW. J. Org. Chem. 1985, 50: 3427

Crossref Google Scholar
5e Chuang C.-P. Wu Y.-L. Jiang M.-C. Tetrahedron 1999, 55: 11229

Crossref Google Scholar
5f Prato M. Scorrano G. Stiranello M. Tecilla P. Lucchini V. Gazz. Chim. Ital. 1987, 117: 325

Crossref Google Scholar
5g Alvarez M. Ajana W. López-Calahorra F. Joule JA. J. Chem. Soc., Perkin Trans. 1 1994, 917

Crossref Google Scholar
6a Staudinger H. Meyer J. Helv. Chim. Acta 1919, 2: 635

Crossref Google Scholar
6b Gololobov YG. Kasukhin LF. Tetrahedron 1992, 48: 1353

Crossref Google Scholar
6c Gololobov YG. Zhmurova IN. Kasukhin LF. Tetrahedron 1981, 37: 437

Crossref Google Scholar
7 Smith PAS. Chou SP. J. Org. Chem. 1981, 46: 3970

Crossref Google Scholar
10a Alkhader MA. Smalley RK. Mohajerani B. Synthesis 1980, 381

Crossref Google Scholar
10b Bassoli A. Maddinelli G. Rindone B. Tollari S. Chioccara F. J. Chem. Soc., Chem. Commun. 1987, 150

Crossref Google Scholar
11 Taylor EC. McKillop A. Hawks GH. Org. Synth. 1973, 52: 36

Google Scholar
12 Le Corre M. Hercouet A. Le Stanc Y. Le Baron H. Tetrahedron 1985, 41: 5313

Crossref Google Scholar

8

Compound 2 ³¹P NMR (121.4 MHz, CDCl₃): δ = 1.29.

9

The heating of the toluene solutions of the ketenimines 10 at 130 °C in a sealed tube gave mixtures of 5,11,11a,12-tetrahydro, 5,12-dihydro and the fully aromatic 11-aryl-6-phenylbenz[b]acridines, and the same results were obtained when this thermal treatment was carried out in the presence of Pd/C.