Bis 2,2ꢀ-Bipyridine Alkyl Sulfoxides
1253
3a: Yellow oil. Method A: [α]D = −99 (c 1.9, CH2Cl2); Method B:
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[α]D = +148 (c 1.1, CH2Cl2); H NMR (400 MHz, CDCl3): δ = 2.67 (s,
CH3), 2.92 (s, CH3), 7.24 (d, J = 5.5 Hz, pyridine-H), 7.63 (t, J = 7.8 Hz,
pyridine-H), 8.01–8.14 (m, pyridine-H), 8.55 (d, J = 6.5 Hz, pyridine-H);
13C NMR (100 MHz, CDCl3): δ = 13.1 (CH3), 41.3 (CH3), 116.4, 119.0,
121.7, 122.3, 136.6, 138.7, 154.0, 156.0, 159.4, 165.4. HRMS (CI): Calcd
for C12H12ON2S2, 264.03910; Found: 264.03909.
3b: Yellow oil. Method A: [α]D = −127.6 (c 2.4, CH2Cl2); Method B:
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[α]D = +138 (c 1.1, CH2Cl2); H NMR (400 MHz, CDCl3): δ = 1.22 (t,
J = 7.4 Hz, CH3), 1.44 (t, J = 7.4 Hz, CH3), 2.99 (q, J = 7.2 Hz, CH2),
3.23 (q, J = 7.2, CH2), 7.1 (d, J = 8.2, pyridine-H), 7.5 (t, J = 7.8 Hz,
pyridine-H), 7.94–8.06 (m, pyridine-H), 8.47 (d, J = 1.6 Hz, pyridine-
H); 13C NMR (100 MHz, CDCl3): δ = 5.4 (CH3), 14.5 (CH3), 24.4 (CH2),
47.4 (CH2), 116.5, 120.0, 121.4, 136.6, 138.4, 154.1, 156.0, 158.9, 163.4;
HRMS (CI) Calcd for C12H12ON2S2, 292.07041, Found 292.06918.
3c: Yellow oil. Method A: [α]D = −179 (c 0.6, CH2Cl2); Method B:
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[α]D = +148 (c 1.2, CH2Cl2); H NMR (400 MHz, CDCl3): δ = 1.05 (d,
J = 6.7 Hz, CH3), 1.46 (d, J = 7 Hz, CH3), 3.24 (sept, J = 6.9 Hz, CH),
4.12 (sept, J = 6.8 Hz, CH), 7.21 (t, J = 10.3 Hz, pyridine-H), 7.6 (t,
J = 7.7 Hz, pyridine-H), 7.91–8.12 (m, pyridine-H), 8.39 (d, J = 7.51 Hz,
pyridine-H); 13C NMR (100 MHz, CDCl3): δ = 12.7 (CH3), 16.9 (CH3),
22.9 (CH3), 23.2 (CH3), 42.0 (CH), 52.9 (CH), 116.5, 119.8, 120.4, 123.2,
136.6, 138.2, 154.3, 155.9, 159.2, 163.2; CI-MS (M+1)+321.
3d: White oil. Method A: [α]D = +17 (c 0.61, CH2Cl2); Method B:
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[α]D = −43.7 (c 0.6, CH2Cl2); H NMR (400 MHz, CDCl3): δ = 1.22 (t,
J = 7.1 Hz, CH3), 4.00 (AB, J = 24.2 Hz, CH2), 4.16 (s, CH2), 4.06–4.36
(m, CH2), 7.28 (d, J = 9.4 Hz, pyridine-H), 7.64 (t, J = 7.1 Hz, pyridine-
H), 7.99–8.11 (m, pyridine-H), 8.52 (d, J = 7.3 Hz, pyridine-H), 13C
NMR (100 MHz, CDCl3): δ = 14.5 (CH3), 14.1 (CH3), 32.6 (CH2), 58.6
(CH2), 61.6 (CH2), 62.0 (ester carbon atom), 117.2, 120.1, 122.3, 122.7,
137.7, 138.9, 154.0, 155.8, 164.9, 169.5; CI-MS (M+1)+409.
3e: White oil. Method A: [α]D = −129 (c 1.1, CH2Cl2); Method B:
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[α]D = +19 (c 1.0, CH2Cl2); H NMR (400 MHz, CDCl3): δ = 4.29 (AB,
J = 51.7 Hz, CH2), 4.58 (s, CH2), 7.00–7.18 (m, phenyl-H), 7.20–7.28 (m,
arom-H), 7.32–7.49 (m, phenyl-H), 7.60–7.97 (m, pyridine-H), 11.00 (d,
J = 7.5 Hz, pyridine-H), 8.44 (d, J = 7.3 Hz, pyridine-H), 13C NMR (100
MHz, CDCl3): δ = 34.4 (CH2), 60.1 (CH2), 117.0, 120.4, 121.7, 122.7,
127.1, 128.1, 128.3, 128.5, 128.7, 129.3, 130.3, 136.9, 137.9, 138.4, 154.2,
155.6, 158.5, 163.2; HRMS Calcd for C24H20N2OS2|416.10170, Found
416.10089.
4a: White solid. mp 134◦C, Method A: [α]D = −165 (c 0.3, CH2Cl2);
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Method B: [α]D = +389 (c 0.33, CH2Cl2); H NMR (400 MHz, CDCl3):