Photoinduced Elimination in 2,3-Dihydro-2-tert-butyl-3-benzyl-4(1H)-­quinazolinone: Theoretical Calculations and Radical Trapping Using TEMPO Derivatives

Fanny Araceli Cabrera-Rivera; Claudia Ortíz-Nava; Jaime Escalante; Julio M. Hernández-Pérez; Minhhuy Hô

doi:10.1055/s-0031-1290492

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(7): 1057-1063
DOI: 10.1055/s-0031-1290492

letter

Photoinduced Elimination in 2,3-Dihydro-2-tert-butyl-3-benzyl-4(1H)-quinazolinone: Theoretical Calculations and Radical Trapping Using TEMPO Derivatives

Fanny Araceli Cabrera-Rivera

^aCentro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, C. P. 62209 Cuernavaca, Morelos, México, Fax: +52(777)3297000 eMail: jaime@ciq.uaem.mx

,

Claudia Ortíz-Nava

^aCentro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, C. P. 62209 Cuernavaca, Morelos, México, Fax: +52(777)3297000 eMail: jaime@ciq.uaem.mx

,

Jaime Escalante*

^aCentro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, C. P. 62209 Cuernavaca, Morelos, México, Fax: +52(777)3297000 eMail: jaime@ciq.uaem.mx

,

Julio M. Hernández-Pérez

^bFacultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 14 Sur y Av. San Claudio, Col. San Manuel, 72530 Puebla, México

,

Minhhuy Hô

^aCentro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, C. P. 62209 Cuernavaca, Morelos, México, Fax: +52(777)3297000 eMail: jaime@ciq.uaem.mx

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

Photochemical irradiation of 2,3-dihydro-2-tert-butyl-3-benzyl-4(1H)-quinazolinone produced 3-benzyl-4(3H)-quinazolinone through photoinduced elimination via a radical mechanism. The use of photochemical conditions such as chloroform and UV irradiation (λ = 254 nm) got the 3-benzyl-4(3H)-quinazolinone in a high yield. Some theoretical calculations were achieved to explain the mechanism and the presence of radical intermediates was confirmed by trapping with different 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) derivatives.

Key words

2,3-dihydro-4(1H)-quinazolinones - mechanism - photochemical reaction - 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) - AIM - MO analysis - density analysis

Volltext

Referenzen

References and Notes
1 Mhaske SB, Argade NP. Tetrahedron 2006; 62: 9787

2a Larksarp C, Alper H. J. Org. Chem. 2000; 65: 2773 ; and references cited therein
2b Padala SR, Padi PR, Thipireddy V. Heterocycles 2003; 60: 183
2c Maarouf AR, El-Bendary ER, Goda FE. Arch. Pharm. Pharm. Med. Chem. 2004; 337: 527
2d Xu Z, Zhang Y, Fu H, Zhong H, Hong K, Zhu W. Bioorg. Med. Chem. Lett. 2011; 21: 4005

3a Errede LA, Hill JR, McBrady JJ. J. Org. Chem. 1982; 47: 3829
3b Connolly DJ, Cusack D, O’Sullivan TP. O, Guiry PJ. Tetrahedron 2005; 61: 10153
3c Leol YC, Fettinger JC, Kurth MJ. J. Org. Chem. 2005; 70: 6941
3d Acharyulu PV. R, Dubey PK, Prasada Reddy PV. V, Suresh T. ARKIVOC 2008; (xi): 104
3e Hasegawa H, Muraoka M, Ohmori M, Matsui K, Kojima A. Bioorg. Med. Chem. 2005; 13: 3721

4a Tangirala R, Antony S, Agama K, Pommier Y, Curran DP. Synlett 2005; 2843
4b Bowman WR, Elsegood MR. J, Stein T, Weaver GW. Org. Biomol. Chem. 2007; 5: 103

5 Andersin R, Mesilaakso M. J. Pharm. Biomed. Anal. 1995; 13: 667
6 Nishio T, Kameyama S, Omote Y, Kashima C. Heterocycles 1990; 30: 493
7 Kaneko C, Kasai K, Katagiri N, Chiba T. Chem. Pharm. Bull. 1986; 34: 3672

8a Escalante J, Flores P, Priego JM. Heterocycles 2004; 63: 2019
8b Priego J, Flores P, Ortiz-Nava C, Escalante J. Tetrahedron: Asymmetry 2004; 15: 3545
8c Escalante J, Ortiz-Nava C, Flores P, Priego JM, García-Martínez C. Molecules 2007; 12: 173
8d Coppola GM. Synthesis 1980; 505

9 Spectral assignments were made with the help of extensive decouplings on authentic samples of the started material 2 and the product 3

10a Keana JF. W. Chem. Rev. 1978; 78: 37
10b Vogler T, Studer A. Synthesis 2008; 1979 ; and references cited therein
10c Barriga S. Synlett 2001; 563
10d Naik N, Braslau R. Tetrahedron 1998; 54: 667
10e Calderón F. Synlett 2006; 657

11 Schoening KU, Fisher W, Hauck S, Dichtl A, Kuepfert M. J. Org. Chem. 2009; 74: 1567

12a Villamena FA, Xia S, Merle JK, Lauricella R, Tuccio B, Hadad CM, Zweier JL. J. Am. Chem. Soc. 2007; 129: 8177
12b Pou S, Halpern HJ, Tsain P, Rosen GM. Acc. Chem. Res. 1999; 32: 155
12c Villamena FA, Hadad CM, Zweier JL. J. Am. Chem. Soc. 2004; 126: 1816

13 Frisch MJ, Trucks GW, Head-Gordon M, Gill PM. W, Wong MW, Foresman JB, Johnson BG, Schlegel HB, Robb MA, Repogle ES, Gomperts R, Andres JL, Raghavachari K, Binkley JS, Gonzalez C, Martin RL, Fox DJ, DeFrees DJ, Baker J, Stewart JJ. P, Pople JA. GAUSSIAN 98. Gaussian Inc; Pittsburgh, PA: 1998

14a Nyden MR, Petersson GA. J. Chem. Phys. 1981; 75: 1843
14b Petersson GA, Al-Laham MA. J. Chem. Phys. 1991; 94: 6081
14c Petersson GA, Tensfeldt T, Montgomery JA. J. Chem. Phys. 1991; 94: 6091
14d Montgomery JA, Ochterski JW, Peterson GA. J. Chem. Phys. 1994; 101: 5900

15a Ochterski JW, Petersson GA, Montgomery JA, Pople JA. J. Chem. Phys. 1996; 104: 2598
15b Curtiss LA, Raghavachari K, Redfern PC, Stefanov BB. J. Chem. Phys. 1998; 108: 692

16 Bader RF. W. Atoms in Molecules: A Quantum Theory. Oxford University Press; Oxford: 1990
17 PROAIM, obtained from R. F. W. Bader, Department of Chemistry, McMaster University, Hamilton, Ontario, Canada
18 Pryor WA, Tang FY, Tang RH, Church DF. J. Am. Chem. Soc. 1982; 104: 2885
19 Zierhut M, Roth W, Fischer I. J. Phys. Chem. A. 2004; 108: 8125
20 Washida N, Bayes KD. J. Phys. Chem. 1980; 84: 1309
21 Typical Procedure A solution of 2 (0.34 mmol) in CHCl₃ was stirred and irradiated with UV light in the Rayonet equipment RPR-100. The reaction mixture was monitored by TLC (hexane–EtOAc = 80:20) until the disappearance of the starting material. The reaction mixture was concentrated under reduced pressure, and the crude of the reaction was purified by flash chromatography. When the reaction was examined by ¹H NMR at 400 MHz, peak ratios were determined by integration of the spectrum with an estimated error of ca. 5%

Zusatzmaterial

Supporting Information

Photoinduced Elimination in 2,3-Dihydro-2-tert-butyl-3-benzyl-4(1H)-­quinazolinone: Theoretical Calculations and Radical Trapping Using TEMPO Derivatives

Photoinduced Elimination in 2,3-Dihydro-2-tert-butyl-3-benzyl-4(1H)-quinazolinone: Theoretical Calculations and Radical Trapping Using TEMPO Derivatives