Introduction
Materials and methods
Materials
GC–MS analysis
LC–MS analysis
MS analysis with direct flow injection
ATR-FTIR
Raman spectroscopy
NMR spectroscopy
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1D: 1H, 13C, selective 1H-1H total correlated spectroscopy (s-TOCSY)
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2D: 1H-1H correlation spectroscopy (COSY), 1H-1H nuclear Overhauser effect spectroscopy (NOESY), 1H-13C multiplicity edited heteronuclear single quantum coherence (e-HSQC) spectroscopy, 1H-13C heteronuclear multiple bond correlation (HMBC) spectroscopy, and refocused 1,1 adequate sensitivity double quantum transfer experiment (1,1-ADEQUATE) spectroscopy.
Powder X-ray diffraction
Single crystal diffraction
Results
GC–MS
LC–MS and direct flow injection ESI-MS2
HR-MS: | ||||
Theoretical mass [M + H]+ (Da) | Experimental mass [M + H]+ (Da) | Δ mDa | Δ ppm | Formula |
392.27019 | 392.27011 | − 0.08 | 0.19 | C25H34N3O |
Direct flow injection MS2: | ||||
m/z | Relative intensity (%) | |||
132.9 | 7.2 | |||
134.8 | 100 | |||
136.0 | 2.3 | |||
185.8 | 2.8 | |||
247.1 | 1.3 | |||
253.0 | 2.1 | |||
257.5 | 21.5 | |||
258.7 | 11.0 | |||
314.1 | 4.1 | |||
317.4 | 1.8 | |||
329.6 | 2.1 | |||
330.3 | 1.9 | |||
349.5 | 1.7 | |||
352.3 | 1.5 | |||
366.2 | 1.6 |
IR, Raman, and UV–VIS spectroscopies
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two bands of secondary amide group representing carbonyl stretching and N–H bending modes at 1655 cm−1 and 1524 cm−1, respectively;
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weak bands of N–H stretching around 3400 cm−1;
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asymmetric aromatic ring stretching vibrations appearing at 1490 cm−1 along with out-of-plane bending of aromatic ring and C-H bonds modes giving rise to the signals in the region of 800 to 700 cm−1.
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carbonyl stretching and N–H bending vibrations at 1660 and 1530 cm−1, respectively, similar positions as in the IR spectrum;
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strong bands from symmetric stretching modes of an aromatic ring appearing at positions 1617 cm−1 and 1576 cm−1, and weak signal from asymmetric vibrations at 1494 cm−1.
NMR spectroscopy
No. | 1H | 13C | COSY | HMBC and 1,1-ADEQUATEa | NOESY |
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3 | – | 138.0 | – | – | – |
3′ | – | 122.7 | – | – | – |
4 | 8.38 (dt, J = 8.3, 1.0 Hz, 1H) | 123.0 | H5; Overlapped H6 and H7 | C6, C7′, C3, C7 | H5 |
5 | 7.23 (ddd, J = 8.0, 4.6, 2.9 Hz, 1H) | 122.2 | Overlapped H6 and H7 | C7, C6, C7′, C3′ | – |
6 | 7.37 (m, 1H) | 126.4 | – | C4 or C7′ | – |
7 | 7.37 (m, 1H) | 109.3 | C4 or C7′ | H1a | |
7′ | – | 141.4 | – | – | – |
1a | 4.17 (d, J = 7.3 Hz, 2H) | 55.6 | H2a | C7′, C2a, C3a | H3aax, H3aeq |
2a | 1.98 (m, 1H) | 38.7 | H3aax, H3aeq | C3a, C1a | H3aeq, H4aax |
3a | 1.59 eq (dd, J = 13.0, 2.4 Hz, 2H) | 30.9 | H4aax, H4aeq | C2a, C4a | H4aeq, H4aax |
1.01 ax (qd, J = 12.0, 3.1 Hz, 2H) | H3aeq, H4aeq H4aax | C2a, C4a | H4aeq | ||
4a | 1.71 eq (m, 2H) | 25.7 | H4aax | – | – |
1.19 ax (m, 2H) | – | C5a, C3a | – | ||
5a | 1.66 eq (m, 1H) | 26.2 | – | – | – |
1.18 ax (m, 1H) | – | C4a | – | ||
1b | – | 162.1 | – | – | – |
2b | 6.81 (s, 1H) | – | H4b | C1b, C3b, C4b | H4b |
3b | – | 51.8 | – | – | – |
4b | 2.21 (d, J = 2.6 Hz, 6H) | 41.9 | H5b, H6b’ | C3b, C5b, C6b | H5b, H6b |
5b | 2.14 (brs, 3H) | 29.6 | H6b, H6b’ | C3b, C6b | H6b, H6b’ |
6b | 1.77 (brd, J = 11.7 Hz, 3H) | 36.5 | – | C5b | – |
6b’ | 1.72 (brd, J = 12.1 Hz, 3H) | – | C5b, C4b | – |
X-ray diffraction
Empirical formula | C25 H33 N3 O |
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Formula weight | 391.54 |
Temperature | 293(2) K |
Wavelength | 1.54184 Å (Cu rotating anode) |
Crystal system | Monoclinic |
Space group | P 21/c |
Unit cell dimensions | a = 16.867(1) Å |
b = 12.515(1) Å | |
c = 21.745(1) Å β = 104.65(1)° | |
Volume | 4440.9(5) Å3 |
Z/Z’ | 8/2 |
Density (calculated) | 1.171 g cm−3 |
Absorption coefficient | 0.557 mm−1 |
F(000) | 1696 |
Crystal size | 0.34 × 0.3 × 0.28 mm3 |
Independent reflections | 8062 [R(int) = 0.0631] |
Absorption correction | None |
Refinement method | Full-matrix least-squares on F2 |
Data/parameters | 8062/523 |
H-atom positions | Calculated/riding |
Goodness-of-fit on F2 | 1.054 |
Final R indices [I > 2sigma(I)] | R1 = 0.0711, wR2 = 0.1925 |
R indices (all data) | R1 = 0.0802, wR2 = 0.2054 |
Largest diff. peak and hole | 0.37 and -0.23 e. Å−3 |