152
Short Communications
H 6; 7 65, t, Jortho 7 6 Hz, 1H, H 5; 7 95, d, Jortho 7 6 Hz,
1H, H 7. 13C n.m.r. 59 2, 86 6, 123 9, 126 2, 126 8, 127 1,
127 4, 129 1, 129 4, 129 6, 135 5, 135 7, 137 5, 140 4, 146 8,
153 4, 207 0. Mass spectrum (20 eV) m/z 300 (100%), 282
(9 2), 195 (92 8), 105 (22 6), 94 (5 6).
The mixture was then poured into NH4Cl/H2O and the organic
product extracted with chloroform. After evaporation of the
solvent the residue was puri ed by p.l.c. (chloroform), a ording
(11a) (400 mg) (upper band) and a mixture of (11a,b) (200 mg)
(2 : 1).
When the reaction mixture was poured into acetic acid/water
solution the major products, puri ed by p.l.c. (chloroform),
were compound (8) (1 3 g), yield 51% (upper band), and
compound (10) (220 mg), yield 11% (lower band).
1,2,3-Triphenylindene (8).
135 (methanol)]. 1H n.m.r.
7 25–7 75, m, 19H, Ar.
r-3-Hydroxy-t-2,3-diphenylindan-1-one (11a).
(Found: C,
84 0; H, 5 3. C21H16O2 requires C, 84 1; H, 5 4%). 1H n.m.r.
(CDCl3) 2 30, br s, 1H, OH; 4 33, s, 1H, H 2; 6 75–7 72,
m, 13H, Ar; 7 92, d, Jortho 7 9 Hz, 1H, H 7. 13C n.m.r.
69 2, 80 1, 123 6, 125 5, 126 1, 127 4, 128 1, 128 4, 128 5,
128 8, 129 7, 130 5, 133 6, 135 9, 144 7, 157 0, 203 6.
M.p. 125–127 (ethanol) [lit.2
(CDCl3) 5 30, s, 1H, H 3;
Mixture of (11a,b).
2 30, br s, OH; 4 33, s, H 2; 4 40, s, H 2; 6 65–8 03, m, Ar.
13C n.m.r.
69 2, 70 5, 80 1, 84 0, 123 6, 125 5, 126 1,
1H n.m.r. (CDCl3) 1 60, br s, OH;
Reaction of cis-2,3-Diphenylindan-1-one (5) with PhMgBr
126 5, 126 8, 127 2, 127 4, 127 7, 128 1, 128 4, 128 5, 128 8,
129 5, 129 7, 130 1, 130 5, 131 4, 133 2, 134 3, 135 8, 135 9,
142 6, 144 7, 155 7, 157 0, 191 2, 203 6.
The ketone (5) was obtained by a procedure similar to that
used for the indanone (4). The reaction mixture when puri ed
by p.l.c. (chloroform) gave the indanol (9) (1 g, yield 57%)
(upper band) and the hydroxy ketone (10) (340 mg, yield 21%)
(lower band).
2,c-3-Diphenylindan-r-1,t-2-diol (12)
1,c-2,c-3-Triphenylindan-r-1-ol (9).
M.p. 108–110 (etha-
Compound (10) was reduced with NaBH4 in methanol by
employing the procedure described previously by us.10 Yield
72%, m.p. 144–145 (ethanol–water) (Found: C, 83 4; H, 6 1.
nol) (Found: C, 89 5; H, 6 2. C27H22O requires C, 89 6; H,
6 1%). 1H n.m.r. (CDCl3) 2 55, s, 1H, OH; 4 20, d, J2,3
7 7 Hz, 1H, H 2; 5 90, d, J2,3 7 7 Hz, 1H, H 3; 6 75–6 95,
m, 2H, Ar; 7 00–7 75, m, 17H, Ar. 13C n.m.r. 53 7, 67 1,
85 8, 123 9, 125 7, 126 3, 126 6, 127 1, 127 4, 127 8, 128 0,
128 6, 129 3, 129 5, 129 8, 130 5, 139 8, 140 8, 145 0, 145 6,
148 2.
C
21H18O2 requires C, 83 5; H, 6 0%). 1H n.m.r. (CDCl3)
2 60, br s, OH; 3 15, br s, OH; 4 70, s, H 3; 5 50, s, H 1;
6 75–7 60, m, 14H, Ar. 13C n.m.r. 60 5, 83 9, 92 7, 122 2,
125 1, 126 7, 126 8, 127 3, 127 5, 127 6, 127 8, 128 1, 129 6,
136 9, 138 5, 140 1, 143 3.
Hydrogenolysis with Raney Nickel (W-2)
Acknowledgments
General procedure. A mixture of the corresponding indanol
(150 mg), Raney nickel (W-2) (6 g) and dry ethanol was shaken
under a hydrogen atmosphere at 20 psi during 8 h. The
ethanolic solution was ltered and the solvent was removed in
vacuum. The mixture was puri ed by p.l.c. (benzene). The
following compounds were obtained by using this procedure.
The authors express their gratitude to the Secretaria
de Ciencia y Tecnica, Universidad de Buenos Aires,
and CONICET for support of this study.
References
r-1,t-2,c-3-Triphenylindan (1).
obtained from (6), m.p. 124–125 (ethanol) (lit.4 125 ). 13C
n.m.r. (CDCl3) 58 4, 67 6, 124 7, 126 5, 127 7, 128 0,
128 3, 128 6, 129 2, 129 4, 142 7, 146 8, 148 1.
The title compound was
1
Alesso, E. N., Tombari, D. G., Ibanez, A. F., Moltrasio
Iglesias, G. Y., and Aguirre, J. M., Can. J. Chem., 1991,
69, 1166.
Kohler, E. P., and Mydans, W. E., J. Am. Chem. Soc.,
1932, 54, 4667.
Miller, L. L., and Boyer, R. F., J. Am. Chem. Soc., 1971,
93, 646.
Marcuzzi, F., and Melloni, G., J. Chem. Res. (M), 1979,
2287.
Hiscock, M., and Porter, G. B., J. Chem. Soc. B, 1971,
163.
Kirrstetter, R. G., and Vagt, U., Chem. Ber., 1981, 114,
630.
Garbisch, E. J., J. Org. Chem., 1962, 27, 3363.
Monahan, A., Campbell, P., Cheh, S., Fong, J., Grossman,
S., Miller, J., Rankin, P., and Vallee, J., Synth. Commun.,
1977, 7, 553.
Clark, T. H., J. Chem. Educ., 1971, 48, 554.
Alesso, E. N., Moltrasio Iglesias, G. Y., and Aguirre, J.
M., An. Quim., 1993, 89, 242.
2
r-1,c-2,t-3-Triphenylindan (2).
The title compound was
obtained from (7) or (9), m.p. 147–149 (ethanol) (lit.4 154 ).
3
13C n.m.r.
54 1, 56 1, 62 1, 125 1, 125 4, 126 1, 126 5,
127 4, 127 5, 127 6, 128 4, 128 5, 128 8, 129 1, 139 4, 140 9,
142 8, 145 2, 147 0.
4
5
r-1,c-2,c-3-Triphenylindan (3)
6
The indene (8) (200 mg) was hydrogenated with Pd/C (10%;
250 mg) in ethanol (80 ml) at 50 psi during 8 h. After workup
(3) (120 mg) was obtained. Yield 60%, m.p. 153–154 (ethanol)
(lit.4 143–144 ). 13C n.m.r. 56 2, 62 8, 124 9, 125 9, 126 0,
126 7, 127 5, 129 5, 129 9, 137 9, 139 2, 145 2.
7
8
3-Hydroxy-2,3-diphenylindan-1-ones (11a) and (11b)
9
10
Benzalphthalide (1 g) was treated with phenylmagnesium
bromide in tetrahydrofuran by following the procedure of Clark.9