1
207 ЊC; H NMR (CDCl3) δ 4.44 (s, 1H), 2.34–1.71 (m, 13H)
δ 148.84, 128.41, 126.20, 124.64, 111.86, 44.50, 42.88, 38.16,
and 1.42 (s, 3H); 13C NMR (CDCl3) δ 111.30, 60.35, 49.96,
43.82, 42.19, 37.49, 31.99, 30.90, 30.72 and 20.38; MS m/z
(relative intensity) 294 [(M ϩ 2)ϩ, 5%], 292 (Mϩ, 5), 213 (100),
147 (26), 105 (13), 91 (18) and 77 (10). Calc. for C14H17N2Br: C,
57.35; H, 5.84; N, 9.55. Found: C, 57.42; H, 5.84; N, 9.55%.
35.67, 34.43, 31.79, 31.59, 27.29 and 21.20; MS m/z (relative
intensity) 290 (Mϩ, 100%), 225 (65), 169 (21), 155 (56), 115 (18),
91 (45) and 77 (12). Calc. for C20H22N2: C, 82.71; H, 7.63; N,
9.64. Found: C, 82.38; H, 7.82; N, 9.71%.
(Z)-2-Methyl-2-dicyanomethyl-5-phenyladamantane ((Z)-5-
Ph (Me)). This compound is colorless and the melting point is
(E)-5-Bromo-2-ethyl-2-dicyanomethyladamantane ((E)-5-Br
(Et)). This compound is colorless and the melting point is 145–
1
138–140 ЊC; H NMR (CDCl3) δ 7.36–7.19 (m, 5H), 4.42 (s,
1
146 ЊC; H NMR (CDCl3) δ 4.36 (s, 1H), 2.72–2.13 (m, 11H),
1H), 2.16–1.74 (m, 13H) and 1.50 (s, 3H); 13C NMR (CDCl3)
δ 148.56, 128.46, 126.30, 124.47, 111.71, 45.00, 42.77, 37.72,
35.43, 34.35, 32.01, 31.96, 27.60 and 20.67; MS (EI) m/z (rel int)
290 (Mϩ, 100%), 225 (65), 169 (21), 155 (56), 115 (18), 91 (45)
and 77 (12). Calc. for C20H22N2: C, 82.71; H, 7.63; N, 9.64.
Found: C, 82.62; H, 7.45; N, 9.74%.
2.08 (q, J 7.8, 2H), 1.82 (s, 2H) and 1.16 (t, J 7.8, 3H); 13C NMR
(CDCl3) δ 111.68, 60.93, 50.16, 43.91, 43.53, 36.02, 31.01, 30.66,
28.12, 27.42 and 7.54; MS (EI) m/z (rel int) 308 [(M ϩ 2)ϩ, tr],
306 (Mϩ, tr), 279 (tr), 277 (tr), 227 (2), 197 (100), 155 (15) and
141 (10). Calc. for C15H19N2Br: C, 58.64; H, 6.23; N, 9.12.
Found: C, 58.71; H, 6.36; N, 8.86%.
(E)-2-Ethyl-2-dicyanomethyl-5-phenyladamantane ((E)-5-Ph
(Et)). This compound is colorless and the melting point is 139–
140 ЊC; H NMR (CDCl3) δ 7.36–7.17 (m, 5H), 4.56 (s, 1H),
2.32–1.85 (m, 13H), 2.04 (q, J 7.8, 2H) and 1.16 (t, J 7.8, 3H);
13C NMR (CDCl3) δ 148.98, 128.48, 126.26, 124.70, 112.18,
44.76, 44.58, 37.74, 35.40, 32.79, 32.11, 28.19, 27.58, 27.37 and
7.63; MS (EI) m/z (rel int) 304 (Mϩ, 89%), 276 (46), 239 (63),
155 (100), 91 (41) and 77 (10) (HRMS (EI) Calc. for C21H24N2:
M, 304.1940. Found: 304.1944. Calc.: C, 82.85; H, 7.95; N,
9.20. Found: C, 82.93; H, 7.48; N, 9.41%).
(Z)-5-Bromo-2-ethyl-2-dicyanomethyladamantane ((Z)-5-Br
(Et)). This compound is colorless and the melting point is 163–
164 ЊC; H NMR (CDCl3) δ 4.49 (s, 1H), 2.38–2.08 (m, 11H),
1.95 (q, J 7.8, 2H), 1.74–1.68 (m, 2H) and 1.14 (t, J 7.8, 3H);
13C NMR (CDCl3) δ 111.53, 60.65, 50.23, 44.17, 43.92, 36.13,
30.60, 30.53, 28.56, 26.91 and 7.80; MS (EI) m/z (rel int) 308
[(M ϩ 2)ϩ, tr], 306 (Mϩ, tr), 227 (100), 161 (21) and 105 (5).
Calc. for C15H19N2Br: C, 58.64; H, 6.23; N, 9.12. Found: C,
58.70; H, 6.18; N, 9.07%.
1
1
(E)-5-Bromo-2-dicyanomethyl-2-isopropyladamantane ((E)-5-
Br (i-Pr)). This compound is colorless and the melting point is
(Z)-2-Ethyl-2-dicyanomethyl-5-phenyladamantane ((Z)-5-Ph
(Et)). This compound is colorless and the melting point is
110 ЊC; H NMR (CDCl3) δ 7.39–7.17 (m, 5H), 4.47 (s, 1H),
2.16–1.69 (m, 13H), 2.05 (q, J 7.8, 2H) and 1.17 (t, J 7.8, 3H);
13C NMR (CDCl3) δ 148.67, 128.51, 126.36, 124.55, 112.06,
45.29, 44.47, 37.99, 35.69, 32.77, 31.53, 28.43, 27.33, 26.93 and
7.74; MS (EI) m/z (rel int) 304 (Mϩ, 100%), 276 (12), 239 (70),
155 (75), 91 (31) and 77 (6) (HRMS (EI) Calc. for C 21H24N2:
M, 304.1940. Found: 304.1934. Calc.: C, 82.85; H, 7.95; N,
9.20. Found: C, 82.53; H, 7.29; N, 9.24%).
1
1
134 ЊC; H NMR (CDCl3) δ 4.41 (s, 1H), 2.72–1.85 (m, 14H)
and 1.25 (d, J 7.2, 6H); 13C NMR (CDCl3) δ 112.26, 60.90,
50.45, 45.55, 43.30, 35.26, 31.36, 30.59, 30.24, 24.10 and 16.77;
GC-MS (EI) m/z (rel int) 322 [(M ϩ 2)ϩ, 46], 320 (Mϩ, 52), 241
(100), 207 (17), 169 (8), 149 (24), 131 (19) and 91 (27) (HRMS
(EI) Calc. for C15H18N2Br: M Ϫ 15, 305.0653. Found
305.0653).
(Z)-5-Bromo-2-dicyanomethyl-2-isopropyladamantane ((Z)-5-
Br (i-Pr)). 1H NMR (CDCl3) δ 4.60 (s, 1H), 2.67 (septet, J 7.2,
1H), 2.16–1.66 (m, 13H) and 1.23 (d, J 7.2, 6H); 13C NMR
(CDCl3) δ 112.84, 46.97, 39.37, 33.43, 32.26, 31.36, 30.50, 29.85,
26.75, 24.48 and 17.11; MS (EI) m/z (rel int) 322 [(M ϩ 2)ϩ, tr],
320 (Mϩ, tr), 241 (6), 199 (100), 172 (6), 133 (20) and 91 (17)
(HRMS (EI) Calc. for C16H22N2Br: M ϩ 1, 321.0789. Found
321.0815. Calc.: M Ϫ 1, 319.0851. Found 319.0790).
(E)-5-Bromo-2-dicyanomethyladamantane ((E)-5-Br (H)).
This compound is colorless and the melting point is 187–
189 ЊC; 1H NMR (CDCl3) δ 3.90 (d, J 12.0, 1H) and 2.57–1.65
(m, 14H); 13C NMR (CDCl3) δ 111.83, 60.68, 48.67, 48.63,
44.23, 33.13, 30.87, 28.92 and 25.10; MS (EI) m/z (rel int) 280
[(M ϩ 2)ϩ, 35%], 278 (Mϩ, 35), 199 (60), 108 (45) and 91 (100).
Calc. for C13H15N2Br: C, 55.93; H, 5.41; N, 10.03. Found: C,
56.00; H, 5.44; N, 9.90%.
(E)-2-Benzyl-2-dicyanomethyl-5-phenyladamantane ((E)-5-Ph
(Bz)). This compound is colorless and the melting point is
(Z)-5-Bromo-2-dicyanomethyladamantane ((Z)-5-Br (H)).
This compound is colorless and the melting point is 137–
138 ЊC; 1H NMR (CDCl3) δ 3.96 (d, J 12.2, 1H) and 2.35–1.78
(m, 14H); 13C NMR (CDCl3) δ 111.74, 60.74, 48.76, 44.21, 42.29,
35.83, 33.49, 30.99 and 25.34; MS (EI) m/z (rel int) 280
[(M ϩ 2)ϩ, 15%], 278 (Mϩ, 15), 199 (60), 108 (45) and 91 (100).
Calc. for C13H15N2Br: C, 55.93; H, 5.41; N, 10.03. Found: C,
56.31; H, 5.32; N, 10.05%.
1
178–180 ЊC; H NMR (CDCl3) δ 7.42–7.20 (m, 10H), 4.54 (s,
1H), 3.26 (s, 2H) and 2.62–1.85 (m, 13H); 13C NMR (CDCl3)
δ 148.81, 135.10, 130.72, 128.89, 128.55, 128.11, 126.38, 124.71,
110.92, 46.12, 44.96, 39.25, 37.99, 35.84, 33.08, 32.11, 28.10 and
27.36; MS (EI) m/z (rel int) 366 (Mϩ, 37%), 275 (7), 249 (24),
129 (6), 115 (8) and 91 (100). Calc. for C26H26N2: C, 85.20; H,
7.15; N, 7.64. Found: C, 85.22; H, 7.15; N, 7.68%.
(Z)-2-Benzyl-2-dicyanomethyl-5-phenyladamantane ((Z)-5-Ph
(Bz)). This compound is colorless and the melting point is 200–
(E)-2-Dicyanomethyl-5-phenyladamantane ((E)-5-Ph (H)).
This compound is colorless and the melting point is 167 ЊC; 1H
NMR (CDCl3) δ 7.35–7.22 (m, 5H), 4.02 (d, J 12.0, 1H), 2.46
(d, J 12.0, 1H) and 2.36–1.73 (m, 13H); 13C NMR (CDCl3)
δ 148.84, 128.37, 126.16, 124.69, 112.31, 45.31, 43.15, 42.91,
35.44, 30.06, 29.89, 27.62 and 25.25; MS (EI) m/z (rel int) 276
(Mϩ, 88%), 169 (11), 155 (100), 115 (14), 91 (30) and 77 (8).
Calc. for C19H20N2: C, 82.57; H, 7.29; N, 10.14. Found: C,
82.28; H, 7.57; N, 10.23%.
1
201 ЊC; H NMR (CDCl3) δ 7.44–7.22 (m, 10H), 4.49 (s, 1H),
3.29 (s, 2H) and 2.51–1.86 (m, 13H); 13C NMR (CDCl3)
δ 148.43, 135.30, 130.71, 128.92, 128.56, 128.11, 126.44, 124.54,
110.78, 46.07, 45.38, 38.84, 38.08, 35.54, 33.09, 31.84, 28.35 and
27.73; MS (EI) m/z (rel int) 366 (Mϩ, 37%), 275 (7), 249 (24),
129 (6), 115 (8) and 91 (100). Calc. for C26H26N2: C, 85.20; H,
7.15; N, 7.64. Found: C, 84.62; H, 7.38; N, 7.64%.
(E)-2-Methyl-2-dicyanomethyl-5-phenyladamantane ((E)-5-
Ph (Me)). This compound is colorless and the melting point is
(Z)-2-Dicyanomethyl-5-phenyladamantane ((Z)-5-Ph (H)).
This compound is colorless and the melting point is 145 ЊC; 1H
NMR (CDCl3) δ 7.34–7.20 (m, 5H), 3.95 (d, J 12.0, 1H) and
2.46–1.77 (m, 14H); 13C NMR (CDCl3) δ 148.96, 128.48,
1
148–149 ЊC; H NMR (CDCl3) δ 7.34–7.20 (m, 5H), 4.48 (s,
1H), 2.29–1.77 (m, 13H) and 1.40 (s, 3H); 13C NMR (CDCl3)
J. Chem. Soc., Perkin Trans. 1, 1999, 2383–2390
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