VASIN et al.
1820
1
hexane). IR spectrum, ν, cm–1: 3059 v.w, 3020 v.w,
2909 w, 1404 s, 1265 m, 1157 m, 937 m, 763 s, 703 s.
1H NMR spectrum, δ, ppm: 3.20 d.d (1H, 3-H, J = 7.6,
8.8 Hz), 3.83 d.d (1H, 3-H, J = 6.9, 8.8 Hz), 5.86 t
(1H, 2-H, J = 8.2 Hz), 7.55 m (5H). Found, %:
C 32.93; H 1.64. C14H8Br4O. Calculated, %: C 32.85;
H 1.58.
1300 s, 1149 s, 922 w, 879 w, 744 s. H NMR spec-
trum (CDCl3 or DMSO-d6, 25°C; a mixture of di-
ketone and enol tautomers at a ratio of 1:5), δ, ppm:
diketone tautomer: 2.16 s (6H, CH3), 5.34 s (1H, CH),
7.36 s (2H, Harom); enol tautomer: 1.86 s (6H, CH3),
7.48 s (2H, Harom), 10.01 s (1H, OH), 13.82 s (1H,
OH, enol). 13C NMR spectrum, δC, ppm: 23.9, 26.4,
30.1 (CH3); 111.8, 112.6, 120.1, 122.5, 127.1, 130.6,
133.1, 134.8, 150.0, 150.3, 190.1, 196.1, 202.8. Found,
%: C 37.69; H 2.92. C11H10Br2O3. Calculated, %:
C 37.75; H 2.88.
Reaction of polybrominated quinone diazides
1–5 with acetylacetone (general procedure). A mix-
ture of 3.5 mmol of quinone diazide 1–5 and 17 equiv
of acetylacetone was heated for 2 h at 90–95°C and
was then refluxed for 2 h until nitrogen no longer
evolved. Excess acetylacetone was distilled off under
reduced pressure (water-jet pump), and the residue was
purified by flash chromatography on silica gel.
3-(2,3,5,6-Tetrabromo-4-hydroxyphenyl)pen-
tane-2,4-dione (28). Yield 26%, mp 167–168°C. IR
spectrum, ν, cm–1: 3356 br.w, 2920 v.w, 1597 s, 1543
1
v.s, 1331 v.s, 1257 s, 1157 v.s, 918 m. H NMR
spectrum, δ, ppm: 1.81 s (6H, CH3), 6.49 s (1H, CH);
OH signal was not observed. 13C NMR spectrum, δC,
ppm: 23.3 (2C, CH3), 113.1, 118.1, 129.4, 132.7,
151.4 (Carom, C3); 190.6 (C2, C4). Mass spectrum:
m/z 504.7276 [M + H]+. C11H9Br4O3. M + H 504.7280.
3-(3,5-Dibromo-2-hydroxyphenyl)-4-hydroxy-
pent-3-en-2-one (24). Yield 55%, mp 176°C. IR spec-
trum, ν, cm–1: 3222 br.w, 3086 w, 2924 w, 1655 v.s,
1
1516 v.s, 1365 m, 1300 s, 1138 m, 937 m. H NMR
spectrum, δ, ppm: 1.57 s (3H, CH3), 1.64 s (3H, CH3),
6.68 d (1H, Harom, J = 2.3 Hz), 6.85 d (1H, Harom, J =
2.3 Hz), 9.67 s (1H, OH), 13.42 s (1H, OH, enol).
13C NMR spectrum, δC, ppm: 26.6 (CH3), 31.4 (CH3);
112.9, 113.1, 116.4, 129.8, 133.9, 142.5 (Carom, C3);
196.5, 197.2 (C2, C4). Mass spectrum: m/z 348.9083
[M + H]+. C11H11Br2O3. Calculated: M + H 348.9070.
REFERENCES
1. Ershov, V.V., Nikiforov, G.A., and de Jonge, C.R.H.I.,
Quinone Diazides, Amsterdam: Elsevier, 1981.
2. Ershov, V.V. and Nikiforov, G.A., Russ. Chem. Rev.,
1975, vol. 64, p. 816.
3-(3,4,6-Tribromo-2-hydroxy-5-methylphenyl)-
4-hydroxypent-3-en-2-one (25). Yield 30%, mp 156–
157°C. IR spectrum, ν, cm–1: 3456 br.m, 2429 m,
1678 v.s, 1624 s, 1512 s, 1354 s, 1180 s, 929 m, 810 m.
1H NMR spectrum, δ, ppm: 2.45 s (3H, CH3), 2.66 s
(6H, CH3), 11.41 s (1H, OH), 14.7 s (1H, OH, enol).
13C NMR spectrum, δC, ppm: 25.6 (CH3), 27.0
(CH3), 32.0 (CH3); 113.3, 115.2, 123.7, 124.5, 130.74,
131.7, 145.6 (Carom, C3); 194.2, 198.3 (C2, C4). Found,
%: C 32.45; H 2.34. C12H11Br3O3. Calculated, %:
C 32.54; H 2.50.
3. Birchall, J.M., Haszeldine, R.N., Nikokavouras, J., and
Wilks, E.S., J. Chem. Soc. C, 1971, p. 562.
4. Kraus, G.A., Nagy, J.O., and DeLano, J., Tetrahedron,
1985, vol. 41, p. 2337.
5. Huisgen, R., König, H., Binsch, G., and Sturm, H.J.,
Angew. Chem., 1961, vol. 73, p. 368.
6. Huisgen, R., Angew. Chem., Int. Ed. Engl., 1963, vol. 2,
p. 565.
7. Huisgen, R., Binsch, G., and König, H., Chem. Ber.,
1964, vol. 97, pp. 2868, 2884, 2893.
8. Rodina, L.L. and Korobitsyna, I.K., Russ. Chem. Rev.,
3-(3,4,5,6-Tetrabromo-2-hydroxyphenyl)-4-hy-
droxypent-3-en-2-one (26). Yield 25%, mp 160–
161°C. IR spectrum, ν, cm–1: 3406 br.m, 2970 v.w,
2916 v.w, 2854 v.w, 1670 s, 1508 v.s, 1358 m, 1176 m,
1967, vol. 36, p. 260.
9. Bohmer, C., J. Prakt. Chem., 1881, vol. 24, p. 449.
10. Dewar, M.J.S. and James, A.N., J. Chem. Soc., 1958,
p. 917; ibid., p. 4265.
1
929 w. H NMR spectrum, δ, ppm: 2.55 s (3H, CH3),
11. Huisgen, R. and Fleischmann, R., Justus Liebigs Ann.
Chem., 1959, vol. 623, p. 47.
2.61 s (3H, CH3), 11.01 s (1H, OH), 14.10 s (1H, OH,
enol). 13C NMR spectrum, δC, ppm: 27.1 (CH3), 31.6
(CH3); 114.7, 115.7, 124.4, 127.5, 127.7, 141.9, 148.0
(Carom, C3); 195.8, 197.8 (C2, C4). Found, %: C 26.10;
H 1.55. C11H8Br4O3. Calculated, %: C 26.02; H 1.59.
12. Orton, K.J.P., J. Chem. Soc., Trans., 1903, vol. 83,
p. 796.
13. Nikiforov, G.A., Plekhanova, L.G., Efremenko, A.A.,
Pobedinskii, D.G., and Ershov, V.V., Bull. Acad. Sci.
USSR, Div. Chem. Sci., 1971, vol. 20, no. 1, p. 124.
3-(3,5-Dibromo-4-hydroxyphenyl)pentane-
2,4-dione (27). Yield 45%, mp 109°C. IR spectrum, ν,
cm–1: 3321 m, 3059 w, 2924 w, 1589 s, 1481 v.s,
14. Burya, G.F., Efremenko, A.A., Nikiforov, G.A., and
Ershov, V.V., Khim. Fiz., 1996, vol. 15, p. 65.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 12 2017