J. Jamrozik et al. / Journal of Molecular Structure 687 (2004) 79–86
81
7.19–7.21 (m, 2H, arom.H); 13C NMR (CDCl3), d : 14.0,
31.5, 34.5, 40.1, 40.6, 60.4, 61.6, 121.0, 123.6, 124.0, 136.9,
139.8, 150.0, 171.8.
(s, 6H, CH3), 2.70 (s, 2H, CH2), 2.73 (s, 2H, CH2), 3.94 (s,
4H, OCH2), 6.99 (d, J ¼ 8:0 Hz, 1H, arom.H), 7.09 (s, 1H,
arom.H) 7.15 (dd, J ¼ 1:8 Hz, J ¼ 8:0 Hz, 1H, arom.H),
7.33 (d, J ¼ 8:4 Hz, 4H, arom.H), 7.73 (d, J ¼ 8:4 Hz, 4H,
arom.H); 13C NMR (CDCl3), d : 21.6, 31.4, 34.5, 37.8, 38.3,
47.0, 71.3, 121.7, 124.2, 124.4, 127.9, 129.4, 132.5, 136.6,
139.5, 145.0, 150.3.
2.1.3. 2,2-Bis(hydroxymethyl)-4,5,6,7-tetramethyl-indan (3)
A solution of 1 (8.45 g, 27.8 mmol) in anhydrous THF
(21 ml) was added dropwise into a solution of LiAlH4
(69.5 ml of 1 M, 69.5 mmol) in anhydrous THF. The
reaction mixture was heated under reflux for 4 h. Then
water was added and the mixture was neutralized with 20%
sulfuric acid solution. A white solid was filtered off. The
filtrate was evaporated off. Resulting solid was crystallized
from methanol to give 2 g (30.7%) of colourless crystals;
m.p. 185–186 8C; IR (KBr, cm21): 3270 (board, O–H),
2935, 2872, 2832, 1453, 1377, 1271, 1224, 1163, 1086,
1033, 740, 686; 1H NMR (DMSO-d6), d : 2.06 (s, 6H, CH3),
2.09 (s, 6H, CH3), 2.61 (s, 4H, CH2), 3.35 (d, J ¼ 5:2 Hz
4H, OCH2), 4.52 (t, J ¼ 5:2 Hz, 2H, OH); 13C NMR
(DMSO-d6), d : 15.5, 16.1, 37.4, 48.0, 64.8, 128.5, 131.6,
137.7.
2.1.7. Spiro[2H-(7-methylbenzo)[f ]-3,4-dihydro-1,5-
dioxepine-3,20-indan] (7)
A mixture of cellosolve (13 ml), sodium (0.31 g,
13.5 mmol), 4-methylcatechol (0.87 g, 7.0 mmol) and
bistosylate of 2,2-bis(hydroxymethyl)-indan (3.00 g,
7.0 mmol) in sealed tube was heated at 120 8C for 80 h.
After opening the tube and evaporation of the solvent the
residue was dissolved in toluene and sodium tosylate was
filtered off. The product 7 was chromatographed on Al2O3
using toluene as an eluent. Colourless crystals (chloroform–
methanol); 210 mg (11%); m.p. 104–106 8C; IR (KBr,
cm21): 3067, 3022, 2961, 2941, 2882, 2851 (CH2), 1503,
1482, 1460, 1386, 1308, 1272, 1251, 1197, 1107, 1038,
1017, 922, 859, 816, 742; 1H NMR (CDCl3), d : 2.25 (s, 3H,
CH3), 2.96 (s, 4H, CH2), 4.01 (s, 2H, OCH2), 4.02 (s, 2H,
OCH2), 6.73 (dd, J ¼ 1:7 Hz, J ¼ 8:0 Hz, 1H, arom.H),
6.81 (d, J ¼ 1:7 Hz, 1H, arom.H), 6.88 (d, J ¼ 8:0 Hz, 1H,
arom.H), 7.15–7.21 (m, 4H, arom.H); 13C NMR (CDCl3),
d : 20.5, 39.5, 49.6, 78.7, 78.8, 121.1, 121.9, 124.0, 125.0,
126.7, 133.2, 141.1, 149.1, 151.0.
2.1.4. 2,2-Bis(hydroxymethyl)-5-t-butyl-indan (4)
Colourless crystals (methanol); yield 31.4%; m.p. 123–
124 8C; IR (KBr, cm21): 3285 (broad, O–H), 2962, 2871,
2837, 1495, 1380, 1362, 1082, 1048, 1018, 887, 824, 717,
604; 1H NMR (CDCl3), d : 1.30 (s, 9H, tert-butyl), 2.78 (s,
2H, CH2), 2.82 (s, 2H, CH2), 2.93 (broad s, 2H, OH), 3.74 (s,
4H, OCH2), 7.10 (d, J ¼ 7:9 Hz, 1H, arom.H), 7.17–7.20
(m, 2H, arom.H); 13C NMR (CDCl3), d : 31.6, 34.5, 38.1,
38.6, 49.0, 69.5, 121.9, 123.6, 124.4, 138.5, 141.4, 149.7.
Spiro compounds 8, 9, 10, 11 and 12 were obtained
according to procedures as described for 7.
2.1.5. Bistosylate of 2,2-bis(hydroxymethyl)-4,5,6,7-
tetramethyl -indan (5)
2.1.8. Spiro[2H-(7-methylbenzo)[f ]-3,4-dihydro-1,5-
dioxepine-3,20-(40,50,60,70-tetramethyl)-indan) (8)
Compound 3 (2.0 g, 8.6 mmol) was dissolved in dry
pyridine (10 ml). Toluene-4-sulfonyl chloride (3.5 g,
18.0 mmol) was added in small portions to cooled and
stirred solution of 3. The resulting solution was stirred
overnight at room temperature and poured into cold
hydrochloric acid (1:1). Colourless solid was filtered off,
washed with water to pH7 and dried under vacuum. Crude
product was crystallized from methanol to give 4.34 g
(93.7%); m.p. 156–157 8C; IR (KBr, cm21): 3068, 2953,
2923, 2898, 2848 (CH2, CH3), 1596, 1465, 1376, 1359,
1176 (SO2), 1095, 985, 966, 831, 791, 665; 1H NMR
(CDCl3), d : 2.04 (s, 6H, CH3), 2.14 (s, 6H, CH3), 2.45 (s,
6H, CH3), 2.69 (s, 4H, CH2), 3.95 (s, 4H, OCH2), 7.33 (d,
J ¼ 8:0 Hz, 4H, arom.H) 7.74 (d, J ¼ 8:0 Hz, 4H, arom.H);
13C NMR (CDCl3), d : 16.0, 16.4, 21.6, 38.1, 45.4, 71.7,
127.9, 129.7, 129.9, 132.6, 133.8, 135.4, 145.0.
Colourless crystals (chloroform–methanol); yield
35.7%; m.p. 107–109 8C; IR (KBr, cm21): 2921, 2865
(CH2), 1577, 1505, 1448, 1389, 1292, 1261, 1199, 1095,
1036, 1015, 922, 867, 818, 800, 756; 1H NMR (CDCl3), d :
2.17 (s, 6H, CH3), 2.20 (s, 6H, CH3), 2.26 (s, 3H, CH3), 2.94
(s, 4H, CH2), 4.02 (s, 2H, OCH2), 4.03 (s, 2H, OCH2), 6.74
(dd, J ¼ 2:0 Hz, J ¼ 8:1 Hz, 1H, arom.H), 6.82 (d,
J ¼ 2:0 Hz, 1H, arom.H) 6.88 (d, J ¼ 8:1 Hz, 1H,
arom.H); 13C NMR (CDCl3), d : 16.0, 16.5, 20.5, 39.4,
48.1, 79.3, 79.4, 121.1, 121.9, 124.0, 129.9, 133.3, 133.5,
136.9, 149.2, 151.1.
2.1.9. Spiro[2H-(7-methylbenzo)[f ]-3,4-dihydro-1,5-
dioxepine-3,20-(50-t-butyl)-indan) (9)
Colourless crystals (chloroform–methanol); yield
20.2%; m.p. 102–104 8C; IR (KBr, cm1): 3010, 2960,
2900, 2856 (CH2), 1505, 1436, 1388, 1363, 1289, 1261,
1170, 1064, 1032, 1013, 916, 885, 826, 759; 1H NMR
(CDCl3), d : 1.31 (s, 9H, tert-butyl), 2.56 (s, 3H, CH3), 2.92
(s, 2H, CH2), 2.97 (s, 2H, CH2), 4.02 (AB, J ¼ 12:0 Hz, 2H,
OCH2), 4.03 (AB, J ¼ 12:0 Hz, 2H, OCH2), 6.73 (dd,
J ¼ 2:0 Hz, J ¼ 8:0 Hz, 1H, arom.H), 6.80 (d, J ¼ 2:0 Hz,
1H, arom.H), 6.87 (d, J ¼ 8:0 Hz, 1H, arom.H), 7.13 (d,
2.1.6. Bistosylate of 2,2-bis(hydroxymethyl)-
5-t-butyl-indan (6)
Colourless crystals (methanol); yield 91.9%; m.p. 107–
108 8C; IR (KBr, cm21): 3055, 2954, 2902, 2862 (CH2,
CH3), 1598, 1496, 1456, 1362, 1176 (SO2), 1095, 964, 853,
787, 666; 1H NMR (CDCl3), d : 1.28 (s, 9H, tert-butyl), 2.44