Spectroscopic and Theoretical Studies of Some 3-(4′-Substituted phenylsulfanyl)-1-methyl-2-piperidones
Abstract
:1. Introduction
2. Results and Discussion
Compound | Y | n-C6H14 | CCl4 | CHCl3 | CH2Cl2 | CH3CN | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
ν | Pa | ν | Pa | νb | P | ν | P | ν | P | ν | P | |||
1 | NO2 | -c | - | 1660 | 61 | 3300 | 60 | 1648 | 43 | 1656 | 9 | - | - | |
- | - | 1652 | 39 | 3289 | 40 | 1637 | 57 | 1641 | 91 | 1645 | 100 | |||
2 | Br | 1668 | 84 | 1658 | 68 | 3299 | 63 | 1645 | 33 | 1652 | 12 | - | - | |
1656 | 16 | 1650 | 32 | 3291 | 37 | 1635 | 67 | 1641 | 88 | 1644 | 100 | |||
3 | Cl | 1668 | 79 | 1660 | 45 | 3306 | 49 | 1647 | 30 | 1656 | 13 | - | - | |
1656 | 21 | 1652 | 55 | 3292 | 51 | 1635 | 70 | 1641 | 87 | 1644 | 100 | |||
4 | H | 1669 | 83 | 1659 | 62 | 3300 | 59 | 1647 | 32 | 1656 | 9 | - | - | |
1654 | 17 | 1651 | 38 | 3290 | 41 | 1635 | 68 | 1641 | 91 | 1644 | 100 | |||
5 | Me | 1668 | 72 | 1657 | 57 | 3300 | 57 | 1645 | 16 | 1652 | 12 | - | - | |
1659 | 28 | 1651 | 43 | 3286 | 43 | 1634 | 84 | 1640 | 88 | 1643 | 100 | |||
6 | OMe | 1668 | 78 | 1660 | 44 | 3301 | 41 | 1647 | 25 | 1652 | 15 | - | - | |
1657 | 22 | 1651 | 56 | 3288 | 59 | 1635 | 75 | 1639 | 85 | 1643 | 100 |
Conf. a | E b | P c | μ | νCO | Torsion angles/º d | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
α | β | γ | δ | θ | θ’ | ω | ω' | ||||||
gas | ax | 0 | 96.8 | 3.62 | 1713.4 | 82.0 | −101.3 | 48.2 | 2.13 | 167.9 | −154.3 | 23.6 | −50.8 |
eq | 8.45 | 3.2 | 5.39 | 1720.1 | 30.4 | −176.5 | 73.2 | −3.90 | −170.8 | 157.1 | −23.7 | 50.8 | |
C7H16 | ax | 0 | 84.4 | 4.08 | 1696.7 | 82.0 | −101.9 | 48.4 | 2.06 | 168.2 | −154.5 | 23.3 | −50.7 |
eq | 4.20 | 15.6 | 6.21 | 1699.0 | 31.6 | −177.4 | 72.9 | −3.74 | −172.2 | 158.2 | −22.8 | 50.3 | |
CCl4 | ax | 0 | 80.0 | 4.16 | 1694.2 | 81.9 | −102.1 | 49.1 | 2.06 | 168.1 | −154.5 | 23.4 | −50.7 |
eq | 3.43 | 20.0 | 6.37 | 1694.3 | 31.1 | −176.2 | 73.3 | −3.75 | −171.7 | 157.7 | −23.1 | 50.6 | |
CHCl3 | ax | 0.17 | 48.3 | 4.61 | 1676.8 | 81.9 | −102.4 | 47.7 | 2.11 | 168.3 | −154.5 | 23.2 | −50.7 |
eq | 0 | 51.7 | 7.20 | 1673.0 | 33.4 | −178.1 | 72.1 | −3.28 | −174.9 | 159.9 | −20.6 | 49.7 | |
CH2Cl2 | ax | 2.01 | 30.8 | 4.89 | 1668.9 | 80.6 | −104.3 | 48.5 | 2.57 | 169.3 | −155.7 | 23.1 | −50.1 |
eq | 0 | 69.2 | 7.62 | 1663.8 | 32.7 | −178.4 | 71.4 | −3.20 | −174.3 | 159.1 | −20.8 | 50.9 | |
CH3CN | ax | 3.93 | 16.9 | 5.18 | 1659.5 | 80.0 | −105.6 | 48.9 | 2.60 | 169.8 | −156.2 | 22.6 | −49.8 |
eq | 0 | 83.1 | 8.10 | 1652.3 | 32.1 | −178.4 | 70.7 | −3.11 | −173.2 | 158.5 | −21.7 | 50.2 | |
X-ray e | - | - | - | - | - | 31.0 (3) | −176.2 (2) | −155.5(2) | −4.1 (4) | −177.6(3) | 157.2(3) | −14.3(4) | 53.1 (3) |
Conf. | O(1) | C(2) | S(4) | N(6) | H(26) | H(30) | H(5) | H(11) | H(16) | H(17) |
---|---|---|---|---|---|---|---|---|---|---|
ax | −0.557 | 0.525 | −0.321 | −0.187 | 0.131 | 0.102 | 0.048 | 0.088 | 0.028 | 0.065 |
eq | −0.537 | 0.605 | −0.320 | −0.311 | 0.103 | 0.061 | 0.027 | 0.058 | 0.030 | 0.045 |
Conf. a | O[1]...S[4] b | Δl c | O[1]...H[11] d | Δl | O[1]...H[26] d | Δl | O[1]...H[5] d | Δl |
---|---|---|---|---|---|---|---|---|
ax | 3.37 | +0.05 | 2.28 | −0.44 | 2.35 | −0.37 | 2.52 | −0.20 |
eq | 2.89 | −0.43 | 2.27 | −0.45 | 4.75 | +2.03 | 2.83 | +0.11 |
Orbitals | ax | eq |
---|---|---|
LPN6→π*C2=O1 | 65.3 | 50.6 |
LPO1→σ*C2-N6 | 25.4 | 25.5 |
LPO1→σ*C2-C3 | 18.9 | 20.3 |
LPO1→σ*C21-H26 | 3.0 | - |
LPO1→σ*C10-H11 | 1.0 | 1.2 |
LPO1→ σ*S4-C20 | - a | 0.9 |
LPS4→ π*C2=O1 | 2.0 | - |
LPS4→ π *C20-C21 | 8.3 | 2.7 |
σC3-S4→π*C2=O1 | 4.2 | 0.7 |
σC3-S4→σ*C2-N6 | - | 3.4 |
πC2=O1→σ*C3-S4 | 1.7 | 0.6 |
π*C2=O1→σ*C3-S4 | 5.5 | 0.8 |
∑ Eb | 135.3 | 106.7 |
3. Experimental
3.1. Materials
3.2. IR Measurements
Compd. | Y | Mp (°C) | 1H- and 13C-NMR a |
---|---|---|---|
1 | NO2 | 77–78 | 1H-NMR: 8.14–8.12 (m, 2H), 7.64–7.63 (m, 2H), 4.06 (t, 1H, J = 5.5 Hz), 3.41–3.32 (m, 2H), 2.99 (s, 3H), 2.30–2.27 (m, 1H), 2.09–2.03 (m, 2H), 1.92–1.88 (m, 1H). 13C-NMR: 167.83, 146.07, 145.77, 128.67, 123.86, 49.82, 46.90, 35.36, 28.68, 20.76. |
2 | Br | 64–64 | 1H-NMR: 7.44–7.40 (m, 4H), 3.82 (t, 1H, J = 5.7Hz), 3.33–3.26 (m. 2H), 2.96 (s, 3H), 2.11–2.04 (m, 2H), 1.99–1.94 (m, 1H), 1.82–1.77 (m, 1H). 13C-NMR: 168.36, 134.27, 134.07, 132.19, 121.82, 50.06, 49.02, 35.47, 28.83, 20.59. |
3 | Cl | b | 1H-NMR: 7.53–7.51 (m, 2H), 7.30–7.29 (m, 2H), 3.84 (t, 1H, J = 5.7Hz), 3.36–3.28 (m, 2H), 2.99 (s, 3H), 2.17–2.08 (m, 2H), 2.02–1.96 (m, 1H), 1.83–1.80 (m, 1H) 13C-NMR: 168.19, 133.77, 133.64, 133.33, 129.06, 49.86, 48.96, 35.27, 28.62, 20.38. |
4 | H | 38–39 | 1H-NMR: 7.56–7.54 (m, 2H), 7.32–7.28 (m, 2H), 7.26–7.24 (m, 1H), 3.88 (t, 1H, J = 5.0 Hz), 3.30–3.24 (m, 2H), 2.97 (s, 3H), 2.12–2.07 (m, 2H), 1.98–1.94 (m, 1H), 1.77–1.74 (m, 1H). 13C-NMR: 168.47, 134.96, 132.61, 129.12, 127.61, 50.08, 49.03, 35.44, 28.75, 20.46. |
5 | CH3 | 44–45 | 1H-NMR: 7.47–7.46 (m, 2H), 7.15–7.13 (m, 2H), 3.83 (t, 1H, J = 5,5Hz), 3.34–3.25 (m, 2H), 2.98 (s, 3H), 2.35 (s, 3H), 2.13–2.05 (m, 2H), 1.96-1.92 (m, 1H), 1.80–1.75 (m, 1H) 13C-NMR: 168.37, 137.77, 133.25, 130.79, 129.71, 49.89, 49.21, 35.23, 28.35, 21.12, 20.12. |
6 | OCH3 | b | 1H-NMR: δ (ppm): 7.51–7.49 (m, 2H), 6.85–6.83 (m, 2H), 3.79 (s, 3H), 3,71 (t, 1H, J = 6,0Hz), 3.25–3,23 (m, 2H), 2.94 (s, 3H), 2.10–2,01 (m, 2H), 1.94–1,89 (m, 1H), 1.75–1,71 (m, 1H). 13C-NMR: 168.36, 159.85, 135.93, 124.61, 114.50, 55.31, 49.89, 49.80, 35.20, 28.28, 20.12 |
Compd | Y | Molecular formula | Analysis (%) | |||
---|---|---|---|---|---|---|
C | H | N | ||||
1 | NO2 | C12H14N2O3S | Calc.Found | 54.1254.34 | 5.305.23 | 10.5210.46 |
2 | Br | C12H14BrNOS | Calc. Found | 48.0147.91 | 4.704.77 | 4.674.79 |
3 | Cl | C12H14ClNOS | Calc. Found | 56.3556.26 | 5.525.22 | 5.485.27 |
4 | H | C12H15NOS | Calc. Found | 65.1265.12 | 6.836.56 | 6.336.46 |
5 | CH3 | C13H17NOS | Calc. Found | 66.3466.23 | 7.287.20 | 5.956.01 |
6 | OCH3 | C13H17NO2S | Calc. Found | 62.1262.13 | 6.826.81 | 5.575.55 |
3.3. X-ray Measurements
3.3.1. Data Collection and Processing
3.4. Theoretical Calculations
4. Conclusions
Supplementary Materials
Acknowledgments
Conflicts of Interest
References and Notes
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Olivato, P.R.; Santos, J.M.M.; Contieri, B.; Cerqueira, C.R., Jr.; Rodrigues, D.N.S.; Vinhato, E.; Zukerman-Schpector, J.; Colle, M.D. Spectroscopic and Theoretical Studies of Some 3-(4′-Substituted phenylsulfanyl)-1-methyl-2-piperidones. Molecules 2013, 18, 7492-7509. https://doi.org/10.3390/molecules18077492
Olivato PR, Santos JMM, Contieri B, Cerqueira CR Jr., Rodrigues DNS, Vinhato E, Zukerman-Schpector J, Colle MD. Spectroscopic and Theoretical Studies of Some 3-(4′-Substituted phenylsulfanyl)-1-methyl-2-piperidones. Molecules. 2013; 18(7):7492-7509. https://doi.org/10.3390/molecules18077492
Chicago/Turabian StyleOlivato, Paulo R., Jean M. M. Santos, Bruna Contieri, Carlos R. Cerqueira, Jr., Daniel N. S. Rodrigues, Elisângela Vinhato, Julio Zukerman-Schpector, and Maurizio Dal Colle. 2013. "Spectroscopic and Theoretical Studies of Some 3-(4′-Substituted phenylsulfanyl)-1-methyl-2-piperidones" Molecules 18, no. 7: 7492-7509. https://doi.org/10.3390/molecules18077492