İaroslav BAGLAI, Valérie MARAVAL, Zoia Vsevolodivna VOITENKO

On the peculiar reactivity of a C,N-annelated isoindole core

C-, N-, and/or O-methylation products were generated from 11H-isoindolo[2,1-a]quinazoline-5-one upon treatment with NaH followed by iodomethane under air, and possible recrystallization from methanol. Two products were fully characterized by NMR and X-ray diffraction analysis. In accordance with the HSAB principle, this soft methylating agent (MeI) leads mainly to the C,C-dimethylated product 11,11-dimethyl-11H-isoindolo[2,1-a]quinazoline-5-one, which was previously not observed, beside the N-methylated product, in a procedure using methyl tosylate as a hard methylating agent of the same substrate in the initial absence of a base. A mechanism is finally proposed for the formation of methyl 2-(3-methyl-4-oxo-3,4-dihydroquinazolin-2-yl)benzoate as an oxidation side product.

Anahtar Kelimeler:

Isoindoles, methylation processes, oxidative ring opening, quinazolines

On the peculiar reactivity of a C,N-annelated isoindole core

Keywords:

Isoindoles, methylation processes, oxidative ring opening, quinazolines,

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Baglai, I.; Maraval, V.; Voitenko, Z. V.; Duhayon, C.; Volovenko, Y. M.; Chauvin, R. Tetrahedron 2012, 68, 6908–6913.
Babichev, F. S.; Kovtunenko, V. A.; Tyltin, A. K. Russ. Chem. Rev. 1981, 50, 1087–1103.
Voitenko, Z. V.; Samoylenko, V. P.; Tyltin A. K.; Turov. O. V. Ukr. Khim. Zh. 2001, 67, 111–114.
Voitenko, Z. V.; Halaev, O. I.; Samoylenko, V. P.; Kolotilov, S. V.; Lepetit, C.; Donnadieu B.; Chauvin, R. Tetrahedron 2010, 66, 8214–8222.
Pearson, R. G. J. Am. Chem. Soc. 1963, 85, 3533–3539.
Voitenko, Z. V.; Rudyuk, S. O.; Samoylenko, V. P.; Ryabov, S. V.; Zubatyuk, R. I.; Shishkin. O. V. Dopovidi Natsional’noi Akademii Nauk Ukraini 2005, 8, 132–138.
Lightner, D. A.; Kirk, D. I.; Norris, R. D. J. Heterocyclic Chem. 1974, 11, 1097–1098.
Walter T.; Werner, S. Liebigs Ann. Chem. 1957, 605, 43–49.
Babichev, F. S.; Khil’ko, L. G.; Mel’nichenko, N. V. Ukr. Khim. Zh., 1969, 35, 615–618.
Wilkinson, F.; Helman, W. P.; Ross, A. B. J. Phys. Chem. Ref. Data 1993, 22, 113–262.
Bunelle, W. H. Chem. Rev. 1991, 91, 335–362.
Babichev, F. S.; Tyltin, A. K. Ukr. Khim. Zh. 1970, 36, 175–178.
Lyaskovskyy, V. V.; Voitenko Z. V.; Kovtunenko, V. A. Chem. Heterocyc. Compd. 2007, 43, 253–276.
Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A.; Burla, M. C.; Polidori, G.; Camalli, M. J. Appl. Cryst. 1994, 27, 435–436.
Palatinus, L.; Chapuis, G. J. Appl. Cryst. 2007, 40, 786–790.
Betteridge, P. W.; Carruthers, J. R.; Cooper, R. I.; Prout, K.; Watkin, D. J. J. Appl. Cryst. 2003, 36, 1487. International Tables for X-ray Crystallography, vol. IV, Kynoch Press: Birmingham, England, 1974.
Blessing, R. H. Acta Cryst. 1995, A51, 33–38.