M. Ghiaci et al. / Tetrahedron 61 (2005) 5529–5534
5533
3.5. Dichlorocarbene addition to cyclooctene
29.4; 29.7; 30.2; 31.9, 53.8, 130.7. MS (EI), m/z (%): 283
(MC, 0.6), 251 (17.6), 250 (86.1), 115 (91.9), 83 (17), 72
(20.9), 69 (38.3), 57 (44.1), 55 (88.5), 43 (92.6), 41 (99.1),
29 (45.3). Anal. Calcd for C17H33NS: C, 72.08; H, 11.66; N,
4.95; S, 11.31. Found: C, 72.21: H, 11.76; N, 4.89; S, 11.26.
Cyclooctene (2 ml, 7.7 mmol) dissolved in 25 ml of
chloroform was added to 25 ml of 50% aqueous sodium
hydroxide solution, plus 1a-clay (0.5 g) contained in a
Morton flask. After addition of an internal standard
(n-dodecane) the mixture was stirred with a mechanical
stirrer and allowed to remain at 58 8C for 24 h. Analysis of
the organic phase by GLC (SE-30 column) indicated a 96%
yield of 9,9-dichlorobicyclo[6.1.0]nonane.
3.6.6. n-Cetyl cyanide.26 1H NMR (300 MHz, CDCl3): d
0.96 (3H), 1.29 (24H), 1.33 (2H), 1.66 (2H), 2.41 (2H).13C
NMR (75 MHz, CDCl3): d 14.1, 17.5, 22.8, 25.5, 28.6, 28.9,
29.4, 29.7, 31.9, 117.7. MS (EI), m/z (%): 208 (9.3), 138
(13.8), 110 (27), 97 (46.1), 96 (22), 70 (26.6), 57 (74.7), 55
(52.5), 43 (99.9), 41 (89.4), 29 (57.5). IR (KBr): 718, 1471,
2245, 2873, 2915, 2948, 2977 cmK1. Anal. Calcd for
C17H33N: C, 81.27; H, 13.15; N, 5.78. Found: C, 81.30; H,
13.18; N, 5.75.
3.6. Displacement of thiocyanate ion on organic halides
Procedures similar to that described for the conversion of
n-cetyl bromide to n-cetyl thiocyanate was followed for all
of the thiocyanate forming reactions described in Table 2.
To a Morton flask containing 0.5 g of 1a-clay was added a
solution of 0.32 g (3.2 mmol) of potassium thiocyanate
dissolved in 25 ml of distilled water followed by 1 ml
(3.2 mmol) of n-cetyl bromide plus 25 ml chloroform.
An internal standard (n-dodecane) was added to the reaction
mixture and the flask was stirred with a mechanical stirrer,
placed in an oil bath maintained at 58 8C for 24 h.
1
3.6.7. n-Cetyl iodide. H NMR (300 MHz, CDCl3): d 0.96
(3H), 1.29 (24H), 1.33 (2H), 1.86 (2H), 3.13 (2H). 13C NMR
(75 MHz, CDCl3): d 6.8, 14.1, 22.8, 28.5, 29.4, 29.7, 30.4,
31.9, 33.6. MS (EI), m/z (%): 225 (10.3), 85 (54.6), 71
(75.5), 57 (99.9), 43 (60.8), 29 (8.6). IR (KBr) 604, 719,
1179, 1204, 1377, 1369, 1377, 1467, 2853, 2918, 2966 cmK1
.
Bp 130 8C/0.2 mm (lit.27 152–154 8C/0.7 mm).
3.6.1. 9,9-Dichloro-bicyclo[6.1.0]nonane.22 1H NMR
(300 MHz, CDCl3): d 1.3 (4H), 1.24 (4H), 1.13 (4H), 0.82
(2H). 13C NMR (75 MHz, CDCl3): d 23.6, 27.4, 28.2, 28.8,
66.1. MS (EI), m/z (%): 192 (MC, 10), 124 (50.7), 122
(84.9), 109 (25.9), 96 (44.3), 81 (99.9), 68 (33.9), 67 (83.6),
55 (63.9), 41 (76.7), 39 (51.6). IR (KBr): 685, 790, 875, 920,
1020, 1050, 1180, 1190, 1465, 1450, 1410, 2798, 2850,
2920 cmK1. Anal. Calcd for C9H14Cl2: C, 55.96; H, 7.25.
Found; C, 55.98; H, 7.29.
3.6.8. 1,6-Diiodohexane. H NMR (300 MHz, CDCl3): d
1.29 (4H), 1.86 (4H), 3.13 (4H). 13C NMR (75 MHz,
CDCl3): d 6.8, 29.2, 33.6. MS (EI), m/z (%): 338 (MC, 0.4),
211 (29.4), 169 (28.5), 155 (45.5), 128 (12.5), 127 (24.9), 83
(61.5), 55 (99.1), 43 (18.1), 41 (88.5), 39 (46.8), 29 (29.2),
27 (60). IR (KBr): 596, 719, 1179, 1216, 1425, 1456, 2950,
2953 cmK1. Bp 72–74 8C/0.2 mm (lit.28 141–142 8C/
10 mm).
1
3.6.9. 1-Bromo-6-iodohexane. 1H NMR (300 MHz,
CDCl3): d 1.29 (4H), 1.79 (2H), 1.86 (2H), 3.13 (2H), 3.3
(2H). 13C NMR (75 MHz, CDCl3): d: 6.8, 26.9, 29.4, 32.7,
33.6, 33.7. MS (EI), m/z (%): 292 (MC, 1.9), 165 (25.7), 163
(25.4), 123 (17.9), 121 (19.1), 109 (16.7), 107 (17.3), 84
(16.3), 83 (98.3), 56 (16.7), 55 (99.9), 43 (80.3), 41 (83.9),
39 (68.7). Anal. Calcd for C6H12BrI: C, 24.74; H, 4.12.
Found: C, 24.71; H, 4.05.
1
3.6.2. 1-Benzyl-2-naphthol. H NMR (300 MHz, CDCl3):
d 4.25 (2H), 5.0 (1H), 6.84 (1H), 7.07 (1H), 7.14 (2H), 7.18
(1H), 7.29 (1H), 7.46 (1H), 7.6 (3H), 7.63 (1H). 13C NMR
(75 MHz, CDCl3): d 118.9, 120.4, 122.5, 123.2, 126.3,
128.3, 129.3, 133.5, 133.9, 141.6, 153.5. IR (KBr): 621,
741, 813, 844, 905, 958, 1172, 1216, 1276, 1406, 1466,
1512, 1600, 1630, 2923, 3050, 3200–3500 (bs) cmK1. Mp
110–112 8C (lit.23 110–111 8C).
3.6.10. 1,6-Dicyanohexane. 1H NMR (300 MHz, CDCl3): d
1.29 (4H), 1.66 (4H), 2.41 (4H). 13C NMR (75 MHz,
CDCl3): d 17.5, 25.5, 27.8, 117.7. MS (EI), m/z (%): 137
(MC, 1.2), 96 (99.9), 83 (16.3), 82 (26.5), 69 (63.4), 68
(16.9), 55 (84.7), 54 (54.5), 42 (34.7), 41 (87.9). IR: 850,
1398, 1440, 2225, 2840, 2950 cmK1. Anal. Calcd for
C8H12N2: C, 70.59; H, 8.82; N, 20.59. Found: C, 70.68; H,
8.91; N, 20.68.
3.6.3. Benzyl-2-naphthyl ether. 1H NMR (300 MHz,
CDCl3): d 5.3 (2H), 6.97 (1H), 7.04 (1H), 7.19 (5H), 7.21
(1H), 7.3 (1H), 7.6 (2H), 7.64 (1H). 13C NMR (75 MHz,
CDCl3): d 70.9, 105.9, 118.8, 124, 126.7, 126.9, 127.2,
127.7, 127.8, 129, 129.5, 129.6, 134.8, 141.2, 157.3. IR
(KBr): 632, 751, 843, 905, 959, 1277, 1378, 1466, 1511,
1630, 1701, 2922, 3055 cmK1. Mp 98–100 8C (lit.23 98–
99.5 8C).
3.6.11. 7-Bromoheptanenitrile. 1H NMR (300 MHz,
CDCl3): d 1.29 (4H), 1.66 (2H), 1.79 (2H), 2.41 (2H), 3.3
(2H). 13C NMR (75 MHz, CDCl3): d 17.5, 25.5, 27.3, 27.6,
32.7, 33.7, 117.7. MS (EI), m/z (%): 190 (MC, 0.2), 110
(99.9), 109 (10.7), 83 (44.9), 82 (44.3), 69 (92.9); 55 (66.2),
54 (47.8), 43 (15.1), 42 (22.9), 41 (87.6), 39 (44.2). Bp 96–
98 8C/2 mm (lit.29 140–141 8C/14 mm).
3.6.4. n-Cetyl thiocyanate.24 1H NMR (300 MHz, CDCl3):
d 0.96 (3H), 1.29 (24H), 1.33 (2H), 1.66 (2H), 2.44 (2H).
13C NMR (75 MHz, CDCl3): d 14.1, 22.8, 28.6, 29, 29.4,
29.7, 29.9, 31.9, 32.1, 117.3. MS (EI), m/z (%): 99 (13.4), 85
(43.7), 71 (63.8), 57 (99.9), 55 (24.2). Anal. Calcd for
C17H33NS: C, 72.08; H, 11.66; N, 4.95; S, 11.31. Found: C,
72.15; H, 11.71; N, 4.91; S, 11.28.
3.6.5. n-Cetyl isothiocyanate.25 1H NMR (300 MHz,
CDCl3): d 0.96 (3H), 1.29 (24H), 1.3 (2H), 1.33 (2H), 3.6
(2H). 13C NMR (75 MHz, CDCl3): d 14.1; 22.8, 26.6; 29;
Acknowledgements
Thanks are due to the Research Council of Isfahan