4324
F. Nador et al. / Tetrahedron 66 (2010) 4318e4325
734 cmꢂ1
;
1H NMR (300 MHz, CDCl3)
d
2.88 (t, J¼7.3 Hz, 2H, CH2),
CH2), 1.78e1.86 (m, 2H, CH2), 2.41 (t, J¼6.4 Hz, 2H, CH2), 2.71 (t,
J¼6.1 Hz, 2H, CH2), 3.41 (s, 2H, NH2), 6.46e6,53 (m, 2H, 2ꢃCH), 6.92
3.19 (t, J¼7.3 Hz, 2H, CH2), 7.11e7.26 (m, 3H, 3ꢃCH), 7.32e7.44 (m,
2H, 2ꢃCH), 7.68e7.90 (m, 4H, 4ꢃCH), 8.02 (d, J¼7.7 Hz, 1H); 13C
(t, J¼7.6 Hz, 1H, CH); 13C NMR (75 MHz, CH3OD)
d 23.2, 23.5, 24.0,
NMR (75 MHz, CDCl3)
d
23.8, 28.6, 122.3, 123.7, 124.1, 125.4, 126.1,
30.1,113.0,119.7,122.5,125.8,137.7,144.8; MS-EI (m/z): 147 (Mþ, 59%),
146 (25), 132 (14), 131 (13), 130 (16), 119 (100), 118 (32), 115 (12), 106
(12), 91 (19), 77 (13), 65 (10), 51 (10), 39 (13). HRMS-EI (m/z): [M]þ
calcd for C10H13N, 147.1048; found 147.1051.
127.0,127.3,127.8,128.5,131.4,131.7,132.8,133.1,135.0,136.9; MS-EI
(m/z): 230 (Mþ, 100%), 229 (76), 228 (42), 227 (14), 226 (23), 215
(23), 202 (14), 114 (11). HRMS-EI (m/z): [M]þ calcd for C18H14
,
230.1096; found 230.1098.
4.4.11. 1,2,2a,5-Tetrahydroacenaphthylene (3h)33. Pale yellow oil; IR
(film) 3070, 3023, 2962, 2830, 1670, 1632, 1458, 750 cmꢂ1; 1H NMR
(300 MHz, CDCl3) d: 1.56e1.88 (m, 2H, CH2), 2.32e2.56 (m, 2H,
4.4.5. 9,10-Dideuterio-9,10-dihydroanthracene (d2-2b)29. White solid,
mp 69e72 ꢁC; IR (KBr) 3058, 3027, 2953, 2925, 2828, 1474, 1450, 746,
726, 715 cmꢂ1
;
1H NMR (300 MHz, CDCl3)
d
3.93e3.95 (m, 2H,
CH2), 3.30 (br s, 3H, CH2, and CHalkylic), 5.96 (br s, 2H, 2ꢃCHvinylic),
2ꢃCDH), 7.18e7.22 (m, 4H, 4ꢃCH), 7.27e7.31 (m, 4H, 4ꢃCH); 13C
6.80e7.00 (m, 3H, 3ꢃCH); 13C NMR (75 MHz, CDCl3)
d: 29.5, 32.0,
NMR (75 MHz, CDCl3)
d
35.7 (t, JCeD¼19.5 Hz, 2ꢃCD), 126.0, 127.3,
34.1, 41.0, 121.5, 124.0, 126.0, 126.3, 130.4, 132.3, 141.8, 142.9; MS-EI
(m/z): 156 (Mþ, 85%),155 (100),154 (15),153 (31),152 (26),141 (60),
129 (27), 128 (91), 127 (24), 115 (37). HRMS-EI (m/z): [M]þ calcd for
C12H12, 156.0939; found 156.0945.
136.6; MS-EI (m/z): 182 (Mþ, 100%), 181 (90), 180 (55), 179 (26), 178
(14), 167 (23), 166 (13), 154 (16), 153 (19), 90 (17), 77 (14), 76 (12), 63
(15), 51 (11). HRMS-EI (m/z): [M]þ calcd for C14H10D2,182.1065; found
182.1069.
4.4.12. 5,8-Dihydro-1-naphthalenol (3i)34. Brown solid, mp 70e72 ꢁC;
4.4.6. 1,2,3,4-Tetrahydroquinoline (2e)30. Pale yellow oil; IR (film)
IR (KBr) 3338, 3017, 2840, 1666, 1627, 1462, 1227, 785 cmꢂ1; 1H NMR
3407, 3053, 3016, 2928, 2867, 1607, 1505, 1311, 747 cmꢂ1
;
1H NMR
(300 MHz, CDCl3)
d
3.13 (d, J¼5.5 Hz, 2H, CH2), 3.23 (d, J¼5.6 Hz, 2H,
(300 MHz, CDCl3)
d
1.92 (q, J¼8.0 Hz, 2H, CH2), 2.72 (t, J¼8.0 Hz, 2H,
CH2), 5.19 (br s, 1H, OH), 5.70e5.78 (m, 2H, 2ꢃCHvinylic), 6.44
(d, J¼7.8 Hz, 1H, CH), 6.55 (d, J¼7.6 Hz, 1H, CH), 6.86 (t, J¼7.7 Hz, 1H,
CH2), 3.25 (t, J¼8.0 Hz, 2H, CH2), 3.62 (s, 1H, NH), 6.35e7.10 (m, 4H,
4ꢃCH); 13C NMR (75 MHz, CDCl3)
d
22.1, 26.9, 41.9, 114.4, 116.9,
CH); 13C NMR (75 MHz, CDCl3)
d 23.8, 29.3, 112.0, 120.7, 121.2, 123.7,
121.4, 126.6, 129.4, 144.7; MS-EI (m/z): 133 (Mþ, 84%), 132 (100), 130
(12), 118 (21), 117 (18), 105 (35), 104 (13), 51 (10), 39 (12). HRMS-EI
(m/z): [M]þ calcd for C9H11N, 133.0891; found 133.0883.
124.2, 126.3, 135.6, 153.0; MS-EI (m/z): 146 (Mþ, 100%), 145 (64), 131
(57), 129 (10), 128 (17), 127 (40), 117 (33), 116 (18), 115 (57), 91 (17), 89
(12), 77 (12), 63 (18), 51 (17). HRMS-EI (m/z): [M]þ calcd for C10H10O,
146.0732; found 146.0725.
4.4.7. 1,2,3,4-Tetrahydro-1,10-phenanthroline (2f)30. Pale yellow oil;
IR (film) 3410, 3045, 2930, 2780, 1617, 1540, 1468, 1210, 940 cmꢂ1
;
4.4.13. 1,4-Dihydronaphthalene (3a)35. Colorless oil; IR (film) 3062,
1H NMR (300 MHz, CDCl3)
d
1.88e2.08 (m, 2H, CH2), 2.82 (t,
3030, 2981, 2866, 2821, 1666, 1580, 1497, 1456, 1426, 1183, 1041,
J¼6.0 Hz, 2H, CH2), 3.41e3.45 (m, 2H, CH2), 5.85 (br s, 1H, NH), 6.87
(d, J¼8.1 Hz, 1H, CH), 7.05 (d, J¼8.0 Hz, 1H, CH), 7.15e7.20 (m, 1H,
CH), 7.89 (d, J¼8.0 Hz, 1H, CH), 8.57e8.60 (m, 1H, CH); 13C NMR
998, 920, 745 cmꢂ1
;
1H NMR (300 MHz, CDCl3)
d
3.78 (s, 4H,
2ꢃCH2), 6.30e6.33 (m, 2H, 2ꢃCHvinylic), 7.44e7.49 (m, 4H, 4ꢃCH);
13C NMR (75 MHz, CDCl3)
d 29.7, 124.7, 125.8, 128.3, 134.2; MS-EI
(75 MHz, CDCl3)
d
26.8, 30.2, 47.0, 113.4, 116.4, 121.2, 125.5, 127.8,
(m/z): 130 (Mþ, 100%), 129 (74), 128 (45), 127 (17), 115 (38), 51 (10).
HRMS-EI (m/z): [M]þ calcd for C10H10, 130.0783; found 130.0790.
136.0, 136.8, 139.9, 155.8; MS-EI (m/z): 184 (Mþ, 80%), 183 (100), 181
(14),169 (22),168 (14),156 (24),155 (15),154 (14),129 (17),128 (16).
HRMS-EI (m/z): [M]þ calcd for C12H12N2, 184.1000; found 184.0994.
4.4.14. 5,8-Dihydro-1-naphthalenamine (3k)36. Orange solid; mp
37e38 ꢁC; IR (KBr) 3470, 3385, 3050, 2853, 1652, 1630, 1470,
4.4.8. 2-(1,2,3,4-Tetrahydro-2-naphthalenyl)-1H-indole (2g). Red-
dish-brown semi-solid; IR (film) 3409, 3076, 2963, 2920, 1642,
761 cmꢂ1 1H NMR (300 MHz, CDCl3)
; d 3.09e3.12 (m, 2H, CH2),
3.40e3.45 (m, 2H, CH2), 3.58e3.68 (m, 2H, NH2), 5.92 (br s, 1H,
CHvinylic), 5.95 (br s, 1H, CHvinylic), 6.56 (d, J¼7.8 Hz, 1H, CH), 6.59 (d,
J¼7.8 Hz, 1H, CH), 7.01 (t, J¼7.6 Hz, 1H, CH); 13C NMR (75 MHz,
1619, 1262, 1095, 796 cmꢂ1
;
1H NMR (300 MHz, CDCl3)
d
2.29e237 (m, 2H, CH2), 2.93e2.99 (m, 3H, AreCH2 and CH),
3.43e3.45 (m, 2H, AreCH2), 6.31 (br s, 1H, CHindole), 7.09e7.21 (m,
8H, AreCH), 7.55 (br s, 1H, NH); 13C NMR (75 MHz, CDCl3)
28.8,
CDCl3)
d 25.0, 29.6, 112.4, 118.9, 119.2, 123.1, 124.7, 126.4, 134.5,
d
143.7; MS-EI (m/z): 145 (Mþ, 77%), 144 (100), 143 (28), 130 (49), 128
(23), 127 (27), 117 (16), 116 (15), 115 (44), 91 (12), 89 (16), 77 (14), 65
(13), 63 (21), 52 (13), 51 (19), 39 (22). HRMS-EI (m/z): [M]þ calcd for
C10H11N, 145.0891; found 145.0901.
29.3, 33.8, 35.5, 98.1, 110.4, 119.6, 119.9, 121.1, 125.7, 125.9, 128.5,
128.9, 129.0, 135.5, 135.7, 136.0, 143.5; MS-EI (m/z): 247 (Mþ,
80%), 246 (15), 232 (23), 218 (21), 217 (14), 143 (100), 131 (50), 130
(77), 129 (23), 128 (19), 118 (21), 117 (79), 116 (14), 115 (42), 104
(22), 103 (19), 89 (21), 78 (20), 77 (20). HRMS-EI (m/z): [M]þ calcd
for C18H17N, 247.1361; found 247.1358.
Acknowledgements
We thank the CONICET (Consejo Nacional de Investigaciones
Científicas y Técnicas, Project PIP 5104) and SGCyT-UNS (Secretaría
General de Ciencia y Tecnología-Universidad Nacional del Sur,
Project 24/Q026) from Argentina for financial support. F.N. thanks
CIC (Comisión de Investigaciones Científicas) from Argentina for
a doctoral fellowship. We are grateful to Prof. L. Bengochea (UNS)
for XRD analysis. This work was also supported by the Spanish
Ministerio de Educación y Ciencia (MEC; grant no. CTQ2007-65218
and Consolider Ingenio 2010-CSD2007-00006) and the Generalitat
Valenciana (grant no. PROMETEO/2009/039).
4.4.9. 1,2,2a,3,4,5-Hexahydroacenaphthylene (2h)31. Pale yellow oil;
IR (film) 3039, 3021, 2926, 2866, 2839, 1606, 1474, 1460, 1449, 823,
760 cmꢂ1 1H NMR (300 MHz, CDCl3)
; d 1.17e1.30 (m, 1H, CHH),
1.48e1.62 (m, 1H, CHH), 1.71e1.86 (m, 1H, CHH), 2.04e2.19 (m, 2H,
2ꢃCHH), 2.28e2.36 (m, 1H, CHH), 2.63e2.94 (m, 5H, 2ꢃCH2 and
CHalkylic), 6.90e6.93 (m, 1H, CH), 7.04e7.12 (m, 2H, 2ꢃCH); 13C NMR
(75 MHz, CDCl3) d 23.8, 26.4, 29.3, 31.9, 35.1, 42.1, 121.1, 125.0, 126.4,
134.0, 143.1, 144.7; MS-EI (m/z): 158 (Mþ, 23%), 130 (100), 129 (47),
128 (31), 115 (40). HRMS-EI (m/z): [M]þ calcd for C12H14, 158.1096;
found 158.1094.
References and notes
4.4.10. 5,6,7,8-Tetrahydro-1-naphthalenamine (2k)32. Reddish-brown
solid, mp 38e40 ꢁC; IR (film) 3530, 3470, 3050, 2950, 2850, 1630,
1. (a) Keith, L. H.; Telliard, W. A. Environ. Sci. Technol. 1979, 13, 416e423; (b)
Holland, P. T.; Hickey, C. W.; Roper, D. S.; Trower, T. M. Arch. Environ. Contam.
1600, 1470, 768 cmꢂ1; 1H NMR (300 MHz, CDCl3)
d 1.70e1.77 (m, 2H,