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K. Nishiwaki et al. / Bioorg. Med. Chem. 15 (2007) 2856–2859
Table 1. Yields of 1-aryl-3,3-dialkyltriazenes
J = 9.0 Hz, 2H), 7.49 (d, J = 9.0 Hz, 2H), 3.83 (s, 4H),
1.72 (s, 6H); 13C NMR (CDCl3) d: 153.76, 127.25
(q, J = 32.3 Hz), 125.97 (q, J = 3.7 Hz), 125.28 (q,
J = 269.8 Hz), 120.65, 48.28, 25.39, 24.34; IR (neat)
cmꢀ1: 2900 (S), 2850 (S), 1650 (s), 1400 (w), 1260 (w),
1220 (w), 1060 (w), 950 (m), 920 (w); MS (EI) (m/z,
%): 257 (M+, 22), 238 (5.2), 173 (33), 145 (100), 125
(6.7), 84 (10); HRMS (m/z): 257.1141 (Calcd for
C12H14F3N3, 257.1140).
Entry
1
Structure
Compound
Yield (%)
92
N
N
N
N
N
N
N
N
4
F3C
2
3
5
6
79
F3C
4.3.4. 1-(4-Fluorophenyl)-3,3-dimethyltriaz-1-ene (7).
1
Yellow oil, 83%; H NMR (CDCl3) d: 7.38 (m, 2H),
47
7.05 (m, 2H), 3.32 (br s, 6H); 13C NMR (CDCl3) d:
160.92 (d, J = 243.5 Hz), 147.43, 121.75 (d,
J = 8.5 Hz), 115.28 (d, J = 22.6 Hz), 38.96; IR (neat)
cmꢀ1: 2850 (m), 1645 (m), 1425 (s), 1300 (s), 1190 (m),
1050 (br m), 810 (m); MS (EI) (m/z, %): 167 (M+, 18),
123 (27), 95 (75), 75 (13), 58 (33), 43 (100); HRMS
(m/z): 167.0849 (Calcd for C8H10FN3, 167.0859).
N
N
F3C
F
N
N
4
7
83
N
N
N
4.3.5. 1-(4-Chlorophenyl)-3,3-dimethyltriaz-1-ene (8).
Yellow crystal, Quant.; mp 56 ꢁC (recryst from hexane);
1H NMR (CDCl3) d: 7.35 (m, 2H), 7.27 (m, 2H), 3.33
(br s, 6H); 13C NMR (CDCl3) d: 149.48, 130.42, 128.81,
121.65, 42.14; IR (KBr) cmꢀ1: 2850 (m), 1645 (m),
1425 (s), 1300 (s), 1190 (m), 1050 (br m), 810 (m); MS
(EI) (m/z, %): 183 (M+, 25), 139 (43), 111 (100), 75
(23); HRMS (m/z): 183.0552 (Calcd for C8H10ClN3,
183.0563).
5
8
Quant.
Cl
N
N
N
N
6
9
85
N
N
N
7
10
11
12
13
14
83
N
4.3.6. 1-(2,6-Dimethylphenyl)-3,3-dimethyltriaz-1-ene (9).
Brown oil, 85%; 1H NMR (CDCl3) d: 6.98 (m, 3H), 3.30
(s, 6H), 2.17 (s, 6H); 13C NMR (CDCl3) d: 148.91,
8
82
N
N
130.07, 128.39, 124.62, 38.87, 18.37; IR (neat) cmꢀ1
:
2900 (m), 1460 (s), 1400 (s), 1300 (s), 1190 (w), 1070
(s), 760 (m); MS (EI) (m/z, %): 177 (M+, 25), 139 (43),
111 (100), 75 (23); HRMS (m/z): 177.1261 (Calcd for
C10H15N3, 177.1266).
N
N
N
9
91
N
N
N
4.3.7. 1-((2,6-Dimethylphenyl)diazenyl)pyrrolidine (10).
1
N
N
Brown oil, 83%; H NMR (CDCl3) d: 6.96 (m, 3H),
10
11
77
3.75 (t, J = 6.5 Hz, 4H), 2.19 (s, 6H), 2.01 (m, 4H);
13C NMR (CDCl3) d: 149.14, 129.99, 128.28, 124.42,
48.29, 23.81, 18.44; IR (neat) cmꢀ1: 2950 (m), 1580
(w), 1420 (s), 1320 (s), 1200 (m), 1150 (m), 1090 (m),
1020 (w), 760 (m) ; MS (EI) (m/z, %): 203 (M+, 14),
174 (8.5), 133 (24), 105 (100), 91 (22), 79 (28); HRMS
(m/z): 203.1418 (Calcd for C12H17N3, 203.1422).
64
4.3.2. 1-((4-(Trifluoromethyl)phenyl)diazenyl)pyrrolidine
(5). Yellow crystal, 79%; mp 104–107 ꢁC (recryst from
4.3.8. 1-((2,6-Dimethylphenyl)diazenyl)piperidine (11).
Brown oil, 82%; H NMR (CDCl3) d: 6.98 (m, 3H),
1
1
hexane); H NMR (CDCl3) d: 7.56 (d, J = 9.0 Hz, 2H),
3.72 (t, J = 5.5 Hz, 4H), 2.18 (s, 6H), 1.68 (m, 6H);
13C NMR (CDCl3) d: 148.79, 129.87, 128.32, 124.70,
47.90, 25.05, 24.46, 18.40; IR (neat) cmꢀ1: 2900 (s),
1740 (m), 1590 (w), 1440 (s), 1360 (s), 1290 (s), 1260
(m), 1160 (s), 1090 (s), 980 (m), 850 (m), 760 (m); MS
(EI) (m/z, %): 217 (M+, 8), 133 (24), 105 (100), 91 (52),
77 (19); HRMS (m/z): 217.1584 (Calcd for C13H19N3,
217.1579).
7.48 (d, J = 9.0 Hz, 2H), 3.93 (br s, 2H), 3.70 (br s,
2H), 2.05 (s, 4H); 13C NMR (CDCl3 at 60 ꢁC) d:
154.26, 126.75 (q, J = 32.4 Hz), 125.90 (q, J = 3.7 Hz),
124.63 (q, J = 264.3 Hz), 120.49, 48.92, 23.67; IR (Nu-
jol) cmꢀ1: 2850 (s), 1600 (m), 1470 (w), 1300 (m), 1090
(w), 1060 (w), 830 (m); MS (EI) (m/z, %): 243 (M+,
12), 173 (16), 145 (100), 125 (4.5), 95 (5.8); HRMS
(m/z): 243.0972 (Calcd for C11H12F3N3, 243.0983).
4.3.9. 1-Mesityl-3,3-dimethyltriaz-1-ene (12). Brown oil,
1
4.3.3. 1-((4-(Trifluoromethyl)phenyl)diazenyl)piperidine
91%; H NMR (CDCl3) d: 6.83 (s, 2H), 3.29 (s, 6H),
(6). Brown oil, 47%; 1H NMR (CDCl3) d: 7.58 (d,
2.25 (s, 3H), 2.14 (s, 6H); 13C NMR (CDCl3) d: 146.39,