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S1
Supporting Information
Cobalt-Catalyzed C2α-acyloxylation
of 2-Substituted Indoles with tert-Butyl Peresters
Yuxiang Zhou, Chenglong Li, Xiaoyan Yuan, Feiyan Zhang, Xiaozu Liu,* and Peijun Liu*
Generic Drug Research Center of Guizhou Province, Green Pharmaceuticals Engineering Research Center of Guizhou Province, School of Pharmacy, Zunyi
Medical University, Zunyi 563006, P. R. China
*E-mail: pjliu@zmc.edu.cn
*E-mail: lxz307@126.com
Table of Contents
1. General information ............................................................................ S2
2. Preparation of starting materials ........................................................................... S2
3. General procedure for the Co(II)-catalyzed C2α-acyloxylation ........ S2
4. Characterization data of products ......................................................................... S3
5. Gram-scale synthesis and synthetic applications ............................. S17
6. Radical trapping experiments ........................................................... S19
7. References ......................................................................................... S19
8. Single crystal data of product 3aa .................................................. S21
9. Single crystal data of product 3ga .................................................. S27
10. NMR spectra of products ................................................................ S33
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2019
S2
1. General information
Unless otherwise noted, all commercial materials and solvents were used without
further purification. Commercially available chemicals were obtained from Energy
Chemical, TCI, Alfa Aesar and J&K. Thin layer chromatography (TLC) was carried
out on GF254 plates (0.25 mm layer thickness) and visualized under UV light (254
nm). The silica gel (200-300 meshes) was used for column chromatography. 1H and 13C NMR spectra were recorded on Agilent 400 MHz spectrometer using TMS as
internal standard. Spin multiplicities are given as s (singlet), d (doublet), t (triplet), q
(quartet), m (multiplet), dd (doublet of doublet), td (triplet of doublet), as well as brs
(broad). Coupling constants (J) are given in hertz (Hz). High resolution mass spectra
were obtained on Agilent 6210 ESI/TOF spectrometer.
2. Preparation of starting materials
(1) N-Pyrimidinyl-2-methyl indoles 1a-f, N-pyrimidinyl-2,3-dimethyl indole 1g,
9-(pyrimidin-2-yl)-2,3,4,9-tetrahydro-1H-carbazole 1x, and 1-(5-bromopyrimidin
-2-yl)-2-ethyl-1H-indole 1y were prepared according to literature procesure.1
(2) N-Pyrimidinyl-2,3-disubstituted indoles 1h-v were prepared via a modified
Fischer indole synthesis2 followed by protection for the indole -NH.1
(3) 1-(5-Bromopyrimidin-2-yl)-2-methyl-3-propyl-1H-indole-5-carbonitrile 1w was
prepared via a Fischer indole synthesis3 followed by protection for the indole
-NH.1
(4) All the tert-butyl peresters were prepared according to literature procedure.4
3. General procedure for the Co(II)-catalyzed C2α-acyloxylation
To a 25 mL of Schlenk tube equipped with a Teflon-coated magnetic stir bar were
added indole 1 (0.5 mmol, 1.0 equiv), perester 2 (1.5 mmol, 3.0 equiv), Co(acac)2
(0.05 mmol, 10 mol%), and toluene (3 mL). The resulting mixture was stirred at 80 oC
for 1.5 to 24 hours. Upon completion of the reaction as monitored by TLC, the
reaction mixture was then cooled to room temperature, and concentrated under
reduced pressure. The crude residue was purified by flash column chromatography on
silic
3.
4.
(1-(
Foll
76%
= 8.
7.41
6.86
135
62.0
(1-(
N
Foll
60%
1H)
(t, J
(s, 2
132
HRM
(1-(
ca gel (petro
Characte
(Pyrimidin-
N
N N
OBz
3aa
lowing the g
%). mp 132-
.4 Hz, 1H),
1 (t, J = 8.0
6 (s, 1H), 5
.1, 132.9,
0; HRMS (E
(5-Methylp
N
N N
Me
OBz
3ba
lowing the g
%). mp 105-
), 7.97 (d, J
J = 8.0 Hz, 2
2H), 2.27 (s
2.9, 130.2, 1
MS (ESI/[M
(5-Fluoropy
oleum ether
erization d
-2-yl)-1H-in
general pro
-134 oC; 1H
7.98 (d, J =
Hz, 2H), 7.
.97 (s, 2H);
130.1, 129.
ESI/[M + N
yrimidin-2
general pro
-107 oC; 1H
J = 8.4 Hz, 2
2H), 7.32 (t
s, 3H); 13C N
29.6, 128.7
M + Na]+) c
yrimidin-2-
r/ethyl acet
data of pr
ndol-2-yl)m
ocedure, pro
H NMR (400
= 8.3 Hz, 2H
.36 – 7.32 (
; 13C NMR
.5, 128.9, 1
Na]+) calcd f
2-yl)-1H-ind
cedure, pro
NMR (400
2H), 7.61 (d
t, J = 7.8 Hz
NMR (101 M
7, 128.3, 126
alcd for C21
-yl)-1H-ind
S3
tate = 30/1
roducts
methyl benz
oduct 3aa w
0 MHz, CD
H), 7.62 (d,
(m, 1H), 7.2
(101 MHz,
128.3, 123.8
for C20H15O
dol-2-yl)me
oduct 3ba w
0 MHz, CDC
d, J = 7.8 H
z, 1H), 7.23
MHz, CDC
6.2, 123.7,
1H17O2N3Na
dol-2-yl)me
as eluent) t
zoate (3aa)
was obtained
Cl3) δ 8.72
J = 8.0 Hz
27 – 7.23 (m
CDCl3) δ
8, 122.2, 1
O2N3Na+: 35
ethyl benzo
was obtained
Cl3) δ 8.54 (
Hz, 1H), 7.5
3 (t, J = 7.4
Cl3) δ 166.1,
121.9, 120.
a+: 366.121
ethyl benzo
to give the
d as a white
(d, J = 4.8,
, 1H), 7.56
m, 1H), 7.06
166.2, 158.
20.5, 116.8
2.1056, fou
oate (3ba)
d as a white
(s, 2H), 8.4
53 (t, J = 8.0
Hz, 1H), 6.
158.0, 156
5, 114.6, 10
3, found 36
ate (3ca)
desired pro
e solid (125
, 2H), 8.57
– 7.52 (m,
6 (t, J = 4.8,
1, 158.0, 13
8, 115.1, 10
und 352.105
e solid (103
6 (d, J = 8.4
0 Hz, 1H),
84 (s, 1H),
6.3, 137.0, 1
08.1, 61.7, 1
66.1214.
oduct
mg,
(d, J
1H),
1H),
37.1,
08.7,
59.
mg,
4 Hz,
7.40
5.94
35.1,
15.0;
S4
Following the general procedure, product 3ca was obtained as a white solid (107 mg,
62%). mp 112-114 oC; 1H NMR (400 MHz, CDCl3) δ 8.57 (s, 2H), 8.44 (d, J = 8.4 Hz,
1H), 7.97 (d, J = 8.3 Hz, 2H), 7.62 (d, J = 7.7 Hz, 1H), 7.55 (t, J = 7.6 Hz, 1H), 7.41
(t, J = 7.6 Hz, 2H), 7.34 (t, J = 7.8 Hz, 1H), 7.27 – 7.23 (m, 1H), 6.86 (s, 1H), 5.91 (s,
2H); 13C NMR (101 MHz, CDCl3) δ 166.1, 154.7 (d, J = 260.4 Hz), 154.2 (d, J = 2.9
Hz), 145.8 (d, J = 21.9 Hz), 137.1 , 135.1, 133.1, 130.0, 129.6, 128.7, 128.4, 124.0,
122.4, 120.7, 114.6, 109.0, 61.6; HRMS (ESI/[M + Na]+) calcd for C20H14O2N3FNa+:
370.0962, found 370.0965.
(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)methyl benzoate (3da)
Following the general procedure, product 3da was obtained as a white solid (147 mg,
72%). mp 115-116 oC; 1H NMR (400 MHz, CDCl3) δ 8.73 (s, 2H), 8.51 (d, J = 8.4 Hz,
1H), 8.00 (d, J = 8.0 Hz, 2H), 7.61 – 7.54 (m, 2H), 7.42 (t, J = 7.6 Hz, 2H), 7.34 (t, J
= 7.8 Hz, 1H), 7.27 – 7.24 (m, 1H), 6.86 (s, 1H), 5.91 (s, 2H); 13C NMR (101 MHz,
CDCl3) δ 166.1, 158.5, 156.3, 137.0, 135.3, 133.1, 130.0, 129.6, 129.0, 128.4, 124.1,
122.6, 120.7, 115.3, 114.2, 109.5, 61.8; HRMS (ESI/[M + Na]+) calcd for
C20H14O2N3BrNa+: 430.0162, found 430.0164.
(5-Methyl-1-(pyrimidin-2-yl)-1H-indol-2-yl)methyl benzoate (3ea)
Following the general procedure, product 3ea was obtained as a colorless oil (95 mg,
55%). 1H NMR (400 MHz, CDCl3) δ 8.70 (d, J = 4.8, 2H), 8.46 (d, J = 8.6, Hz, 1H),
7.98
1H)
MH
128
C21H
(5-C
Cl
Foll
74%
(d, J
2H)
NM
129
calc
(3-M
Foll
44%
= 8.
1H)
NM
129
Na]
(1-(
8 (d, J = 8.0
), 7.04 (d, J
Hz, CDCl3)
.3, 125.3, 1
H17O2N3Na
Chloro-1-(p
N
N N
O
3fa
lowing the
%). mp 139-
J = 8.8 Hz,
), 7.26 (d, J
MR (101 MH
9.6, 128.4, 1
cd for C20H1
Methyl-1-(p
N
Me
N N
OBz
3ga
lowing the
%). mp 91-9
.2 Hz, 1H),
), 7.38 – 7.
MR (101 MH
9.4, 128.2, 1+) calcd for
(5-Bromopy
0 Hz, 2H), 7
J = 4.8, 1H
δ 166.2, 15
20.4, 116.5
a+: 366.1213
pyrimidin-2
OBz
general pro
-141 oC; 1H
1H), 7.99 (
J = 8.4 Hz,
Hz, CDCl3)
27.72 , 123
14O2N3ClNa
pyrimidin-2
general pro
92 oC; 1H NM
7.82 (d, J =
26 (m, 4H)
Hz, CDCl3)
124.5, 121.8
r C21H17O2N
yrimidin-2-
7.54 (t, J = 8
H), 6.78 (s,
58.2, 157.9,
5, 114.9, 108
3, found 366
2-yl)-1H-in
ocedure, pro
H NMR (400
(d, J = 8.0 H
1H), 7.10 (t
) δ 166.1, 1
3.9, 119.9, 1
a+: 386.0667
2-yl)-1H-in
ocedure, pro
MR (400 M
= 7.4 Hz, 2
), 7.02 (t, J
) δ 166.3, 1
8, 119.0, 1
N3Na+: 366.
-yl)-3-ethyl
S5
8.0 Hz, 1H)
1H), 5.95 (
135.4, 135
8.5, 62.1, 2
6.1216.
ndol-2-yl)m
oduct 3fa w
0 MHz, CD
Hz, 2H), 7.5
t, J = 4.8 H
158.1, 157.
117.1, 116.4
7, found 38
ndol-2-yl)m
oduct 3ga w
MHz, CDCl3
2H), 7.62 (d
J = 3.8 Hz,
158.1, 158.
18.2, 116.7
1213, found
l-1H-indol-
), 7.42 – 7.3
(s, 2H), 2.4
5.3, 132.9, 1
1.3; HRMS
methyl benzo
was obtained
DCl3) δ 8.73
57 – 7.53 (m
Hz, 1H), 6.78
9, 136.9, 1
4, 107.6, 61
86.0670.
methyl benz
was obtaine
3) δ 8.69 (d,
d, J = 7.7 Hz
1H), 5.99
0, 136.5, 1
7, 114.4, 58
d 366.1216.
-2-yl)methy
8 (m, 3H),
45 (s, 3H);
131.6, 130.2
(ESI/[M +
oate (3fa)
d as a white
3 (d, J = 4.8
m, 2H), 7.42
8 (s, 1H), 5
35.4, 133.1
.9; HRMS (
oate (3ga)
d as a whit
J = 4.4 Hz,
z, 1H), 7.47
(s, 2H), 2.4
32.7, 130.2
.4, 8.9; HR
.
yl benzoate
7.15 (d, 8.613C NMR
2, 129.6, 12
+ Na]+) calcd
e solid (134
8 Hz, 2H),
2 (t, J = 7.6
.95 (s, 2H);
1, 130.1, 13
(ESI/[M + N
te solid (76
, 2H), 8.44
7 (t, J = 7.3
47 (s, 3H);
2, 129.9, 12
RMS (ESI/[
e (3ha)
6 Hz,
(101
29.1,
d for
mg,
8.52
6 Hz,
; 13C
30.0,
Na]+)
mg,
(d, J
3 Hz,
; 13C
29.7,
M +
S6
Following the general procedure, product 3ha was obtained as a white solid (135 mg,
62%). mp 101-102 oC; 1H NMR (400 MHz, CDCl3) δ 8.70 (s, 2H), 8.41 (d, J = 8.3 Hz,
1H), 7.85 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.1 Hz, 1H), 7.52 – 7.48 (m, 1H), 7.38 –
7.33 (m, 3H), 7.29 (d, J = 7.4 Hz, 1H), 5.91 (s, 2H), 2.93 (q, J = 7.5 Hz, 2H), 1.33 (t,
J = 7.6 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.3, 158.4, 156.3, 136.59 , 132.9,
130.1, 129.4, 129.3, 128.9, 128.3, 125.6, 124.7, 122.2, 119.2, 114.8, 114.1, 58.0, 17.5,
15.7; HRMS (ESI/[M + H]+) calcd for C22H19O2N3Br+: 436.0655, found 436.0658.
(1-(5-Bromopyrimidin-2-yl)-3-isopropyl-1H-indol-2-yl)methyl benzoate (3ia)
Following the general procedure, product 3ia was obtained as a white solid (126 mg,
56%). mp 65-66 oC; 1H NMR (400 MHz, CDCl3) δ 8.72 (s, 2H), 8.35 (d, J = 8.4 Hz,
1H), 7.88 – 7.83 (m, 3H), 7.51 (t, J = 7.3 Hz, 1H), 7.38 – 7.32 (m, 3H), 7.27 – 7.23 (m,
1H), 5.92 (s, 2H), 3.51 – 3.44 (m, 1H), 1.54 (d, J = 7.1 Hz, 6H); 13C NMR (101 MHz,
CDCl3) δ 166.2, 158.5, 156.2, 136.9, 132.9, 130.1, 129.4, 129.0, 128.4, 128.2, 127.7,
124.2, 121.7, 120.8, 114.5, 114.4, 57.8, 26.2, 22.8; HRMS (ESI/[M + H]+) calcd for
C23H21O2N3Br+: 450.0812, found 450.0811.
(3-Propyl-1-(pyrimidin-2-yl)-1H-indol-2-yl)methyl benzoate (3ja)
Following the general procedure, product 3ja was obtained as a white solid (130 mg,
70%). mp 58-60 oC; 1H NMR (400 MHz, CDCl3) δ 8.68 (d, J = 4.8 Hz, 2H), 8.43 (d, J
= 8.3 Hz, 1H), 7.80 (d, J = 7.8 Hz, 2H), 7.65 (d, J = 7.8 Hz, 1H), 7.47 (t, J = 7.4 Hz,
S7
1H), 7.37 – 7.24 (m, 4 H), 7.01 (t, J = 4.8 Hz, 1H), 5.95 (s, 2H), 2.89 (t, J = 7.5 Hz,
2H), 1.80 – 1.71 (m, 2H), 1.02 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ
166.3, 158.1, 158.0, 136.7, 132.7, 130.2, 129.9, 129.4, 129.2, 128.2, 124.3, 122.9,
121.7, 119.2, 116.7, 114.5, 58.3, 26.2, 24.0, 14.1; HRMS (ESI/[M + Na]+) calcd for
C23H21O2N3Na+: 394.1526, found 394.1529.
(3-Isobutyl-1-(pyrimidin-2-yl)-1H-indol-2-yl)methyl benzoate (3ka)
Following the general procedure, product 3ka was obtained as a white solid (116 mg,
60%). mp 114-116 oC; 1H NMR (400 MHz, CDCl3) δ 8.68 (d, J = 4.8 Hz, 2H), 8.42
(d, J = 8.4 Hz, 1H), 7.78 (d, J = 7.5 Hz, 2H), 7.63 (d, J = 7.8 Hz, 1H), 7.46 (t, J = 7.4
Hz, 1H), 7.36 – 7.23 (m, 4H), 7.01 (t, J = 4.8 Hz, 1H), 5.94 (s, 2H), 2.77 (d, J = 7.3
Hz, 2H), 2.10 – 2.00 (m, 1H), 1.01 (d, J = 6.6 Hz, 6H); 13C NMR (101 MHz, CDCl3)
δ 166.3, 158.1, 158.0, 136.6, 132.7, 130.2, 130.1, 129.4, 129.4, 128.2, 124.3, 122.0,
121.7, 119.5, 116.8, 114.3, 58.4, 33.4, 29.7, 22.7; HRMS (ESI/[M + Na]+) calcd for
C24H23O2N3Na+: 408.1682, found 408.1685.
(3-Benzyl-1-(5-bromopyrimidin-2-yl)-1H-indol-2-yl)methyl benzoate (3la)
Following the general procedure, product 3la was obtained as a white solid (204 mg,
82%). mp 61-62 oC; 1H NMR (400 MHz, CDCl3) δ 8.72 (s, 2H), 8.40 (d, J = 8.4 Hz,
1H), 7.81 (d, J = 8.3 Hz, 2H), 7.59 – 7.45 (m, 2H), 7.39 – 7.28 (m, 5H), 7.25 – 7.12
(m, 4H), 5.95 (s, 2H), 4.30 (s, 2H); 13C NMR (101 MHz, CDCl3) δ 166.2, 158.5,
156.2, 139.9, 136.6, 132.9, 130.8, 130.0, 129.5, 129.2, 128.5, 128.3, 128.2, 126.1,
124.8, 122.4, 121.9, 119.7, 114.7, 114.4, 58.1, 30.1; HRMS (ESI/[M + H]+) calcd for
C27H21BrN3O2+: 498.0812, found 498.0819.
S8
(1-(5-Bromopyrimidin-2-yl)-3-(4-methoxyphenyl)-1H-indol-2-yl)methyl benzoate
(3ma)
Following the general procedure, product 3ma was obtained as a white solid (131 mg,
51%). mp 174-175 oC; 1H NMR (400 MHz, CDCl3) δ 8.69 (s, 2H), 8.45 (d, J = 8.5 Hz,
1H), 7.86 (d, J = 8.0 Hz, 2H), 7.66 (d, J = 7.9 Hz, 1H), 7.53 – 7.49 (m, 3H), 7.42 –
7.34 (m, 3H), 7.28 (t, J = 7.6 Hz, 1H), 7.05 (d, J = 8.5 Hz, 2H), 5.81 (s, 2H), 3.88 (s,
3H); 13C NMR (101 MHz, CDCl3) δ 166.2, 159.2, 158.6, 156.2, 136.4, 132.9, 131.2,
130.1, 129.7, 129.5, 128.8, 128.3, 125.3, 125.2, 125.0, 122.7, 120.2, 114.7, 114.6,
114.2, 59.3, 55.3; HRMS (ESI/[M + Na]+) calcd for C27H20O3N3BrNa+: 536.0580,
found 536.0583.
(5-Chloro-3-(4-methoxyphenyl)-1-(pyrimidin-2-yl)-1H-indol-2-yl)methyl
benzoate (3na)
N
N N
Cl
OMe
OBz
3na
Following the general procedure, product 3na was obtained as a light yellow solid
(120 mg, 51%). mp 138-139 oC; 1H NMR (400 MHz, CDCl3) δ 8.69 (d, J = 4.8 Hz,
2H), 8.42 (d, J = 8.9 Hz, 1H), 7.80 (d, J = 7.8 Hz, 2H), 7.62 (d, J = 2.2 Hz, 1H), 7.50
– 7.47 (m, 3H), 7.35 – 7.31 (m, 3H), 7.06 – 7.04 (m, 3H), 5.84 (s, 2H), 3.88 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 166.1, 159.3, 158.2, 157.8, 134.9, 132.8, 131.2, 130.1,
129.93, 129.4, 128.2, 128.0, 124.8, 124.8, 123.8, 119.5, 117.3, 115.8, 114.4, 59.3,
55.4; HRMS (ESI/[M + Na]+) calcd for C27H20O3N3ClNa+: 492.1085, found
492.1089.
(1-(5-Bromopyrimidin-2-yl)-3-(4-fluorophenyl)-1H-indol-2-yl)methyl benzoate
(3oa)
S9
Following the general procedure, product 3oa was obtained as a white solid (125 mg,
50%). mp 129-131 oC; 1H NMR (400 MHz, CDCl3) δ 8.71 (s, 2H), 8.45 (d, J = 8.4 Hz,
1H), 7.85 (d, J = 8.4 Hz, 2H), 7.62 (d, J = 7.9 Hz, 1H), 7.58 – 7.50 (m, 3H), 7.43 –
7.35 (m, 3H), 7.30 (t, J = 7.5 Hz, 1H), 7.21 (t, J = 8.7 Hz, 2H), 5.80 (s, 2H); 13C NMR
(101 MHz, CDCl3) δ 166.1, 162.4 (d, J = 247.1 Hz), 158.6, 156.1, 136.3, 133.0, 131.7
(d, J = 8.1 Hz), 130.1, 130.0, 129.4, 128.9 (d, J = 3.2 Hz), 128.5, 128.3, 125.1, 124.4,
122.8, 119.9, 115.8 (d, J = 21.5 Hz), 114.8, 114.7, 59.0; HRMS (ESI/[M + Na]+)
calcd for C26H17O2N3BrFNa+: 524.0380, found 524.0382.
(1-(5-Bromopyrimidin-2-yl)-3-(4-chlorophenyl)-1H-indol-2-yl)methyl benzoate
(3pa)
Following the general procedure, product 3pa was obtained as a white solid (133 mg,
51%). mp 139-141 oC; 1H NMR (400 MHz, CDCl3) δ 8.71 (s, 2H), 8.44 (d, J = 8.4 Hz,
1H), 7.84 (d, J = 8.0 Hz, 2H), 7.62 (d, J = 7.9 Hz, 1H), 7.54 – 7.47 (m, 5H), 7.43 –
7.37 (m, 3H), 7.30 (t, J = 7.5 Hz, 1H), 5.79 (s, 2H); 13C NMR (101 MHz, CDCl3) δ
166.0, 158.6, 156.1, 136.4, 133.6, 133.0, 131.4, 131.3, 130.2, 129.9, 129.4, 129.0,
128.3, 128.3, 125.2, 124.2, 122.9, 119.9, 114.9, 114.7, 59.0; HRMS (ESI/[M + H]+)
calcd for C26H18BrClN3 O2+: 518.0265, found 518.0268.
(3-(4-Bromophenyl)-1-(5-bromopyrimidin-2-yl)-1H-indol-2-yl)methyl benzoate
(3qa)
S10
Following the general procedure, product 3qa was obtained as a white solid (145 mg,
52%). mp 146-148 oC; 1H NMR (400 MHz, CDCl3) δ 8.72 (s, 2H), 8.43 (d, J = 8.4 Hz,
1H), 7.83 (d, J = 8.2 Hz, 2H), 7.65 – 7.61 (m, 3H), 7.54 – 7.50 (m, 1H), 7.47 (d, J =
8.2, 2H), 7.43 – 7.35 (m, 3H), 7.30 (t, J = 7.7 Hz, 1H), 5.79 (s, 2H); 13C NMR (101
MHz, CDCl3) δ 166.1, 158.7, 156.1, 136.4, 133.0, 131.9, 131.7, 130.2, 129.9, 129.4,
128.3, 128.2, 125.2, 124.2, 122.9, 121.8, 119.8, 114.9, 114.7, 59.0; HRMS (ESI/[M +
Na]+) calcd for C26H17O2N3Br2Na+: 583.9580, found 583.9583.
(1-(5-Bromopyrimidin-2-yl)-5-methyl-3-propyl-1H-indol-2-yl)methyl benzoate
(3ra)
Following the general procedure, product 3ra was obtained as a white solid (151 mg,
65%). mp 96-98 oC; 1H NMR (400 MHz, CDCl3) δ 8.66 (s, 2H), 8.31 (d, J = 8.5 Hz,
1H), 7.85 (d, J = 8.4 Hz, 2H), 7.52 – 7.48 (m, 1H), 7.41 (s, 1H), 7.35 (t, J = 7.7 Hz,
2H), 7.17 (d, J = 8.6 Hz, 1H), 5.89 (s, 2H), 2.85 (t, J = 7.5 Hz, 2H), 2.49 (s, 3H), 1.78
– 1.69 (m, 2 H), 1.02 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.4, 158.3,
156.3, 134.8, 132.8, 131.6, 130.2, 129.8, 129.5, 129.4, 128.2, 126.0, 123.7, 119.1,
114.7, 113.7, 58.2, 26.2, 23.9, 21.4, 14.1; HRMS (ESI/[M + Na]+) calcd for
C24H22O2N3BrNa+: 486.0788, found 486.0791.
(1-(5-bromopyrimidin-2-yl)-5-methoxy-3-propyl-1H-indol-2-yl)methyl benzoate
(3sa)
S11
Following the general procedure, product 3sa was obtained as a white solid (139 mg,
58%). mp 135-136 oC; 1H NMR (400 MHz, CDCl3) δ 8.65 (s, 2H), 8.37 (d, J = 9.1 Hz,
1H), 7.86 (d, J = 7.8 Hz, 2H), 7.50 (t, J = 7.3 Hz, 1H), 7.35 (t, J = 7.6 Hz, 2H), 7.06 (s,
1H), 6.98 (d, J = 9.1 Hz, 1H), 5.88 (s, 2H), 3.90 (s, 3H), 2.84 (t, J = 7.4 Hz, 2H), 1.78
– 1.69 (m, 2H), 1.02 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.4, 158.3,
156.2, 155.6, 132.8, 131.4, 130.5, 130.2, 130.1, 129.4, 128.3, 123.7, 116.0, 113.6,
113.4, 101.7, 58.3, 55.8, 26.2, 23.8, 14.1; HRMS (ESI/[M + Na]+) calcd for
C24H22O3N3BrNa+: 502.0737, found 502.0739.
(1-(5-Bromopyrimidin-2-yl)-5-fluoro-3-propyl-1H-indol-2-yl)methyl benzoate
(3ta)
Following the general procedure, product 3ta was obtained as a white solid (187 mg,
80%). mp 120-122 oC; 1H NMR (400 MHz, CDCl3) δ 8.68 (s, 2H), 8.38 (ddd, J = 9.1,
4.6, 1.0 Hz, 1H), 7.84 (d, J = 8.4 Hz, 2H), 7.50 (td, J = 7.4, 1.4 Hz, 1H), 7.35 (t, J =
8.4 Hz, 2H), 7.28 – 7.25 (m, 1H), 7.10 – 7.04 (m, 1H), 5.88 (s, 2H), 2.83 (t, J = 7.5
Hz, 2H), 1.76 – 1.67 (m, 2H), 1.01 (t, J = 7.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ
166.3, 158.9 (d, J = 238.9 Hz), 158.4, 156.0, 132.9, 132.8, 131.4, 130.2 (d, J = 9.5
Hz), 130.0, 129.4, 128.3, 123.5 (d, J = 4.2 Hz), 116.0 (d, J = 8.8 Hz), 114.2, 112.4 (d,
J = 25.0 Hz), 104.6 (d, J = 23.4 Hz), 58.1, 26.1, 23.8, 14.0; HRMS (ESI/[M + Na]+)
calcd for C23H19O2N3BrFNa+: 490.0537, found 490.0540.
(1-(5-Bromopyrimidin-2-yl)-5-chloro-3-propyl-1H-indol-2-yl)methyl benzoate
(3ua)
S12
N
Cl
N N
Br
OBz
3ua
Following the general procedure, product 3ua was obtained as a white solid (196 mg,
81%). mp 123-125 oC; 1H NMR (400 MHz, CDCl3) δ 8.68 (s, 2H), 8.34 (d, J = 8.9 Hz,
1H), 7.84 (d, J = 8.3 Hz, 2H), 7.58 (s, 1H), 7.53 – 7.48 (m, 1H), 7.35 (t, J = 7.5 Hz,
2H), 7.30 – 7.27 (m, 1H), 5.87 (s, 2H), 2.83 (t, J = 7.5 Hz, 2H), 1.76 – 1.67 (m, 2H),
1.01 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.2, 158.4, 156.0, 134.8,
132.9, 131.2, 130.5, 130.0, 129.4, 128.3, 127.7, 124.6, 123.1, 118.8, 116.1, 114.4,
58.0, 26.1, 23.8, 14.0; HRMS (ESI/[M + Na]+) calcd for C23H19O2N3BrClNa+:
506.0241, found 506.0244.
(5-Bromo-1-(5-bromopyrimidin-2-yl)-3-propyl-1H-indol-2-yl)methyl benzoate
(3va)
Following the general procedure, product 3va was obtained as a white solid (166 mg,
63%). mp 103-104 oC; 1H NMR (400 MHz, CDCl3) δ 8.68 (s, 2H), 8.29 (d, J = 8.9 Hz,
1H), 7.84 (d, J = 7.9 Hz, 2H), 7.74 (s, 1H), 7.50 (t, J = 7.3 Hz, 1H), 7.42 (d, J = 8.9
Hz, 1H), 7.35 (t, J = 7.6 Hz, 2H), 5.88 (s, 2H), 2.83 (t, J = 7.5 Hz, 2H), 1.77 – 1.67 (m,
2H), 1.01 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.2, 158.5, 156.0,
135.2, 132.9, 131.1, 131.1, 130.0, 129.4, 128.3, 127.3, 123.0, 121.9, 116.4, 115.4,
114.5, 57.9, 26.1 , 23.9, 14.09; HRMS (ESI/[M + Na]+) calcd for C23H19O2N3Br2Na+:
549.9736, found 549.9738.
(1-(5-Bromopyrimidin-2-yl)-5-cyano-3-propyl-1H-indol-2-yl)methyl benzoate
(3wa)
S13
Following the general procedure, product 3wa was obtained as a white solid (147 mg,
62%). mp 195-196 oC; 1H NMR (600 MHz, CDCl3) δ 8.74 (s, 2H), 8.42 (d, J = 8.7 Hz,
1H), 7.97 (d, J = 1.8 Hz, 1H), 7.81 (d, J = 7.8 Hz, 2H), 7.57 (dd, J = 8.7, 1.8 Hz,1H),
7.51 (t, J = 7.8 Hz, 1H), 7.35 (t, J = 7.8 Hz, 2H), 5.88 (s, 2H), 2.88 (t, J = 7.5 Hz, 2H),
1.76 – 1.70 (m, 2H), 1.02 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 166.1,
158.8, 155.7, 138.2, 133.1, 132.3, 129.7, 129.4, 129.2, 128.3, 127.4, 124.5, 123.2,
120.0, 115.5, 115.4, 105.3, 57.6, 26.0, 24.0, 14.0; HRMS (ESI/[M + Na]+) calcd for
C24H19O2N4BrNa+: 497.0584, found 497.0586.
9-(Pyrimidin-2-yl)-2,3,4,9-tetrahydro-1H-carbazol-1-yl benzoate (3xa)
Following the general procedure, product 3xa was obtained as a white solid (83 mg,
45%). mp 148-150 oC; 1H NMR (400 MHz, CDCl3) δ 8.61 (d, J = 8.3 Hz, 1H), 8.54
(d, J = 4.7 Hz, 2H), 7.87 (d, J = 7.9 Hz, 2H), 7.60 (d, J = 7.7 Hz, 1H), 7.46 (t, J = 7.2
Hz, 1H), 7.37 (t, J = 7.7 Hz, 1H), 7.31 (t, J = 7.6 Hz, 2H), 7.27 (d, J = 6.4 Hz, 1H),
7.04 – 7.02 (m, 1H), 6.85 (t, J = 4.7 Hz, 1H), 3.00 (dt, J = 16.5, 4.4 Hz, 1H), 2.80 –
2.72 (m, 1H), 2.36 – 2.30 (m, 1H), 2.24 – 2.17 (m, 1H), 2.12 – 1.98 (m, 2H); 13C
NMR (101 MHz, CDCl3) δ 166.0, 158.1, 157.8, 136.6, 132.5, 132.2, 130.9, 129.4,
128.7, 128.1, 124.5, 121.9, 120.6, 118.7, 116.2, 115.5, 67.1, 30.2, 21.3, 18.5; HRMS
(ESI/[M + Na]+) calcd for C23H19O2N3Na+: 392.1369, found 392.1374.
1-(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)ethyl benzoate (3ya)
S14
Following the general procedure, product 3ya was obtained as a white solid (115 mg,
55%). mp 107-109 oC; 1H NMR (400 MHz, CDCl3) δ 8.67 (s, 2H), 8.31 (d, J = 8.3 Hz,
1H), 7.90 (d, J = 7.8 Hz, 2H), 7.62 (d, J = 7.7 Hz, 1H), 7.52 (t, J = 7.3 Hz, 1H), 7.37
(t, J = 7.6 Hz, 2H), 7.32 (t, J = 7.7 Hz, 1H), 7.25 (t, J = 7.6 Hz, 1H ), 7.02 (q, J = 6.4
Hz, 1H), 6.92 (s, 1H), 1.86 (d, J = 6.4 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ 165.7,
158.5, 156.2, 140.4, 136.9, 132.9, 130.2, 129.4, 128.6, 128.2, 124.0, 122.4, 120.7,
114.7, 114.4, 107.1, 67.3, 19.8; HRMS (ESI/[M + H]+) calcd for C21H17BrN3O2+
422.0499, found 422.0496.
(1-Methyl-1H-indol-2-yl)methyl benzoate (3za)
Following the general procedure, product 3za was obtained as a white solid (72 mg,
54%). mp 94-95 oC; 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.4 Hz, 2H), 7.63 (d, J
= 7.9 Hz, 1H), 7.56 (t, J = 7.4 Hz, 1H), 7.43 (t, J = 8.1 Hz, 2H), 7.35 (d, J = 8.3 Hz,
1H), 7.29 – 7.25 (m, 1H), 7.13 (t, J = 7.6 Hz, 1H), 6.67 (s, 1H), 5.53 (s, 2H), 3.82 (s,
3H); 13C NMR (101 MHz, CDCl3) δ 166.2, 138.0, 133.6, 133.2, 129.8, 129.7, 128.4,
127.1, 122.4, 121.0, 119.7, 109.3, 104.0, 58.8, 29.9; HRMS (ESI/[M + H]+) calcd for
C17H16 NO2+: 266.1176, found 266.1177.
(1-Acetoxy-1H-indol-2-yl)methyl benzoate (3aaa)
N
OCOMe
OBz
3aaa
Following the general procedure, product 3aaa was obtained as a white solid (86 mg,
56%). mp 41-43 oC; 1H NMR (600 MHz, CDCl3) δ 8.17 (d, J = 8.4 Hz, 1H), 8.11 –
8.08 (m, 2H), 7.61 – 7.56 (m, 1H), 7.54 (dt, J = 7.8, 1.0 Hz, 1H), 7.46 (t, J = 7.8 Hz,
2H), 7.34 (ddd, J = 8.4, 7.1, 1.1 Hz, 1H), 7.28 – 7.24 (m, 1H), 6.76 (s, 1H), 5.71 (s,
2H), 4.03 (s, 3H); 13C NMR (151 MHz, CDCl3) δ 166.1, 152.0, 136.8, 134.8, 133.1,
129.9, 129.7, 128.7, 128.4, 124.9, 123.3, 120.8, 115.6, 110.8, 61.0, 53.9; HRMS
(ESI/[M + H]+) calcd for C18H16NO4+: 310.1074, found 310.1077.
(1-(4-Chlorobenzoyl)-5-methoxy-3-(2-methoxy-2-oxoethyl)-1H-indol-2-yl)methyl
benzoate (7)
S15
N
CO2Me
Cl
MeO
O
OBz
7
Following the general procedure, product 7 was obtained as a light yellow solid (142
mg, 58%). mp 106-108 oC; 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 8.3 Hz, 2H),
7.69 (d, J = 8.5 Hz, 2H), 7.51 (t, J = 7.6 Hz, 1H), 7.44 (d, J = 8.5 Hz, 2H), 7.35 (t, J =
7.8 Hz, 2H), 7.03 (s, 1H), 6.75 – 6.74 (m, 2H), 5.65 (s, 2H), 3.92 (s, 2H), 3.84 (s, 3H),
3.65 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 170.9, 168.1, 165.9, 156.0, 139.7, 133.4,
133.2, 133.1, 131.3, 131.3, 129.6, 129.6, 129.2, 128.3, 116.7, 115.1, 113.9, 101.7,
56.9, 55.7, 52.3, 30.1; HRMS (ESI/[M + Na]+) calcd for C27H22O6NClNa+: 514.1028,
found 514.1033.
(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)methyl 4-methoxybenzoate (3db)
Following the general procedure, product 3db was obtained as a light yellow solid
(158 mg, 72%). mp 129-131 oC; 1H NMR (400 MHz, CDCl3) δ 8.71 (s, 2H), 8.51 (d,
J = 8.0 Hz, 1H), 7.97 (d, J = 8.0 Hz, 2H), 7.60 (d, J = 7.7 Hz, 1H), 7.34 (t, J = 7.8 Hz,
1H), 7.28 – 7.24 (m, 1H), 6.91 (d, J = 8.1 Hz, 2H), 6.85 (s, 1H), 5.87 (s, 2H), 3.86 (s,
3H); 13C NMR (101 MHz, CDCl3) δ 165.8, 163.4, 158.4, 156.2, 136.9, 135.5, 131.6,
129.0, 124.0, 122.5, 122.4, 120.6, 115.2, 114.1, 113.6, 109.2, 61.5, 55.4; HRMS
(ESI/[M + H]+) calcd for C21H17O3N3Br+: 438.0448, found 438.0450.
(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)methyl 3-methylbenzoate (3dc)
S16
Following the general procedure, product 3dc was obtained as a white solid (148 mg,
70%). mp 87-88 oC; 1H NMR (400 MHz, CDCl3) δ 8.73 (s, 2H), 8.50 (d, J = 8.4 Hz,
1H), 7.79 (d, J = 8.8 Hz, 1H), 7.78 (s, 1H), 7.60 (d, J = 7.7 Hz, 1H), 7.37 – 7.30 (m,
3H), 7.28 – 7.24 (m, 1H), 6.85 (s, 1H), 5.89 (s, 2H), 2.38 (s, 3H); 13C NMR (101 MHz,
CDCl3) δ 166.3, 158.5, 156.3, 138.2, 137.0, 135.3, 133.8, 130.1, 129.9, 129.0, 128.3,
126.7, 124.1, 122.6, 120.7, 115.2, 114.2, 109.5, 61.7, 21.3; HRMS (ESI/[M + Na]+)
calcd for C21H16O2N3BrNa+: 444.0318, found 444.0321.
(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)methyl 4-chlorobenzoate (3dd)
Following the general procedure, product 3dd was obtained as a white solid (144 mg,
65%). mp 114-116 oC; 1H NMR (400 MHz, CDCl3) δ 8.73 (s, 2H), 8.52 (d, J = 8.4 Hz,
1H), 7.93 (d, J = 8.3 Hz, 2H), 7.60 (d, J = 7.7 Hz, 1H), 7.39 (d, J = 8.3 Hz, 2H), 7.34
(t, J = 7.8 Hz, 1H), 7.28 – 7.24 (m, 1H), 6.84 (s, 1H), 5.90 (s, 2H); 13C NMR (101
MHz, CDCl3) δ 165.3, 158.5, 156.3, 139.5, 137.0, 134.9, 131.0, 128.9, 128.8, 128.5,
124.3, 122.7, 120.7, 115.3, 114.2, 109.8, 61.9; HRMS (ESI/[M + Na]+) calcd for
C20H13O2N3BrClNa+: 463.9772, found 463.9773.
(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)methyl 1-naphthoate (3de)
Following the general procedure, product 3de was obtained as a white solid (143 mg,
62%). mp 114-115 oC; 1H NMR (400 MHz, CDCl3) δ 8.92 (d, J = 8.6 Hz, 1H), 8.75 (s,
2H), 8.53 (d, J = 8.4 Hz, 1H), 8.08 (d, J = 7.2 Hz, 1H), 8.01 (d, J = 8.2 Hz, 1H), 7.88
(d, J = 8.1 Hz, 1H), 7.60 (t, J = 7.9 Hz, 2H), 7.55 – 7.52 (m, 1H), 7.45 (t, J = 7.7 Hz,
1H), 7.35 (t, J = 7.7 Hz, 1H), 7.28 – 7.25 (m, 1H), 6.91 (s, 1H), 5.99 (s, 2H); 13C
NMR (101 MHz, CDCl3) δ 167.0, 158.5, 156.3, 137.0, 135.2, 133.8, 133.5, 131.4,
130.3, 129.0, 128.5, 127.8, 126.8, 126.2, 125.7, 124.5, 124.2, 122.6, 120.7, 115.3,
S17
114.2, 109.9, 61.8; HRMS (ESI/[M + Na]+) calcd for C24H16O2N3BrNa+: 480.0318,
found 480.0320.
(1-(5-Bromopyrimidin-2-yl)-1H-indol-2-yl)methyl acetate (3df)
Following the general procedure, product 3df was obtained as a white solid (56 mg,
32%). mp 93-95 oC; 1H NMR (400 MHz, CDCl3) δ 8.75 (s, 2H), 8.50 (d, J = 8.4 Hz,
1H), 7.58 (d, J = 7.6 Hz, 1H), 7.32 (t, J = 7.5 Hz, 1H), 7.26 – 7.22 (m, 1H), 6.78 (s,
1H), 5.66 (s, 2H), 2.08 (s, 3H); 13C NMR (101 MHz, CDC3) δ 170.6, 158.4, 156.2,
136.9, 135.2, 128.9, 124.1, 122.6, 120.6, 115.3, 114.1, 109.5, 61.3, 21.0; HRMS
(ESI/[M + Na]+) calcd for C15H12O2N3BrNa+: 368.0005, found 368.0009.
5. Gram-scale synthesis and synthetic applications
(1) Gram-scale synthesis
Following the general procedure, to a solution of indole 1d (1.15 g, 4.0 mmol) in
toluene (24 mL) were added perester 2a (2.32 mL, 12.0 mmol) and Co(acac)2 (0.104 g,
0.4 mmol). The resulting mixture was stirred at 80 oC for 3 hours. The reaction
mixture was then cooled to room temperature, and concentrated under reduced
pressure. The crude residue was purified by flash column chromatography on silica
gel (petroleum ether/ethyl acetate = 30/1 as eluent) to give the desired product 3da as
a white solid (0.88 g, 54% yield).
S18
Following the general procedure, to a solution of indole 1g (0.65 g, 2.5 mmol) in
toluene (15 mL) were added perester 2a (1.45 mL, 5.0 mmol) and Co(acac)2 (0.065 g,
0.25 mmol). The resulting mixture was stirred at 80 oC for 1.5 hours. The reaction
mixture was then cooled to room temperature, and concentrated under reduced
pressure. The crude residue was purified by flash column chromatography on silica
gel (petroleum ether/ethyl acetate = 30/1 as eluent) to give the desired product 3ga as
a white solid (0.31 g, 36% yield).
Following the general procedure, to a solution of indole 1za (1.45 g, 10.0 mmol) in
toluene (60 mL) were added perester 2a (5.71 mL, 30.0 mmol) and Co(acac)2 (0.26 g,
1.0 mmol). The resulting mixture was stirred at 60 oC for 5 hours. The reaction
mixture was then cooled to room temperature, and concentrated under reduced
pressure. The crude residue was purified by flash column chromatography on silica
gel (petroleum ether/ethyl acetate = 30/1 as eluent) to give the desired product 3za as
a white solid (1.15 g, 43% yield).
(2) Synthetic applications
To a stirred solution of NaOH (12.0 mg, 0.30 mmol) in methanol (1.5 mL) was
added 3da (55.0 mg, 0.13 mmol), and the mixture was stirred for 3 hours at room
temperature (Monitored by TLC). After that, the reaction mixture was concentrated under reduced pressure. The crude residue was purified by flash column chromatography on silica gel (petroleum ether/acetate ethyl = 8/1 as eluent) to give the desired product 4 as a white solid (37.1 mg, 90% yield). mp 122-124 oC; 1H NMR (400 MHz, CDCl3) δ 8.78 (s, 2H), 8.48 (d, J = 8.4 Hz, 1H), 7.58 (d, J = 7.6 Hz, 1H), 7.32 (t, J = 7.8 Hz, 1H), 7.25 (t, J = 7.6 Hz, 1H), 6.71 (s, 1H), 4.76 (s, 2H); 13C NMR (101 MHz, CDCl3) δ 158.7, 155.9, 139.7, 136.8, 129.2, 124.2, 122.9, 120.9, 115.5, 113.7, 110.2, 58.0; HRMS (ESI/ [M+H]+) calcd for C13H11BrN3O
+: 304.0080, found 304.0079.
S19
To a stirred solution of 3za (40.0 mg, 0.15 mmol) in dry CH2Cl2 (1.5 mL) was added
TMSOTf (5.6 µL, 0.03 mmol) at -25 °C, and the mixture was stirred for 12 hours at the same
temperature. After that, the reaction mixture was quenched with a saturated solution of
NaHCO3 and extracted with CH2Cl2, and the organic layer was washed with brine and dried
with Na2SO4. After removal of the solvent under reduced pressure, the residue was purified by
flash column chromatography on silica gel (petroleum ether/AcOEt = 15:1 as eluent) to give 5
as a colorless oil (17.4 mg, 56% yield), together with 12.3 mg of 3za recovered (82 % yield
based on recovered starting material). 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 7.8 Hz, 2H), 7.56-7.51 (m, 2H), 7.43-7.36 (m, 4H), 7.30-7.23 (m, 1H), 7.15-7.01 (m, 4H), 6.12 (s, 1H), 5.55 (s, 2H), 4.41 (s, 2H), 3.87 (s, 3H), 3.72 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 166.2 , 139.7, 137.6, 137.3, 133.1, 130.8, 129.7, 129.6, 128.4, 127.7, 127.0, 122.7, 120.6, 119.9, 119.6, 119.5, 119.1, 112.0, 109.2, 108.7, 100.5, 56.2, 30.0, 29.7, 22.9; HRMS (ESI/ [M+Na]+) calcd for C27H24O2 N2Na+: 431.1730, found 431.1733.
6. Radical trapping experiments
Followed the General Procedure, to a mixture of indole 1d (0.144 g, 0.5 mmol),
perester 2a (0.29 mL, 1.5 mmol), and Co(acac)2 (13 mg, 10 mol%) in toluene (3 mL) was added TEMPO (0.234 g, 1.5 mmol) or BHT (0.330 g, 1.5 mmol). The reaction mixture was then stirred at 80 oC for 5 hours. No desired product 3da was detected.
7. References
[1] Xu, D.; Sun, W.-W.; Xie, T.; Liu, J.-K.; Liu, B.; Zhou, Y.; Wu, B. J. Org. Chem. 2016, 81,
11081–11094.
[2] Siddalingamurthy, E.; Mahadevan, K. M.; Masagalli, J. N.; Harishkumar, H. N. Tetrahedron
Lett. 2013, 54, 5591–5596.
S20
[3] Rodríguez, J. G.; Urrutia, A. Tetrahedron, 1999, 55, 11095–11108.
[4] Wei, W.; Zhang, C.; Xu, Y.; Wan. X. Chem. Commun., 2011, 47, 10827–10829.
8.
Awitdep18
Single cry
A single cryth pentane posited in t61986.
ystal data
ystal of 3aaas the anti-the Cambri
a of produ
a was obtainsolvent at ridge Crysta
S21
uct 3aa
ned by evaproom tempeallographic
porative diferature. This
Data Centr
ffusion in ds crystal strure and assig
dichloromethructure has bgned as CC
hane been CDC
S22
Table 1. Crystal data and structure refinement for 3aa.
Identification code 3aa
Empirical formula C20H15N3O2
Formula weight 329.35
Temperature/K 100.01(10)
Crystal system monoclinic
Space group P21/c
a/Å 8.8758(8)
b/Å 14.7297(12)
c/Å 11.9629(11)
α/° 90
β/° 101.831(9)
γ/° 90
Volume/Å3 1530.8(2)
Z 4
ρcalcg/cm3 1.429
μ/mm-1 0.095
F(000) 688.0
Crystal size/mm3 0.13 × 0.12 × 0.11
Radiation MoKα (λ = 0.71073)
2Θ range for data collection/° 4.444 to 58.936
Index ranges -9 ≤ h ≤ 12, -20 ≤ k ≤ 19, -16 ≤ l ≤ 11
Reflections collected 8002
Independent reflections 3637 [Rint = 0.0331, Rsigma = 0.0519]
Data/restraints/parameters 3637/0/226
Goodness-of-fit on F2 1.029
Final R indexes [I>=2σ (I)] R1 = 0.0482, wR2 = 0.1047
Final R indexes [all data] R1 = 0.0620, wR2 = 0.1144
Largest diff. peak/hole / e Å-3 0.24/-0.28
S23
Table 2. Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 3aa. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor.
Atom x y z U(eq)
O(1) 3743.4(11) 5704.4(7) 4274.7(8) 17.0(2)
O(2) 3280.9(12) 5573.1(8) 2361.5(9) 21.6(3)
N(1) 1411.9(13) 4392.2(8) 5942.8(10) 14.5(3)
N(3) 623.5(14) 3603.3(9) 4244.9(10) 18.1(3)
N(2) -430.0(14) 3252.7(9) 5876.4(11) 18.8(3)
C(17) 489.5(15) 3714.1(10) 5324.4(12) 15.1(3)
C(11) 5021.9(16) 6713.8(10) 3279.0(12) 16.6(3)
C(8) 2488.5(16) 4947.2(10) 5532.2(12) 15.1(3)
C(1) 1545.0(16) 4588.1(10) 7114.2(12) 15.0(3)
C(7) 3266.4(16) 5451.9(10) 6401.7(12) 16.5(3)
C(10) 3928.0(16) 5939.4(10) 3227.6(12) 16.1(3)
C(9) 2690.3(16) 4960.3(10) 4322.7(12) 15.8(3)
C(2) 737.7(17) 4263.3(10) 7916.1(13) 17.6(3)
C(6) 2713.3(16) 5239.5(10) 7408.5(13) 16.8(3)
C(20) -280.5(17) 2967.0(11) 3663.5(13) 20.8(3)
C(16) 5488.2(16) 7223.7(10) 4266.2(13) 18.7(3)
C(12) 5599.4(17) 6923.7(11) 2309.5(13) 19.2(3)
C(4) 2358.9(18) 5211.2(11) 9338.0(13) 22.4(4)
C(18) -1301.6(17) 2616.4(11) 5263.5(13) 20.5(3)
C(5) 3135.2(18) 5545.4(11) 8535.3(13) 20.6(3)
C(19) -1283.6(17) 2445.2(11) 4137.5(14) 22.0(3)
C(3) 1165.5(18) 4585.4(11) 9022.6(13) 20.6(3)
C(13) 6630.2(17) 7635.7(11) 2339.7(13) 21.6(3)
C(14) 7077.0(17) 8146.6(11) 3319.2(14) 22.1(4)
C(15) 6511.3(17) 7936.1(11) 4286.0(14) 21.5(3)
S24
Table 3. Anisotropic Displacement Parameters (Å2×103) for 3aa. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].
Atom U11 U22 U33 U23 U13 U12
O(1) 17.4(5) 17.6(5) 16.5(5) 0.8(4) 4.9(4) -3.7(4)
O(2) 22.7(6) 25.2(6) 16.3(6) -1.2(5) 2.6(4) -4.2(5)
N(1) 14.4(6) 15.4(6) 14.2(6) 0.0(5) 3.9(5) -0.1(5)
N(3) 17.6(6) 17.9(6) 18.5(7) -2.0(5) 2.7(5) -0.1(5)
N(2) 18.3(6) 16.6(6) 22.1(7) 0.7(5) 5.3(5) -1.3(5)
C(17) 13.4(7) 12.4(7) 19.0(7) 1.1(6) 2.3(5) 2.3(6)
C(11) 13.9(7) 16.6(7) 19.0(8) 3.3(6) 2.5(6) 2.2(6)
C(8) 12.2(7) 14.5(7) 18.5(7) 1.7(6) 3.0(5) 2.7(6)
C(1) 15.2(7) 14.5(7) 14.9(7) 0.1(6) 1.9(5) 3.6(6)
C(7) 15.6(7) 15.4(7) 18.6(8) 0.9(6) 3.8(6) 1.0(6)
C(10) 15.0(7) 16.8(7) 16.6(7) 2.1(6) 3.8(5) 3.6(6)
C(9) 15.3(7) 14.1(7) 18.5(8) -0.4(6) 4.8(6) -2.3(6)
C(2) 18.1(7) 15.3(7) 19.7(8) 1.5(6) 5.0(6) 2.1(6)
C(6) 16.5(7) 14.7(7) 18.8(8) 0.0(6) 2.8(6) 3.4(6)
C(20) 21.2(8) 20.9(8) 19.9(8) -4.6(6) 3.4(6) 0.9(6)
C(16) 17.0(7) 18.8(8) 20.4(8) 2.6(6) 4.1(6) 1.4(6)
C(12) 18.9(7) 21.3(8) 17.1(7) 1.4(6) 3.1(6) 1.4(6)
C(4) 29.4(9) 20.3(8) 16.5(8) -2.6(6) 2.7(6) 3.6(7)
C(18) 18.3(7) 16.3(7) 27.9(9) -0.2(6) 6.7(6) -3.2(6)
C(5) 22.2(8) 19.3(8) 19.2(8) -3.5(6) 1.9(6) -0.9(6)
C(19) 18.0(7) 18.6(8) 28.5(9) -6.0(7) 2.8(6) -2.0(6)
C(3) 24.3(8) 20.4(8) 18.3(8) 2.6(6) 7.6(6) 3.8(6)
C(13) 20.7(8) 24.0(8) 21.2(8) 6.7(7) 7.0(6) 1.2(7)
C(14) 17.2(7) 17.8(8) 30.4(9) 5.3(7) 2.8(6) -0.3(6)
C(15) 22.4(8) 19.3(8) 21.8(8) -0.2(6) 2.6(6) -0.9(7)
S25
Table 4 Bond Lengths for 3aa.
Atom Atom Length/Å Atom Atom Length/Å
O(1) C(10) 1.3416(17) C(8) C(9) 1.494(2)
O(1) C(9) 1.4492(17) C(1) C(2) 1.394(2)
O(2) C(10) 1.2044(17) C(1) C(6) 1.404(2)
N(1) C(17) 1.4024(18) C(7) C(6) 1.425(2)
N(1) C(8) 1.4195(19) C(2) C(3) 1.384(2)
N(1) C(1) 1.4118(18) C(6) C(5) 1.398(2)
N(3) C(17) 1.3309(19) C(20) C(19) 1.383(2)
N(3) C(20) 1.3331(19) C(16) C(15) 1.385(2)
N(2) C(17) 1.3361(19) C(12) C(13) 1.387(2)
N(2) C(18) 1.3349(19) C(4) C(5) 1.382(2)
C(11) C(10) 1.491(2) C(4) C(3) 1.396(2)
C(11) C(16) 1.389(2) C(18) C(19) 1.374(2)
C(11) C(12) 1.395(2) C(13) C(14) 1.381(2)
C(8) C(7) 1.348(2) C(14) C(15) 1.387(2)
Table 5. Bond Angles for 3aa.
Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚
C(10) O(1) C(9) 115.81(11) O(1) C(10) C(11) 111.23(12)
C(17) N(1) C(8) 126.10(12) O(2) C(10) O(1) 124.03(14)
C(17) N(1) C(1) 126.17(12) O(2) C(10) C(11) 124.74(14)
C(1) N(1) C(8) 107.49(11) O(1) C(9) C(8) 104.75(11)
C(17) N(3) C(20) 115.37(13) C(3) C(2) C(1) 117.48(14)
C(18) N(2) C(17) 115.44(13) C(1) C(6) C(7) 107.62(13)
N(3) C(17) N(1) 116.13(13) C(5) C(6) C(1) 120.03(14)
N(3) C(17) N(2) 127.04(13) C(5) C(6) C(7) 132.34(15)
N(2) C(17) N(1) 116.83(13) N(3) C(20) C(19) 123.10(15)
C(16) C(11) C(10) 121.78(14) C(15) C(16) C(11) 120.29(15)
C(16) C(11) C(12) 119.38(14) C(13) C(12) C(11) 119.90(15)
C(12) C(11) C(10) 118.84(13) C(5) C(4) C(3) 120.40(14)
S26
N(1) C(8) C(9) 124.43(12) N(2) C(18) C(19) 123.07(14)
C(7) C(8) N(1) 108.98(13) C(4) C(5) C(6) 118.82(15)
C(7) C(8) C(9) 126.59(13) C(18) C(19) C(20) 115.97(14)
C(2) C(1) N(1) 131.49(14) C(2) C(3) C(4) 121.93(15)
C(2) C(1) C(6) 121.29(14) C(14) C(13) C(12) 120.49(15)
C(6) C(1) N(1) 107.21(13) C(13) C(14) C(15) 119.72(15)
C(8) C(7) C(6) 108.69(13) C(16) C(15) C(14) 120.22(15)
Table 6. Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement
Parameters (Å2×103) for 3aa.
Atom x y z U(eq)
H(7) 4036.27 5869.37 6352.9 20
H(9A) 3120.12 4391.1 4125.87 19
H(9B) 1713.66 5063.23 3802.07 19
H(2) -58.08 3846.04 7714.93 21
H(20) -234.23 2869.39 2903.24 25
H(16) 5111.62 7086.09 4916.59 22
H(12) 5293.69 6586.88 1644.08 23
H(4) 2632.95 5404.2 10092.59 27
H(18) -1951.41 2273.04 5615.17 25
H(5) 3924.23 5966.4 8741.38 25
H(19) -1908.46 2004.8 3719.23 26
H(3) 642.96 4379.04 9572.2 25
H(13) 7023.1 7769.75 1695.44 26
H(14) 7754.4 8629.79 3330.71 27
H(15) 6820.19 8274.51 4949.76 26
9.
Acryand
Single cry
A single cryystal structud assigned a
ystal data
ystal of 3gaure has beenas CCDC 1
a of produ
a was obtainn deposited861984.
S27
uct 3ga
ned by recryd in the Cam
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nol at 0 oC. hic Data Ce
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S28
Table 7. Crystal data and structure refinement for 3ga.Identification code 3ga
Empirical formula C21H17N3O2
Formula weight 343.38
Temperature/K 100.00(10)
Crystal system monoclinic
Space group P21/c
a/Å 8.7751(5)
b/Å 13.7237(7)
c/Å 14.5990(10)
α/° 90
β/° 101.524(6)
γ/° 90
Volume/Å3 1722.67(18)
Z 4
ρcalcg/cm3 1.324
μ/mm-1 0.087
F(000) 720.0
Crystal size/mm3 0.13 × 0.12 × 0.11
Radiation MoKα (λ = 0.71073)
2Θ range for data collection/° 4.112 to 50
Index ranges -8 ≤ h ≤ 10, -16 ≤ k ≤ 16, -17 ≤ l ≤ 14
Reflections collected 9225
Independent reflections 2973 [Rint = 0.0455, Rsigma = 0.0526]
Data/restraints/parameters 2973/0/236
Goodness-of-fit on F2 1.056
Final R indexes [I>=2σ (I)] R1 = 0.0464, wR2 = 0.0981
Final R indexes [all data] R1 = 0.0606, wR2 = 0.1070
Largest diff. peak/hole / e Å-3 0.20/-0.23
S29
Table 8. Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for 5-570. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor. Atom x y z U(eq)
O1 5583.3(14) 3186.3(8) 4490.5(9) 21.4(3)
O2 3631.9(14) 3715.8(9) 3358.7(10) 29.4(4)
N1 7659.9(16) 1558.9(10) 4891.3(11) 17.1(4)
N3 7333.0(16) 1997.1(10) 3318.8(11) 20.3(4)
N2 9726.2(17) 2313.8(11) 4391.5(11) 22.3(4)
C17 8267.1(19) 1980.4(12) 4160.2(13) 17.6(4)
C8 6088.6(19) 1567.2(12) 4992.6(13) 18.1(4)
C6 7437(2) 616.0(12) 6133.1(13) 18.4(4)
C7 5920(2) 1006.4(12) 5733.8(13) 19.0(4)
C10 4858(2) 3861.9(13) 3892.1(13) 20.1(4)
C20 7950(2) 2389.2(13) 2637.2(14) 23.2(5)
C5 8501(2) 983.9(12) 5615.6(12) 17.0(4)
C4 10084(2) 759.3(12) 5846.3(13) 19.7(4)
C11 5753(2) 4791.2(13) 3955.4(13) 20.3(4)
C1 7967(2) 13.4(13) 6907.1(14) 22.7(5)
C16 5087(2) 5593.8(13) 3441.1(13) 21.2(4)
C9 4916(2) 2209.5(12) 4401.9(14) 21.1(4)
C19 9462(2) 2731.9(13) 2780.3(14) 24.5(5)
C18 10304(2) 2672.6(13) 3678.8(14) 24.2(5)
C3 10579(2) 169.5(13) 6618.8(14) 22.7(5)
C2 9537(2) -196.3(13) 7144.7(14) 24.3(5)
C21 4476(2) 823.1(13) 6107.5(14) 24.5(5)
C12 7263(2) 4861.9(13) 4484.2(14) 24.8(5)
C15 5913(2) 6454.0(13) 3453.2(14) 23.9(5)
C14 7413(2) 6521.2(13) 3978.6(14) 26.0(5)
C13 8082(2) 5727.5(13) 4489.3(15) 28.1(5)
Table 9. Anisotropic Displacement Parameters (Å2×103) for 3ga. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…]. Atom U11 U22 U33 U23 U13 U12
O1 21.2(7) 18.1(7) 22.9(8) 0.0(6) -0.4(6) 0.8(5)
O2 19.1(7) 32.6(8) 33.3(9) 9.4(7) -2.8(6) -4.7(6)
N1 14.3(8) 19.2(8) 17.8(9) 1.3(7) 3.1(6) -0.9(6)
N3 20.0(8) 20.6(8) 19.9(9) 2.7(7) 3.0(7) -0.2(6)
N2 19.4(9) 22.5(8) 24.9(10) 1.3(7) 4.3(7) -4.3(6)
S30
C17 17.0(10) 15.2(9) 20.8(11) -1.1(8) 4.1(8) 0.7(7)
C8 14.3(9) 18.5(9) 21.4(11) -4.6(8) 3.7(8) -3.0(7)
C6 20.7(10) 14.6(9) 19.8(11) -3.7(8) 3.9(8) -1.6(7)
C7 20.3(10) 16.5(9) 21.0(11) -5.3(8) 5.9(8) -2.7(7)
C10 16.1(10) 26.9(10) 18.4(11) 0.0(8) 5.8(8) 2.6(7)
C20 24.6(11) 22.3(10) 21.1(11) 4.6(9) 0.9(8) 3.9(8)
C5 20.6(10) 15.0(9) 14.7(10) -2.6(8) 2.1(7) -1.1(7)
C4 19.5(10) 19.6(10) 20.9(11) -4.3(8) 6.2(8) -0.3(7)
C11 20.3(10) 23.4(10) 18.9(11) -2.5(8) 8.3(8) 2.1(7)
C1 28.1(11) 17.7(10) 24.3(11) -0.2(8) 9.9(8) -1.0(8)
C16 18.6(10) 26.6(10) 18.4(11) -2.5(8) 3.5(8) 2.6(7)
C9 17.8(10) 20.7(10) 25.1(11) -1.8(8) 4.5(8) -2.3(7)
C19 24.9(11) 22.9(10) 27.0(12) 6.9(9) 8.2(9) 1.3(8)
C18 17.6(10) 23.1(10) 32.2(12) 3.7(9) 6.1(9) -4.3(7)
C3 21.2(10) 20.3(10) 25.8(12) -2.5(9) 2.9(8) 5.4(7)
C2 31.2(11) 18.7(10) 22.7(11) 3.8(8) 4.4(9) 5.2(8)
C21 24.4(10) 24.8(11) 26.2(12) -0.7(9) 9.3(8) -1.2(8)
C12 21.8(10) 22.9(10) 28.4(12) 0.4(9) 1.8(8) 2.8(8)
C15 26.6(11) 21.5(10) 23.8(11) -1.8(9) 5.8(8) 5.3(8)
C14 26.7(11) 21.3(10) 31.3(12) -6.4(9) 9.2(9) -1.6(8)
C13 19.9(10) 27.5(11) 34.8(13) -5.1(9) 0.4(9) 0.0(8)
Table 10. Bond Lengths for 3ga. Atom Atom Length/Å Atom Atom Length/Å
O1 C10 1.344(2) C7 C21 1.497(3)
O1 C9 1.458(2) C10 C11 1.491(3)
O2 C10 1.212(2) C20 C19 1.383(3)
N1 C17 1.409(2) C5 C4 1.397(2)
N1 C8 1.416(2) C4 C3 1.386(3)
N1 C5 1.405(2) C11 C16 1.394(2)
N3 C17 1.334(2) C11 C12 1.397(2)
N3 C20 1.337(2) C1 C2 1.381(3)
N2 C17 1.338(2) C16 C15 1.383(3)
N2 C18 1.339(2) C19 C18 1.373(3)
C8 C7 1.360(3) C3 C2 1.399(3)
C8 C9 1.491(2) C12 C13 1.388(3)
C6 C7 1.445(2) C15 C14 1.388(3)
C6 C5 1.407(3) C14 C13 1.383(3)
C6 C1 1.402(3)
S31
Table 11. Bond Angles for 3ga. Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚
C10 O1 C9 116.57(13) O2 C10 C11 124.77(16)
C17 N1 C8 126.83(14) N3 C20 C19 122.90(17)
C5 N1 C17 125.40(14) N1 C5 C6 107.47(15)
C5 N1 C8 107.59(15) C4 C5 N1 130.78(17)
C17 N3 C20 115.24(15) C4 C5 C6 121.74(16)
C17 N2 C18 114.91(16) C3 C4 C5 117.38(18)
N3 C17 N1 116.67(15) C16 C11 C10 118.92(15)
N3 C17 N2 127.42(18) C16 C11 C12 119.48(17)
N2 C17 N1 115.91(15) C12 C11 C10 121.55(16)
N1 C8 C9 121.19(16) C2 C1 C6 118.60(19)
C7 C8 N1 109.97(15) C15 C16 C11 120.35(16)
C7 C8 C9 128.51(17) O1 C9 C8 105.89(13)
C5 C6 C7 107.88(16) C18 C19 C20 116.15(19)
C1 C6 C7 132.38(18) N2 C18 C19 123.32(17)
C1 C6 C5 119.69(16) C4 C3 C2 121.55(17)
C8 C7 C6 107.04(16) C1 C2 C3 121.03(18)
C8 C7 C21 128.28(16) C13 C12 C11 119.69(17)
C6 C7 C21 124.67(17) C16 C15 C14 120.02(17)
O1 C10 C11 112.02(14) C13 C14 C15 119.94(18)
O2 C10 O1 123.21(16) C14 C13 C12 120.53(17)
Table 12. Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement Parameters (Å2×103) for 3ga. Atom x y z U(eq)
H20 7336.43 2433.23 2040.69 28
H4 10778.75 996.34 5495.21 24
H1 7277.01 -239.65 7253.05 27
H16 4082.28 5550.69 3088.07 25
H9A 4724.03 1997.24 3755.23 25
H9B 3942.38 2197.27 4619.95 25
H19 9883.27 2987.85 2295.88 29
H18 11326.46 2892.82 3798.18 29
H3 11628.17 12.96 6791.92 27
H2 9905.98 -586.67 7662.11 29
H21A 4613.8 1070.18 6733.89 37
H21B 4277.57 135.33 6109.06 37
H21C 3612.05 1146.44 5719.25 37
S32
H12 7717.15 4331.24 4831.07 30
H15 5462.09 6987.42 3109.38 29
H14 7968.38 7099.5 3986.88 31
H13 9088.49 5774.27 4839.15 34
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
2.14
1.001.081.671.122.040.990.971.91
1.031.81
0.015
5.971
6.859
7.049
7.061
7.073
7.231
7.249
7.260
7.263
7.267
7.268
7.316
7.319
7.322
7.333
7.337
7.340
7.343
7.358
7.385
7.406
7.426
7.521
7.524
7.540
7.542
7.558
7.561
7.606
7.626
7.974
7.995
8.561
8.583
8.715
8.727
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
61.953
76.681
76.999
77.318
108.660
115.083
116.791
120.538
123.833
128.302
132.928
135.314
137.076
158.011
158.085
166.146
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.15
2.12
1.00
1.081.182.071.071.091.96
1.001.93
0.013
2.269
5.936
6.836
7.210
7.228
7.247
7.260
7.298
7.319
7.337
7.378
7.397
7.417
7.514
7.534
7.554
7.604
7.623
7.957
7.978
8.451
8.472
8.540
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
14.970
61.733
76.684
77.000
77.318
108.081
114.615
120.509
121.927
123.649
126.176
128.658
132.883
135.125
137.045
156.256
158.001
166.132
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
2.05
0.971.741.162.081.101.022.01
1.001.85
0.015
5.911
6.855
7.234
7.253
7.262
7.271
7.316
7.337
7.355
7.391
7.411
7.430
7.531
7.549
7.568
7.609
7.628
7.964
7.985
8.434
8.455
8.586
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
61.606
76.683
77.000
77.318
108.987
114.558
120.699
122.376
124.021
128.372
133.046
135.100
137.046
145.639
145.857
153.431
154.162
156.021
166.117
110120130140150160f1 (ppm)
108.987
114.558
120.699
122.376
124.021
128.372
128.709
129.551
133.046
135.100
137.046
145.639
145.857
153.431
154.162
156.021
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
1.99
0.98
2.021.152.112.09
1.91
1.001.97
0.007
5.907
6.860
7.235
7.260
7.273
7.315
7.336
7.354
7.404
7.423
7.442
7.538
7.557
7.575
7.592
7.611
7.989
8.009
8.502
8.523
8.731
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
61.770
76.682
77.000
77.317
109.524
114.173
115.268
120.679
122.603
124.117
128.380
133.048
135.249
136.975
156.291
158.451
166.117
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.30
2.12
1.001.031.123.081.24
1.99
1.071.91
0.009
2.465
5.952
6.775
7.024
7.036
7.048
7.137
7.158
7.260
7.381
7.382
7.385
7.388
7.390
7.392
7.400
7.402
7.420
7.423
7.516
7.536
7.557
7.973
7.993
8.449
8.471
8.694
8.706
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
21.293
62.079
76.683
77.000
77.318
108.536
114.934
116.528
120.355
125.271
128.293
129.552
131.608
135.319
135.382
157.943
158.145
166.179
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
2.06
1.001.011.522.011.93
1.93
1.001.92
0.005
5.947
6.776
7.087
7.099
7.110
7.251
7.260
7.272
7.398
7.417
7.436
7.532
7.535
7.554
7.559
7.569
7.572
7.983
8.003
8.511
8.533
8.721
8.733
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
61.898
76.682
77.000
77.318
107.621
116.444
117.058
119.916
123.878
127.724
129.583
133.054
135.407
136.911
157.869
158.085
166.088
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.03
2.09
1.004.391.011.001.93
1.001.95
0.019
2.471
5.987
7.006
7.014
7.025
7.260
7.278
7.299
7.321
7.341
7.365
7.383
7.457
7.475
7.493
7.612
7.632
7.809
7.828
8.435
8.455
8.681
8.692
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
8.928
58.390
76.683
77.000
77.319
114.426
116.665
118.168
119.014
121.777
124.460
128.154
132.708
136.525
157.985
158.073
166.335
127.5128.5129.5130.5131.5f1 (ppm)
128.154
129.395
129.721
129.869
130.173
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.28
2.17
2.02
0.983.131.131.071.90
1.02
1.85
0.004
1.309
1.328
1.347
2.899
2.918
2.937
2.956
5.908
7.260
7.278
7.296
7.333
7.337
7.351
7.370
7.375
7.378
7.480
7.483
7.498
7.501
7.517
7.520
7.640
7.661
7.840
7.861
8.400
8.420
8.696
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
15.694
17.543
58.035
76.682
77.001
77.319
114.121
114.795
119.189
122.150
124.652
128.272
132.869
136.586
156.285
158.435
166.341
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
6.25
1.13
2.00
1.583.131.093.10
1.00
1.91
0.023
1.531
1.549
3.441
3.459
3.476
3.494
3.512
5.923
7.234
7.253
7.260
7.271
7.320
7.341
7.361
7.380
7.489
7.507
7.526
7.826
7.853
7.873
8.342
8.363
8.720
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
22.765
26.181
57.745
76.682
77.001
77.319
114.386
114.461
120.814
121.715
124.209
127.648
128.951
132.853
136.890
156.154
158.500
166.232
127.5128.5129.5130.5131.5f1 (ppm)
127.648
128.242
128.408
128.951
129.408
130.061
113.0114.0115.0116.0f1 (ppm)
114.386
114.461
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.32
2.39
2.11
2.06
1.054.991.121.071.93
1.001.86
0.009
0.998
1.017
1.035
1.706
1.725
1.743
1.762
1.780
1.799
2.871
2.890
2.908
5.953
6.999
7.011
7.023
7.240
7.260
7.278
7.294
7.313
7.331
7.349
7.367
7.452
7.471
7.489
7.637
7.656
7.789
7.809
8.420
8.441
8.676
8.688
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
14.050
24.007
26.169
58.326
76.682
77.000
77.319
114.453
116.728
119.237
121.719
124.330
128.169
132.714
136.678
158.007
158.104
166.331
157.4157.8158.2158.6f1 (ppm)
158.007
158.104
128.0128.5129.0129.5130.0130.5131.0131.5f1 (ppm)
128.169
129.160
129.400
129.880
130.194
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
6.29
1.25
2.00
2.00
1.227.141.171.171.90
1.031.87
0.004
0.999
1.015
1.996
2.013
2.030
2.047
2.064
2.081
2.098
2.762
2.780
5.935
6.994
7.006
7.018
7.232
7.250
7.260
7.285
7.304
7.323
7.343
7.361
7.446
7.465
7.483
7.619
7.639
7.766
7.784
8.408
8.429
8.670
8.682
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
22.729
29.698
33.426
58.398
76.682
77.000
77.318
114.332
116.747
119.486
121.681
124.291
128.158
132.713
136.611
157.999
158.068
166.293
157.6157.8158.0158.2158.4f1 (ppm)
157.999
158.068
121122123124125126127128129130131f1 (ppm)
121.681
122.007
124.291
128.158
129.363
129.442
130.128
130.238
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
2.08
2.06
4.115.172.091.90
1.00
1.87
0.010
4.303
5.952
7.139
7.157
7.175
7.196
7.216
7.235
7.236
7.260
7.286
7.305
7.324
7.342
7.362
7.479
7.482
7.500
7.501
7.519
7.538
7.799
7.820
8.394
8.415
8.719
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
30.132
58.062
76.684
77.000
77.318
114.396
114.679
119.687
121.854
122.363
124.779
126.111
128.242
128.269
128.449
129.229
129.455
130.016
130.807
132.876
136.617
139.919
156.238
158.507
166.231
128.0128.5129.0129.5130.0130.5131.0f1 (ppm)
128.242
128.269
128.449
129.229
129.455
130.016
130.807
114.2114.4114.6114.8115.0f1 (ppm)
114.396
114.679
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.01
1.96
2.001.273.183.071.052.00
1.001.91
-0.002
3.875
5.806
7.036
7.057
7.264
7.284
7.303
7.342
7.346
7.361
7.364
7.374
7.377
7.381
7.384
7.391
7.395
7.398
7.402
7.413
7.416
7.420
7.494
7.498
7.501
7.506
7.510
7.516
7.522
7.527
7.531
7.653
7.672
7.850
7.870
8.439
8.460
8.692
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
55.339
59.287
76.682
77.000
77.317
114.238
114.563
114.686
120.181
122.699
125.007
125.149
125.314
128.303
128.842
129.449
129.727
130.140
131.216
132.902
136.409
156.236
158.565
159.161
166.147
125126127128129130131f1 (ppm)
125.007
125.149
125.314
128.303
128.842
129.449
129.727
130.140
113.5114.0114.5115.0115.5f1 (ppm)
114.238
114.563
114.686
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.01
2.03
3.043.013.120.981.94
1.00
1.93
0.002
3.876
5.844
7.040
7.053
7.062
7.260
7.307
7.312
7.318
7.327
7.335
7.341
7.346
7.468
7.476
7.487
7.497
7.613
7.619
7.793
7.812
8.409
8.432
8.681
8.693
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
55.352
59.270
76.683
77.001
77.319
114.355
115.842
117.327
119.477
123.835
124.747
124.832
127.992
128.221
129.418
129.934
130.105
131.185
132.808
134.892
157.833
158.185
159.268
166.059
156157158159160161f1 (ppm)
157.833
158.185
159.268
127.5128.0128.5129.0129.5130.0130.5131.0f1 (ppm)
127.992
128.221
129.418
129.934
130.105
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
2.12
2.151.183.273.161.051.95
1.00
1.92
-0.002
5.115
5.797
7.184
7.206
7.228
7.260
7.278
7.297
7.316
7.349
7.369
7.389
7.410
7.413
7.428
7.431
7.434
7.502
7.505
7.523
7.544
7.555
7.557
7.563
7.566
7.576
7.579
7.613
7.633
7.840
7.861
8.438
8.459
8.710
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
59.015
76.682
76.999
77.318
114.704
114.786
115.645
115.859
119.897
122.832
124.434
125.138
128.316
128.525
128.839
128.871
129.413
129.967
130.088
131.644
131.724
132.972
136.322
156.113
158.598
161.119
163.577
166.046
127.0127.5128.0128.5129.0129.5130.0130.5131.0f1 (ppm)
128.316
128.525
128.839
128.871
129.413
129.967
130.088
113.5114.0114.5115.0115.5116.0116.5f1 (ppm)
114.704
114.786
115.645
115.859
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
2.09
1.283.475.140.971.93
1.00
1.87
-0.014
5.793
7.260
7.279
7.298
7.317
7.347
7.367
7.386
7.392
7.411
7.414
7.432
7.471
7.492
7.501
7.505
7.522
7.541
7.613
7.633
7.827
7.847
8.426
8.447
8.714
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
58.959
76.682
77.000
77.318
114.703
114.897
119.848
122.901
124.185
125.195
128.309
128.327
128.980
129.418
129.926
130.202
131.341
131.434
132.999
133.595
136.366
156.083
158.639
166.017
128.5129.0129.5130.0130.5131.0131.5f1 (ppm)
128.309
128.327
128.980
129.418
129.926
130.202
131.341
131.434
114.3114.5114.7114.9115.1115.3f1 (ppm)
114.703
114.897
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
2.20
1.213.201.941.192.901.90
1.00
1.85
0.001
5.791
7.260
7.277
7.297
7.316
7.347
7.366
7.383
7.386
7.390
7.412
7.430
7.458
7.479
7.500
7.504
7.520
7.523
7.538
7.541
7.611
7.624
7.628
7.632
7.645
7.649
7.823
7.843
8.422
8.443
8.715
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
58.955
76.683
77.001
77.318
114.707
114.917
116.334
119.833
121.767
122.917
124.182
125.206
128.237
128.329
129.419
129.924
130.189
131.666
131.932
133.001
136.385
156.084
158.646
166.007
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128.237
128.329
129.419
129.924
130.189
131.666
131.932
113.5114.0114.5115.0115.5116.0116.5f1 (ppm)
114.707
114.917
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.11
2.18
3.10
2.02
2.18
1.001.981.011.071.82
1.02
1.96
0.009
0.999
1.017
1.035
1.689
1.707
1.726
1.744
1.763
1.781
2.491
2.828
2.847
2.865
5.887
7.161
7.182
7.260
7.332
7.350
7.370
7.408
7.482
7.485
7.501
7.517
7.519
7.839
7.860
8.304
8.326
8.660
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
14.063
21.390
23.882
26.165
58.234
76.682
77.001
77.318
113.706
114.652
119.118
123.675
126.034
128.244
129.417
129.498
129.835
130.167
131.572
132.811
134.800
156.279
158.293
166.348
129.5130.0130.5f1 (ppm)
129.417
129.498
129.835
130.167
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.19
2.23
2.06
3.21
2.11
1.001.001.991.02
1.93
1.08
1.83
0.007
1.000
1.018
1.036
1.688
1.706
1.725
1.743
1.761
1.779
2.822
2.841
2.859
3.905
5.885
6.972
6.995
7.056
7.260
7.334
7.353
7.372
7.483
7.501
7.519
7.851
7.870
8.362
8.384
8.645
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
14.052
23.761
26.171
55.795
58.255
76.683
77.001
77.318
101.737
113.410
113.628
116.035
123.713
128.264
129.437
130.143
130.163
130.491
131.394
132.838
155.561
156.194
158.291
166.361
129.0129.5130.0130.5131.0131.5132.0f1 (ppm)
129.437
130.143
130.163
130.491
131.394
113.0113.2113.4113.6113.8114.0114.2f1 (ppm)
113.410
113.628
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.21
2.24
2.11
2.00
1.081.572.061.041.89
0.99
1.82
-0.014
0.991
1.010
1.028
1.672
1.691
1.709
1.727
1.746
1.764
2.809
2.827
2.846
5.881
7.042
7.045
7.049
7.052
7.065
7.068
7.072
7.075
7.088
7.091
7.095
7.098
7.248
7.251
7.257
7.259
7.261
7.270
7.274
7.277
7.280
7.331
7.352
7.373
7.484
7.487
7.502
7.506
7.521
7.524
7.833
7.853
8.364
8.366
8.375
8.378
8.387
8.389
8.398
8.401
8.680
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
14.006
23.775
26.134
58.049
76.682
77.001
77.319
104.462
104.695
112.277
112.526
114.211
115.987
116.075
123.465
123.506
128.286
129.416
129.995
130.128
130.222
131.428
132.840
132.921
156.041
157.753
158.417
160.129
166.255
130.0130.5131.0131.5132.0132.5133.0f1 (ppm)
129.995
130.128
130.222
131.428
132.840
132.921
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.31
2.35
2.18
2.09
1.082.081.071.001.96
1.04
1.90
-0.000
0.991
1.009
1.028
1.672
1.690
1.709
1.727
1.746
1.764
2.808
2.827
2.845
5.873
7.260
7.270
7.273
7.276
7.278
7.292
7.295
7.298
7.301
7.334
7.353
7.371
7.481
7.485
7.488
7.491
7.500
7.503
7.507
7.511
7.522
7.525
7.585
7.830
7.851
8.331
8.353
8.679
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
13.997
23.835
26.047
57.947
76.681
77.000
77.319
114.415
116.051
118.816
123.083
124.641
127.702
128.279
129.399
129.968
130.505
131.213
132.920
134.833
155.970
158.440
166.206
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.14
2.17
2.08
2.11
1.931.011.051.001.93
0.99
1.96
0.009
0.994
1.012
1.031
1.674
1.692
1.711
1.729
1.748
1.766
2.807
2.825
2.844
5.875
7.260
7.333
7.352
7.371
7.405
7.427
7.486
7.504
7.523
7.740
7.829
7.848
8.279
8.301
8.681
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
14.015
23.862
26.054
57.919
76.682
77.000
77.319
114.484
115.371
116.431
121.916
122.994
127.300
128.294
129.412
129.973
131.062
131.094
132.938
135.199
155.981
158.475
166.209
129.0129.5130.0130.5131.0131.5132.0f1 (ppm)
129.412
129.973
131.062
131.094
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.45
2.26
2.11
2.00
2.001.021.071.911.00
0.97
1.85
-0.001
1.007
1.019
1.031
1.701
1.713
1.726
1.738
1.750
1.762
2.866
2.879
2.891
5.882
7.260
7.338
7.351
7.364
7.497
7.509
7.522
7.561
7.563
7.575
7.578
7.799
7.812
7.966
7.969
8.412
8.427
8.743
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
13.995
23.966
25.970
57.591
76.682
76.999
77.317
105.251
115.438
115.525
120.012
123.204
124.461
127.365
128.342
129.220
129.389
129.729
132.320
133.088
138.182
155.684
158.758
166.079
128.8129.0129.2129.4129.6129.8130.0130.2130.4f1 (ppm)
129.220
129.389
129.729
115.1115.2115.3115.4115.5115.6115.7115.8115.9f1 (ppm)
115.438
115.525
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
2.361.211.14
1.151.19
0.981.002.062.331.161.071.012.00
1.811.02
0.008
1.983
2.007
2.015
2.060
2.085
2.115
2.168
2.176
2.184
2.211
2.231
2.240
2.301
2.309
2.316
2.323
2.332
2.345
2.356
2.718
2.733
2.743
2.759
2.774
2.784
2.799
2.963
2.974
2.985
3.005
3.016
3.027
6.836
6.848
6.860
7.024
7.034
7.044
7.260
7.276
7.295
7.314
7.333
7.352
7.372
7.391
7.443
7.461
7.479
7.585
7.605
7.857
7.877
8.530
8.541
8.597
8.618
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
18.463
21.325
30.229
67.124
76.683
77.000
77.319
115.520
116.152
118.661
120.637
121.887
124.500
128.121
128.742
129.377
130.908
132.194
132.490
136.576
157.783
158.053
166.031
157.4157.6157.8158.0158.2158.4f1 (ppm)
157.783
158.053
128129130131132f1 (ppm)
128.121
128.742
129.377
130.908
132.194
132.490
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)
3.07
1.001.012.601.121.981.030.991.921.01
1.75
0.010
1.851
1.867
6.915
6.994
7.010
7.026
7.042
7.228
7.247
7.260
7.298
7.318
7.337
7.352
7.371
7.390
7.499
7.517
7.535
7.614
7.633
7.891
7.910
8.298
8.318
8.666
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
19.759
67.308
76.682
77.000
77.318
107.097
114.387
114.657
120.739
122.391
124.044
128.240
128.628
129.348
130.233
132.892
136.938
140.396
156.193
158.474
165.732
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.27
2.25
1.071.192.861.132.161.061.012.06
0.003
3.820
5.534
6.672
7.109
7.128
7.148
7.247
7.260
7.264
7.268
7.285
7.339
7.360
7.411
7.432
7.452
7.547
7.565
7.584
7.620
7.640
8.037
8.058
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
29.928
58.802
76.682
77.001
77.319
104.009
109.274
119.737
121.041
122.370
127.071
128.421
129.667
129.774
133.194
133.603
138.041
166.145
129.5130.0130.5131.0131.5132.0132.5133.0133.5f1 (ppm)
129.667
129.774
133.194
133.603
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.05
2.20
0.98
1.361.092.091.031.02
1.971.00
0.014
4.031
5.715
6.760
7.247
7.248
7.260
7.271
7.273
7.330
7.332
7.342
7.344
7.346
7.356
7.358
7.448
7.460
7.474
7.533
7.534
7.536
7.546
7.547
7.549
7.567
7.570
7.572
7.580
7.582
7.584
7.592
7.595
7.597
8.089
8.092
8.104
8.106
8.166
8.180
0102030405060708090100110120130140150160170180190200210f1 (ppm)
53.861
60.991
76.789
77.001
77.212
110.805
115.641
120.764
123.308
124.860
128.431
128.734
129.692
129.944
133.128
134.812
136.758
151.962
166.056
128.0128.5129.0129.5130.0130.5f1 (ppm)
128.431
128.734
129.692
129.944
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.11
2.06
1.072.001.561.111.00
1.90
1.011.82
0.030
3.857
5.875
6.846
6.899
6.919
7.241
7.260
7.270
7.274
7.279
7.317
7.337
7.356
7.592
7.612
7.959
7.979
8.502
8.522
8.713
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
55.379
61.506
76.683
77.000
77.318
109.230
113.597
115.224
120.597
122.369
123.990
128.948
131.590
135.517
136.904
156.234
158.367
163.393
165.806
122.3122.4122.5122.6122.7f1 (ppm)
122.369
122.529
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.10
2.19
0.94
2.042.801.001.83
0.981.87
0.006
2.381
5.893
6.854
7.235
7.254
7.260
7.273
7.284
7.303
7.315
7.321
7.336
7.354
7.372
7.594
7.613
7.777
7.799
8.493
8.514
8.734
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
21.247
61.675
76.683
77.000
77.318
109.524
114.208
115.203
120.693
122.591
124.112
126.728
130.076
133.823
135.294
136.980
138.177
156.305
158.463
166.290
129.4129.8130.2130.6f1 (ppm)
129.933
130.076
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
2.09
0.95
1.791.011.871.001.87
0.951.84
0.006
5.895
6.844
7.240
7.260
7.277
7.321
7.342
7.360
7.383
7.403
7.593
7.612
7.915
7.936
8.505
8.526
8.731
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
-0.131
61.918
76.682
77.000
77.319
109.819
114.221
115.315
120.727
124.250
128.476
128.884
134.930
139.544
156.278
158.482
165.268
128.0128.5129.0129.5f1 (ppm)
128.476
128.757
128.884
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
2.14
1.031.761.071.081.141.931.001.000.84
1.011.820.82
0.014
5.995
6.908
7.245
7.260
7.282
7.329
7.349
7.367
7.430
7.449
7.469
7.517
7.535
7.554
7.580
7.600
7.619
7.871
7.892
8.002
8.022
8.073
8.091
8.519
8.540
8.746
8.906
8.927
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
61.777
76.682
77.000
77.318
109.940
114.222
115.307
120.724
122.618
124.172
124.455
125.663
126.205
126.840
127.812
128.539
128.954
130.260
133.492
156.314
158.498
166.990
134.0135.0136.0137.0f1 (ppm)
133.492
133.795
135.180
137.024
124125126127128129f1 (ppm)
124.172
124.455
125.663
126.205
126.840
127.812
128.539
128.954
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.09
2.04
1.09
2.261.100.97
1.001.92
0.008
2.079
5.663
6.775
7.224
7.243
7.260
7.301
7.320
7.338
7.574
7.593
8.488
8.509
8.754
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
20.973
61.256
76.682
77.000
77.319
109.528
114.105
115.318
120.613
122.570
124.079
128.890
135.177
136.917
156.226
158.402
170.548
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
2.06
1.00
1.24
1.06
1.02
1.04
1.99
0.006
4.761
6.709
7.230
7.248
7.260
7.267
7.301
7.321
7.339
7.569
7.588
8.470
8.491
8.779
0102030405060708090100110120130140150160170180190200210f1 (ppm)
-0.019
58.004
76.683
77.000
77.317
110.194
113.708
115.506
120.899
122.857
124.242
129.171
136.797
139.721
155.874
158.729
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
3.033.00
2.04
2.04
0.97
4.074.394.132.16
2.04
0.017
3.719
3.871
4.407
5.552
6.119
7.005
7.023
7.042
7.057
7.075
7.094
7.112
7.132
7.150
7.233
7.260
7.277
7.297
7.362
7.382
7.400
7.412
7.432
7.507
7.525
7.538
7.557
7.934
7.953
0102030405060708090100110120130140150160170180190200210f1 (ppm)
22.683
29.730
30.002
56.209
76.683
77.000
77.318
100.492
108.656
109.239
112.015
119.111
119.484
119.639
120.575
127.003
129.582
133.125
137.300
137.603
139.718
166.155
119.0119.4119.8120.2120.6f1 (ppm)
119.111
119.484
119.639
119.861
120.575
129.55129.65129.75129.85f1 (ppm)
129.582
129.692
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)
2.903.142.00
1.95
1.871.002.091.951.091.981.84
0.001
3.653
3.839
3.915
5.654
6.744
6.747
6.750
7.033
7.260
7.328
7.347
7.367
7.430
7.452
7.486
7.505
7.524
7.678
7.699
7.886
7.907
0102030405060708090100110120130140150160170180190200210220f1 (ppm)
30.124
52.262
55.738
56.920
76.682
77.001
77.319
101.739
113.893
115.065
116.678
128.306
129.176
129.565
129.637
131.262
133.068
139.647
156.035
165.867
168.114
170.881
132.9133.1133.3133.5133.7f1 (ppm)
133.068
133.237
133.353
129.50129.60129.70129.80f1 (ppm)
129.565
129.637
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