Regioselectivitity of indanone formation
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 5, May, 2009
935
about 5 °C. After 1 h the cooling was removed, and the mixture
was left to stay at ambient temperature. Then the reaction
mixture was carefully quenched with a mixture of a saturated
solution of HCl (30 mL), cold water (150 mL), and ice (150 g).
The organic layer was separated, and the aqueous solution was
extracted with chloroform (3×50 mL). The combined organic
phases were washed with water, a 5% solution of Na2CO3, and
again with a minimum water, dried over Na2SO4, and conꢀ
centrated in vacuo.
3ꢀChloroꢀ1ꢀ(3,4ꢀdimethylphenyl)propanꢀ1ꢀone (1). The yield
was 98% (light gray powder). 1H NMR, δ: 2.33 (br.s, 6 H); 3.42
(t, 2 H, J = 6.8 Hz); 3.92 (t, 2 H, J = 6.8 Hz); 7.23 (d, 1 H,
J = 7.7 Hz); 7.69 (d, 1 H, J = 7.7 Hz); 7.74 (s, 1 H).
3ꢀChloroꢀ1ꢀ(5,6,7,8ꢀtetrahydroꢀ2ꢀnaphthyl)propanꢀ1ꢀone
(2). The yield was 98% (beige powder). 1H NMR, δ: 1.83 (m,
4 H); 2.82 (m, 4 H); 3.42 (t, 2 H, J = 6.8 Hz); 3.91 (t, 2 H,
J = 6.8 Hz); 7.16 (d, 1 H, J = 8.4 Hz); 7.69—7.65 (m, 3 H).
3ꢀChloroꢀ1ꢀ(2,3ꢀdihydroꢀ1Hꢀindenꢀ5ꢀyl)propanꢀ1ꢀone (3).
The yield was 94%. 1H NMR, δ: 2.13 (q, 2 H, J = 7.5 Hz);
2.97 (t, 4 H, J = 7.5 Hz); 3.44 (t, 2 H, J = 6.9 Hz); 3.92 (t, 2 H,
J = 6.9 Hz); 7.31 (d, 1 H, J = 7.9 Hz); 7.76 (d, 1 H, J = 7.9 Hz);
7.82 (s, 1 H).
1ꢀ(Bicyclo[4.2.0]octaꢀ1,3,5ꢀtrienꢀ3ꢀyl)ꢀ3ꢀchloropropanꢀ
1ꢀone (4) was obtained according to the general procedure using
nitromethane as a solvent. The residue after evaporation was
recrystallized from hexane. The yield was 63% (pale pink
powder). 1H NMR, δ: 3.23 (br.s, 4 H); 3.43 (t, 2 H, J = 6.8 Hz);
3.92 (t, 2 H, J = 6.8 Hz); 7.15 (d, 1 H, J = 8 Hz); 7.65 (s, 1 H);
7.85 (d, 1 H, J = 8 Hz).
compound 8, δ: 1.80—1.90 (m, 4 H); 2.62—2.71 (m, 4 H); 2.83
(t, 2 H, J = 5.7 Hz); 3.04 (t, 2 H, J = 5.7 Hz); 7.16 (s, 1 H); 7.45
(s, 1 H).
1,6,7,8ꢀTetrahydroꢀasymmꢀ(2H)ꢀindacenꢀ3ꢀone (9) and
3,5,6,7ꢀtetrahydroꢀsymmꢀ(2H)ꢀindacenꢀ1ꢀone (10). The overall
yield was 75%, white powder. The ratio 9 : 10 was 1 : 4.5.
1H NMR spectrum of compound 9, δ: 2.20 (q, 2 H, J = 7.3 Hz);
2.68—2.71 (2 H); 2.90—3.02 (6 H); 7.24 (d, 1 H, J = 7.7 Hz);
7.58 (d, 1 H). 1Н NMR spectrum of compound 10, δ: 2.13
(q, 2 H, J = 7.3 Hz); 2.68 (t, 2 H, J = 7.3 Hz); 2.92 (t, 2 H,
J = 7.3 Hz); 2.95 (t, 2 H, J = 5.8 Hz); 3.07 (t, 2 H, J = 5.8 Hz);
7.29 (s, 1 H); 7.57 (s, 1 H).
1,2,5,6ꢀTetrahydroꢀ4Hꢀcyclobuta[f]indenꢀ4ꢀone (12). The
yield was 45%, pale pink powder. 1H NMR, δ: 2.65 (t, 2 H,
J = 5.8 Hz); 3.10 (t, 2 H, J = 5.8 Hz); 3.19 (br.s, 4 H); 7.14 (s,
1 H); 7.41 (s, 1 H).
References
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Synthesis of compounds 5—8 (general procedure). The
corresponding 1ꢀarylꢀ3ꢀchloropropanꢀ1ꢀone (0.1 mol) was
added in small portions with vigorous stirring to concentrated
H2SO4 (150 mL) heated to 80 °C. The stirring was continued
at 85—90 °C until the end of gas evolution (1 h), monitoring
by TLC in chloroform. Then the reaction mixture was cooled to
20 °С, carefully poured into water (150 mL) with ice (150 g),
and extracted with chloroform (3×50 mL). The combined
extracts were dried over Na2SO4 and concentrated by evaporaꢀ
tion. The ratio of the cyclization products was determined by
1
the analysis of the H NMR spectra.
4,5ꢀDimethylindanꢀ1ꢀone (5) and 5,6ꢀdimethylindanꢀ1ꢀone
(6). The overall yield was 80%, white powder. 1H NMR spectrum
of compound 5, δ: 2.25 (s, 3 H); 2.37 (s, 3 H); 2.67 (t, 2 H,
J = 5.8 Hz); 3.00 (t, 2 H, J = 5.8 Hz); 7.17 (d, 1 H, J = 7.7 Hz);
12. W. J. Stevens, H. Basch, M. Krauss, J. Chem. Phys., 1984,
81, 6026.
13. W. J. Stevens, M. Krauss, H. Basch, P.G.Jasien, Can. J.
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1
7.51 (1 H). H NMR of compound 6, δ: 2.30 (s, 3 H); 2.34 (s,
3 H); 2.64 (t, 2 H, J = 5.9 Hz); 3.04 (t, 2 H, J = 5.9 Hz); 7.24
(s, 1 H); 7.50 (s, 1 H).
14. T. R. Cundari, W. J. Stevens, J. Chem. Phys., 1993, 98, 5555.
1,2,6,7,8,9ꢀHexahydroꢀ3Hꢀcyclopenta[a]naphthalenꢀ3ꢀone
(7) and 2,3,5,6,7,8ꢀhexahydroꢀ1Hꢀcyclopenta[b]naphthalenꢀ
1ꢀone (8). The overall yield was 53%, white powder. 1H NMR
spectrum of compound 7, δ: 1.80—1.90 (m, 4 H); 2.62—2.71
(m, 4 H); 2.84 (t, 2 H, J = 5.6 Hz); 2.93 (t, 2 H, J = 5.6 Hz);
7.08 (d, 1 H, J = 7.9 Hz); 7.48 (d, 1 H, J = 7.9 Hz). 1H NMR of
Received July 15, 2008;
in revised form January 12, 2009