Oxidation of Nꢀacylꢀ2ꢀ(alkꢀ1ꢀenyl)anilines
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 1, January, 2002
127
Table 3. 13C NMR spectra of compounds 2—5, 9, 10, and 12 (CDCl3) and 7 and 8 (DMSOꢀd6) and mass spectra of compounds 3, 7,
8, 10, and 12
Comꢀ
pound
δ (J/Hz)
[M]+, m/z
2
3
4
18.2 (Me); 23.5, 33.9, 35.4 (3 СH2); 117.6 (СF3); 124.5 (С(4)); 128.6 (С(2)); 130.5 (С(6));
131.2 (С(3)); 132.6 (С(5)); 132.7 (С(2´)); 139.1 (С(1´)); 141.9 (С(1)); 154.7 (С=О)
17.1 (Me); 23.4, 25.6, 29.3 (С(5´)), (С(4´)), (С(3´)); 68.5 (С(6´)); 79.8 (С(2´)); 117.2 (С(5));
122.5 (С(3)); 124.7 (С(4)); 125.3 (С(2)); 129.4 (С(6)); 143.1 (С(1))
18.8, 20.9 (2 Me); 19.9, 31.6, 40.5 (3 СH2); 52.8 (ОМе)2; 104.1 (СН(ОМе)2); 125.3 (С(5´));
126.4 (С(6´)); 131.7 (С(3´)); 134.7 (С(1´)); 134.9 (С(4´)); 135.9 (С(2´)); 169.7 (NHС=О);
204.3 (РhC=O)
—
191
—
5
18.7 (Me); 19.2, 31.6, 39.8 (3 СH2); 52.7 (ОМе)2; 104.1 (СН(ОМе)2); 116.0 (q, СF3, J = 280);
126.8 (С(5´)); 127.3 (С(6´)); 130.8 (С(3´)); 132.4 (С(1´)); 135.7 (С(4´)); 135.9 (С(2´));
155.0 (q, С=О, J = 37); 203.8 (PhC=O)
—
7
17.7, 22.7 (2 Me), 19.0, 39.5, 32.7 (3 CH2); 124.8 (C(5´)), 125.6 (C(6´)), 132.5 (C(3´)),
132.8 (C(1´)), 134.7 (C(4´)), 137.4 (C(2´)); 168.3 (NHC=О); 174.0 (COOH); 202.7 (PhC=O)
24.6 (Me); 23.4, 24.0, 33.5, 39.2 (4 CH2); 120.8 (C(3´)); 122.9 (C(5´)); 124.5 (C(1´));
130.5 (C(6´)); 133.7 (C(4´)); 138.9 (C(2´)); 168.7 (NC=О); 174.4 (COOH); 204.3 (PhC=O)
24.4 (Me); 23.2, 33.7, 36.4 (3 СН2); 121.7 (С(6)); 124.0 (С(4)); 127.3 (С(2´)); 127.6 (С(3));
128.7 (С(1´)); 130.1 (С(5)); 134.4 (С(2)); 140.6 (С(1)); 168.2 (С=О)
263
263
—
8
9
10
12
21.5 (Me); 20.5, 31.6, 34.7 (3 СН2); 75.9 (СНОН); 90.0 (С(4)); 123.5 (С(4а)); 123.6 (С(6));
125.1 (С(7)); 125.8 (С(8)); 129.1 (С(5)); 139.1 (С(8а)); 160.3 (С(2))
24.5 (Me); 24.0, 27.3 (2 СН2); 46.4 (С(1´)); 58.5, 60.0 (С(2´), С((3´)); 122.8 (С(6)); 124.4 (С(4));
127.8 (С(5)); 130.0 (С(2)); 130.9 (С(3)); 136.7 (С(1)); 169.1 (С=О)
217
217
1ꢀyl)aniline10 or orthoꢀ(cyclopentꢀ2ꢀenꢀ1ꢀyl)aniline11 (1.6 g,
10 mmol) with Ac2O (1.3 g, 13 mmol). The products were reꢀ
crystallized from benzene.
Khim., 1999, 398 [Russ. Chem. Bull., 1999, 49, 396 (Engl.
Transl.)].
5. V. J. Traynelis, W. L. Hergenrother, H. T. Hanson, and J. A.
Valicenti, J. Org. Chem., 1964, 29, 123.
6. R. R. Gataullin, I. S. Afon´kin, A. A. Fatykhov, L. V.
Spirikhin, and I. B. Abdrakhmanov, Izv. Akad. Nauk, Ser.
Khim., 2000, 118 [Russ. Chem. Bull., Int. Ed., 2000, 49, 122].
7. R. R. Gataullin, I. S. Afon´kin, A. A. Fatykhov, L. V.
Spirikhin, E. V. Tal´vinskii, and I. B. Abdrakhmanov, Izv.
Akad. Nauk, Ser. Khim., 2001, 633 [Russ. Chem. Bull., Int.
Ed., 2001, 50, 659].
2ꢀMethylspiro[4Hꢀbenzo[d][1,3]oxazineꢀ4,1´ꢀcyclopentan]ꢀ
2´ꢀol (10) and Nꢀacetylꢀ2ꢀ(2,3ꢀepoxycyclopentꢀ1ꢀyl)aniline (12).
The known procedure8 was modified. A 50% solution of H2O2
(0.34 g, 4.98 mmol) was added to a mixture of amide 9 (or 11)
(0.5 g, 2.48 mmol), a solution of Na2WO4 (50 mg, 0.17 mmol) in
0.2 mL of water, and a drop of conc. H3PO4 in 5 mL of MeOH.
The reaction mixture was kept at 30 °C for 24 h, dissolved in
50 mL of CH2Cl2, washed with saturated solutions of Na2CO3
and Na2S2O3 and with water, and dried with MgSO4. After
CH2Cl2 was evaporated, benzooxazine 10 began to crystallize
on the flask walls. The crystals were recrystallized from Et2O.
Compound 12 was isolated by chromatography on silica gel in
benzene.
8. C. Venturello, E. Alneri, and M. Ricci, J. Org. Chem., 1983,
48, 3831.
9. B. M. Trost and D. L. Van Vranken, J. Am. Chem. Soc.,
1990, 112, 1261.
10. R. R. Gataullin, T. V. Kazhanova, A. A. Fatykhov, L. V.
Spirikhin, and I. B. Abdrakhmanov, Izv. Akad. Nauk, Ser.
Khim., 2000, 171 [Russ. Chem. Bull., Int. Ed., 2000, 49, 174].
11. I. B. Abdrakhmanov, V. M. Sharafutdinov, and G. A.
Tolstikov, Izv. Akad. Nauk SSSR, Ser. Khim., 1982, 2160
[Bull. Acad. Sci. USSR, Div. Chem. Sci., 1982, 31 (Engl.
Transl.)].
12. A. F. Plate, A. A. Mel´nikov, T. A. Italinskaya, and R. A.
Zelenko, Zh. Org. Khim., 1960, 30, 1250 [J. Org. Chem. USSR,
1960, 30 (Engl. Transl.)].
References
1. Comprehensive Organic Chemistry, Ed. D. Barton and W. D.
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3. G. Florence, Bull. Sci. Pharmacol., 1933, 40, 325.
4. R. R. Gataullin, I. S. Afon´kin, I. V. Pavlova, I. B.
Abdrakhmanov, and G. A. Tolstikov, Izv. Akad. Nauk, Ser.
Received February 15, 2001;
in revised form September 10, 2001