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PAPER
Anal. Calcd for C15H19ClN2: C, 68.56; H, 7.29; N, 10.66. Found: C,
68.81; H, 7.04; N, 10.29.
MS (EI, 70 eV): m/z (%) = 334, 332 (9, 9) [M]+, 318, 316 (5, 5) [M
– CH4]+, 291, 289 (26, 26) [M – C3H7]+, 253 (100) [M – Br]+.
Anal. Calcd for C17H21BrN2: C, 61.27; H, 6.35; N, 8.41. Found: C,
61.51; H, 6.27; N, 8.18.
2-Bromo-6-(diisopropylamino)pyridine (7e)
Slightly colored oil; yield: 78 mg (10%).
1H NMR (400 MHz, CDCl3): d = 1.23 (d, J = 6.9 Hz, 12 H), 4.13
(sept, J = 6.9 Hz, 2 H), 6.24 (d, J = 8.4 Hz, 1 H), 6.68 (d, J = 7.5 Hz,
1 H), 7.24 (dd, J = 8.4 Hz, J = 7.5 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 20.5, 46.2, 106.0, 113.5, 138.3,
139.5, 157.4.
MS (EI, 70 eV): m/z (%) = 258, 256 (19, 19) [M]+, 243, 241 (31, 32)
[M – CH3]+, 215, 213 (71, 71) [M – C3H7]+, 201, 199 (100, 100) [M
– C4H9]+.
HRMS: m/z [M]+ calcd for C11H1779BrN2: 256.0575; found:
256.0541.
2,6-Bis[(2,6-dimethylphenyl)amino]pyridine (7k)
A sealed tube was charged with 2,6-dibromopyridine (2c, 711 mg,
3.0 mmol) and 2,6-dimethylaniline (1.45 g, 12.0 mmol). The mix-
ture was heated in an oil bath to 230 °C for 9 h. The workup was
performed as for 3c to give the product as an off-white solid; yield:
836 mg (88%); mp 174 °C.
1H NMR (300 MHz, CDCl3): d = 2.22 (s, 12 H), 5.31 (d, J = 7.8 Hz,
2 H), 6.30 (br s, 2 H, NH), 7.04–7.14 (m, 7 H).
13C NMR (75 MHz, CDCl3): d = 18.3, 95.0, 126.4, 128.3, 128.4,
136.9, 139.5, 157.2.
MS (EI, 70 eV): m/z (%) = 317 (100) [M]+, 302 (24) [M – CH3]+,
2-Bromo-6-(cis-2,6-dimethylpiperidin-1-yl)pyridine (7g)
197 (17) [M – C8H10N]+.
Slightly yellow oil; yield: 775 mg (96%).
Anal. Calcd for C21H23N3: C, 79.46; H, 7.30; N, 13.24. Found: C,
79.21; H, 7.16; N, 12.97.
1H NMR (300 MHz, CDCl3): d = 1.17 (d, J = 7.2 Hz, 6 H),1.41–
1.70 (m, 6 H), 4.42–4.50 (m, 2 H), 6.39 (d, J = 8.4 Hz, 1 H), 6.62
(d, J = 7.5 Hz, 1 H), 7.21 (dd, J = 8.4 Hz, J = 7.5 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 19.3, 27.3, 31.0, 46.0, 104.8,
114.4, 139.4, 140.7, 158.3.
Acknowledgment
The work was supported by the SFB 624 (German Research Foun-
dation) and the University of Münster.
MS (EI, 70 eV): m/z (%) = 270, 268 (43, 43) [M]+, 255, 253 (100,
100) [M – CH3]+, 213, 211 (33, 33) [M – C4H9]+, 189 (5) [M – Br]+.
Anal. Calcd for C12H17BrN2: C, 53.54; H, 6.37; N, 10.41. Found: C,
53.65; H, 6.59; N, 10.37.
References
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2-Chloro-6-(cis-2,6-dimethylpiperidin-1-yl)pyridine (7h)
Colorless oil; yield: 304 mg (45%).
1H NMR (300 MHz, CDCl3): d = 1.14 (d, J = 7.3 Hz, 6 H), 1.39–
1.68 (m, 6 H), 4.42–4.48 (m, 2 H), 6.33 (d, J = 7.9 Hz, 1 H), 6.51
(d, J = 7.8 Hz, 1 H), 7.23 (dd, J = 7.9 Hz, J = 7.8 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 19.5, 27.2, 31.1, 45.7, 105.8,
111.4, 139.1, 149.7, 157.9.
MS (EI, 70 eV): m/z (%) = 226, 224 (33, 100) [M]+, 211, 209 (32,
100) [M – CH3]+, 181, 179 (10, 32) [M – C4H9]+.
Anal. Calcd for C12H17ClN2: C, 64.13; H, 7.62; N, 12.47. Found: C,
64.41; H, 7.79; N, 12.13.
2-Bromo-6-[(2,6-dimethylphenyl)amino]pyridine (7i)
Brown solid; yield: 466 mg (56%); mp 113 °C.
1H NMR (300 MHz, CDCl3): d = 2.23 (s, 6 H), 5.88 (d, J = 8.4 Hz,
1 H), 6.34 (br s, 1 H, NH), 6.78 (d, J = 7.8 Hz, 1 H), 7.15–7.25 (m,
4 H).
13C NMR (75 MHz, CDCl3): d = 18.3, 103.6, 116.7, 127.3, 128.7,
135.5, 136.9, 139.9, 140.7, 158.4.
MS (EI, 70 eV): m/z (%) = 278, 276 (76, 76) [M]+, 263, 261 (57, 57)
[M – CH3]+, 197 (100) [M – Br]+, 182 (32) [M – CH3Br]+.
Anal. Calcd for C13H13BrN2: C, 56.34; H, 4.73; N, 10.11. Found: C,
56.32; H, 4.60; N, 9.89.
2-Bromo-6-[(2,6-diisopropylphenyl)amino]pyridine (7j)
Brown solid; yield: 201 mg (20%); mp 159 °C.
1H NMR (300 MHz, CDCl3): d = 1.13 (d, J = 6.9 Hz, 12 H), 3.18
(sept, J = 6.9 Hz, 2 H), 5.85 (d, J = 8.3 Hz, 1 H), 6.18 (br s, 1 H,
NH), 6.75 (d, J = 8.3 Hz, 1 H), 7.14 (dd, J = 8.3 Hz, J = 8.3 Hz, 1
H), 7.22 (d, J = 6.6 Hz, 2 H), 7.32 (t, J = 6.6 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 27.9, 28.3, 103.7, 116.5, 124.1,
128.5, 132.4, 139.8, 140.3, 147.8, 159.4.
Synthesis 2009, No. 1, 155–159 © Thieme Stuttgart · New York