3.1. Optimization of conformers and rotational barriers.
During the exploration of the conformational space of 2.3.4-TMP, the local symmetry C2V of the two peripheral isopropyl groups C1C2C6 and C5C4C8 was not used to reduce the number of conformers to optimize, because the axis of symmetry C2 does not coincide with the rotational bond C2C3 and C3C4 axes. Moreover, the global symmetry of the molecule is C1. Thereby, the quasi-total exploration of the configurational space of 2,3,4-TMP through the torsional angles τ1 and τ2 values, in steps of 30°, generates 144 (12*12) conformations combining τ1 and τ2 values as presented in Fig. 2.
The optimization and the energy calculation by the two methods CAM-B3LYP and WB97XD with the aug-cc-pvtz base, led us to 3 stable conformers A (τ1 = 172, τ2 = -172), B (τ1 = -56, τ2 = 91) and C (τ1 = 173, τ2 = 93) in a range of 1.5 kcal / mol according to the first method and 1.25 kcal/mol according to the second and two higher conformers D (τ1 = -45, τ2 = 179) and E (τ1 = 100, τ2 = -179) respectively at 2.53 and 3.26 kcal/mol for the first method and at 2.32 and 3.51 kcal/mol for the second. It’s worth noting that the first secondary conformer B is of lesser stability than A conformer by 1.36 kcal/mol and 1.09 kcal/mol through CAM-B3LYP/aug-cc-pvtz and WB97XD/aug-cc-pvtz respectively.
On consulting their Newman projections, we noted that the conformation trans concerns both the most stable conformer A and the C conformer, knowing that the stability of the former is due to the optimal interaction between the two opposing lateral methyls C6 and C8 carbons. Moreover, the relative stability acquired by the B conformer is due to the opposition of the two isopropyl groups C1C2C6 and C5C4C8 (Fig. 3).
Further, the effect of the optimization method on the structural parameters shows that the modification of the CAM-B3LYP method by WB97XD did not significantly change all obtained results except in torsion angles exceeding 3° for all conformers. Besides, the calculated lengths and bond angles of the 2,3,4-TMP were compared with their experimental data [11]. The distance r(C1-C2) was found to be very close to the experiment for both methods, while the experimental α(C1-C2-C3) angle is distant from its theoretical counterpart by 2 to 6° (Tab. S1 in Supplementary Information).
According to the torsion angle values of the five conformers A (τ1 = 172, τ2= -172), B (τ1= -56, τ2 = 91), C (τ1 = 173, τ2 = 93), D (τ1= -45, τ2 = 179) and E (τ1 = 100, τ2= -179), the possible transitions between conformers are as follows:
Following C2C3 (τ1)
|
|
|
|
|
A (τ1 = 172, τ2= -172)
|
→
|
E (τ1 = 100, τ2= -179)
|
|
E (τ1 = 100, τ2= -179)
|
→
|
D (τ1= -45, τ2 = 179)
|
|
B (τ1= -56, τ2 = 91)
|
→
|
C (τ1 = 173, τ2 = 93)
|
Following C3C4 (τ2)
|
|
|
|
|
A (τ1 = 172, τ2= -172)
|
→
|
C (τ1 = 173, τ2 = 93)
|
|
B (τ1= -56, τ2 = 91)
|
→
|
D (τ1= -45, τ2 = 179)
|
According to the results summarized in Table 1 and Fig. 4, the rotational barrier of the transitions B→ C and E→ D are the most important because of the interactions between branching methyls of C2 with those of C3 of the eclipsed form in τ1, followed in intensity by those of A → C, B → D and then A → E. Unfortunately, no experimental result is available to compare with. Furthermore, both methods' calculations led us to WB97XD/aug-cc-pvtz rotational barriers slightly larger by 0.2 to 0.4 kcal/mol than the CAM-B3LYP/aug-cc-pvtz values. Like for 2.2.3TMP, we have adopted WB97XD/aug-cc-pvtz in the remaining calculations. Indeed, it’s thermodynamically favorable (more stabilizing in terms of energy) for the four lowest conformer A-D.
Table 1
CAM-B3LYP/ aug-cc-pvtz and WB97XD/aug-cc-pvtz optimized values (kcal/mol) of possible rotational barriers to torsional angle τ1 = C1C2C3C4 and τ2 = C2C3C4C5 and their correspondent inversion (in parentheses) for 2,3,4-TMP.
|
A →C
|
A→ E
|
B →D
|
B→ C
|
E→ D
|
CAM-B3LYP / aug-cc-pvtz
|
2.82 (1.31)
|
3.07 (0.13)
|
2.35 (0.83)
|
7.13 (7,02)
|
3.87 (2.89)
|
WB97XD / aug-cc-pvtz
|
3.00 (1.83)
|
3.42 (0.20)
|
2.80 (0.50)
|
7.27 (7.18)
|
3.93 (3.36)
|
3.2. Natural Bond Orbital analysis (NBO)
Natural Bonding Orbital analysis helps to quantify the intramolecular charge transfer (ICT) causing the system stabilization. Measured by E(2) [12][13], ICT is due to the overlap between bonding and antibonding orbitals.
Therefore, the larger the E(2) value, the more intensive is the interaction between electron donors and electron acceptors [12][10]. The second-order Perturbation theory analysis of the Fock matrix evaluates the donor and acceptor from the NBO analysis of the titled molecule.
Based on the results collected in Tab. S2 (Supplementary Information), we have noted that the most significant delocalization concerns the interactions σCH-σ*CC, in particular σ(C2-H12)-σ*(C3-C7) for conformers A et C, σ(C3-H13)-σ*(C1-C2) for conformer B and σ(C3-H13)-σ*(C2-C6) for conformers A et C.
The intensity of these interactions, which exceed 5kcal/mol, is due, to the trans configuration of the interacting CH and CC bond. Also, the interactions σCH-σ*CH and σCC-σ*CH, being in the ranges [0.50, 4.50] and [0.50, 2.50] respectively, are less intense than the interactions σCH-σ*CC.
The differentiation between conformers via the intramolecular interaction of the carbon-carbon bond σCC-σ*CC allowed us to notice that:
-
The interaction of σC1C2 and σC2C6 bonds of the isopropyl group, carried by the C2 carbon, with σ*C3C4 and σ*C3C7 respectively, for the two conform A and C have values around 3 kcal/mol.
-
The interaction of σC4C5 and σC4C8 of the isopropyl group, carried by the C4 carbon, with σ*C2C3 and σ*C3C7 respectively, for conformers A, D, and E take values exceeding 3 kcal/mol except for the conformer E for the first interaction.
-
The interaction of the σC3C7 bond of the internal isopropyl, carried by the C3 carbon, with σ*(C4-C8) gives a value of 3.20 and 3.41 kcal/mol the A and D conformities, respectively.
3.3. Non-linear optical effects (NLO)
The dipole moment µ, polarizability α, and the first-order hyperpolarizability β were calculated by WB97XD/aug-cc-pvtz theoretical level [14], [15]. According to the results summarized in Table 2, all the dipole moment values are very low, with a slight superiority for the B and C conformers, with the respective values 0.164 and 0.187 Debye. The values of static polarizability α0 are very close for the five A-E conformers, whereas the total polarizability or anisotropy of polarizability Δα is not, and takes the highest value for the least stable E conformer. The most sensitive quantity to the conformational aspect is the first order hyperpolarizability (β0), whose extreme values concern the C conformer with the smallest value (125.673 10− 33esu) and the D conformer with the highest value (507.627 10− 33esu).
Table 2
Total static dipole moment (µ, in Debye), static polarizability (α0, in 10− 24 esu), total polarizability Δα (∆α, in 10− 24 esu), and the mean first-order hyperpolarizability (β0, in 10− 33 esu) for 2,3,4-TMP calculated at WB97XD/aug-cc-pvtz level.
Conformers
|
µ
|
α0 esu(10− 24)
|
∆α esu(10− 24)
|
β0 esu(10− 33)
|
A
|
0.106
|
14.957
|
2.557
|
343.770
|
B
|
0.164
|
14.909
|
1.687
|
313.591
|
C
|
0.187
|
14.932
|
2.563
|
125.673
|
D
|
0.108
|
14.954
|
2.240
|
507.627
|
E
|
0.127
|
15.003
|
3.158
|
460.005
|
3.4. U-V Visible spectral and FMO analysis
The UV visible spectra of the titled molecule are also investigated. The excitation wavelengths (λ), energies (E), oscillator strengths (f), and the assignment of electronic excitation for each isolated conformer of the A-E optimized conformers and in the presence of the solvent DMSO were determined by time-dependent density functional theory TD-DFT and presented in Table 3. At the same time, Fig. 5 shows their theoretical electronic spectra. The result of conformation A reveals five electronic transition peaks in a small range from 155 to 146 nm, assigned to the excitation HOMO -> LUMO, HOMO-1 -> LUMO and HOMO-2 -> LUMO, HOMO-1 -> LUMO + 3 and HOMO -> LUMO + 2 as main contributions, where the oscillator force value does not exceed a maximum of 0.045 a.u which corresponds to the penultimate transition.
The transitions HOMO -> LUMO, HOMO-1 -> LUMO, and HOMO-2 -> LUMO, when they reappear in B-F conformers, their positions change little, and their oscillator strength is weaker. On the other hand, new transitions appear with more perceptible oscillator forces. This is the case, for example, with HOMO -> LUMO + 1 at 149.74 (f = 0.083) for B, and HOMO -> LUMO + 1 combined with HOMO -> LUMO + 3 at 149.83 (f = 0.04).
When considering 2,3,4-TMP in the DMSO solvent, the distribution of the transitions in terms of the position remains the same. However, the oscillator's strength and peak intensity increase by about 20 to 25% for all conformers.
The values of HOMO, LUMO, their energy gap ΔΕ and softness [16], which are collected in Table 4, do not differentiate between the five conformers A-E, since their values are of the same order. The visualization of frontiers orbitals HOMO and LUMO of all conformers, shown in Fig. 6, reproduces a delocalization over the whole molecule for the HOMO orbitals and a localization of the LUMOs at the level of the carbon atoms.
Table 3
Calculated absorption wavelength λ, excitation energies E, and oscillator strengths (f) of 2,3,4-TMP conformers using TD-DFT/WB97XD/aug-cc-pvtz level in the gas phase and DMSO solvent.
Confs
|
GAS
|
DMSO
|
λ (nm)
|
E (eV)
|
f
|
Major Contributions
|
λ (nm)
|
E (eV)
|
F
|
Major Contributions
|
A
|
155.08
|
7.9948
|
0.0153
|
HOMO -> LUMO 60%
|
155.01
|
7.9985
|
0.0193
|
HOMO -> LUMO 60%
|
152.99
|
8.1042
|
0.0186
|
HOMO-1 -> LUMO 60%
|
153.02
|
8.1027
|
0.025
|
HOMO-1 -> LUMO 59%
|
149.38
|
8.2998
|
0.014
|
HOMO-2 -> LUMO 57%
|
149.41
|
8.298
|
0.0223
|
HOMO-2 -> LUMO 58%
|
|
|
|
|
148.75
|
8.3353
|
0.01
|
HOMO -> LUMO + 3 50%
|
147.3
|
8.4173
|
0.0454
|
HOMO-1 -> LUMO + 3 45%
|
147.36
|
8.4136
|
0.0633
|
HOMO-1 -> LUMO + 3 45%
|
146.66
|
8.4537
|
0.02
|
HOMO -> LUMO + 2 53%
|
146.77
|
8.4476
|
0.0246
|
HOMO -> LUMO + 2 52%
|
B
|
154.01
|
8.0505
|
0.0104
|
HOMO-1 -> LUMO 60%
|
154.01
|
8.0505
|
0.0152
|
HOMO-1 -> LUMO 60%
|
150.24
|
8.2525
|
0.0301
|
HOMO-2 -> LUMO 58%
|
150.2
|
8.2545
|
0.0383
|
HOMO-2 -> LUMO 57%
|
149.74
|
8.2801
|
0.083
|
HOMO -> LUMO + 1 54%
|
149.89
|
8.2719
|
0.1082
|
HOMO -> LUMO + 1 53%
|
|
|
|
|
148.2
|
8.3661
|
0.0125
|
HOMO -> LUMO + 3 48%
|
C
|
157.35
|
7.8794
|
0.022
|
HOMO -> LUMO 61%
|
157.17
|
7.8888
|
0.0286
|
HOMO -> LUMO 61%
|
153.66
|
8.0685
|
0.0189
|
HOMO-1 -> LUMO 60%
|
153.7
|
8.0664
|
0.0243
|
HOMO-1 -> LUMO 59%
|
151.63
|
8.1769
|
0.0229
|
HOMO-2 -> LUMO 58%
|
151.71
|
8.1726
|
0.0315
|
HOMO-2 -> LUMO 57%
|
147.79
|
8.3893
|
0.0144
|
HOMO -> LUMO + 2 58%
|
147.79
|
8.389
|
0.0182
|
HOMO -> LUMO + 2 59%
|
146.64
|
8.4552
|
0.0126
|
HOMO -> LUMO + 1 51%
|
146.81
|
8.445
|
0.0147
|
HOMO -> LUMO + 1 53%
|
D
|
|
|
|
|
155.91
|
7.9523
|
0.0105
|
HOMO -> LUMO 61%
|
151.89
|
8.1628
|
0.011
|
HOMO-1 -> LUMO 59%
|
151.87
|
8.1637
|
0.0178
|
HOMO-1 -> LUMO 59%
|
150.78
|
8.2226
|
0.0286
|
HOMO-2 -> LUMO 39%
|
150.83
|
8.22
|
0.0375
|
HOMO-2 -> LUMO 37%
|
|
|
|
HOMO -> LUMO + 1 38%
|
|
|
|
HOMO -> LUMO + 1 35%
|
|
|
|
|
149.28
|
8.3053
|
0.0306
|
HOMO -> LUMO + 3 42%
|
148.09
|
8.3725
|
0.0203
|
HOMO -> LUMO + 3 43%
|
148.16
|
8.3685
|
0.0289
|
HOMO -> LUMO + 3 42%
|
|
|
|
|
|
|
|
HOMO -> LUMO + 2 36%
|
146.91
|
8.4397
|
0.0181
|
HOMO -> LUMO + 2 45%
|
147.09
|
8.429
|
0.0192
|
HOMO -> LUMO + 1 44%
|
|
|
|
|
|
|
|
HOMO -> LUMO + 2 36%
|
E
|
154.3
|
8.0353
|
0.0186
|
HOMO -> LUMO 60%
|
154.27
|
8.037
|
0.0212
|
HOMO -> LUMO 57%
|
153.12
|
8.097
|
0.0103
|
HOMO-1 -> LUMO 57%
|
153.13
|
8.0967
|
0.0157
|
HOMO-1 -> LUMO 56%
|
149.83
|
8.2748
|
0.04
|
HOMO -> LUMO + 3 44%
|
149.88
|
8.2721
|
0.0738
|
HOMO -> LUMO + 3 44%
|
|
|
|
HOMO -> LUMO + 1 38%
|
|
|
|
|
148.37
|
8.3563
|
0.0208
|
HOMO-1 -> LUMO + 1 36%
|
148.35
|
8.3575
|
0.0253
|
HOMO-1 -> LUMO + 1 36%
|
|
|
|
HOMO-2 -> LUMO 31%
|
|
|
|
HOMO-1 -> LUMO + 3 35%
|
148.08
|
8.3729
|
0.0251
|
HOMO-2 -> LUMO 48%
|
148.06
|
8.3736
|
0.023
|
HOMO-2 -> LUMO 54%
|
|
|
|
|
146.97
|
8.4358
|
0.01
|
HOMO -> LUMO + 2 51%
|
The outline of the MEP surface of 2,3,4-TMP, also given in Fig. 6, shows some specific nuances of the carbons' charges through the yellow color distribution.
Table 4
The HOMO-LUMO energy gap value (eV) and softness (eV-1) for the five lowest energy conformers of 2.3.4-TMP at WB97XD/aug-cc-pvtz.
Conformers
|
HOMO
|
LUMO
|
ΔΕ
|
S
|
A
|
-10.221
|
0.849
|
11.070
|
0.181
|
B
|
-10.143
|
0.838
|
10.981
|
0.182
|
C
|
-10.153
|
0.827
|
10.980
|
0.182
|
D
|
-10.155
|
0.854
|
11.009
|
0.182
|
E
|
-10.220
|
0.869
|
11.089
|
0.180
|
3.5. 13C-NMR spectrum and NPA charge calculations
To calculate gas-phase 1H and 13C RMN chemical shifts, which helps in the spectral assignment and structural elucidation, DFT at the Gauge Invariant Atomic Orbitals (GIAO) approach [17], [18] was employed. Therefore, we have used the optimized geometry of all conformers from WB97XD using the aug-cc-pvtz basis set in the DMSO solution for further optimization while employing Integral equation formalism (IEF-PCM) [19].
Table 5
The experimental [16] and calculated 13C NMR isotropic chemical shifts (ppm) with all A-E conformers' NPA charges at WB97XD/aug-cc-pvtz level.
|
A
|
B
|
C
|
D
|
E
|
Exp
|
|
NPA
|
δ
|
NPA
|
δ
|
NPA
|
δ
|
NPA
|
δ
|
NPA
|
δ
|
C1
|
-0.583
|
16.64
|
-0.592
|
10.81
|
-0.586
|
16.32
|
-0.591
|
8.43
|
-0.581
|
21.04
|
21.80
|
C2
|
-0.212
|
23.47
|
-0.205
|
28.84
|
-0.203
|
29.56
|
-0.208
|
30.61
|
-0.212
|
26.28
|
29.83
|
C3
|
-0.199
|
40.81
|
-0.199
|
37.17
|
-0.198
|
36.53
|
-0.200
|
41.47
|
-0.202
|
40.50
|
45.31
|
C4
|
-0.212
|
26.99
|
-0.217
|
18.65
|
-0.211
|
27.52
|
-0.215
|
27.03
|
-0.204
|
33.75
|
29.83
|
C5
|
-0.582
|
15.88
|
-0.591
|
13.02
|
-0.591
|
12.27
|
-0.582
|
17.98
|
-0.586
|
15.53
|
21.80
|
C6
|
-0.593
|
7.52
|
-0.582
|
15.93
|
-0.592
|
9.53
|
-0.581
|
18.79
|
-0.584
|
13.54
|
18.38
|
C7
|
-0.595
|
4.54
|
-0.591
|
7.98
|
-0.600
|
3.40
|
-0.584
|
15.75
|
-0.589
|
10.03
|
10.86
|
C8
|
-0.587
|
15.07
|
-0.578
|
19.29
|
-0.578
|
16.88
|
-0.585
|
18.18
|
-0.586
|
16.03
|
18.38
|
The 13C NMR nuclear shielding constants were predicted using GIAO approximation with the above method. The theoretical and experimental values of 13C and 1H chemical displacements are collected in Tables 5 and 6 for all conformers and illustrated for the most stable A-conformer in Fig. 7. Experimentally, the highest value exceeding 45 ppm concerns the central C3 carbon, followed by that of its adjacent carbons (C2 and C4) of about 29 ppm, and then the peripheral carbons (C1, C5, C6, C7, and C8) whose smallest displacement reaches 11 ppm for C7 [16].
Table 6 The adjusted. R-Squared between observed and calculated
13C-NMR chemical shifts for all A-E conformers.
Conformers
|
A
|
B
|
C
|
D
|
E
|
Adjusted, R-Squared
|
0.95085
|
0.73344
|
0.89247
|
0.8184
|
0.89332
|
he order of magnitude and classification of chemical displacements has been well respected. The NPA atomic charges calculation confirms these values since it detects the low electron density of C2, C3, and C4. As expected, we noted the ability of C7 carbon, by its position, to differentiate between these conformers. Indeed, its chemical displacement takes the following values: 4.54 ppm for A, 7.98 ppm for B, 3.40 ppm for C, 15.75 for D, and about 10.86 ppm for E. Moreover, the experimental and calculated correlation of chemical shifts in 13C NMR led to an autocorrelation coefficient of about 0.95 at best for conformer A (Fig. 8, Table 6). The experimental chemical shifts of hydrogens H12 and H14 of the tertiary carbons C2 and C4 were also the highest. Such a result, reproduced theoretically, also allows the differentiation between conformers.
3.6. Vibrational analysis
The Raman spectrum of 2,3,4 trimethylpentane in the liquid phase shows that frequencies below 600 cm− 1 at the temperature range from 293 to 163 K (Fig. 9) did not reveal any conformational exchange between conformers, except for an extremely weak Raman band, located at 517 cm− 1, which disappears entirely from 239K onwards (Fig. 10) [20].
Concerning IRTF spectra, apart from the sharpening of the bands due to the decrease in temperature from 273K to 170K, the low frequencies zone, below 600 cm− 1, did not detect the conformational sensitivity of any pair of bands. The lack of temperature sensitive bands may be related to the fact that the vibrational frequencies of the most stable conformer and the secondary ones are common. To confirm this, calculations of normal modes of vibration were performed, with scaling factors allowing to adjust the harmonic frequencies to the observable frequencies. The distribution of potential energy for each normal mode was also evaluated. All the symmetry coordinates used, derived from the internal coordinates, are detailed in Tab. S3 (Supplementary Information).
Table 7
Local symmetry coordinates scale factors of the most stable conformer A for 2,3,4-TMP at WB97XD / aug-cc-pvtz level.
Symmetry coordinates
|
WB97XD / aug-cc-pvtz
|
CCs
|
0.9478
|
CH3s
|
0.8994
|
CHs
|
0.9053
|
CH3sb
|
0.9368
|
CH3ab
|
0.9409
|
CH3r
|
0.9365
|
Def CH
|
0.9200
|
Def CCC
|
0.9438
|
CCtors
|
0.9876
|
The observed Raman and IR frequencies in the liquid phase and the adjusted calculated frequencies are collected together in Table 7. Only the PED of A is given; all minor contributions (contributions < 5%) are eliminated unless they consolidate the significant contribution. Overall, the calculated frequencies are in good agreement with the experimental results, leading to a standard deviation (RMS) of 4 cm− 1 below 1500 cm− 1 and 6 cm− 1 for all other frequencies.
The 2.3.4-TMP molecule contains five CH3 and three CH. Its different vibration modes are subdivided into two groups. The first group (18 modes) contains 10 CH3ds of degenerate asymmetric elongation (in-plane and out-of-plane), 5 CH3ts of symmetric elongation, and 3 CHs. Their respective frequencies are well predicted and observed in the region [2970, 2860 cm− 1] in the following order: CH3ds > CH3ts > CHs. However, the CHs of the central tertiary carbon C3 is positioned between the asymmetrical elongations of the five methyl groups and their symmetrical elongations, observed around 2904 cm− 1 in Raman and 2911 cm− 1 in infrared and predicted in the same order of magnitude for all the conformers (A-E).
The second group contains, in pure mode, 10 asymmetric CH3ab degenerate deformations (in-plane and out-of-plane), 5 symmetrical CH3sb deformations, 6 tertiary carbon CCH deformations (3 in-plane and 3 out-of-plane) in the order CH3ab > CH3sb > CCH, observed in the same order, respectively in the intervals : [1470,1455], [1387,1363] and [1346,1264] respectively. It also contains 10 degenerate CH3dr rotations (in-plane and out-of-plane), observed from 1190 to 920 cm− 1, and often combined with CC elongations. The latter has been predicted with strong contributions, in terms of PED, for the observed modes at 1071, 993, and 926 cm− 1 calculated for A at 1076, 997, 927 cm− 1 and almost pure for the observed modes at 886 and 810 cm− 1 and calculated for A at 888 and 808 cm− 1. Indeed, the latter modes are highly polarised in Raman and express the symmetrical elongation of the skeleton. The CCC deformations appear from 475 up to 200 cm− 1 while combining with the CC torsions towards the low frequencies. It should also be noted that the C2C3 and C3C4 internal torsions gave rise to the weakest modes.
To complete this conformational analysis, the normal modes of the secondary conformers (B-E) were determined, with a variation in scale factors from A not exceeding 8%. We noticed that all the observed frequencies were reproduced by calculating the vibrational mode of the B, C, D, and E conformers, indicating that all the experimental bands are common for both the most stable and the secondary conformers. A credible argument for supporting the assignment of the only Raman sensitive weak Raman band located at 517 cm-1 to one less stable conformer than E.
Table 8
Experimental, calculated wavenumbers (cm − 1), and potential energy distribution (PED) assignment for 2,3,4-TMP conformers.
Experimental wavenumbers/cm
|
Theoretical wavenumbers/cm
|
PED (5%) with assignments
|
Raman
|
FT-IR
|
A
|
B
|
C
|
D
|
E
|
I°RA
|
I°IR
|
|
2967
|
2962
|
2984
|
2989
|
2990
|
2986
|
2983
|
22.80
|
74.04
|
C7H3ds2(70)-C5H3ds2(18)
|
2967
|
2962
|
2973
|
2969
|
2977
|
2979
|
2977
|
50.93
|
40.20
|
C5H3ds2(44)C7H3ds2(25)-C7H3ds1(15)-C5H3ds1(7)
|
2967
|
2962
|
2968
|
2965
|
2969
|
2977
|
2974
|
32.98
|
55.01
|
C7H3ds1(48)C8H3ds2(25)C5H3ds2(11)
|
2967
|
2962
|
2967
|
2961
|
2963
|
2967
|
2972
|
22.56
|
60.13
|
C8H3ds2(55)-C7H3ds1(20)-C5H3ds2(8)-C8H3ds1(7)
|
2967
|
2962
|
2960
|
2960
|
2962
|
2954
|
2969
|
46.93
|
52.28
|
C6H3ds1(32)C1H3ds1(24)C1H3ds2(22)-C6H3ds2(6)-C8H3ds2(6)
|
2967
|
2962
|
2958
|
2959
|
2961
|
2953
|
2963
|
56.86
|
52.99
|
C6H3ds1(59)C6H3ds2(15)-C1H3ds2(13)-C1H3ds1(6)
|
2954
|
2962
|
2955
|
2958
|
2959
|
2950
|
2953
|
60.10
|
117.75
|
C1H3ds1(52)C6H3ds2(20)-C1H3ds2(11)C5H3ds1(6)
|
2954
|
2962
|
2954
|
2954
|
2955
|
2949
|
2952
|
42.28
|
85.19
|
C5H3ds1(35)C8H3ds1(31)-C1H3ds1(10)C5H3ds2(8)
|
2954
|
2962
|
2951
|
2953
|
2950
|
2946
|
2946
|
2.12
|
9.72
|
C6H3ds2(51)C1H3ds2(41)
|
2954
|
2962
|
2948
|
2947
|
2947
|
2941
|
2943
|
1.30
|
11.34
|
C8H3ds1(46)-C5H3ds1(35)-C5H3ds2(8)C8H3ds2(7)
|
2904
|
2911
|
2914
|
2903
|
2905
|
2910
|
2903
|
9.52
|
182.72
|
C2Hs(86)
|
2904
|
2911
|
2901
|
2899
|
2901
|
2906
|
2894
|
36.77
|
163.22
|
C7H3ts(84)C7H3ds1(8)
|
2904
|
2911
|
2890
|
2895
|
2892
|
2890
|
2890
|
31.45
|
115.69
|
C6H3ts(34)-C5H3ts(23)C4Hs(19)-C8H3ts(12)C1H3ts(6)
|
2904
|
2911
|
2889
|
2892
|
2889
|
2887
|
2888
|
30.03
|
324.24
|
C1H3ts(39)C5H3ts(24)C6H3ts(20)C8H3ts(8)
|
2904
|
2911
|
2887
|
2889
|
2884
|
2886
|
2884
|
31.37
|
9.95
|
C1H3ts(52)-C6H3ts(34)-C5H3ts(8)
|
2904
|
2911
|
2885
|
2883
|
2880
|
2883
|
2882
|
21.71
|
17.01
|
C8H3ts(60)-C5H3ts(31)
|
2866
|
2877
|
2882
|
2878
|
2874
|
2881
|
2881
|
12.24
|
53.88
|
C4Hs(63)C8H3ts(11)-C6H3ts(7)C5H3ts(6)
|
2866
|
2877
|
2857
|
2871
|
2866
|
2880
|
2869
|
18.00
|
88.79
|
C3Hs(90)C4Hs(7)
|
*
|
1470
|
1486
|
1484
|
1487
|
1488
|
1490
|
2.69
|
1.72
|
C7H3ab1(46)C5H3ab1(20)C1H3ab1(13)C8H3ab1(6)
|
*
|
1470
|
1478
|
1479
|
1481
|
1478
|
1484
|
11.92
|
0.76
|
C6H3ab2(16)C5H3ab2(14)C8H3ab1(13)-C7H3ab1(11)C6H3ab1(10)C5H3ab1(9)C8H3ab2(7)
|
*
|
1470
|
1476
|
1475
|
1475
|
1473
|
1474
|
7.29
|
5.77
|
C1H3ab1(36)C6H3ab1(26)-C8H3ab1(9)-C5H3ab1(7)
|
*
|
1470
|
1471
|
1469
|
1469
|
1469
|
1467
|
6.71
|
3.37
|
C6H3ab2(52)-C6H3ab1(15)-C1H3ab2(9)C7H3ab2(7)
|
*
|
1470
|
1464
|
1466
|
1462
|
1463
|
1461
|
3.59
|
4.22
|
C5H3ab2(47)-C8H3ab1(22)C8H3ab2(7)-C6H3ab1(6)
|
*
|
1470
|
1462
|
1460
|
1459
|
1459
|
1460
|
8.24
|
1.50
|
C1H3ab1(28)C8H3ab1(18)-C7H3ab1(15)C7H3ab2(10)-C6H3ab1(10)
|
1458
|
1455
|
1454
|
1455
|
1453
|
1454
|
1457
|
4.80
|
6.33
|
C5H3ab1(23)-C8H3ab2(22)-C7H3ab2(13)-C6H3ab1(8)-C7H3ab1(8)C1H3ab1(7)-C8H3ab1(7)
|
1458
|
1455
|
1449
|
1450
|
1450
|
1454
|
1447
|
1.77
|
2.89
|
C7H3ab2(31)C5H3ab1(24)-C8H3ab1(12)-C7H3ab1(7)-C5H3ab2(6)C8H3ab2(5)
|
1458
|
1455
|
1446
|
1449
|
1447
|
1447
|
1446
|
5.04
|
4.79
|
C1H3ab2(49)C8H3ab2(17)-C5H3ab2(7)C6H3ab2(7)-C7H3ab2(5)
|
1458
|
1455
|
1442
|
1442
|
1445
|
1444
|
1442
|
2.14
|
2.58
|
C8H3ab2(28)-C1H3ab2(25)-C7H3ab2(16)-C6H3ab2(7)-C5H3ab2(7)-C6H3ab1(7)
|
1383
|
1387
|
1389
|
1392
|
1390
|
1390
|
1392
|
3.40
|
0.71
|
C6H3sb(48)C1H3sb(16)C5H3sb(9)C8H3sb(8)C7H3sb(7)
|
1383
|
1387
|
1385
|
1387
|
1383
|
1383
|
1383
|
14.65
|
0.51
|
C5H3sb(46)C8H3sb(23)-C6H3sb(13)-C1H3sb(6)
|
1383
|
1380
|
1377
|
1370
|
1379
|
1372
|
1376
|
10.40
|
0.73
|
C7H3sb(67)C3C7s(10)
|
1363
|
1368
|
1370
|
1367
|
1367
|
1365
|
1370
|
7.34
|
0.81
|
C8H3sb(29)-C1H3sb(25)-C5H3sb(17)C6H3sb(5)
|
1363
|
1368
|
1364
|
1365
|
1364
|
1364
|
1365
|
6.95
|
0.79
|
C1H3sb(39)C8H3sb(22)-C6H3sb(13)-C5H3sb(11)
|
1346
|
*
|
1356
|
1357
|
1349
|
1360
|
1346
|
1.36
|
4.19
|
DefC4H(17)DefC2H(17)Def'C3H(16)-DefC3H(10)-C3C4s(9)
|
1346
|
*
|
1340
|
1344
|
1343
|
1347
|
1338
|
0.14
|
1.19
|
Def'C2H(24)-DefC3H(22)-Def'C3H(9)C7H3sb(8)-C6H3sb(8)
|
1315
|
1321
|
1323
|
1321
|
1321
|
1323
|
1335
|
0.32
|
6.34
|
Def'C4H(42)DefC2H(18)
|
1315
|
1321
|
1319
|
1318
|
1316
|
1319
|
1318
|
2.22
|
6.88
|
DefC2H(24)-Def'C4H(17)-DefC4H(13)-Def'C2H(12)
|
1289
|
1297
|
1294
|
1283
|
1301
|
1295
|
1301
|
0.52
|
3.75
|
Def'C2H(20)DefC3H(17)Def'C3H(14)-C2C3s(12)-Def'C4H(7)
|
1264
|
1270
|
1270
|
1279
|
1273
|
1270
|
1256
|
1.05
|
0.39
|
DefC4H(29)-Def'C3H(26)DefC3H(12)
|
*
|
*
|
1188
|
1195
|
1191
|
1190
|
1183
|
1.36
|
3.52
|
C2C3s(14)C6H3r1(11)C1H3r1(8)-C3C4s(7)C1C2C6b(6)C4C3C7b(6)Def'C2H(5)
|
1181
|
1187
|
1171
|
1178
|
1183
|
1177
|
1176
|
0.42
|
3.15
|
C3C4s(17)-C2C3C4b(7)C5H3r2(7)DefC4H(6)C1H3r1(6)-C2C6s(6)-C3C4C5b(6)
|
1156
|
1160
|
1164
|
1166
|
1172
|
1167
|
1164
|
0.50
|
2.75
|
C8H3r2(15)C5C4C8b(12)-C5H3r1(11)-C4C5s(11)-C8H3r1(7)C5H3r2(6)C2C3C4b(6)
|
1156
|
1160
|
1159
|
1153
|
1148
|
1148
|
1152
|
0.53
|
3.69
|
C1H3r2(10)C3C7s(7)C6H3r1(7)C4C8s(7)C1C2C3b(6)-C1C2s(6)
|
1119
|
1124
|
1126
|
1132
|
1106
|
1134
|
1131
|
12.12
|
0.99
|
C6H3r2(13)-C7H3r2(13)C4C8s(9)-C2C3C6b(8)-C5H3r2(7)-C1H3r2(7)C2C3C7b(7)
|
1071
|
1075
|
1076
|
1061
|
1076
|
1061
|
1076
|
3.16
|
2.56
|
C4C5s(16)-C4C8s(13)-C1C2s(12)C2C6s(9)-C8H3r2(6)-C7H3r2(6) C6H3r1(5)
|
1035
|
1038
|
1036
|
1031
|
1048
|
1027
|
1033
|
6.17
|
1.18
|
C7H3r2(19)DefC3H(12)-C1H3r1(12)-C1C2s(8)C2C6s(7)C5H3r1(5) C2C3s(5)
|
993
|
997
|
997
|
1002
|
993
|
1007
|
1016
|
1.31
|
4.80
|
C3C7s(37)-C1H3r2(16)Def'C2H(8)C6H3r2(6)-C3C4s(6)C7H3r1(6)
|
966
|
973
|
966
|
980
|
975
|
969
|
964
|
2.89
|
1.53
|
C7H3r1(30)Def'C3H(12)-C5H3r1(10)-DefC4H(8)-C1C2s(6)
|
951
|
*
|
955
|
948
|
954
|
953
|
950
|
0.21
|
1.46
|
C6H3r2(26)C1H3r2(18)-C1H3r1(10)-C2C6s(9)C1C2s(8)C7H3r1(6)C6H3r1(5)
|
951
|
*
|
949
|
943
|
946
|
952
|
946
|
0.26
|
3.34
|
C5H3r2(28)-C8H3r2(22)C4C8s(13)-C4C5s(9)-C8H3r1(8)
|
926
|
*
|
927
|
927
|
926
|
931
|
928
|
0.61
|
6.38
|
C7H3r2(17)C3C4s(13)-C2C3s(12)C6H3r1(11)-C4C5s(8)C1C2s(7) -C8H3r2(6)
|
*
|
919
|
917
|
917
|
916
|
921
|
919
|
1.12
|
1.17
|
C8H3r1(27)-C5H3r1(19)-C8H3r2(11)Def'C4H(10)
|
*
|
919
|
909
|
913
|
911
|
912
|
917
|
0.99
|
0.36
|
C1H3r1(25)-C6H3r1(19)C1H3r2(10)C6H3r2(9)DefC2H(7)C5H3r1(7)
|
886
|
890
|
888
|
887
|
884
|
879
|
889
|
0.34
|
4.60
|
C2C6s(17)C4C8s(14)C4C5s(11)C1C2s(10)-C3C7s(9)C1H3r1(5)
|
810
|
812
|
808
|
805
|
794
|
804
|
792
|
0.85
|
3.06
|
C3C4s(15)C4C8s(12)C4C5s(11)-C2C3s(9)C7H3r2(9)-C2C6s(9)-C1C2s(8)
|
749
|
754
|
746
|
722
|
729
|
720
|
750
|
0.44
|
11.44
|
C2C3s(17)-C2C3C4b(13)C2C6s(9)C3C7s(8)-C3C4C5b(7)-C7H3r1(7)C3C4s(6)
|
472
|
575
|
570
|
586
|
581
|
551
|
|
0.96
|
2.32
|
C2C3C7b(25)-C2C3C6b(22)-C1C2C3b(10)-C6H3r2(6)
|
|
|
|
532
|
525
|
505
|
502
|
|
|
C3C2C6b(16)C4C3C7b(15)-C3C4C5b(12)-C5C4C8b(8)-C3C4C8b(6)C1C2C3b(5)-C2C3C4b(5)
|
472
|
475
|
470
|
469
|
471
|
|
481
|
0.22
|
3.70
|
C2C3C4b(17)C1C2C3b(17)C5C4C8b(14)C1C2C6b(11)C4C3C7b(7) C3C4s(5)
|
*
|
*
|
439
|
|
|
435
|
446
|
0.08
|
1.61
|
C3C4C8b(31)C5C4C8b(16)C2C3C6b(12)C4C3C7b(12)-C2C3C4b(6)
|
417
|
415
|
413
|
401
|
401
|
406
|
410
|
0.09
|
0.94
|
C1C2C6b(30)C3C4C5b(27)C3C4C8b(13)-C4C3C7b(6)
|
397
|
400
|
394
|
|
|
387
|
387
|
0.14
|
0.61
|
C5C4C8b(37)-C4C3C7b(15)C3C4C5b(11)-C1C2C3b(7)
|
358
|
355
|
360
|
364
|
346
|
|
352
|
0.06
|
0.16
|
C3C4C5b(28)-C2C3C7b(21)-C1C2C6b(9)-C1C2C3b(7)C4C3C7b(6)-C3C4C8b(6)
|
318
|
313
|
321
|
329
|
338
|
333
|
337
|
0.09
|
2.37
|
C1C2C3b(25)-C1C2C6b(18)C2C6tr(7)C3C4C5b(7)C2C3s(5)C2C3C6b(5)
|
318
|
313
|
|
311
|
312
|
319
|
|
|
|
C3C4C5b(32)C4C3C7b(23)C4C5tr(13)C1C2C6b(6)-C1C2C3b(6)
|
286
|
281
|
291
|
|
|
305
|
297
|
0.07
|
0.30
|
C2C3C6b(30)C2C3C7b(22)-C5C4C8b(8)C4C3C7b(8)-C3C4C8b(7)-C4C8tr(5)
|
286
|
281
|
|
288
|
289
|
|
289
|
|
|
C1C2tr(50)C4C5tr(18)C2C3C7b(6)
|
*
|
*
|
270
|
|
279
|
274
|
272
|
0.03
|
0.04
|
C2C6tr(71)C1C2C6b(6)
|
*
|
*
|
|
261
|
260
|
|
|
|
|
C1C2tr(25)-C2C6tr(17)-C2C3C7b(15)-C1C2C3b(12)C3C2C6b(7)-C2C3C4b(6)
|
*
|
*
|
244
|
254
|
|
257
|
247
|
0.03
|
0.07
|
C1C2tr(41)-C4C8tr(26)-C2C3C4b(11)
|
237
|
236
|
235
|
239
|
239
|
235
|
231
|
0.06
|
0.47
|
C4C5tr(55)-C2C3C7b(13)
|
*
|
*
|
|
229
|
226
|
227
|
|
|
|
C2C6tr(25)-C4C5tr(20)-C3C7tr(16)C2C3C4b(10)-C4C8tr(8)C1C2tr(7)
|
200
|
*
|
210
|
220
|
219
|
|
211
|
0.01
|
0.06
|
C1C2tr(42)C4C8tr(20)C2C3C4b(8)-C1C2C3b(8)C4C3C7b(6)
|
200
|
*
|
195
|
204
|
207
|
197
|
190
|
0.00
|
0.22
|
C4C8tr(28)C4C5tr(24)-C2C3C4b(18)-C3C7tr(11)
|
*
|
*
|
170
|
|
|
145
|
|
0.04
|
0.09
|
C3C7tr(50)C4C3C7b(14)-C3C4C8b(10)C4C8tr(8)-C2C6tr(6)
|
*
|
*
|
83
|
103
|
95
|
108
|
99
|
0.01
|
0.05
|
C3C4tr(68)-C2C6tr(9)C3C7tr(6)
|
*
|
*
|
73
|
83
|
78
|
86
|
42
|
0.02
|
0.51
|
C2C3tr(55)C3C7tr(22)C1C2tr(9)
|